孔结构可调聚合物微球的制备及贯通性能

doi:10.16085/j.issn.1000-6613.2019-0870

摘要/Abstract

摘要：

具备贯通性能的聚合物微球在微球材料中具有广泛应用。本文采用溶剂挥发法制备孔结构可调的聚甲基丙烯酸甲酯微球并对微球的贯通性能进行研究。通过调控聚合物浓度、致孔剂用量、溶剂组成以及升温速率等实现微球孔结构可调并研究以上参数对微球贯通性能的影响。结果表明：当聚合物的浓度逐渐升高时，微球内部由中空向多孔结构演变，且随着聚合物浓度的增加，微球内部孔数量增多，孔径变小，贯通性能降低；当致孔剂用量逐渐增加时，微球内部结构由多孔向中空演变，且伴随致孔剂用量的减少，微球孔数量增多，孔径变小，贯通性能降低；无论是调控聚合物浓度还是致孔剂用量，微球的贯通性能与结构密切相关，当微球中空或者内部为稀疏的大孔结构时，贯通性较好，在水溶液中沉降率高达80%以上；使用混合溶剂替代单一溶剂以提高多孔聚合物微球的贯通性，发现微球多孔结构的变化趋势并不明显，但是可以较为显著地改变聚合物微球的贯通性，其中当R_TCM/DCM=3∶10时，微球贯通性最佳，相比单一溶剂条件下，在水溶液中沉降率从30%提高到60%。升温速率对微球贯通性影响巨大，升温过快或过慢均对微球贯通性产生不利影响，40℃/25min条件下所制备微球沉降率较高，约60%。

关键词: 孔结构可调, 贯通孔, 聚甲基丙烯酸甲酯微球, 溶剂挥发, 相分离

Abstract:

Polymer microspheres with inter-connecting pores are widely used as microsphere materials. In this paper, the solvent-evaporation method was used to prepare poly(methyl methacrylate) microspheres with the controllable structures and their inter-connecting properties was studied. It was found that the structure of polymer microspheres was a function of the polymer concentration and the dosage of porogen. By increasing the polymer concentration and decreasing the dosage of porogen, the structure of microspheres evolved from the hollow to the porous; and as the concentration of the polymer increased and the dosage of porogen decreased, the number of the internal pores increased and the pore diameter decreased; at the same time, the inter-connecting performance of the microspheres decreased. A better inter-connecting performance was observed when the microspheres were in hollow structures or with few big pores inside, compared with those ones with the compacted porous structures. In order to improve the inter-connecting properties of the porous polymer microspheres, a mixed organic solvent was used to instead of the single organic solvent and the results showed that the change on the porous structures of the microspheres was not obvious; however, the inter-connecting properties of the polymer microspheres increased. Microspheres were observed to have the best interconnecting property at R_TCM/DCM=3∶10, compared to single solvent conditions, at which the sedimentation rate of polymer microspheres in aqueous solution increased from 30% to 60%. The temperature incremental rate had a great influence on the microspheres’ inter-connecting properties. A slow or fast temperature incremental rate was adverse to the microspheres’ inter-connecting properties. The sedimentation rate of the prepared microspheres in water is the highest at 40℃/25min, which was about 60%.

Key words: controllable structure, inter-connecting pores, PMMA microspheres, solvent evaporation, phase separation

中图分类号:

TQ317

郝军正,祝琳华,王红,司甜,何艳萍,孙彦琳. 孔结构可调聚合物微球的制备及贯通性能[J]. 化工进展, 2020, 39(2): 658-666.

Junzheng HAO,Linhua ZHU,Hong WANG,Tian SI,Yanping HE,Yanlin SUN. Preparation of polymer microspheres with controllable structures and investigation of their inter-connecting properties[J]. Chemical Industry and Engineering Progress, 2020, 39(2): 658-666.

图/表 7

图1 微球制备工艺示意图

表1 实验配方及升温速率

实验序号	二氯甲烷/g	三氯甲烷/g	PMMA/g	正己烷/g	升温速率/℃·min^-1
1a	31.33	—	2	3.5	40/25
1b	23.00	—	2	3.5	40/25
1c	18.00	—	2	3.5	40/25
1d	14.66	—	2	3.5	40/25
1e	11.33	—	2	3.5	40/25
2a	18	—	2	2	40/25
2b	18	—	2	3	40/25
2c	18	—	2	3.5	40/25
2d	18	—	2	4	40/25
2e	18	—	2	6	40/25
3a	18	—	2	3.5	40/25
3b	16.87	2.13	2	3.5	40/25
3c	13.75	4.25	2	3.5	40/25
3d	11.25	6.75	2	3.5	40/25
3e	9.5	8.5	2	3.5	40/25
4a	13.75	4.25	2	3.5	40/60
4b	13.75	4.25	2	3.5	40/40
4c	13.75	4.25	2	3.5	40/25
4d	13.75	4.25	2	3.5	40/20
4e	13.75	4.25	2	3.5	40/15

图2 不同PMMA浓度条件下微球表观和截面的SEM图片以及PMMA浓度与沉降率的关系

图3 不同PMMA浓度条件下的微球样品吸咐量与相对压力的关系

图4 不同致孔剂用量条件下微球表观和截面的SEM图片以及致孔剂用量与沉降率的关系

图5 不同溶剂组成条件下微球表观和截面的SEM图片以及溶剂组成与沉降率的关系

图6 不同升温速率条件下微球表观和截面的SEM图片以及升温速率与沉降率的关系

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