含磷有机聚硅氧烷/地聚物防火涂层在RPUF中的应用

刘杨; 胡胜利; 林贵德; 赵璧; 王俊胜

含磷有机聚硅氧烷/地聚物防火涂层在RPUF中的应用

刘杨^{1, 2, 3},
胡胜利^{1, 2, 3},
林贵德^{1, 2, 3},
赵璧^{1, 2, 3},
王俊胜^{1, 2, 3, ,}

1.
应急管理部天津消防研究所, 天津 300381
2.
工业与公共建筑火灾防控技术应急管理部重点实验室, 天津 300381
3.
天津市消防安全技术重点实验室, 天津 300381

基金项目: 天津市应用基础研究多元投入--城市消防项目(22 JCZDJC00890)；应急管理部天津消防研究所基础科研业务费(2024 SJ26)

详细信息

通讯作者:
王俊胜，博士，研究员，研究方向为防火阻燃材料和消防员个人防护装备　E-mail: wangjunsheng@tfri.com.cn

中图分类号: TB332
计量
- 文章访问数: 27
- HTML全文浏览量: 33
- 被引次数: 0
出版历程
- 收稿日期: 2024-08-20
- 修回日期: 2024-09-30
- 录用日期: 2024-10-07
- 网络出版日期: 2024-10-19

Application of phosphorus-containing organic polysiloxane/geopolymer fireproof coating in RPUF

LIU Yang^{1, 2, 3},
HU Shengli^{1, 2, 3},
LIN Guide^{1, 2, 3},
ZHAO Bi^{1, 2, 3},
WANG Junsheng^{1, 2, 3
, ,}

1.
Tianjin Fire Science and Technology Research Institute of MEM, Tianjin 300381, China
2.
Key Laboratory of Fire Protection Technology for Industry and Public Building, Ministry of Emergency Management, Tianjin 300381, China
3.
Tianjin Key Laboratory of Fire Safety Technology, Tianjin 300381, China

Funds: Applied Basic Research Foundation of Tianjin Municipality--Urban Fire Protection (22 JCZDJC00890); Basic Scientific Research Expenses of Tianjin Fire Science and Technology Research Institute of MEM (2024 SJ26)

摘要

摘要: 为提高地聚物胶凝材料的抗裂性和与有机基体的粘结性，本文以9, 10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)和乙烯基三乙氧基硅烷(VTES)为主要原料合成了含磷有机聚硅氧烷(PDV)并用于地聚物胶凝材料改性，然后将其涂覆于硬质聚氨酯泡沫(RPUF)表面作为防火涂层。探究了PDV引入量对地聚物胶凝材料表干时间、抗裂性及粘结强度的作用机制，并考察了有机改性地聚物防火涂层厚度对RPUF阻燃性能和燃烧行为的影响。结果表明，PDV的引入可缩短地聚物涂层的表干时间，并有利于改善其抗裂性和与RPUF基体间的粘结强度；有机改性地聚物涂层可赋予RPUF阻燃/防火能力，能够有效抑制、延缓其燃烧热释放及生烟速率，仅涂覆400 μm厚度RPUF的极限氧指数(LOI)≥48%并可通过UL-94 V-0等级；随着涂层厚度的增加，样品的残炭含量逐渐提高，且PDV的引入未对地聚物胶凝材料的热降解行为产生显著影响。
- 地聚物 /
- 聚硅氧烷 /
- 硬质聚氨酯泡沫 /
- 阻燃性能 /
- 燃烧行为
Abstract: In order to improve the crack resistance and adhesion with organic matrix of geopolymer cementitious materials, a novel phosphorus-containing organic polysiloxane (PDV) was synthesized using 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and vinyl triethoxysilane (VTES) as raw materials for the modification of geopolymer cementitious materials. The prepared organic-modified geopolymer cementitious materials were then coated on the surface of the rigid polyurethane foam (RPUF) as a fireproof coating. The effects of PDV content on the surface drying time, crack resistance, and adhesive strength of geopolymer cementitious materials were studied. In addition, the influences of thickness of organic-modified geopolymer fireproof coating on the flame retardant performance and combustion behavior of RPUF were investigated. The results show that the introduction of PDV shortens the surface drying time of geopolymer coating, and is beneficial to improve its crack resistance and adhesive strength with RPUF matrix. The organic-modified geopolymer coating can endow RPUF with flame retardancy/fire resistance, and effectively inhibit the heat release rate and smoke production rate during combustion. Specifically, the coated RPUF (400 μm) can achieve UL-94 V-0 certification, and its limit oxygen index (LOI) is greater than 48%. With the increase of coating thickness, the char residue of the prepared samples gradually increases. Importantly, the introduction of PDV has no significant impact on the thermal degradation behavior of geopolymer cementitious materials.
- geopolymer /
- polysiloxane /
- rigid polyurethane foam /
- flame retardancy /
- combustion behavior

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图 1 含磷有机聚硅氧烷(PDV)的合成路线

Figure 1. Synthetic process of phosphorus-containing organic polysiloxane (PDV)

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图 2 VTES、DOPO、DV及PDV的FT-IR (a)谱图；PDV的¹H NMR (b)谱图

Figure 2. FT-IR spectra (a) of VTES, DOPO, DV and PDV; ¹H NMR spectra (b) of PDV

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图 3 RPUF/GP-PDV样品的表干时间(a)和粘结强度(b)

Figure 3. Surface drying time (a) and adhesive strength (b) of RPUF/GP-PDV samples

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图 4 RPUF/GP-PDV样品经力学测试前后的外观

Figure 4. Appearance of RPUF/GP-PDV samples before and after mechanical testing

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图 5 RPUF/GP-PDV样品(涂层厚度：~400 μm)的LOI (a)和UL-94等级(b)

Figure 5. LOI (a) and UL-94 rating (a) of RPUF/GP-PDV samples (coating thickness: ~400 μm)

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图 6 RPUF/GP-PDV样品经垂直燃烧测试后的外观

Figure 6. Appearance of RPUF/GP-PDV samples after UL-94 testing

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图 7 不同涂层厚度RPUF/GP-PDV-2.0样品经垂直燃烧测试后的外观

Figure 7. Appearance of RPUF/GP-PDV-2.0 samples with different coating thickness after UL-94 testing

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图 8 不同涂层厚度RPUF/GP-PDV-2.0样品的热释放速率(a)、总热释放(b)、烟气释放(c)和质量损失(d)曲线

Figure 8. HRR(a), THR(b), SPR(c) and mass loss (d) curves of RPUF/GP-PDV-2.0 samples with different coating thickness

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图 9 不同涂层厚度RPUF/GP-PDV-2.0样品经锥形量热测试后残炭的数码图像

Figure 9. Photographs of carbon residues for RPUF/GP-PDV-2.0 samples with different coating thickness after cone calorimeter testing

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图 10 RPUF/GP-PDV-2.0 (400 μm)样品的耐火性能

Figure 10. Fire resistance performance of RPUF/GP-PDV-2.0 (400 μm) sample

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图 11 GP和GP-PDV-2.0的TGA (a)和DTG (b)曲线

Figure 11. TG (a) and DTG (b) curves of GP and GP-PDV-2.0

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表 1 含磷有机聚硅氧烷改性地聚物(GP-PDV)胶凝材料的基础配方

Table 1. Basic formulation for phosphorus-containing organic polysiloxane modified geopolymer (GP-PDV) cementitious materials

Sample	Slag/g	Silica fume/g	Na₂O·nSiO₂/g	NaOH/g	Water/g	PDV/g
GP	10	1	4.1	0.9	3	0
GP-PDV-0.5	10	1	4.1	0.9	3	0.5
GP-PDV-1.0	10	1	4.1	0.9	3	1.0
GP-PDV-2.0	10	1	4.1	0.9	3	2.0
GP-PDV-3.0	10	1	4.1	0.9	3	3.0
Notes: GP−geopolymer; PDV−phosphorus-containing organic polysiloxane; GP-PDV−phosphorus-containing organic polysiloxane modified geopolymer.

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表 2 不同涂层厚度RPUF/GP-PDV-2.0样品的阻燃性能

Table 2. Flame retardancy of RPUF/GP-PDV-2.0 samples with different coating thickness

Coating thickness/μm	LOI/%	UL-94
Coating thickness/μm	LOI/%	t₁/s	t₂/s	rating
200	40	12	2	V-1
400	≥48	7	1	V-0
600	≥48	1	1	V-0
Notes: LOI−Limit oxygen index; UL-94−Vertical burning test; t₁−The first afterflame time; t₂−The second afterflame time.

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表 3 不同涂层厚度RPUF/GP-PDV-2.0样品的锥形量热数据

Table 3. Cone calorimeter data of RPUF/GP-PDV-2.0 samples with different coating thickness

Coating thickness/μm	TTI/s	PHRR/(kW·m⁻²)	TTPHRR/s	THR/(MJ·m⁻²)	PSPR/(m²·s⁻¹)	Residue/wt%
0	5	154.4	20	11.8	0.072	16.8
200	22	144.2	40	11.6	0.063	56.5
400	44	130.3	75	11.1	0.042	70.6
600	70	108.6	100	10.7	0.039	74.2
Notes: TTI−Time to ignition; PHRR−Peak of heat release rate; TTPHRR−Time to PHRR; THR−Total heat release; PSPR−Peak of smoke production rate.

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