有机羧酸改性氧化铝纳米颗粒在聚丙烯中的成核效果研究

doi:10.11949/0438-1157.20190578

摘要/Abstract

摘要：

利用正庚酸、硬脂酸、环己基甲酸和苯甲酸对氧化铝纳米粒子表面进行化学改性，研究了改性粒子表面的基团结构以及接枝量对其在聚丙烯(iPP)基体中成核效果的影响。结果表明：与直链烷基和环烷基羧酸相比，苯甲酸改性颗粒(BA-Al₂O₃)具有优异的成核效果，当BA-Al₂O₃的添加量为0.1%(质量)时，成核聚丙烯的结晶温度和弯曲模量相对于纯iPP分别提高了9.4℃和21.9%。改性纳米颗粒BA-Al₂O₃的苯甲酸接枝量对复合材料的结晶温度和力学性能也有重要影响，接枝量小于1.3 mmol/(g Al₂O₃)时，BA-Al₂O₃的成核效果随接枝量增加而显著增加；接枝量大于1.3 mmol/(g Al₂O₃)时，成核效果略微增加。所以，通过调控改性颗粒的表面结构，可以有效提升iPP复合材料的结晶和力学性能。

关键词: 纳米粒子, 合成, 基团结构, 接枝量, 聚丙烯, 复合材料, 成核

Abstract:

A series of modified alumina (Al₂O₃) nanoparticles (NPs) were synthesized by grafting heptanoic acid, stearic acid, cyclohexanecarboxylic acid and benzoic acid onto Al₂O₃ NPs. The effect of organic structures and grafting yield on the nucleation effect of modified NPs in isotactic polypropylene (iPP) matrix was investigated. The results show that the benzoic acid modified particles (BA-Al₂O₃) have excellent nucleation effect compared with linear alkyl and cycloalkyl carboxylic acids. The crystallization temperature and flexural modulus of nucleated iPP with 0.1% (mass) BA-Al₂O₃ increase by 9.4℃ and 21.9% compared with that of virgin iPP, respectively. The crystallization temperature and mechanical properties of composites are heavily affected by the grafting yield of the benzoic acid on the modified NPs BA-Al₂O₃. When the grafting yield is smaller than 1.3 mmol/(g Al₂O₃), the nucleation effect of BA-Al₂O₃ increases significantly with increasing grafting yield; however, when the grafting yield is higher than 1.3 mmol/(g Al₂O₃), the nucleation effect increases slightly. By regulating the surface structures of modified NPs, it can effectively improve the crystallization behavior and mechanical properties of iPP.

Key words: nanoparticles, synthesis, organic structures, grafting yield, polypropylene, composites, nucleation

中图分类号:

TQ 316.6

蒋晓峰, 赵世成, 辛忠. 有机羧酸改性氧化铝纳米颗粒在聚丙烯中的成核效果研究[J]. 化工学报, 2019, 70(10): 4052-4061.

Xiaofeng JIANG, Shicheng ZHAO, Zhong XIN. Nucleation effect of carboxylic acid modified alumina nanoparticles on polypropylene[J]. CIESC Journal, 2019, 70(10): 4052-4061.

图/表 11

图1 未改性氧化铝颗粒,苯甲酸和改性氧化铝颗粒HA-Al2O3、SA-Al2O3、ChA-Al2O3和BA-Al2O3的红外谱图

Fig.1 FTIR spectra of pristine alumina NPs, benzoic acid, functionalized alumina NPs HA-Al2O3, SA-Al2O3, ChA-Al2O3 and BA-Al2O3

图2 未改性氧化铝颗粒、改性氧化铝颗粒的XRD谱图

Fig.2 XRD patterns of pristine alumina NPs and functionalized alumina NPsa—Al2O3；b—HA-Al2O3；c—SA-Al2O3；d—ChA-Al2O3；e—BA-Al2O3

图3 未改性氧化铝颗粒,改性氧化铝颗粒HA-Al2O3、SA-Al2O3、ChA-Al2O3和BA-Al2O3的TGA曲线

Fig.3 TGA of pristine alumina NPs, functionalized alumina NPs HA-Al2O3, SA-Al2O3, ChA-Al2O3 and BA-Al2O3

表1 改性氧化铝颗粒HA-Al2O3、SA-Al2O3、ChA-Al2O3和BA-Al2O3的总热失重和接枝量

Table 1 Overall mass loss and grafting yield of HA-Al2O3, SA-Al2O3, ChA-Al2O3 and BA-Al2O3

样品	反应比R/ (mmol/(g Al₂O₃))	ΔW/%	接枝量Y/ (mmol/(g Al₂O₃))
HA-Al₂O₃	7	8.4	0.7
SA-Al₂O₃	7	14.4	0.6
ChA-Al₂O₃	7	13.2	1.2
BA-Al₂O₃	1	6.9	0.6

图4 未改性氧化铝颗粒、改性氧化铝颗粒对PP结晶温度以及结晶度(a)和弯曲模量(b)的影响

Fig.4 Effect of pristine alumina NPs, functionalized alumina NPs on crystallization temperature and degree of crystallinity (a) and flexural modulus (b) of iPP

图5 PP纳米复合材料的低温断面形貌SEM图

Fig.5 SEM cryo-fractographs of iPP nanocomposites

图6 未改性氧化铝颗粒、苯甲酸改性氧化铝颗粒BA-Al2O3-x的红外谱图(a)与XRD谱图(b)

Fig.6 FTIR spectra (a) and XRD patterns (b) of pristine alumina NPs and benzoic acid functionalized alumina NPs BA-Al2O3-xa—Al2O3；b—BA-Al2O3-1；c—BA-Al2O3-2；d—BA-Al2O3-3；e—BA-Al2O3-4；f—BA-Al2O3-5；g—BA-Al2O3-6；h—BA-Al2O3-7

表2 苯甲酸改性氧化铝颗粒BA-Al2O3-x的总热失重和接枝量

Table 2 Overall mass loss and grafting yield of BA-Al2O3-x

样品	反应比（R）/ (mmol/(g Al₂O₃))	ΔW/%	接枝量Y/ (mmol/(g Al₂O₃))
BA-Al₂O₃-1	1	6.9	0.6
BA-Al₂O₃-2	2	10.0	0.9
BA-Al₂O₃-3	3	13.3	1.3
BA-Al₂O₃-4	4	20.9	2.2
BA-Al₂O₃-5	5	23.5	2.5
BA-Al₂O₃-6	6	28.7	3.3
BA-Al₂O₃-7	7	30.8	3.6

图7 改性氧化铝颗粒BA-Al2O3-x的苯环接枝量对PP结晶温度、结晶度、力学性能和结合系数的影响

Fig.7 Effect of aromatic group grafting yield of BA-Al2O3-x on crystallization temperature, degree of crystallinity, mechanical properties and adhesion parameter of iPP

图8 PP纳米复合材料的低温断面形貌SEM图

Fig.8 SEM cryo-fractographs of iPP nanocomposites

图9 PP和BA-Al2O3-3成核PP等温结晶过程的POM图

Fig.9 POM micrographs for pure PP and BA-Al2O3-3 nucleated PP crystallized during isothermal crystallization

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