铟酞菁功能化的四臂星型聚甲基丙烯酸甲酯的合成及三阶非线性光学性质

doi:10.7503/cjcu20130689

摘要/Abstract

摘要：

以四(2-氯丙酰胺基)氯代铟酞菁[InClPc(NHCOCHClCH₃)₄]为引发剂, 通过原子转移自由基聚合(ATRP)法制得一种新型的以氯代铟酞菁为核的四臂星型聚甲基丙烯酸甲酯(PMMA-InClPc). 通过傅里叶红外光谱(FTIR)、紫外-可见光谱(UV-Vis)和核磁共振氢谱(¹H NMR)表征了PMMA-InClPc的结构; 通过凝胶渗透色谱(GPC)测定了聚合物的分子量及分子量分布; 研究了所制备聚合物的聚合反应动力学, 其聚合过程符合一级反应动力学. 使用调Q倍频Nd∶YAG脉冲激光系统, 在输出激光波长为532 nm, 脉冲宽度为21 ps条件下, 通过Z扫描测试研究了聚合物的三阶非线性光学性质. 通过计算可知, 当PMMA-InClPc的分子量为2902时, 其三阶非线性极化率值最大, 为7.216×10^-10esu.

关键词: 氯代铟酞菁, 原子转移自由基聚合, 三阶非线性极化率, Z扫描

Abstract:

Using tetra-kis(2-chloropropionamido) indium(Ⅲ) phthalocyanine chloride [InClPc(NHCOCHClCH₃)₄] as initiator, a novel four-arm star polymethylmethacrylate(PMMA-InClPc) with an indium chloride phthalocyanine core was synthesized by atom transfer radical polymerization(ATRP) method. PMMA-InClPc structure was characterized by Fourier transform infrared(FTIR) spectroscopy, ultraviolet-visible(UV-Vis) spectroscopy and hydrogen nuclear magnetic resonance spectroscopy(¹H NMR) techniques. The molecular weight and molecular weight distribution of polymer sample were measured by gel permeation chromatograph(GPC). Polymerization reaction kinetics of the synthesized polymer was also studied by GPC. The results show that polymerization process follows a first-order reaction kinetics. The third order nonlinear optical properties were measured by the Z-scan technique at 532 nm using a frequency-doubled Q-switching Nd∶YAG laser pulse with pulse width of 21 ps. When the molecular weight of polymer is 2902, the third-order nonlinear polarizability χ⁽³⁾ reaches the maximum value, which is 7.216×10^-10 esu by calculation. These results display that the synthesized PMMA-InClPc polymer has potential nonlinear optical applications.

Key words: Indium phthalocyanine chloride, Atom transfer radical polymerization, Third-order nonlinear polarizability, Z-scan

中图分类号:

O631

TrendMD:

沈丽媛, 吴燕英, 刘大军, 何兴权. 铟酞菁功能化的四臂星型聚甲基丙烯酸甲酯的合成及三阶非线性光学性质. 高等学校化学学报, 2014, 35(2): 409.

SHEN Liyuan, WU Yanying, LIU Dajun, HE Xingquan. Synthesis and Third-order Nonlinear Optical Properties of Indiumphthalocyanine-functionalized Four-arm Star Polymethylmethacrylate^†. Chem. J. Chinese Universities, 2014, 35(2): 409.

图/表 9

Scheme 1 Synthetic routes of PMMA-InClPc

Table 1 Data of UV-Vis spectrum of the indiumphtha-locyanine chloride derivatives

Sample	λ(B band)/nm	λ(Q band)/nm
InClPc(NO₂)₄	360	671, 744
InClPc(NH₂)₄	350	653, 710
InClPc(NHCOCHClCH₃)₄	364	626, 696
PMMA-InClPc	347	687

Fig.1 UV-Vis spectra of the indiumphthalocyanine chloride derivatives(0.1 mg/mL) in DMFa. InClPc(NO2)4; b. InClPc(NH2)4; c. InClPc(NHCOCHClCH3)4; d. PMMA-InClPc(NH2)4.

Fig.2 GPC traces of different reaction time of PMMA-InClPc obtained through ATRPReaction time, t/h: a. 1; b. 3; c. 6; d. 9; e. 11; f. 12.

Fig.3 Plots of ln([M0]/[Mt])(a) and conversion(b) versus time

Table 2 Data obtained from GPC traces of PMMA-InClPc

t/h	Conv.(%)	M_n	M_w/M_n
1	21.2	4657	1.22
3	24.9	17017	1.24
6	33.1	37294	1.31
9	37.9	54180	1.33
11	42.3	66231	1.35
12	43.3	75672	1.36

Fig.4 Closed aperture Z-scan curve of samples 1(A), 2(B) and 3(C)

Fig.5 Open aperture Z-scan curve of samples 1(A), 2(B) and 3(C)

Table 3 Nonlinear optical properties of PMMA-InClPc evaluated from Z-scans

Number	M_n	10¹¹β/(m·W^-1)	10¹⁷γ/(m²·W^-1)	10¹⁰χ⁽³⁾/esu	t/h
1	2015	420	7	4.132	0.5
2	2902	640	21	7.216	1
3	6253	330	11	3.845	2
4	9394				3

参考文献 35

[1]	Von Brau A., J. Chem. Ber., 1907, 40, 2709—2712
[2]	Monteath Robertson J.,J. Chem. Soc., 1935, 615—621
[3]	Kondratenko N. V., Nemykin V. N., Lukyanets E. A., Kostromina N. A., Volkov S. V., Yagupolskii L. M., J. Porphyrins Phthalocyanines, 1997, 1(4), 341—346
[4]	Hanack M., Schmid G., Sommerauer M., Angew. Chem. Int. Ed. Engl., 1993, 32(10), 1422—1424
[5]	Sommerauer M., Rager C., Hanack M., J. Am. Chem. Soc., 1996, 118(42), 10085—10092
[6]	Kimura M., Shirai H., In the Porphyrin Handbook, Academic Press, New York, 2003, 19, 151—177
[7]	Ho Z. Z., Ju C. Y., Hetherington Ⅲ W. M., J. Appl. Phys., 1987, 62(2), 716—718
[8]	O’Flaherty S. M., Hold S. V., Cook M. J., Torres T., Chen Y., Hanack M., Blau W. J., Adv. Mater., 2003, 15(1), 19—32
[9]	De la Torre G., Vázquez P., Agulló-López F., Torres T., Chem. Rev., 2004, 104(9), 3723—3750
[10]	De la Torre G., Vázquez P., Agulló-López F., Torres T., J. Mater. Chem., 1998, 8(9), 1671—1683
[11]	Calvete M., Yang G. Y., Hanack M., Synth. Met., 2004, 141(3), 231—243
[12]	Chen Y., Hanack M., Blau W. J., Dini D., Liu Y., Lin Y., Bai J. R., J. Mater. Sci., 2006, 41(8), 2169—2185
[13]	Dini D., Hanack M., In the Porphyrin Handbook, Academic Press, New York, 2003, 17, 1—3
[14]	Hosoda M., Wada T., Yamamoto T., Kaneko A., Garito A. F., Sasabe H., Jpn. J. Appl. Phys., 1992, 31, 1071—1075
[15]	Truong K. D., Bandrauk A. D., Tranthi T. H., Grenier P., Houde D., Palacin S., Thin Solid Films, 1994, 244(1/2), 981—984
[16]	Zhang J. L., Wang J. H., Xia H. P., Mater. Rev., 2002, 12(20), 69—71
	(章践立, 王金浩, 夏海平.材料导报,2002, 12(20), 69—71)
[17]	Gu Y. Z., Wang Y., Gan F. X., Mater. Lett., 2002, 52(6), 404—407
[18]	Ma G. H., Guo L. J., Mi J., Liu Y., Qian S. X., Pan D. C., Huang Y., Thin Solid Films, 2002, 410(1), 205—211
[19]	Mathews S. J., Chaitanya Kumar S., Giribabu L., Venugopal Rao S., Mater. Lett., 2007, 61(22), 4426—4431
[20]	He C. Y., Wu Y. Q., Shi G., Duan W. B., Song W. N., Song Y. L., Organic Electronics, 2007, 8(2), 198—205
[21]	Wang H. L., Qi D. D., Xie Z., Cao W., Wang K., Shang H., Jiang J. Z., Chem. Commun., 2013, 49(9), 889—891
[22]	Liu Y., Chen Y., Feng M., Lin Y., Doyle J. J., Blau W. J., Chem. J. Chinese Universities, 2007, 28(11), 2092—2095
	(刘莹, 陈彧, 冯苗, 林楹, 蔡良珍.高等学校化学学报,2007, 28(11), 2092—2095)
[23]	He C. Y., Wu Y. Q., Song Y. L., Wang Y. X., Zu X., Chem. J. Chinese Universities, 2003, 24(8) 1360—1365
	(贺春英, 吴谊群, 宋瑛林, 王玉晓, 左霞.高等学校化学学报,2003, 24(8), 1360—1365
[24]	Doyle J. J., Wang J., O'Flaherty S. M., Chen Y., Slodek A., Hegarty T., Carpenter II L. E., Wöhrle D., Hanack M., Blau W. J., J. Opt. A: Pure Appl. Opt., 2008, 10(7), 075101
[25]	Venkatram N., Rao D. N., Giribabu L., Rao S. V., Appl. Phys. B, 2008, 91(1), 149—156
[26]	Zhu J., Li Y., Chen Y., Wang J., Zhang B., Zhang J., Blau W. J., Carbon, 2011, 49(6), 1900—1905
[27]	He N., Chen Y., Bai J., Wang J., Blau W. J., Zhu J., J. Phys. Chem. C, 2009, 113(30), 13029—13035
[28]	Yüksek M., Elmali A., Durmuᶊ M., Yaglioglu H. G., Ünver H., Nyokong T., J. Opt., 2010, 12(1), 015208
[29]	Tekin S., Kürüm U., Durmuᶊ M., Yaglioglu H. G., Nyokong T., Elmali A., Opt. Commun., 2010, 283(23), 4749—4753
[30]	Wang J., Blau W. J., Chem. Phys. Lett., 2008, 465(4), 265—271
[31]	Özda&lu Ö., Opt. Commun., 2010, 283(2), 330—334
[32]	Li Y. X., Zhu J., Chen Y., Zhang J., Wang J., Zhang B., Blau W. J., Nanotechnology, 2011, 22(20), 205704
[33]	Mathews S. J., Chaitanya Kumar S., Giribabu L., Venugopal Rao S., Opt. Commun., 2007, 280(1), 206—212
[34]	Xia H. P., Nagami M., Opt. Mater., 2000, 15(2), 93—98
[35]	Bian Y. Z., Li L., Dou J. M., Cheng D. Y. Y., Li R. J., Ma C. Q., Ng D. K. P., Kobayashi N., Jiang J. Z., Inorg. Chem., 2004, 43(23), 7539—7544