Foam phase preparation of porous poly(methyl methacrylate-co-butyl acrylate) microspheres in continuous process

doi:10.11949/j.issn.0438-1157.20181012

Abstract

Abstract:

Porous polymeric microspheres have been widely used since their characteristics in the structure. However, the reported methods are less efficient, especially no continuous process was reported to prepare porous polymeric microspheres. Therefore, there is a need to develop a time-saving method with high yield for producing porous polymeric microspheres. This paper reports a continuous process to prepare porous polymeric microspheres via the solvent evaporation method in foam phase, being efficient and of high yield. Preparation of porous poly(methyl methacrylate-co-butyl acrylate) [P(MMA-BA)] microspheres was carried out in a customized continuous reaction device. At a certain stirring rate and reaction temperature, the oil phase and the aqueous phase were pumped continuously into the reactor. Foam phase gradually generated and flowed out from the outlet of the reactor. Porous P(MMA-BA) microspheres were obtained after collecting the bubble phase followed by defoaming, washing, filtration and drying. The average foam flow rate, the microspheres’ yield, the average particle size and the pore structure were investigated as a function of the experimental conditions including the feed rate of the oil phase, the reaction temperature, the stirring rate and the concentration of PVA. The results showed that the reaction temperature was 45℃, the stirring rate was 500 r/min, the oil phase solution feed rate was 30 g/min, the PVA concentration was 1.0% (mass), and the oil phase solution P (MMA-BA): DCM∶HT is 10∶53∶6 respectively, the yield of the porous P(MMA-BA) microspheres was up to 92% and the average particle size is 130 μm. The temperature and the residual amount of the aqueous phase left in the customized continuous reaction device are critical for the foam behavior and the yield of the porous P(MMA-BA) microspheres. This work validates that the customized continuous reaction device is capable to produce porous polymeric microspheres continuously, based on the method to prepare porous polymeric microspheres via solvent evaporation method in foam phase, with improved efficiency and yield. In addition, the method reported in this work is able to use continuously on an industrial scale potentially.

Key words: foam, polymers, porous microspheres, preparation

摘要：

采用在泡沫相进行溶剂挥发的方法，连续、高效制备聚甲基丙烯酸甲酯-丙烯酸丁酯[P(MMA-BA)]共聚物多孔微球。采用自制的连续化反应装置，在一定搅拌速率和反应温度下，向反应器连续加料，在出口处连续收集溢出的泡沫并进行消泡、分散，再经洗涤、过滤、干燥得到多孔聚合物微球。重点研究了油相进料速率、反应温度、搅拌速率、聚乙烯醇用量(PVA浓度)对平均泡沫溢出速率、微球收率、微球粒径以及多孔形态的影响规律。结果表明：在反应温度为45℃，搅拌速率为500 r/min，油相溶液进料速率为30 g/min，PVA浓度为1.0%(质量)，油相溶液中P(MMA-BA)∶二氯甲烷(DCM)∶正庚烷(HT)=10∶53∶6(质量比)的工艺条件下，聚合物微球的收率高达92%，平均粒径为130 μm，P(MMA-BA)微球球形饱满，呈多孔结构。

关键词: 泡沫, 聚合物：多孔微球, 制备

CLC Number:

TQ 31

Qiang ZHOU, Junzheng HAO, Linhua ZHU, Hong WANG, Tian SI, Yanping HE, Yanlin SUN. Foam phase preparation of porous poly(methyl methacrylate-co-butyl acrylate) microspheres in continuous process[J]. CIESC Journal, 2019, 70(3): 1208-1219.

周强, 郝军正, 祝琳华, 王红, 司甜, 何艳萍, 孙彦琳. 泡沫相相分离制备多孔聚合物微球连续化工艺[J]. 化工学报, 2019, 70(3): 1208-1219.

Figures/Tables 16

Fig.1 Schematic diagram of continuous process to prepare porous polymeric microspheres

Table 1 Preparative conditions of porous polymeric microspheres in continuous process

F_{m-oil phase}/(g/min)	T/℃	ω_PVA/%(mass)	N/(r/min)
10	45	1.0	500
20	45	1.0	500
30	45	1.0	500
40	45	1.0	500
50	45	1.0	500
30	35	1.0	500
30	40	1.0	500
30	45	1.0	500
30	50	1.0	500
30	55	1.0	500
30	45	0.5	500
30	45	1.0	500
30	45	1.5	500
30	45	2.0	500
30	45	2.5	500
30	45	1.0	100
30	45	1.0	300
30	45	1.0	500
30	45	1.0	700
30	45	1.0	900

Fig.2 Optical microscope images (a) and SEM images (b) of porous P(MMA-BA) microspheres

Fig.3 Particle size distribution of porous P(MMA-BA) microspheres

Fig.4 Effect of feed rate of oil phase (Fm-oil phase) on average foam flow rate (Fm-foam phase) and microspheres’ yield (Y)

Fig.5 Effect of feed rate of oil phase on feed rate of DCM (Fm-DCM) and average temperature of continuous phase (Taverage)

Fig.6 Effect of temperature (T) on average foam flow rate (Fm-foam phase) and microspheres’ yield (Y)

Fig.7 SEM images of porous microspheres prepared at different temperatures

Fig.8 Effect of temperature (T) on amount of residual liquid (V) and average temperature of continuous phase (Taverage)

Fig.9 Effect of concentration of PVA on average foam flow rate (Fm-foam phase) and microspheres’yield (Y)

Fig.10 Optical microscope images of porous microspheres with different mass fraction of PVA[0.5%(a), 1.5%(b), 2.5%(c)]， effect of concentration of PVA on average particle size of microspheres(d)

Fig.11 Effect of concentration of PVA (ωPVA) on amount of residual liquid (V) and average temperature of continuous phase (Taverage)

Fig.12 Effect of stirring rate on average foam flow rate (Fm-foam phase) and microspheres’ yield (Y)

Fig.13 Optical microscope images of porous microspheres with different stirring rates

Fig.14 Average particle size (a) and particle size distribution (b) of porous microspheres with different stirring rates

Fig.15 Effect of stirring rate on average temperature of continuous phase (Taverage) and amount of residual liquid (V)

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