Preparation and characterization of flame retardant bio-based polyols polyurethane foam

doi:10.11949/0438-1157.20221316

Abstract

Abstract:

In this paper, two different soybean oil-based polyols (Polyol-E and Polyol-PPOA) were prepared by ring-opening reaction of epoxidized soybean oil with ethanol and phenylphosphoric acid, respectively. Rigid polyurethane foams of all bio-based polyols were prepared by combining them with isocyanate (PM200) according to different ratios. The cell structure, density, mechanical properties, and flame retardant properties of the prepared rigid polyurethane foams were tested and analyzed. The results of scanning electron microscopy showed that with the increase of the mass fraction of Polyol-PPOA, the number of cells in the samples first decreased and then increased, and when the content of Polyol-PPOA increased, the cell size first increased and then decreased. The density increased first and then decreased with the amount of Polyol-PPOA. The compressive strength showed a trend of first decreasing and then increasing. When the Polyol-PPOA was 70% (mass), the compressive strength reached 0.133 MPa, and the residual carbon rate reached 17.57% at 800℃. The limiting oxygen index also reached the highest at this time, which was 23.10%. Through experiments, it can be found that the rigid polyurethane foam material prepared by using mixed polyols can not only have a certain mechanical strength but also improve a certain flame retardant performance.

Key words: bio-based polyols, epoxidized soybean oil, polyurethane, foam, mechanical properties, flame retardant properties

摘要：

利用环氧大豆油分别与乙醇和苯基磷酸发生开环反应，制备了两种不同的大豆油基多元醇(Polyol-E与Polyol-PPOA)，将二者按照不同的配比与异氰酸酯(PM200)反应制备了硬质聚氨酯泡沫材料。对混合多元醇制备的硬质聚氨酯泡沫材料的泡孔结构、密度、力学性能及阻燃性能进行了测试和分析。测试结果表明，随着Polyol-PPOA质量分数的增加，样品的泡孔数量先减少后增加，泡孔尺寸先增大后减小。密度随着Polyol-PPOA的用量增加先增加后减小。压缩强度呈现先降低后升高的趋势，Polyol-PPOA为70%(质量)时的压缩强度达到0.133 MPa，在800℃时的残炭率达到17.57%，极限氧指数也在这时达到最高，为23.10%。

关键词: 生物基多元醇, 环氧大豆油, 聚氨酯材料, 泡沫, 力学性能, 阻燃性能

CLC Number:

TQ 328.3

Shuai WANG, Fukai YANG, Xinyu XU. Preparation and characterization of flame retardant bio-based polyols polyurethane foam[J]. CIESC Journal, 2023, 74(3): 1399-1408.

王帅, 杨富凯, 徐新宇. 阻燃型全生物基多元醇聚氨酯泡沫的制备及性能研究[J]. 化工学报, 2023, 74(3): 1399-1408.

Figures/Tables 15

Fig.1 Synthetic route of Polyol-E

Fig.2 Synthetic route of Polyol-PPOA

Table 1 Polyurethane foam material formulation

Samples	Polyol-E/g	Polyol-PPOA/g	H₂O/ g	A1/ g	T9/ g	AK-158/ g	PM-200/ g
PUF-0	100	0	2.50	0.50	0.15	0.70	73.20
PUF-1	90	10	2.50	0.50	0.15	0.70	70.32
PUF-2	70	30	2.50	0.50	0.15	0.70	64.56
PUF-3	50	50	2.50	0.50	0.15	0.70	58.82
PUF-4	30	70	2.50	0.50	0.15	0.70	53.06

Fig.3 FTIR spectra of ESO and SOPs

Fig.4 1H NMR spectra of ESO，Polyol-E, and Polyol-PPOA

Table 2 Physical parameters of ESO and SOPs

Sample	OH/(mg KOH/g)	M_n	M_w	PD
ESO	—	1057	1107	1.05
Polyol-E	154.56	1148	1232	1.07
Polyol-PPOA	112.86	1833	3110	1.70

Fig.5 Viscosity curves of ESO and SOPs with temperatures

Fig.6 Apparent density map of PUF

Fig.7 SEM images of PUF cell structure

Fig.8 Compressive stress-strain curve of PUF

Fig.9 Compressive strength of PUF

Fig.10 Thermogravimetric curve of PUF

Table 3 Thermogravimetric data of PUF

Sample	T_5%/℃	T_10%/℃	T_50%/℃	T_max/℃	Residual/%
PUF-0	269	302	422	487	15.05
PUF-1	259	297	432	484	15.69
PUF-2	249	289	431	474	16.55
PUF-3	239	274	434	466	16.66
PUF-4	240	275	432	465	17.57

Table 4 Limiting oxygen index data of PUF

Samples	LOI/%
PUF-0	20.15
PUF-1	20.95
PUF-4	23.10

Fig.11 SEM images of PUF combustion residue

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