生物基不饱和聚酯树脂胶液及其棉织物增强复合材料的制备与性能

doi:10.7503/cjcu20160675

摘要/Abstract

摘要：

乙二醇、草酸与马来酸酐通过熔融缩聚制备了一种新型生物基不饱和聚酯(UPOEM). 以丙烯酸环氧大豆油(AESO)与甲基丙烯酸缩水甘油酯(GMA)的共混溶剂作为UPOEM的活性稀释剂, 得到一系列黏度小、生物基含量较高、储存稳定、可与增强棉布浸润良好的生物基不饱和聚酯树脂胶液. 黏度测试表明, GMA可明显降低AESO/UPOEM混合胶液的黏度, 当GMA, AESO和UPOEM以质量比100∶100∶300共混时, 得到的黄色透明树脂胶液的黏度小于780 mPa·s, 仅为原AESO和UPOEM共混胶液黏度的5.4%, 并且可室温储存一个月以上仍保持均匀透明且黏度稳定. 该胶液与增强棉布复合所得绿色复合材料的拉伸断裂强度接近30 MPa, 玻璃化转变温度(T_g)可达90 ℃, 热分解温度( $T d, 5 %$ )在248 ℃以上, 具有潜在应用价值.

关键词: 生物基不饱和聚酯, 丙烯酸环氧大豆油, 甲基丙烯酸缩水甘油酯, 活性稀释剂, 绿色复合材料

Abstract:

A novel blending solvent, the mixture of acrylated epoxidized soybean oil(AESO) and glycidyl methacrylate(GMA), was proposed to prepare bio-based unsaturated polyester systems. The bio-based unsaturated polyester(UPOEM) was synthesized by ethylene glycol, oxalic acid and maleic anhydride via a melt polycondensation. By dilution using the blending solvent of AESO/GMA, the resulting unsaturated polyester resin glues have low viscosity, high bio-based content, good storage stability, and improved wettability with reinforcing fibers. Experimental data show that GMA can effectively reduce the viscosity of the AESO/UPOEM systems. When GMA, AESO and UPOEM are blended in a mass ratio of 100∶ 100∶ 300, the viscosity is decreased to 780 mPa·s, only 5.4% of the original. The GMA/AESO/UPOEM mixture keeps yellow and transparent, and the viscosity is constant at room temperature for more than 30 d. Furthermore, green composites were prepared by compositing the unsaturated polyester systems with cotton fabrics via a free radical polymerization performed at 100 ℃ for 2 h and 150 ℃ for 3 h, under a pressure of 15 MPa in a hot pressing machine, and using a mixture of tert-butyl peroxybenzoate and isophorondiamine as initiator. The tensile and thermo-mechanical properties of the resulting green composites were examined by universal testing machine, dynamic mechanical analysis(DMA) and thermogravimetric analysis(TGA), respectively. The results show that the composites have good tensile strength close to 30 MPa, and their glass transition temperature(T_g) and thermal decomposition temperature(T_d,5%) are greater than 90 ℃ and 248 ℃, respectively. These results suggest that the bio-based unsaturated polyester systems have a great potential for various applications.

Key words: Bio-based unsaturated polyester, Acrylated epoxidized soybean oil, Glycidyl methacrylate, Reactive diluent, Green composite

中图分类号:

O633

TrendMD:

杨泽文, 张艳艳, 付飞亚, 刘向东. 生物基不饱和聚酯树脂胶液及其棉织物增强复合材料的制备与性能. 高等学校化学学报, 2018, 39(5): 1084.

YANG Zewen,ZHANG Yanyan,FU Feiya,LIU Xiangdong. Preparation and Properties of a Bio-based Unsaturated Polyester Resin Glue and Its Cotton Fabric-reinforced Composite^†. Chem. J. Chinese Universities, 2018, 39(5): 1084.

图/表 8

Table 1 Composition ratio, viscosity, bio-based content and gel content for the UPOEM resin gluesa

Resin glue	m(GMA)/g	m(AESO)/g	m(UPOEM)^b/g	Viscosity/(mPa·s)(30 ℃)	Bio-based content(%)	Gel content(%)
UPR1	100	0	400	772±34	80	97.3
UPR2	100	100	300	723±12	79.5	94.1
UPR3	100	200	200	695±14	78.9	93.1
UPR4	100	300	100	572±20	78.4	92.5
UPR5	100	400	0	427±19	77.9	90.4
UPR6	50	200	200	1432±29
UPR7	200	200	200	292±2
UPR8	0	100	300	13406±218
UPR9	0	200	200	9450±263
UPR10	0	300	100	5400±384

Fig.1 FTIR(A) and 1H NMR(B) spectra of UPOEM

Fig.2 Viscosity behavior of the mixture of OA, EG and MA(a) and UPOEM(b) Note:nset: optical image of the mixture of OA, EG and MA(a) and UPOEM(b).

Fig.3 FTIR(A) and 1H NMR(B) spectra of ESO(a) and AESO(b)

Fig.4 Tensile strength and elongation at break of C-UPR1(a), C-UPR2(b), C-UPR3(c), C-UPR4(d) and C-UPR5(e)

Fig.5 Storage modulus(E', A) and loss factor(tanδ, B) of C-UPR1(a), C-UPR2(b), C-UPR3(c), C-UPR4(d) and C-UPR5(e)Note:Inset of (A): E' of C-UPR1(a), C-UPR2(b), C-UPR3(c), C-UPR4(d) and C-UPR5(e) at 25 ℃; inset of (B): Tg of C-UPR1(a), C-UPR2(b), C-UPR3(c), C-UPR4(d) and C-UPR5(e).

Fig.6 TGA curves of C-UPR1(a), C-UPR2(b),C-UPR3(c), C-UPR4(d) and C-UPR5(e)

Table 2 Crosslink density and thermal properties of the C-UPR1—C-UPR5

Composite^a	10^-3 $v e b$ /(mol·m^-3)	$T d, 5 % c$ /℃	$R 600 d$ (%)
C-UPR1	78.6	248.3	17.92
C-UPR2	74.6	263.5	14.97
C-UPR3	71.5	272.5	10.03
C-UPR4	56.8	290.3	7.04
C-UPR5	55.8	295.8	6.74

Table 2 Crosslink density and thermal properties of the C-UPR1—C-UPR5

Composite^a	10^-3 $v e b$ /(mol·m^-3)	$T d, 5 % c$ /℃	$R 600 d$ (%)
C-UPR1	78.6	248.3	17.92
C-UPR2	74.6	263.5	14.97
C-UPR3	71.5	272.5	10.03
C-UPR4	56.8	290.3	7.04
C-UPR5	55.8	295.8	6.74

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