Citation: Han Bao, Yue Zhang, Hui-min Tang, Ding-sheng Yu, Ri-wei Xu. Study on the Structure and Properties of Bisphenol A-type Benzoxazine Resins Catalyzed by Organotin Oligomersesquioxanes[J]. Acta Polymerica Sinica, ;2019, 50(1): 55-61. doi: 10.11777/j.issn1000-3304.2018.18166 shu

Study on the Structure and Properties of Bisphenol A-type Benzoxazine Resins Catalyzed by Organotin Oligomersesquioxanes

Key Laboratory of Carbon Fiber and Functional Polymer, Ministry of Education, Beijing University of Chemical Technology, Beijing 100029

Corresponding author: Ri-wei Xu, xurw@mail.buct.edu.cn
Received Date: 17 July 2018
Revised Date: 3 August 2018
Available Online: 8 September 2018

Polybenzoxazines (PBz) is a new type of phenolic-like resins, which have excellent properties such as good mechanical and thermal properties, no volatile release upon cure, and molecular designing flexiblility. However, their major drawbacks are the high curing temperature and similar brittleness as phenolic resins. In this study, organotin silsesquioxanes (DOSn-Bu) are synthesized via capping reaction based on disilanol-POSS and Bu₂SnCl₂. Due to the cage-type hybrid structure, the metal-based oligomeric silsesquioxane (POMSS) possesses good thermal stability and mechanical properties. The mental centers are Lewis acid that catalyze ring-opening polymerization of benzoxazine monomers. The structure of DOSn-Bu was characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (¹H-NMR) and X-ray single crystal diffraction. A series of benzoxazine/DOSn-Bu hybrid resins were prepared by ultrasonic blending. FTIR results showed that the benzoxazine began to ring-open at 160 – 180 °C. The results of DSC showed that the initial curing temperature decreased by almost 50 °C and the peak curing temperature decreased by approximately 30 °C with the addition of DOSn-Bu. The thermal and mechanical properties of the hybrid material with different DOSn-Bu incorporation were measured by dynamic mechanical thermal analysis (DMTA) and thermal gravimetric analysis (TGA). DMTA result showed that the storage modulus ( E′) and glass transition temperature of the hybrid materials were improved. When 2 wt% of DOSn-Bu was added, the resins retained high storage modulus (E′ = 2.1 GPa at 50 °C) and high glass transtion temperature (T_g = 228 °C). TGA study showed that the hybrid materials possessed good thermal stability. From the scanning electron microscopy (SEM) mapping, it was found that the Si and Sn elements were greatly distributed in the system, thereby indicating that the catalysts were uniformly dispersed in the system with good compatibility with the resin matrix. The fracture surface morphologies of the cured resin were investigated by SEM. The roughness of the fracture surface of the hybrid material was increased compared with that of the pure benzoxazine resin and its texture became more complicated.
- DOSn-Bu,
- Benzoxazine,
- Catalytic curing,
- Hybrid materials
1. [1]
  Li G Z, Wang L C, Ni H L, Pittman Jr. C U. J Inorg Organomet Polym, 2001, 11(3): 123 − 154
2. [2]
  Ye Q, Zhou H, Xu J W. Chem Asian J, 2016, 11(9): 1322 − 1337
3. [3]
  Feher F J. J Am Chem Soc, 1986, 108(13): 3850 − 3852
4. [4]
  Feher F J, Newman D A, Walzer J. J Am Chem Soc, 1989, 111(5): 1741 − 1748
5. [5]
  Ouyang J, Sun H T, Liang Y L, Li D, Commisso A, Xu R W, Yu D S. Curr Org Chem, 2017, 21(28): 2829 − 2848
6. [6]
  Duchateau R, Dijkstra T W, Severn J R, van Santen R A, Korobkov I V. Dalton Trans, 2004, (17): 2677 − 2682
7. [7]
  Gun’ ko Y K, Nagy L, Brüser W, Lorenz V, Fischer A, Gieβmann S, Edelmann F T, Jacob K, Vértes A. Monatsh Chem, 1999, 130(1): 45 − 54
8. [8]
  Strachota A, Rodzeń K, Ribot F, Trchová M, Steinhart M, Starovoytova L, Pavlova E. Macromolecules, 2014, 47(13): 4266 − 4287
9. [9]
  Beletskiy E V, Hou X L, Shen Z L, Gallagher J R, Miller J T, Wu Y Y, Li T H, Kung M C, Kung H H. J Am Chem Soc, 2016, 138(13): 4294 − 4297
10. [10]
  Beletskiy E V, Shen Z L, Riofski M V, Hou X L, Gallagher J R, Miller J T, Wu Y Y, Kung H H, Kung M C. Chem Commun, 2014, 50(99): 15699 − 15701
11. [11]
  Beletskiy E V, Wu Y Y, Kung M C, Kung H H. Organometallics, 2016, 35(3): 301 − 302
12. [12]
  Ishida H, Allen D J. J Polym Sci, Part B: Polym Phys, 1996, 34(6): 1019 − 1030
13. [13]
  Ishida H, Sanders D. J Polym Sci, Part B: Polym Phys, 2000, 38(24): 3289 − 3301
14. [14]
  Holly W F, Cope A C. J Am Chem Soc, 1944, 66(11): 1875 − 1879
15. [15]
  Sudha, Sarojadevi. High Perform Polym, 2015, 28(3): 331 − 339
16. [16]
  Xin N, Ishida H. J Polym Sci, Part A: Polym Chem, 1994, 32(6): 1121 − 1129
17. [17]
  Xu Y, Dai J, Ran Q C, Gu Y. Polymer, 2017, 123: 232 − 239
18. [18]
  Hanbeyoglu B, Kiskan B, Yagci Y. Macromolecules, 2013, 46(21): 8434 − 8440
19. [19]
  Ishida H, Rodriguez Y. J Appl Polym Sci, 1995, 58(10): 1751 − 1760
20. [20]
  Wang Y X, Ishida H. Polymer, 1999, 40: 4563 − 4570
21. [21]
  Ručigaj A, Alič B, Šebenuk U. Express Polym Lett, 2015, 9(7): 647 − 657
22. [22]
23. [23]
  Sharma P, Kumar D, Roy P K. Polymer, 2018, 138: 343 − 351
24. [24]
  Sudo A, Hirayama S J, Endo T. J Polym Sci, Part A: Polym Chem, 2010, 48(2): 479 − 484
25. [25]
26. [26]
  Velez-Herrera P, Doyama K, Abe H, Ishida H. Macromolecules, 2008, 41(24): 9704 − 9714
1. [1]
  Caixia Lin , Zhaojiang Shi , Yi Yu , Jianfeng Yan , Keyin Ye , Yaofeng Yuan . Ideological and Political Design for the Electrochemical Synthesis of Benzoxathiazine Dioxide Experiment. University Chemistry, 2024, 39(2): 61-66. doi: 10.3866/PKU.DXHX202309005
2. [2]
  Yue Wu , Jun Li , Bo Zhang , Yan Yang , Haibo Li , Xian-Xi Zhang . Research on Kinetic and Thermodynamic Transformations of Organic-Inorganic Hybrid Materials for Fluorescent Anti-Counterfeiting Application information: Introducing a Comprehensive Chemistry Experiment. University Chemistry, 2024, 39(6): 390-399. doi: 10.3866/PKU.DXHX202403028
3. [3]
  Jie XIE , Hongnan XU , Jianfeng LIAO , Ruoyu CHEN , Lin SUN , Zhong JIN . Nitrogen-doped 3D graphene-carbon nanotube network for efficient lithium storage. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1840-1849. doi: 10.11862/CJIC.20240216
4. [4]
  Hongxia Yan , Rui Wu , Weixu Feng , Yan Zhao , Yi Yan . Innovation Inspired by Classical Chemistry: Luminescent Hyperbranched Polysiloxanes. University Chemistry, 2025, 40(4): 154-159. doi: 10.12461/PKU.DXHX202409010
5. [5]
  Fugui XI , Du LI , Zhourui YAN , Hui WANG , Junyu XIANG , Zhiyun DONG . Functionalized zirconium metal-organic frameworks for the removal of tetracycline from water. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 683-694. doi: 10.11862/CJIC.20240291
6. [6]
  Yonghui ZHOU , Rujun HUANG , Dongchao YAO , Aiwei ZHANG , Yuhang SUN , Zhujun CHEN , Baisong ZHU , Youxuan ZHENG . Synthesis and photoelectric properties of fluorescence materials with electron donor-acceptor structures based on quinoxaline and pyridinopyrazine, carbazole, and diphenylamine derivatives. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 701-712. doi: 10.11862/CJIC.20230373
7. [7]
  Guangming YIN , Huaiyao WANG , Jianhua ZHENG , Xinyue DONG , Jian LI , Yi'nan SUN , Yiming GAO , Bingbing WANG . Preparation and photocatalytic degradation performance of Ag/protonated g-C₃N₄ nanorod materials. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1491-1500. doi: 10.11862/CJIC.20240086
8. [8]
  Xuejie Wang , Guoqing Cui , Congkai Wang , Yang Yang , Guiyuan Jiang , Chunming Xu . 碳基催化剂催化有机液体氢载体脱氢研究进展. Acta Physico-Chimica Sinica, 2025, 41(5): 100044-. doi: 10.1016/j.actphy.2024.100044
9. [9]
  Feng Sha , Xinyan Wu , Ping Hu , Wenqing Zhang , Xiaoyang Luan , Yunfei Ma . Design of Course Ideology and Politics for the Comprehensive Organic Synthesis Experiment of Benzocaine. University Chemistry, 2024, 39(2): 110-115. doi: 10.3866/PKU.DXHX202307082
10. [10]
  Feng Han , Fuxian Wan , Ying Li , Congcong Zhang , Yuanhong Zhang , Chengxia Miao . Comprehensive Organic Chemistry Experiment: Phosphotungstic Acid-Catalyzed Direct Conversion of Triphenylmethanol for the Synthesis of Oxime Ethers. University Chemistry, 2025, 40(3): 342-348. doi: 10.12461/PKU.DXHX202405181
11. [11]
  Wenxiu Yang , Jinfeng Zhang , Quanlong Xu , Yun Yang , Lijie Zhang . Bimetallic AuCu Alloy Decorated Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312014-. doi: 10.3866/PKU.WHXB202312014
12. [12]
  Jiajie Li , Xiaocong Ma , Jufang Zheng , Qiang Wan , Xiaoshun Zhou , Yahao Wang . Recent Advances in In-Situ Raman Spectroscopy for Investigating Electrocatalytic Organic Reaction Mechanisms. University Chemistry, 2025, 40(4): 261-276. doi: 10.12461/PKU.DXHX202406117
13. [13]
  Lewang Yuan , Yaoyao Peng , Zong-Jie Guan , Yu Fang . 二维共价有机框架作为光催化剂在有机合成中的研究进展. Acta Physico-Chimica Sinica, 2025, 41(8): 100086-. doi: 10.1016/j.actphy.2025.100086
14. [14]
  Xiaofang DONG , Yue YANG , Shen WANG , Xiaofang HAO , Yuxia WANG , Peng CHENG . Research progress of conductive metal-organic frameworks. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 14-34. doi: 10.11862/CJIC.20240388
15. [15]
  Lina Feng , Guoyu Jiang , Xiaoxia Jian , Jianguo Wang . Application of Organic Radical Materials in Biomedicine. University Chemistry, 2025, 40(4): 253-260. doi: 10.12461/PKU.DXHX202405171
16. [16]
  Tiantian MA , Sumei LI , Chengyu ZHANG , Lu XU , Yiyan BAI , Yunlong FU , Wenjuan JI , Haiying YANG . Methyl-functionalized Cd-based metal-organic framework for highly sensitive electrochemical sensing of dopamine. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 725-735. doi: 10.11862/CJIC.20230351
17. [17]
  Wenjie SHI , Fan LU , Mengwei CHEN , Jin WANG , Yingfeng HAN . Synthesis and host-guest properties of imidazolium-functionalized zirconium metal-organic cage. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 105-113. doi: 10.11862/CJIC.20240360
18. [18]
  Chi Li , Jichao Wan , Qiyu Long , Hui Lv , Ying Xiong . N-Heterocyclic Carbene (NHC)-Catalyzed Amidation of Aldehydes with Nitroso Compounds. University Chemistry, 2024, 39(5): 388-395. doi: 10.3866/PKU.DXHX202312016
19. [19]
  .
  CCS Chemistry 综述推荐│绿色氧化新思路：光/电催化助力有机物高效升级
  . CCS Chemistry, 2025, 7(10.31635/ccschem.024.202405369): -.
20. [20]
  Jingjing QING , Fan HE , Zhihui LIU , Shuaipeng HOU , Ya LIU , Yifan JIANG , Mengting TAN , Lifang HE , Fuxing ZHANG , Xiaoming ZHU . Synthesis, structure, and anticancer activity of two complexes of dimethylglyoxime organotin. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1301-1308. doi: 10.11862/CJIC.20240003

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(138)
HTML views(12)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142