以单分散P(DC-TMPTA)聚合物微球为Pickering乳液稳定剂制备石蜡乳液和石蜡微球

doi:10.7503/cjcu20170848

摘要/Abstract

摘要：

以三羟甲基丙烷三丙烯酸酯(TMPTA)和1-十二烯(DC)为单体, 不使用任何乳化剂或分散稳定剂, 通过沉淀聚合制备了高度单分散P(DC-TMPTA)的聚合物微球颗粒. 以此聚合物微粒为Pickering稳定剂, 不添加任何化学助剂, 以乙醇-水混合介质在70 ℃下通过恒速振荡制得了单分散石蜡Pickering乳液. 将该体系迅速降温至石蜡熔点之下, 制得了窄分布的固体石蜡微球. 研究了连续相水含量、振荡频率及稳定粒子尺寸对Pickering乳液及石蜡微球的影响, 优化了石蜡乳液和微球的制备条件. 利用扫描电子显微镜对石蜡微球的表面和内部形貌进行了表征, 结果表明P(DC-TMPTA)微球全部聚集在石蜡液滴和固化后的石蜡微球表面. 基于石蜡微球和聚合物稳定粒子的尺寸, 计算了不同条件下石蜡微球表面聚合物粒子的数量. 通过聚合物粒子在石蜡-乙醇和水混合溶液界面的三相接触角以及石蜡-乙醇和水混合溶液界面张力的测定, 计算了聚合物粒子在石蜡-乙醇和水混合溶液界面吸附能, 为解释该体系Pickering乳液的稳定性提供了理论支持.

关键词: 沉淀聚合, 聚合物微球, Pickering乳液, 石蜡微球

Abstract:

Polymer particles were prepared through precipitation polymerization of trihydroxymethyl propane triacrylate(TMPTA) with 1-dodecene(DC) in binary solvent of ethanol-water(EtOH-H₂O) without any surfactant and stabilizer. The particles of P(DC-TMPTA) were used to prepare Pickering emulsion of paraffin wax in a mixture of EtOH-H₂O by simple shaking at 70 ℃, above the melting point of the wax. By rapidly cooling down the system to temperature far below the melting point of the wax, wax microspheres with narrow size distribution were obtained. The process was optimized with regard to the composition of EtOH-H₂O, shaking rate and the size of P(DC-TMPTA) particles. Morphology of the wax microspheres was examined by SEM, showing the wax spheres were covered by a layer of P(DC-TMPTA) particles. The size of the wax spheres was easily adjustable, from about 50 μm to 480 μm, by changing the shaking rate or the amount and the size of the polymer particles. This process is featured by the absence of any additives except the free radical initiator in the preparation of P(DC-TMPTA) particles. This work provides therefore a novel pathway to the fabrication of uniform and clean wax microspheres.

Key words: Precipitation polymerization, P(DC-TMPTA) particle, Pickering emulsion, Wax microsphere

中图分类号:

O631
O648.2

TrendMD:

肖作旭, 曹红岩, 姜绪宝, 孔祥正. 以单分散P(DC-TMPTA)聚合物微球为Pickering乳液稳定剂制备石蜡乳液和石蜡微球. 高等学校化学学报, 2018, 39(8): 1797.

XIAO Zuoxu, CAO Hongyan, JIANG Xubao, KONG Xiangzheng. Preparation of Pickering Emulsion of Paraffin Wax and Microspheres Using Polymer Particles as Pickering Stabilizer^†. Chem. J. Chinese Universities, 2018, 39(8): 1797.

图/表 11

Fig.1 Structure illustration of closely packed uniform particles on surface of a large sized microsphere

Fig.2 SEM images of polymer particles prepared at different polymerization timePolymerization time/h: (A) 0.5; (B) 2; (C) 4; (D) 6.

Table 1 Size and distribution of P(DC-TMPTA) particles obtained at different polymerization time

Polymerization time/h	D_n/μm	PDI, D_w/D_n
0.5	1.01	1.008
2.0	1.21	1.013
4.0	1.41	1.010
6.0	1.51	1.006
8.0	1.69	1.020

Fig.3 OM pictures of wax microspheres prepared in EtOH-H2O mixture with different H2O contentContent of H2O(%): (A) 0; (B) 10; (C) 12; (D) 28.

Table 2 Experimental data of wax microspheres prepared in EtOH-H2O mixture

$w H 2 O$ /w_EtOH	D_n/μm	PDI, D_w/D_n	Wax spheres^a(%)	PPs on wax spheres^b(%)	θ/(°)	N/μm^-2
0/100	480.5	1.061	43.97	1.00	64.9	0.081
6/94	305.2	1.048	85.93	6.25	74.7	0.124
10/90	279.3	1.019	88.00	14.25	81.1	0.335
12/88	271.3	1.021	96.86	11.40	82.5	0.338
28/72	270.8	1.042	95.42	6.60	101.4	0.136
36/64	271.8	1.045	93.51	7.25	105.3	0.156

Table 2 Experimental data of wax microspheres prepared in EtOH-H2O mixture

$w H 2 O$ /w_EtOH	D_n/μm	PDI, D_w/D_n	Wax spheres^a(%)	PPs on wax spheres^b(%)	θ/(°)	N/μm^-2
0/100	480.5	1.061	43.97	1.00	64.9	0.081
6/94	305.2	1.048	85.93	6.25	74.7	0.124
10/90	279.3	1.019	88.00	14.25	81.1	0.335
12/88	271.3	1.021	96.86	11.40	82.5	0.338
28/72	270.8	1.042	95.42	6.60	101.4	0.136
36/64	271.8	1.045	93.51	7.25	105.3	0.156

Fig.4 OM pictures of wax microspheres prepared under different shaking rateShaking rate/(osc·min-1): (A) 240; (B) 280; (C) 320; (D) 360.

Table 3 Size and distribution of wax microspheres prepared under different shaking rate

Shaking rate/(osc·min^-1)	D_n/μm	PDI, D_w/D_n	N/μm^-2
200	279.3	1.019	0.335
240	186.8	1.021	0.450
280	136.4	1.019	0.563
320	103.6	1.022	0.653
360	101.4	1.037	0.654

Fig.5 OM pictures of wax microspheres prepared using polymer particles with different size as Pickering stabilizerSize/μm: (A) 1.01; (B) 1.21; (C) 1.41; (D) 1.51.

Table 4 Wax microspheres prepared with polymer particles(PPs) with different diameter

Size of PPs^a/μm	10^-11 $N p b$	D_n/μm	PDI, D_w/D_n	N/μm^-2	N_max/μm^-2	N/N_max
1.01	6.74	57.4	1.033	1.200	1.139	1.054
1.21	4.02	67.9	1.024	0.829	0.809	1.062
1.41	2.48	79.8	1.017	0.675	0.588	1.148
1.51	2.02	103.6	1.022	0.653	0.513	1.173
1.69	1.44	112.8	1.023	0.498	0.410	1.215

Table 4 Wax microspheres prepared with polymer particles(PPs) with different diameter

Size of PPs^a/μm	10^-11 $N p b$	D_n/μm	PDI, D_w/D_n	N/μm^-2	N_max/μm^-2	N/N_max
1.01	6.74	57.4	1.033	1.200	1.139	1.054
1.21	4.02	67.9	1.024	0.829	0.809	1.062
1.41	2.48	79.8	1.017	0.675	0.588	1.148
1.51	2.02	103.6	1.022	0.653	0.513	1.173
1.69	1.44	112.8	1.023	0.498	0.410	1.215

Fig.6 SEM images of wax microspheres as prepared(A) and their interior view(B)Insets are the enlarged image of the same surface and interior view.

Fig.7 Variation of interfacial adsorption energy with contact angleRatio of EtOH/H2O is 90/10; radius of microsphere r is 1.51 μm.

参考文献 31

[1]	Zhang W., Lu P., Qian L., Xiao H., Chem. Eng. J., 2014, 250(6), 431—436
[2]	Su J.F., Wang X. Y., Wang S. B., Zhao Y. H., Huang Z, Energy Conv. Manag., 2012, 55, 101—107
[3]	Destribats M., Schmitt V., Backov R., Langmuir, 2010, 26, 1734—1742
[4]	Zhao H., Li H.P., Liao K. J., Pet. Sci. Technol., 2013, 31(3), 284—292
[5]	Du L., Zhu M., Yang Q., Zhang J., Ma X., Kong D., Wang L., Mater. Lett., 2014, 117, 237—240
[6]	Zhang J., Wu L., Jing D., Ding J., Polymer, 2005, 46, 4979—4985
[7]	Ruhland T.M., Gröschel A. H., Walther A., Müller A. H., Langmuir, 2011, 27(16), 9807—9814
[8]	Liu W., Sun D., Li C., Liu Q., Xu J., J. Colloid Interface Sci., 2006, 303(2), 557—563
[9]	Giermanska J., Thivilliers F., Backov R., Schmitt V., Drelon N., Lealcalderon F., Langmuir, 2007, 23, 4792—4799
[10]	Li C., Mei Z., Liu Q., Wang J., Xu J., Sun D., Colloid Surf. A, 2010, 356(1), 71—77
[11]	Chen Z., Zhao C., Ju E., Ji H., Ren J., Binks B.P., Qu X., Adv. Mater., 2016, 28(8), 1682—1688
[12]	Zhao Y., Xu Z., Niu H., Wang X., Lin T., Adv. Funct. Mater., 2015, 25(3), 437—444
[13]	Zhu X., Zhang Z., Kong X.Z., J. Mater. Chem., 2012, 22(23), 11483—11487
[14]	Gu X.L., Zhu X. L., Kong X. Z., Zhang Z., Soft Matter, 2011, 7(8), 4055—4061
[15]	Chen X., Pan J.M., Yan Y. S., Acta Phys.-Chim. Sin., 2016, 32(11), 2794—2802
	(陈香, 潘建明, 闫永胜. 物理化学学报, 2016, 32(11), 2794—2802)
[16]	Qi F., Wu J., Sun G., Nan F., Ngai T., Ma G., J. Mater. Chem. B, 2014, 2(43), 7605—7611
[17]	Jiang J., Ma Y., Cui Z., Binks B.P., Langmuir, 2016, 32, 8668—8675
[18]	González E., Bonnefond A., Barrado M., Barrasa A.M. C., Asua J. M., Leiza J. R., Chem. Eng. J., 2015, 281, 209—217
[19]	Bai R., Xue L., Dou R., Meng S., Xie C., Zhang Q., Guo T., Meng T., Langmuir, 2016, 32, 9254—9264
[20]	Leong J.Y., Tey B. T., Tan C. P., Chan E. S., ACS Appl. Mater. Interfaces, 2015, 7(30), 16169—16176
[21]	Lin Z., Zhang Z., Li Y., Deng Y., Chem. Eng. J., 2016, 288, 305—311
[22]	Peng L., Feng A., Liu S., Huo M., Fang T., Wang K., Wei Y., Yuan J., ACS Appl.Mater. Interfaces, 2016, 8(43), 29203—29207
[23]	Zhang Z., Gu X.L., Zhu X. L., Kong X. Z, Acta Phys.-Chim. Sin., 2012, 28(4), 892—896
	(张召, 顾相伶, 朱晓丽, 孔祥正. 物理化学学报, 2012, 28(4), 892—896)
[24]	Kong X.Z., Gu X. L., Zhu X. L, Zhang L. N, Macromol. Rapid. Commun., 2009, 30(11), 909—914
[25]	Cao H., Zhang L., Wu L., Kong X.Z., ACS Appl. Mater. Interfaces, 2016, 8(42), 29136—29147
[26]	Anton N., Vandamme T.F., Bouriat P., Soft Matter, 2013, 9(4), 1310—1318
[27]	Binks B.P., Liu W. H., Rodrigues J. A., Langmuir, 2008, 24(9), 4443—4446
[28]	Wu J., Ma G., Small, 2016, 12, 4633—4648
[29]	Binks B.P., Fletcher P. D., Holt B. L., Parker J., Beaussoubre P., Wong K, Phys. Chem. Chem. Phys., 2010, 12(38), 11967—11974
[30]	Boucher E.A., J. Chem. Soc. Faraday Trans. 1, 1989, 85(9), 2963—2972
[31]	Klein S.M., Manoharan V. N., Pine D. J., Lange F. F., Langmuir, 2005, 21(15), 6669—6674