J. Mater. Sci. Technol. ›› 2022, Vol. 112: 315-328.DOI: 10.1016/j.jmst.2021.09.062
• Research Article • Previous Articles Next Articles
Menghe Zhua,b, Zhewen Maa, Lei Liua,*(
), Jianzhong Zhanga, Siqi Huoc, Pingan Songd,*()
Received:2021-08-17
Revised:2021-09-25
Accepted:2021-09-26
Published:2021-12-29
Online:2021-12-29
Contact:
Lei Liu,Pingan Song
About author:pingan.song@usq.edu.au, pingansong@gmail.com (P. Song).1 These authors contributed equally to this work.
Menghe Zhu, Zhewen Ma, Lei Liu, Jianzhong Zhang, Siqi Huo, Pingan Song. Recent advances in fire-retardant rigid polyurethane foam[J]. J. Mater. Sci. Technol., 2022, 112: 315-328.
Fig. 1. Progress roadmap for flame-retardant RPUFs.
Fig. 2. Chemical structures of (a) P-, (b) N-, (c) P/N-, and (d) Si/S-containing reactive flame retardants.
Fig. 3. (a) LOI, (b) PHRR, (c) THR, and (d) thermal conductivity (λ) comparisons of RPUF containing reactive flame retardants.
| Flame retardant | ϕVM-0(wt%) | LOI(%) | UL-94rating | Change (%) | Refs. | |||
|---|---|---|---|---|---|---|---|---|
| PHRR | THR | Thermal conductivity | ||||||
| EG and derivatives | EG-300 µm particle size | 10.0 | 29.8 | V-0 | -57.7 | -43.8 | +10.8 | [ |
| EG-500 µm particle size | 10.0 | 31.8 | V-0 | -54.1 | -47.2 | +6.3 | [ | |
| EG@MH | 11.5 | 32.6 | - | - | - | - | [ | |
| EG@PMA | 10.0 | 26.0 | V-1 | - | - | - | [ | |
| EG@PGMA | 10.0 | 27.5 | V-0 | - | - | - | [ | |
| APP and derivatives | APP@MF | 10.4 | 21.3 | V-1 | - | - | +2.8 | [ |
| APP@VMF | 16.7 | 25.5 | V-0 | - | - | - | [ | |
| APP@DFN | 16.7 | 24.5 | V-0 | - | - | - | [ | |
| APP@PM | 25.0 | 25.3 | - | -33.7 | -39.2 | - | [ | |
| APP@PO | 20.0 | 24.8 | - | -39.4 | -33.9 | - | [ | |
| APP@β-Cyclodextrin | 25.0 | 24.9 | - | -43.8 | -37.6 | - | [ | |
| APP@M | 16.6 | 23.1 | V-0 | -47.6 | -32.8 | - | [ | |
| APP@BM | 16.7 | 24.0 | V-0 | - | - | - | [ | |
| APP@MH | 16.7 | 24.4 | V-0 | - | - | - | [ | |
| Melamine-based compounds | PUTM | 6.0 | 26.1 | - | - | -12.3 | - | [ |
| MATMP | 15.0 | 25.5 | V-0 | -34.0 | -16.0 | +16.7 | [ | |
| MIFR | 9.0 | 24.5 | V-0 | - | - | - | [ | |
| DPPM | 9.0 | 29.5 | V-0 | -50.4 | -35.7 | - | [ | |
| ZMD | 10.0 | 25.4 | - | -50.1 | -61.8 | - | [ | |
| Other phosphorus-containing compounds | ADP | 30.0 | 23.0 | V-1 | -20.3 | -3.5 | +19.4 | [ |
| Zn-AMP | 20.0 | 25.0 | V-0 | -61.0 | -46.1 | +3.3 | [ | |
| TSPB | 10.6 | 26.5 | V-0 | - | - | - | [ | |
| DOPO-BA | 20.0 | 28.1 | V-0 | -8.5 | -20.5 | -23 | [ | |
| MFcP | 13.8 | - | V-0 | -22.4 | - | +8.2 | [ | |
| HPCTP | 20.0 | 28.7 | - | -46.8 | -39.0 | - | [ | |
Table 1. One-component system for RPUF.
| Flame retardant | ϕVM-0(wt%) | LOI(%) | UL-94rating | Change (%) | Refs. | |||
|---|---|---|---|---|---|---|---|---|
| PHRR | THR | Thermal conductivity | ||||||
| EG and derivatives | EG-300 µm particle size | 10.0 | 29.8 | V-0 | -57.7 | -43.8 | +10.8 | [ |
| EG-500 µm particle size | 10.0 | 31.8 | V-0 | -54.1 | -47.2 | +6.3 | [ | |
| EG@MH | 11.5 | 32.6 | - | - | - | - | [ | |
| EG@PMA | 10.0 | 26.0 | V-1 | - | - | - | [ | |
| EG@PGMA | 10.0 | 27.5 | V-0 | - | - | - | [ | |
| APP and derivatives | APP@MF | 10.4 | 21.3 | V-1 | - | - | +2.8 | [ |
| APP@VMF | 16.7 | 25.5 | V-0 | - | - | - | [ | |
| APP@DFN | 16.7 | 24.5 | V-0 | - | - | - | [ | |
| APP@PM | 25.0 | 25.3 | - | -33.7 | -39.2 | - | [ | |
| APP@PO | 20.0 | 24.8 | - | -39.4 | -33.9 | - | [ | |
| APP@β-Cyclodextrin | 25.0 | 24.9 | - | -43.8 | -37.6 | - | [ | |
| APP@M | 16.6 | 23.1 | V-0 | -47.6 | -32.8 | - | [ | |
| APP@BM | 16.7 | 24.0 | V-0 | - | - | - | [ | |
| APP@MH | 16.7 | 24.4 | V-0 | - | - | - | [ | |
| Melamine-based compounds | PUTM | 6.0 | 26.1 | - | - | -12.3 | - | [ |
| MATMP | 15.0 | 25.5 | V-0 | -34.0 | -16.0 | +16.7 | [ | |
| MIFR | 9.0 | 24.5 | V-0 | - | - | - | [ | |
| DPPM | 9.0 | 29.5 | V-0 | -50.4 | -35.7 | - | [ | |
| ZMD | 10.0 | 25.4 | - | -50.1 | -61.8 | - | [ | |
| Other phosphorus-containing compounds | ADP | 30.0 | 23.0 | V-1 | -20.3 | -3.5 | +19.4 | [ |
| Zn-AMP | 20.0 | 25.0 | V-0 | -61.0 | -46.1 | +3.3 | [ | |
| TSPB | 10.6 | 26.5 | V-0 | - | - | - | [ | |
| DOPO-BA | 20.0 | 28.1 | V-0 | -8.5 | -20.5 | -23 | [ | |
| MFcP | 13.8 | - | V-0 | -22.4 | - | +8.2 | [ | |
| HPCTP | 20.0 | 28.7 | - | -46.8 | -39.0 | - | [ | |
| Flame retardant | ϕ(wt%) | LOI(%) | UL-94rating | Change (%) | Refs. | |||
|---|---|---|---|---|---|---|---|---|
| PHRR | THR | Thermal conductivity | ||||||
| Two component system | EG/Zr-AMP | 12EG/3Zr-AMP | 30.5 | V-0 | -74.4 | -61.5 | +16.7 | [ |
| EG/APP | 10EG/10APP | 29.7 | V-0 | -54.1 | -14.3 | +15.4 | [ | |
| EG/Mg-AMP | 12EG/3Mg-AMP | 29.5 | V-0 | -52.4 | -42.9 | +13.3 | [ | |
| EG/DOPO-HQ | 10EG/5DOPO-HQ | 28.7 | V-0 | -58.5 | 0.0 | - | [ | |
| EG/BDEMPP | 10EG/15BDEMPP | 25.7 | V-0 | -45.1 | -35.6 | - | [ | |
| EG/mSS | 10EG/10mSS | 24.0 | V-0 | -55.0 | -47.0 | 3.9 | [ | |
| EG/DBDPE | 15EG/5DBDPE | 34.0 | V-0 | - | - | - | [ | |
| EG/BAPP | 7.4EG/0.6BAPP | 29.8 | V-0 | -44.8 | -23.5 | 16.4 | [ | |
| EG/APB | 15EG/5APB | 27.9 | - | -57.5 | -42.8 | +0.5 | [ | |
| EG/AHP | 15EG/5AHP | 37.8 | - | -55.1 | -80.0 | - | [ | |
| EG/EMD | 8EG/18EMD | 31.3 | - | -55.5 | -41.5 | +13.6 | [ | |
| EG/DTP | 7.9EG/15.8DTP | 30.2 | - | -48.3 | -6.5 | - | [ | |
| EG/DMMP | 12.8EG/3.2DMMP | 33.0 | - | -65.0 | -57.8 | +10.0 | [ | |
| EG/MAPP | 8.2EG/8.2MAPP | 23.0 | - | -63.5 | -45.6 | - | [ | |
| EG/PEPA | 15EG/5PEPA | 31.9 | - | -65.0 | -37.2 | - | [ | |
| DMMP/MAPP | 11.5DMMP/4.9MAPP | 25.8 | - | -50.9 | -44.9 | - | [ | |
| DMMP/SNGO | 6.5DMMP/ 0.7SNGO | 24.0 | - | -44.8 | -43.8 | -0.8 | [ | |
| ATH/DMMP | 60ATH/10DMMP | 32.4 | - | - | - | - | [ | |
| ATH/TPP | 29ATH/5.8TPP | 29.5 | - | - | - | +8.7 | [ | |
| ATH/MDH | 7.5ATH/2.5MDH | - | - | -50.8 | -10.7 | - | [ | |
| Multi-component system | EG/DMMP/fGO | 6.8EG/2.3DMMP/ 0.2fGO | 28.1 | V-0 | -32.9 | -25.1 | - | [ |
| EG/SiO2/IL | 5EG/1SiO2/0.33IL | - | - | -70.0 | -19.2 | +3.3 | [ | |
| EG/ATH/BH | 12.0EG/27.4ATH/ 27.4BH | 34.0 | - | -63.7 | -25.8 | - | [ | |
| EG/MPP/LDH | 3.7EG/3.7MPP/ 1.1 LDH | 28.0 | - | -38.8 | -5.2 | +4.3 | [ | |
| APP/EMF/DMMP | 2.8APP/28.3EMF/ 2.8DMMP | 29.1 | - | -10.3 | -22.4 | - | [ | |
| APP/Zeolite/DMMP | 8APP/5Zeolite/ 8DMMP | 29.5 | - | -56.0 | -21.4 | - | [ | |
| MAPP/MEG/ OLDH | 3.7MAPP/3.7MEG/1.1OLDH | 26.6 | - | -43.8 | -20.2 | +4.3 | [ | |
Table 2. The performances of two and multi-component systems.
| Flame retardant | ϕ(wt%) | LOI(%) | UL-94rating | Change (%) | Refs. | |||
|---|---|---|---|---|---|---|---|---|
| PHRR | THR | Thermal conductivity | ||||||
| Two component system | EG/Zr-AMP | 12EG/3Zr-AMP | 30.5 | V-0 | -74.4 | -61.5 | +16.7 | [ |
| EG/APP | 10EG/10APP | 29.7 | V-0 | -54.1 | -14.3 | +15.4 | [ | |
| EG/Mg-AMP | 12EG/3Mg-AMP | 29.5 | V-0 | -52.4 | -42.9 | +13.3 | [ | |
| EG/DOPO-HQ | 10EG/5DOPO-HQ | 28.7 | V-0 | -58.5 | 0.0 | - | [ | |
| EG/BDEMPP | 10EG/15BDEMPP | 25.7 | V-0 | -45.1 | -35.6 | - | [ | |
| EG/mSS | 10EG/10mSS | 24.0 | V-0 | -55.0 | -47.0 | 3.9 | [ | |
| EG/DBDPE | 15EG/5DBDPE | 34.0 | V-0 | - | - | - | [ | |
| EG/BAPP | 7.4EG/0.6BAPP | 29.8 | V-0 | -44.8 | -23.5 | 16.4 | [ | |
| EG/APB | 15EG/5APB | 27.9 | - | -57.5 | -42.8 | +0.5 | [ | |
| EG/AHP | 15EG/5AHP | 37.8 | - | -55.1 | -80.0 | - | [ | |
| EG/EMD | 8EG/18EMD | 31.3 | - | -55.5 | -41.5 | +13.6 | [ | |
| EG/DTP | 7.9EG/15.8DTP | 30.2 | - | -48.3 | -6.5 | - | [ | |
| EG/DMMP | 12.8EG/3.2DMMP | 33.0 | - | -65.0 | -57.8 | +10.0 | [ | |
| EG/MAPP | 8.2EG/8.2MAPP | 23.0 | - | -63.5 | -45.6 | - | [ | |
| EG/PEPA | 15EG/5PEPA | 31.9 | - | -65.0 | -37.2 | - | [ | |
| DMMP/MAPP | 11.5DMMP/4.9MAPP | 25.8 | - | -50.9 | -44.9 | - | [ | |
| DMMP/SNGO | 6.5DMMP/ 0.7SNGO | 24.0 | - | -44.8 | -43.8 | -0.8 | [ | |
| ATH/DMMP | 60ATH/10DMMP | 32.4 | - | - | - | - | [ | |
| ATH/TPP | 29ATH/5.8TPP | 29.5 | - | - | - | +8.7 | [ | |
| ATH/MDH | 7.5ATH/2.5MDH | - | - | -50.8 | -10.7 | - | [ | |
| Multi-component system | EG/DMMP/fGO | 6.8EG/2.3DMMP/ 0.2fGO | 28.1 | V-0 | -32.9 | -25.1 | - | [ |
| EG/SiO2/IL | 5EG/1SiO2/0.33IL | - | - | -70.0 | -19.2 | +3.3 | [ | |
| EG/ATH/BH | 12.0EG/27.4ATH/ 27.4BH | 34.0 | - | -63.7 | -25.8 | - | [ | |
| EG/MPP/LDH | 3.7EG/3.7MPP/ 1.1 LDH | 28.0 | - | -38.8 | -5.2 | +4.3 | [ | |
| APP/EMF/DMMP | 2.8APP/28.3EMF/ 2.8DMMP | 29.1 | - | -10.3 | -22.4 | - | [ | |
| APP/Zeolite/DMMP | 8APP/5Zeolite/ 8DMMP | 29.5 | - | -56.0 | -21.4 | - | [ | |
| MAPP/MEG/ OLDH | 3.7MAPP/3.7MEG/1.1OLDH | 26.6 | - | -43.8 | -20.2 | +4.3 | [ | |
Fig. 4. (a) Preparation and expansion processes of expandable graphite, (b) Preparation of EG@MH, (c) EG-PMA and (d) EG@PGMA. (a) [42], Copyright 2019. Reproduced with permission from Elsevier Science Ltd., (b) [43], Copyright 2018. Reproduced with permission from John Wiley & Sons Inc., (c) [44], Copyright 2011. Reproduced with permission from John Wiley & Sons Inc., and (d) [45], Copyright 2015. Reproduced with permission from John Wiley & Sons Inc.
Fig. 5. (a) Performance comparisons of RPUF containing additive flame retardants with a UL-94 V-0 rating. (b) The relationship between LOI and thermal conductivity of RPUF/ additive flame retardants with a UL-94 V-0 rating. (c) The relationship between foam density and thermal conductivity of RPUF with additive flame retardants.
Fig. 6. Preparation of RPUF coated with (a, b) alginate/clay aerogel, (c, d) UV-curable intumescent coating and (e, f) silicone resin (poly-DDPM) and EG. (a, b) [104], Copyright 2016. Reproduced with permission from American Chemical Society, (c, d) [105], Copyright 2020. Reproduced with permission from Elsevier Science Ltd. and (e, f) [12], Copyright 2020. Reproduced with permission from Elsevier Science Ltd.
Fig. 7. Preparation of RPUF with poly(VS-co-HEA) coatings [106], Copyright 2021. Reproduced with permission from American Chemical Society.
Fig. 8. (a) Flame-retardant performances of RPUF with different coating-type flame retardants, (b) comparisons of THR reduction and TSR reduction, (c) comparisons of time to PHRR and PHRR reduction, (d) comparisons of char-TG700 °C and PHRR reduction.
Fig. 9. Industrial and technical applications of flame-retardant RPUF.
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