木质素基阻燃剂改性聚氨酯保温材料的制备及性能

吴玉涛; 王冰冰; 田飞宇; 陈秀兰; 朱春锋; 徐信武

木质素基阻燃剂改性聚氨酯保温材料的制备及性能

1.
林业资源高效利用协同创新中心, 材料科学与工程学院, 南京林业大学, 南京 210037
2.
大亚人造板集团有限公司, 丹阳212300

基金项目: 江苏省科研与实践创新计划项目(KYCX23_1183)

详细信息

通讯作者:
徐信武，博士，教授，博士生导师，研究方向为木质复合材料。　E-mail: xucarpenter@njfu.edu.cn

中图分类号: TQ328.2;TB332
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- 文章访问数: 104
- HTML全文浏览量: 56
- 被引次数: 0
出版历程
- 收稿日期: 2024-02-26
- 修回日期: 2024-03-19
- 录用日期: 2024-03-30
- 网络出版日期: 2024-05-06

Preparation and properties of lignin-based flame retardant-modified polyurethane insulation materials

1.
School of Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, College of Materials Science and Engineering, Nanjing Forestry University, Nanjing, 210037, China, 2. Dare Wood-Based Panels Group Co., Ltd

Funds: Postgraduate Research &Practice Innovation Program of Jiangsu Province (KYCX23_1183)

摘要

摘要: 建筑保温材料的阻燃抑烟性能事关消防安全。本研究基于聚磷酸铵(APP)，针对其界面相容性和抑烟性能差的问题，利用碱木素(AL)、双(4-异氰酸酯基苯基)甲烷(MDI)，制备了核壳结构的膨胀型阻燃剂APP@AL (APP∶MDI∶AL为9∶2∶1)，并应用于硬质聚氨酯(RPU)泡沫保温材料的阻燃处理(添加量25wt%)。通过SEM-EDS、XPS、FT-IR等方法分析APP@AL的结构及组成，采用锥形量热仪(CONE)、热重(TG)等仪器分析了阻燃抑烟性能。结果表明，APP@AL与RPU泡沫基体具有良好的界面相容性。与添加APP的RPU泡沫复合材料相比，APP@AL改性RPU泡沫复合材料的抗压强度显著提高(达31.8%)，导热系数降低(7.0%)；此外，CONE测试表明，平均放热速率和总放热量分别降低27.2%和24.4%，同时抑烟性能显著增强(总产烟量减少 47.6%，总CO产量降低 57.0%)。TG分析表明，APP@AL阻燃剂的热稳定性明显高于APP，且更有助于构建稳定的残炭层。综上，木质素基膨胀型阻燃剂对RPU泡沫保温材料具备优异的阻燃抑烟作用。
- 保温材料 /
- 硬质聚氨酯泡沫 /
- 木质素基阻燃剂 /
- 核壳结构 /
- 抑烟性能 /
- 协同阻燃
Abstract: The fire retardant and smoke suppression performance of thermal insulation materials are crucial factors in ensuring building fire safety. In this study, based on ammonium polyphosphate (APP), a intumescent flame-retardant APP@AL (APP∶MDI∶AL=9∶2∶1) with core-shell structure was prepared by utilizing alkali lignin (AL) and bis(4-isocyanatophenyl) methane (MDI) for its poor interfacial compatibility and smoke suppression performance, and applied to the flame-retardant treatment of rigid polyurethane (RPU) thermal insulation materials (25wt% addition). The structure and composition of APP@AL were analyzed by SEM-EDS, XPS and FT-IR, and the flame retardant and smoke suppression properties were analyzed by CONE and TG instruments. The results show that APP@AL has excellent interfacial compatibility with the RPU matrix. The compressive strength of the APP@AL-modified RPU foam is significantly increased (up to 31.8%) compared with the APP-added RPU foam and the thermal conductivity is reduced (7.0%). CONE test show that mean heat release rate and total heat release were reduced by 27.2 % and 24.4 %, respectively, while smoke suppression was notably enhanced (47.6% reduction in total smoke production and 57.0% reduction in total CO production). TG analysis show that the thermal stability of APP@AL flame retardant is obviously higher than that of APP, and it is more beneficial to build a stable residual char layer. In conclusion, lignin-based intumescent flame retardant has excellent flame retardant and smoke suppression effect on RPU foam insulation materials.
- insulation materials /
- rigid polyurethane foams /
- lignin-based flame retardant /
- core-shell /
- smoke suppression /
- synergistic flame retardant

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图 1 APP和APP@AL的SEM-EDS图像

Figure 1. SEM-EDS of APP and APP@AL

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图 2 (a-c) APP和APP@AL的XPS能谱；(d) APP和APP@AL的红外光谱

Figure 2. (a-c) XPS fine spectra; (d) FTIR spectra for each flame retardant

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图 3 APP@AL的合成机制示意图

Figure 3. Schematic mechanism of APP@AL synthesis

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图 4 Pure RPU(a-a₂)，25APP/RPU(b-b₂)，25APP@AL1/RPU(c-c₂)，25APP@AL2/RPU(d-d₂) ，25APP@AL3/RPU(e-e₂)的SEM图像

Figure 4. SEM image of Pure RPU(a-a₂), 25APP/RPU(b-b₂), 25APP@AL1/RPU(c-c₂), 25APP@AL 2/RPU(d-d₂), 25APP@AL3/RPU (e-e₂)

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图 5 RPU泡沫复合材料的(a) HRR, (b) TSP, (c) COP和(d) CO₂P曲线

Figure 5. (a) HRR, (b) STP, (c) COP, (d) CO₂P curves of RPU foam composites

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图 6 CONE测试后泡沫复合材料残炭的顶视图

Figure 6. Top view of char residual of RPU foam composites after CONE testing

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图 7 在N₂氛围下RPU泡沫复合材料的热稳定性：(a) TG，(b) DTG

Figure 7. Thermal stability of RPU foam composites under N₂ atmosphere: (a) TG, (b) DTG

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图 8 (a) Pure RPU，(b) 25APP/RPU，(c) 25APP@AL1/RPU，(d) 25APP@AL2/RPU/RPU，(e) 25APP@AL3/RPU，(f) 25APP@AL4/RPU残炭的SEM图像

Figure 8. SEM images char residual of (a) Pure RPU; (b) 25APP/RPU;(c) 25APP@AL1/RPU; (d) 25APP@AL2/RPU/RPU; (e) 25APP@AL3/RPU; (f) 25APP@AL4/RPU

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图 9 RPU泡沫复合材料泡沫残炭的拉曼光谱图

Figure 9. Raman spectra of char residual of RPU foam composites

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图 10 APP、APP@AL3和AL在N₂氛围下的热稳定性：(a)TG，(b)DTG

Figure 10. Thermal stability of APP, APP@AL3 and AL under N₂ atmosphere: (a) TG, (b) DTG

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图 11 APP@AL阻燃机制示意图

Figure 11. Schematic illustration for the proposed flame-retardant mechanism of APP@AL

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表 1 APP改性配方

Table 1. formula of APP modification

Formulation	APP@AL1	APP@AL2	APP@AL3	APP@AL4
APP / g	45	45	45	45
MDI / g	5	7.5	10	11.25
AL / g	10	7.5	5	3.75
Notes: APP−Ammonium polyphosphate; MDI− 4 4'-Methylenebiphenyl isocyanate; AL−Alkali lignin.

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表 2 硬质聚氨酯(RPU)泡沫复合材料配方

Table 2. Preparation formula of rigid polyurethane (RPU) foam composites

Formulation	Pure RPU	25APP/RPU	25APP@AL1/RPU	25APP@AL2/RPU	25APP@AL3/RPU	25APP@AL4/RPU
APP/g	0	50	0	0	0	0
APP@AL1/g	0	0	50	0	0	0
APP@AL2/g	0	0	0	50	0	0
APP@AL3/g	0	0	0	0	50	0
APP@AL4/g	0	0	0	0	0	50
LY-4110/g	100	100	100	100	100	100
AK-8805/g	2	2	2	2	2	2
LC/g	1.5	1.5	1.5	1.5	1.5	1.5
HFC-365 mfc/g	33	33	33	33	33	33
PAPI/g	100	100	100	100	100	100
Notes: LY-4110−Polyetherpolyol; AK-8805−Silicone surfactant; LC−Dibutyltin dilaurate; HFC-365 mfc−Foaming agent；PAPI− Polymethylene polyphenyl isocyanate; 25APP/RPU,25APP@AL1/RPU,25APP@AL2/RPU, 25APP@AL3/RPU,25APP@AL4/RPU, the 25 indicates that the amount of flame retardant added is 25% of the total mass of LY-4110 and PAPI.

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表 3 APP和APP@AL中C、P和N元素含量

Table 3. Elemental C, P and N content in APP and APP@AL

Samples	C/wt%	P/wt%	N/wt%
APP	0	26.0	14.4
APP@AL1	13.8	19.5	11.9
APP@AL2	12.9	20.6	12.2
APP@AL3	11.6	22.1	12.8
APP@AL4	11.1	21.5	13.2

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表 4 RPU泡沫复合材料的孔径尺寸、表观密度、导热系数和压缩强度

Table 4. The cell diameter, apparent density, compression strength and thermal conductivity of RPU foam composites

Samples	Cell diameter/μm	Apparent density/(kg·m⁻³)	Thermal conductivity/(mW·m⁻¹·K⁻¹)	Compressive strength/kg
Pure RPU	533 ± 80^*	50.5 ± 1.2	23.2 ± 0.1	194 ± 20
25APP/RPU	601 ± 90	49.4 ± 1.5	24.2 ± 0.2	173 ± 25
25APP@AL1/RPU	455 ± 60	51.8 ± 1.1	22.7 ± 0.1	214 ± 18
25APP@AL2/RPU	458 ± 55	51.7 ± 1.0	22.7 ± 0.2	215 ± 14
25APP@AL3/RPU	444 ± 65	52.0 ± 0.9	22.5 ± 0.2	228 ± 20
25APP@AL4/RPU	449 ± 70	51.9 ± 1.0	22.6 ± 0.2	221 ± 21
Note: * Average and standard deviations.

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表 5 RPU泡沫复合材料燃烧性能测试结果

Table 5. Test results of fire performance of flame-retardant RPU foam composites

Samples	HRR/(kW·m⁻²)		LOI/%	TTI/s	THR/(MJ·m⁻²)	SPR/(cm²·s⁻¹)	TSP/m²	COY/(kg·kg⁻¹)	Residue/%
Samples	PHRR	MHRR	LOI/%	TTI/s	THR/(MJ·m⁻²)	SPR/(cm²·s⁻¹)	TSP/m²	COY/(kg·kg⁻¹)	Residue/%
Pure RPU	403.8	253.1	18.5	6	56.0	0.0094	5.5	279.2	7.4
25APP/RPU	132.6	68.7	26.2	3	25.0	0.0034	2.1	54.2	25.4
25APP@AL1/RPU	149.2	58.6	26.8	5	19.1	0.0027	1.7	27.1	29.2
25APP@AL2/RPU	145.0	56.5	26.9	5	19.0	0.0026	1.5	26.5	28.5
25APP@AL3/RPU	140.5	50.0	27.0	5	18.9	0.0023	1.1	23.3	28.7
25APP@AL4/RPU	150.1	61.6	26.7	5	19.3	0.0025	1.3	25.8	28.0
Notes: PHRR−Peak heat release rate; MHRR−Mean heat release rate; LOI−Limiting oxygen index; TTI−Time to ignition; THR−Total heat release; SPR−Smoke release rate; TSP−Total smoke release; COY−CO yield; Residue−Charcoal residue rate.

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表 6 在相应温度下RPU泡沫复合材料不同热解阶段和800℃的残炭

Table 6. The corresponding temperatures of RPU foam composites at different pyrolysis stages and the char residue at 800℃

Samples	T_10% / ℃	T_50% / ℃	W₈₀₀ / wt%
Pure RPU	272	348	13.0
25APP/RPU	263	333	26.8
25APP@AL1/RPU	287	361	28.7
25APP@AL2/RPU	281	358	28.1
25APP@AL3/RPU	274	352	28.8
25APP@AL4/RPU	276	355	28.4
Notes: T_10% and T_50% represent the temperature where 10wt% and 50wt% of weight were lost, W₈₀₀ represents the residual weight at 800℃.

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