Novel Macromolecular and Biobased Flame Retardants Based on Cellulose Esters and Phosphorylated Sugar Alcohols
Abstract
:1. Introduction
2. Materials and Method
2.1. Materials
2.2. Methods
2.3. Synthesis of Flame Retardants
2.3.1. Synthesis of the Acrylic Anhydride Solution (AA–AH) (2)
2.3.2. Synthesis of Tetrahydrofuro[3,4-d][1,3,2]dioxaphosphole 2-oxide (5-PAHE) (Phosphorylated Anhydro Erythritol, PAHE)
2.3.3. Synthesis of Cellulose Acrylate Butyrate (4-CeAcBu)
2.3.4. Synthesis of Phosphorylated Cellulose Acrylate Butyrate with PAHE (6-CeAcBu-PAHE)
2.3.5. Synthesis of Phosphorylated Cellulose Acrylate Butyrate with DOPO (6-CeAcBu-DOPO)
2.3.6. Synthesis of Cellulose Acrylate Propionate (4-CeAcPr)
2.3.7. Synthesis of Cellulose Acrylate Propionate (4-CeAcPrSA)
2.3.8. Synthesis of Phosphorylated Cellulose Acrylate Propionate with PAHE (6-CeAcPr-PAHE)
2.3.9. Synthesis of Phosphorylated Cellulose Acrylate Propionate with PAHE (6-CeAcPrSA-PAHE)
2.3.10. Synthesis of Phosphorylated Cellulose Acrylate Propionate with DOPO (6-CeAcPr-DOPO)
2.4. Preparation of Polymer Compounds and UL 94 V Test Specimens
2.5. Flame Test: UL 94 Vertical/DIN EN 60695-11-10
3. Results and Discussion
3.1. Characterization of the Acrylic Acid Anhydride Solution (2)
3.2. Characterization of the Cellulose Esters (4)
3.3. Characterization of Tetrahydrofuro[3,4-d][1,3,2]dioxaphosphole 2-oxide (5-PAHE)
3.4. Characterization of the Flame Retardant (Phosphorylated Cellulose Esters, 6)
3.5. Thermal Analysis of the Flame Retardants
3.6. Processing and Thermal Characterization of Polymer Compounds
3.7. Flame Retardant Results
4. Conclusions
5. Patents
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Appendix A
Appendix B
Formulation No. | Specimen No. | DBDE/ ATO | PBDS | 6-CeAcBu-PAHE | UL 94 V Test a | |||
---|---|---|---|---|---|---|---|---|
First Burning Time [s] | Second Burning Time [s] | Burning Cotton [yes/no] | UL 94 V Rating | |||||
I-PP-PE | 1 | - | - | - | 61 | - | Y | NC |
2 | - | - | - | 68 | - | Y | ||
3 | - | - | - | 60 | - | Y | ||
4 | - | - | - | 59 | - | Y | ||
5 | - | - | - | 71 | - | Y | ||
II-PP-PE | 1 | 6.7/3.3 | - | - | 2 | - | Y | V-2 |
2 | 6.7/3.3 | - | - | 2 | - | Y | ||
3 | 6.7/3.3 | - | - | 1 | 1 | Y | ||
4 | 6.7/3.3 | - | - | - | - | Y | ||
5 | 6.7/3.3 | - | - | - | 1 | Y | ||
III-PP-PE | 1 | - | 10 | - | 57 | - | Y | NC |
2 | - | 10 | - | 56 | - | Y | ||
3 | - | 10 | - | 59 | - | Y | ||
4 | - | 10 | - | 52 | - | Y | ||
5 | - | 10 | - | 58 | - | Y | ||
IV-PP-PE | 1 | - | - | 10 | 4 | 1 | Y | NC |
2 | - | - | 10 | 4 | 55 | Y | ||
3 | - | - | 10 | 6 | 55 | Y | ||
4 | - | - | 10 | 7 | 40 | Y | ||
5 | - | - | 10 | 4 | 52 | Y | ||
V-PP-PE | 1 | - | 2 | 8 | 1 | 1 | Y | V-2 |
2 | - | 2 | 8 | 1 | 0 | Y | ||
3 | - | 2 | 8 | 1 | 0 | Y | ||
4 | - | 2 | 8 | 2 | 0 | Y | ||
5 | - | 2 | 8 | 1 | 0 | Y |
Formulation No. | Specimen No. | DEPAL | 6-CeAcBu-PAHE | UL 94 V Test a | |||
---|---|---|---|---|---|---|---|
First Burning Time [s] | Second Burning Time [s] | Burning Cotton [yes/no] | UL 94 V Rating | ||||
I-PA | 1 | - | - | 3 | 3 | Y | V-2 |
2 | - | - | 4 | - | Y | ||
3 | - | - | 3 | 2 | Y | ||
4 | - | - | 4 | 1 | Y | ||
5 | - | - | 3 | 2 | Y | ||
II-PA | 1 | 20 | - | 1 | 3 | N | V-0 |
2 | 20 | - | 0 | 3 | N | ||
3 | 20 | - | 2 | 3 | N | ||
4 | 20 | - | 0 | 3 | N | ||
5 | 20 | - | 0 | 0 | N | ||
III-PA | 1 | - | 20 | 2 | 0 | N | V-2 |
2 | - | 20 | 0 | 0 | N | ||
3 | - | 20 | 1 | 0 | Y | ||
4 | - | 20 | 0 | 0 | N | ||
5 | - | 20 | 1 | 0 | N |
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Flame Retardant | Cellulose Type | Cellulose Modification | Catalyst for Esterification | Functional Group |
---|---|---|---|---|
6-CeAcPrSA-PAHE | cotton | propionate ester | H2SO4 | PAHE |
6-CeAcBu-PAHE | cotton | butyrate ester | ZnCl2 | PAHE |
6-CeAcBu-DOPO | cotton | butyrate ester | ZnCl2 | DOPO |
Flame Retardants | 2% Mass Loss [°C] | 5% Mass Loss [°C] | Residual Mass at 800 °C [%] |
---|---|---|---|
6-CeAcPrSA-PAHE | 267 | 277 | 32.6 |
6-CeAcBu-PAHE | 288 | 297 | 36.7 |
6-CeAcBu-DOPO | 295 | 312 | 18.7 |
Formulation No. | Composition | 6-CeAcBu-PAHE | PBDS | DBDE | ATO |
---|---|---|---|---|---|
I-PP-PE | PP-co-PE | - | - | - | |
II-PP-PE | PP-co-PE +DBDE + ATO | - | - | 6.7 | 3.3 |
III-PP-PE | PP-co-PE + PBDS | - | 10 | - | |
IV-PP-PE | PP-co-PE + 6-CeAcBu-PAHE | 10 | - | - | |
V-PP-PE | PP-co-PE + 6-CeAcBu-PAHE + PBDS | 8 | 2 | - |
Formulation No. | Composition | 6.1B | DEPAL |
---|---|---|---|
I-PA | PA | - | - |
II-PA | PA + DEPAL | - | 20 |
III-PA | PA + 6-CeAcBu-PAHE | 20 | - |
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Kaplan, M.; Ciesielski, M.; Fuchs, S.; Getterle, C.; Schönberger, F.; Pfaendner, R. Novel Macromolecular and Biobased Flame Retardants Based on Cellulose Esters and Phosphorylated Sugar Alcohols. Polymers 2023, 15, 3195. https://doi.org/10.3390/polym15153195
Kaplan M, Ciesielski M, Fuchs S, Getterle C, Schönberger F, Pfaendner R. Novel Macromolecular and Biobased Flame Retardants Based on Cellulose Esters and Phosphorylated Sugar Alcohols. Polymers. 2023; 15(15):3195. https://doi.org/10.3390/polym15153195
Chicago/Turabian StyleKaplan, Matay, Michael Ciesielski, Sabine Fuchs, Christoffer Getterle, Frank Schönberger, and Rudolf Pfaendner. 2023. "Novel Macromolecular and Biobased Flame Retardants Based on Cellulose Esters and Phosphorylated Sugar Alcohols" Polymers 15, no. 15: 3195. https://doi.org/10.3390/polym15153195