Research on Silicone-modified Boric Phenolic Resin†

doi:10.7503/cjcu20160662

Abstract

Abstract:

(2-Hydroxyphenyl)propyl silicone oil(Si-phenol) was obtained via Williamson ether synthesis, Claisen rearrangement, and hydrosilylation, and then was mixed with phenol. The silicone-modified boric phenolic resin(SBPF) was synthesized via borate esterifieation. The structure of SBPF was analyzed by means of ¹H NMR and FTIR, and the heat-resistance and mechanical performances of SBPF were characterized by TGA, shearing test, tensile test, and impact test. The effects of Si-phenol content on various performances of SBPF were investigated, and the mechanisms were researched. The result shows that the synthesized resin has good heat-resistance, and the introduction of appropriate proportion siloxane segments could improve its adhesive property and enhance its mechanical strength.

Key words: Phenolic resin, Silicon modification, Boric acid, Heat-resistance, Mechanical performance

TrendMD:

GUO Anru, LI Jie, LIU Chang, XIAO Dehai. Research on Silicone-modified Boric Phenolic Resin^†[J]. Chem. J. Chinese Universities, 2016, 37(12): 2284.

Figures/Tables 9

Scheme 1 Synthetic route of Si-phenol(5)

Table1 Reaction ratio of SBPF with different Si-phenol contents*

Sample	Content(%)
Sample	Phenol	Si-phenol	Boron	POM
BPF	100.00	0	21.71	47.87
SBPF-05	95.00	5.00	20.65	45.55
SBPF-10	90.00	10.00	19.60	43.24
SBPF-15	85.00	15.00	18.55	40.92
SBPF-20	80.00	20.00	17.50	38.60
SBPF-25	75.00	25.00	16.45	36.28
SBPF-30	70.00	30.00	15.40	33.96

Fig.1 IR spectrum of Si-phenol(5)

Fig.2 IR spectra of BPF(a) and SBPF(b)

Fig.3 TGA curves of SBPF(a), BPF(b) and PF(c)

Fig.4 Char yield of SBPF with different Si-phenol contents at 800 ℃

Table 2 Char yields and mechanical properties of SBPF with different Si-phenol contentsa

Sample	Char yield at 800 ℃(%)	σ_S/MPa		σ_T/MPa	α/(kJ·m^-2)
Sample	Char yield at 800 ℃(%)	r. t.		σ_T/MPa	200 ℃
BPF	79.5	6.13	5.86	0.97	<0.1^b
SBPF-05	57.7	6.12	5.45	1.06	0.35
SBPF-10	65.2	6.17	5.16	1.17	0.81
SBPF-15	56.7	6.01	5.14	1.15	0.82
SBPF-20	56.4	6.09	4.89	1.01	0.76
SBPF-25	52.7	5.58	3.27	0.95	0.52
SBPF-30	33.7	4.22	1.59	0.88	0.39
PF	43.8	3.95	$c$	0.90	<0.1^b

Table 2 Char yields and mechanical properties of SBPF with different Si-phenol contentsa

Sample	Char yield at 800 ℃(%)	σ_S/MPa		σ_T/MPa	α/(kJ·m^-2)
Sample	Char yield at 800 ℃(%)	r. t.		σ_T/MPa	200 ℃
BPF	79.5	6.13	5.86	0.97	<0.1^b
SBPF-05	57.7	6.12	5.45	1.06	0.35
SBPF-10	65.2	6.17	5.16	1.17	0.81
SBPF-15	56.7	6.01	5.14	1.15	0.82
SBPF-20	56.4	6.09	4.89	1.01	0.76
SBPF-25	52.7	5.58	3.27	0.95	0.52
SBPF-30	33.7	4.22	1.59	0.88	0.39
PF	43.8	3.95	$c$	0.90	<0.1^b

Fig.5 Shear strengths of SBPF with different Si-phenol contents at room temperature(a) and 200 ℃(b)

Fig.6 Impact strengths(A) and tensile strengths(B) of SBPF with different Si-phenol contents

References 12

[1]	Knop A., Scheib W., Chemistry and Application of Phenolic Resins, Springer Press, Berlin, 1979, 1—26
[2]	Knop A., Pilato L.A., Phenolic Resins: Chemistry, Applications, Performance and Future Direction, Springer Press, Berlin, 1985, 1—21
[3]	Sunshine N.B.; Ed.: Kuryla W. C., Papa A. J., Flame Retardancy of Polymeric Materials, Vol. 2 Marcel Dekker Press, New York, 1973, 79—86
[4]	Conley R.T., Quinn D. F.; Ed.: Lewin M., Atlas S. M., Pearce E. M., Flame-retardant Polymeric Materials, Plenum Press, New York, 1965, 133—156
[5]	Pitts A.; Ed.: Kuryla W. C., Papa A. J., Flame Retardancy of Polymeric Materials, Vol. 1, Marcel Dekker Press, New York, 1973, 20—38
[6]	Hilado J.C., Flammability Handbook for Plastics, 2nd Ed., Technomic Press, Westport, Conn, 1974, 142
[7]	Shen K., Griffin T., Fire and Polymers, ACS Symposium Series, Vol. 245, ACS Press, Washington DC, 1990, 215—247
[8]	Yi D. L., Ouyang Z. H., Wu L., Ji C. L., China Adhesives, 2008, 17(1), 12—15
	(易德莲, 欧阳兆辉, 伍林, 吉成林. 中国胶黏剂,2008, 17(1), 12—15)
[9]	Zhang G.W., Study on the Heat Resistant Property of SiC/Organosilicon Modified Phenolic Resin Composite, Wuhan University of Technology, Wuhan, 2012
	(张光武. SiC/有机硅改性酚醛树脂复合材料的耐温性研究, 武汉: 武汉理工大学, 2012)
[10]	Qiu J., Wang G. J., Feng Y. B., Journal of Tongji University(Natural Science), 2007, 35(3), 381—384
	(邱军, 王国建, 冯悦兵. 同济大学学报(自然科学版), 2007, 35(3), 381—384)
[11]	Du Y., Ji F. X., Liu Z. L., Lv C. X., Polymer Materials Science and Engneering, 2003, 19(4), 44—47
	(杜杨, 吉法祥, 刘祖亮, 吕春绪. 高分子材料学与工程,2003, 19(4), 44—47)
[12]	Jones R., Translated by Feng S. Y., Jia F. P., Li M. J., Silicon-containing Polymers, Chemical Industry Press, Beijing, 2008, 2—3
	(冯圣玉, 贾付平, 李美江[译]. 琼斯(美). 含硅聚合物, 北京: 化学工业出版社, 2008, 2—3)

[1]	WANG Junkai, HAN Lei, HUANG Liang, ZHANG Haijun, LI Junyi, LI Saisai. Density Functional Theory Calculation and Experimental Study of Catalytic Synthesis SiC Nano Powders^† [J]. Chem. J. Chinese Universities, 2017, 38(9): 1602.
[2]	CAO Yanfang, SHAO Changzhen, LI Baozong, LI Yi, YANG Yonggang. Preparation of Chiral 3-Aminophenol-formaldehyde Resin Nanofibers Using the Self-assemblies of Tetrapeptides as Template^† [J]. Chem. J. Chinese Universities, 2016, 37(10): 1921.
[3]	WANG Yongpeng, LIU Mengzhu, ZHANG Yuxuan, LIN Yingjian, SHANG Yingshuang, ZHU Xuanbo, ZHANG Haibo, JIANG Zhenhua. Synthesis and Properties of a Novel Boron-containing Poly(arylether ketone) and Its Application in the Preparation of Azo Poly(aryl ether ketone)^† [J]. Chem. J. Chinese Universities, 2014, 35(5): 1086.
[4]	XU Dong-Mei, DING Fei, HAO Jian-Wei, DU Jian-Xin. Preparation of Modified Expandable Graphite and Its Flame Retardant Application in Rigid Polyurethane Foam [J]. Chem. J. Chinese Universities, 2013, 34(11): 2674.
[5]	MA Tao¹, TANG Xiao-Fen², LIU Yu-Zhang², WEI Fa-Lin², TANG Da-Zhen^1*. Preparation and Performance of Water Absorption Rubber with Binary Interpenetrating Networks and Montmorillonite [J]. Chem. J. Chinese Universities, 2009, 30(2): 408.
[6]	LIAN Hui-Qin, WU Xue. Synthesis and Photochromism Property of Three Naphthacenequinone Phenolic Resins [J]. Chem. J. Chinese Universities, 2004, 25(9): 1740.
[7]	LI Juan, LI Jing, QI Yan-Fei, WANG Hong-Fang, WANG En-Bo, HU Chang-Wen, XU Lin, WU Xin-Yu. Synthesis and Anti-liver Cancer Activity of 5-Fluorouracil Salt of 12-Tungstoboric Acid [J]. Chem. J. Chinese Universities, 2004, 25(6): 1010.
[8]	ZHOU De-Feng, ZHAO Yan-Ling, HAO Jie, MA Yue, ZHANG Xi-Yan, SU Zhong-Min, WANG Rong-Shun . Effect of ZnCl₂Doping on the Structure and Properties of Carbonized Phenolic Resin Material [J]. Chem. J. Chinese Universities, 2003, 24(12): 2296.
[9]	WANG Zhong, SHI Zuo-Qing, WANG Rui-Fang . Studies on Sorption Property Forwards Caffeine and Theophylline by Phenolic Resin [J]. Chem. J. Chinese Universities, 2003, 24(10): 1896.
[10]	XIA Ping, JIANG Xu-Lin, YAN De-Yue. Synthesis of Heat-resistant Star-shaped Copolymer of Methyl Methacrylate [J]. Chem. J. Chinese Universities, 2002, 23(2): 336.
[11]	ZHANG Ming, LI You-Rong, YAN Chang-Hao, Nakakita Satoshi, Inoue Shinich, Okamoto Hiroshi. The in situ Reaction of PSBR and the Correlation Study of Hybrid Elastomer [J]. Chem. J. Chinese Universities, 2002, 23(2): 310.
[12]	WAN Xiao-Bo, HE Jin-Bo, XU Ning, XUE Qi, Ishida-H. . New Heat-resistant Polybenzoxazine Synthesized by Electrochemical Method [J]. Chem. J. Chinese Universities, 2001, 22(3): 506.
[13]	JIANG Xu-Lin, YAN De-Yue, LIU Wan-Li . Synthesis of Heat-resistant Copolymers by Atom Transfer Radical Polymerization [J]. Chem. J. Chinese Universities, 2000, 21(10): 1613.
[14]	SHEN Gui-Jun, PENG Zeng-Hui, HUANG Hai-Ying, SHI Yu-Hua, YU Ai-Min, JIN Qin-Han . Studies on Separation of Different Species Containing Boron in Boric Acid Solution Using Electrostatic Ion Chromatography [J]. Chem. J. Chinese Universities, 1999, 20(10): 1538.
[15]	ZHUANG Yin-Feng, YANG Bao-Cheng . Fluorescence Spectra of Sulfomethylated Phenolic Resin Excimer [J]. Chem. J. Chinese Universities, 1992, 13(9): 1275.