松香改性聚硅氧烷阻燃剂的制备及应用研究

doi:10.3969/j.issn.0253-2417.2022.02.010

摘要/Abstract

摘要：

为了提高聚硅氧烷的阻燃效率，利用松香和氨基聚硅氧烷的酰胺化反应，制备了一种新型的松香改性聚硅氧烷阻燃剂(RGSO)，并将其作为“软段”的一部分与聚醚多元醇复配，通过“一步法”制备成阻燃硬质聚氨酯泡沫(RPUF)材料。当松香引入量为5、10、15和20 g时，分别得到阻燃硬质聚氨酯泡沫RPUF-1~RPUF-4。采用红外光谱(FT-IR)和热裂解气相色谱质谱(Py-CG/MS)对阻燃剂的结构进行了表征，并对聚氨酯泡沫的微观形貌、热稳定性、阻燃性能和压缩强度进行了分析。研究结果表明：松香氢化菲环结构限制了环状硅氧烷气体的释放，从而提高了富硅炭层的致密性，使其成为一种有效的隔绝热氧的屏蔽层包覆在基材表面，赋予材料优异的阻燃性能。与未改性的硬质聚氨酯泡沫(P-RPUF)相比，松香引入量15 g的阻燃聚氨酯泡沫(RPUF-3)的极限氧指数(LOI)提升了37.1%，最大热释放速率(PHRR)下降了44.8%，火焰蔓延速率(FIGRA)由10.99 kW/(m²·s)降低至4.33 kW/(m²·s)，表明RGSO的加入使得聚氨酯泡沫的综合阻燃性能显著提高；同时，松香的氢化菲环刚性结构赋予了阻燃聚氨酯泡沫出色的压缩强度，RPUF-4的压缩强度达366.7 kPa，相比S-RPUF的112.5 kPa有明显的提升。

关键词: 阻燃, 有机硅, 松香, 聚氨酯泡沫

Abstract:

In order to enhance the flame retardancy of polysiloxane, a novel flame retardant rosin grafted polysiloxane(RGSO) was synthesized by the amidation reaction of rosin and amino-polysiloxane. The synthesized flame retardant was employed as a part of the soft segment to produce flame-retarding rigid polyurethane foam(RPUF) by "one-pot" process. The flame retardant rigid polyurethane foams(RPUF-1-RPUF-4) were obtained with the rosin amounts of 5, 10, 15 and 20 g. The structure of the flame retardants was characterized by FT-IR and Py-GC/MS. The microstructure, thermal stability, flame retardant property and compressive strength of the RPUFS were analyzed. The results showed that the hydrogenated phenanthrene ring structure of rosin inhibited the gas release of cyclosioxane and promoted the compactness of the silica-rich carbon layer, and invested the materials with excellent flame retardant since it become shielding layer coated on the substrate surface and effectively insulated thermal and oxygen flame retardant. Compared with unmodified RPUF(P-RPUF), the limited oxygen index(LOI) value of the modified sample(RPUF-3) increased by 37.1%, and the peak heat release rate(PHRR) of the modified sample decreased by 44.8%. The fire growth rate(FIGRA) of the modified materials decreased from 10.99 kW/(m²·s) to 4.33 kW/(m²·s), which indicated that the introduction of RGSO could significantly enhance the flame retardant performance of RPUF. Meanwhile, the rigid hydrogenated phenanthrene ring structure of rosin improved the compressive strength of the modified RPUF. The compressive strength of RPUF-4 was 366.7 kPa, which was higher than that of S-RPUF(112.5 kPa).

Key words: flame retardancy, siloxane, rosin, polyurethane foam

中图分类号:

TQ35

黄真, 王诗博, 任春雨, 刘鹤, 徐徐, 宋湛谦. 松香改性聚硅氧烷阻燃剂的制备及应用研究[J]. 林产化学与工业, 2022, 42(2): 71-79.

Zhen HUANG, Shibo WANG, Chunyu REN, He LIU, Xu XU, Zhanqian SONG. Preparation and Application of Rosin Modified Siloxane-based Flame Retardant[J]. Chemistry and Industry of Forest Products, 2022, 42(2): 71-79.

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样品 sample	MTASO/g	松香/g rosin	黏度/(mPa·s) viscosity
RGSO-1	45	5	6500
RGSO-2	40	10	6650
RGSO-3	35	15	6710
RGSO-4	30	20	6800

编号 No.	主要产物 main product	相对峰面积relative peak area/%
编号 No.	主要产物 main product	MTASO	RGSO-3
1	D₃	6.51	6.22
2	D₄	31.02	41.96
3	D₅	28.28	17.98
4	D₆	18.46	9.07
5	D₇	8.18	3.81
6	D₉	1.91	1.42

样品 sample	阻燃剂 flame retardant	初始热分解温度/℃ initial decomposition temp.	最大热失重速率温度/℃ the maximum loss ratio temp.	最大热失重速率/(%·min^-1) the maximum loss ratio	残渣率(800 ℃)/% residual
P-RPUF	无no	286.4	326.4	5.86	2.1
S-RPUF	MTASO	272.2	327.2	5.33	5.3
RPUF-3	RGSO-3	275.1	330.1	3.61	9.4

样品 sample	最大热释放速率/(kW·m^-2) peak heat release rate(PHRR)	总热释放量/(MJ·m^-2) total heat release(THR)	达到最大热释放速率时间/s time to peak heat release rate(T-PHRR)	火焰蔓延速率/(kW·m^-2·s^-1) fire growth rate(FIGRA)
P-RPUF	274.68	42.89	25	10.99
S-RPUF	232.07	42.18	25	9.28
RPUF-3	151.55	40.93	35	4.33

样品 sample	密度/(kg·m^-3) density	压缩强度/MPa compressive strength	比压缩强度/(kN·m·kg^-1) specific compressive strength	水接触角/° water contact angle
P-RPUF	58.0	0.3310	5.71	115.6
S-RPUF	58.3	0.1125	1.93	130.5
RPUF-1	58.4	0.2105	3.60	129.6
RPUF-2	58.4	0.2756	4.72	127.5
RPUF-3	58.6	0.3248	5.54	126.7
RPUF-4	58.7	0.3667	6.25	126.1