Preparation and thermostability of terpenes/sulfur oligomer

doi:10.11949/j.issn.0438-1157.20151351

Abstract

Abstract:

How to develop a simple synthetic process to prepare novel materials with high sulfur content is still sorely lacking but urgent. Here a facile method which was termed "inverse vulcanization" to prepare thermally stable and processable polymeric materials was proposed through the direct radical copolymerization of elemental sulfur with limonene. FTIR, Raman spectroscopy, ¹H NMR, ¹³C NMR, elemental analysis (EA) and GPC were used to investigate the structural composition and molecular weight of the sulfur-limonene oligomers (PSL). DSC and TGA were used to evaluate the thermal behavior of the obtained oligomers. Solubility experiments were also carried out to test whether these oligomers could be dissolved by several common organic solvents at room temperature. The results showed that the prepared sulfur-rich copolymers exhibited excellent thermostability, solubility and adhesion. The sulfur content in the obtained product increased with increasing initial feed ratios of sulfur. For PSL, when reaction time was 2 h and the reaction temperature was 210℃, the best product performance was obtained.

Key words: sulfur, terpenes, limonene, inverse vulcanization, polymerization, synthesis, stability

摘要：

以单萜烯烃(R)-(+)-苧烯为共聚单体,采用"反硫化"的方法将萜烯与单质硫磺直接混合进行本体熔融自由基共聚反应,得到具有良好溶解性的富硫低聚物。利用傅里叶变换红外光谱(FTIR)、核磁共振波谱(¹H NMR和¹³C NMR)、拉曼光谱(Raman)、元素分析(EA)和凝胶渗透色谱(GPC)对低聚物的化学结构和组成进行了表征,并且探索了投料比、反应时间以及反应温度对硫磺-萜烯低聚物(PSL)的结构和性能的影响。又采用热重分析(TGA)和差示扫描量热法(DSC)考察了该低聚物的热稳定性。结果表明:该聚合方法所制备产物具有良好的热稳定性、溶解性和粘接性。反应产物中硫磺的含量随硫磺投料的增多而增加。对于苧烯-硫磺的共聚物(PSL),当反应时间为2 h、反应温度为210℃时,所得产物综合性能最佳。

关键词: 硫磺, 萜烯, 柠檬烯, 反硫化, 聚合, 合成, 稳定性

CLC Number:

O633.3

REN Yuanyuan, XU Kai, PENG Jun, XING Yuxiu, GAO Shuxi, CHEN Mingcai. Preparation and thermostability of terpenes/sulfur oligomer[J]. CIESC Journal, 2016, 67(4): 1580-1585.

任圆圆, 许凯, 彭军, 邢玉秀, 高树曦, 陈鸣才. 硫磺/萜烯低聚物的制备及其热稳定性[J]. 化工学报, 2016, 67(4): 1580-1585.

References 21

[1]	王志霞, 陈鸣才, 刘红波. 不溶性硫磺的生产和发展现状[J]. 现代化工, 2004, 24 (2): 19-22. DOI: 10.3321/j.issn:0253-4320.2004.02.006. WANG Z X, CHEN M C, LIU H B. Production technology and development of insoluble sulfur[J]. Modern Chemical Industry, 2004, 24 (2): 19-22. DOI: 10.3321/j.issn:0253-4320.2004.02.006.
[2]	胡文宾, 高淑美, 郝国阳, 等. 硫磺的几种专门应用[J]. 精细石油化工, 2000, (5): 23-25. DOI: 10.3969/j.issn.1003-9384.2000.05.007. HU W B, GAO S M, HAO G Y, et al. The several special uses of sulphur[J]. Speciality Petrochemicals, 2000, (5): 23-25. DOI: 10.3969/j.issn.1003-9384.2000.05.007.
[3]	由文颖, 赫玉欣, 宋文生, 等. 不溶性硫磺稳定性研究进展[J]. 化学推进剂与高分子材料, 2005, 3 (5): 14-16. DOI: 10.3969/j.issn.1672-2191.2005.05.004. YOU W Y, HE Y X, SONG W S, et al. Research advance of stability of insoluble sulfur[J]. Chemical Propellants & Polymeric Materials, 2005, 3 (5): 14-16. DOI: 10.3969/j.issn.1672-2191.2005.05.004.
[4]	王柳英, 邱祖民, 邱俊明. 不溶性硫磺的研究进展[J]. 化工科技, 2006, 14 (6): 49-53. DOI:10.3969/j.issn.1008-0511.2006.06.013. WANG L Y, QIU Z M, QIU J M. Research and development of insoluble sulfur[J]. Science & Technology in Chemical Industry, 2006, 14 (6):49-53. DOI:10.3969/j.issn.1008-0511.2006.06.013.
[5]	李文灿. 不溶性硫磺的合成, 改性及其对橡胶性能的影响[D]. 青岛:青岛科技大学, 2014. LI W C. Synthesis of insoluble sulfur, modified and its impact on the performance of the rubber[D]. Qingdao: Qingdao University of Science & Technology, 2014.
[6]	欧阳福生, 顾娟, 张宇, 等. 不溶性硫磺新型萃取剂的研究[J]. 精细石油化工, 2008, 25 (3): 7-12. DOI: 10.3969/j.issn.1003-9384.2008.03.003. OUYANG F S, GU J, ZHANG Y, et al. Study on new extractant for insoluble sulfur[J]. Speciality Petrochemicals, 2008, 25 (3):7-12. DOI:10.3969/j.issn.1003-9384.2008.03.003.
[7]	SATOH K, MATSUDA M, NAGAI K, et al. AAB-sequence living radical chain copolymerization of naturally occurring limonene with maleimide: an end-to-end sequence-regulated copolymer[J]. J. Am. Chem. Soc., 2010, 132 (29):10003-10005.
[8]	SHARMA S, SRIVASTAVA A K. Synthesis and characterization of a terpolymer of limonene, styrene, and methyl methacrylate via a free-radical route[J]. J. Appl. Polym. Sci., 2004, 91 (4):2343-2347.
[9]	Kennedy J P. Cationic Polymerization of Olefins: A Critical Inventory[M]. New York: John Wiley & Sons Ltd., 1975:337
[10]	DOIUCHI T, YAMAGUCHI H, MINOURA Y. Cyclocopolymerization of d-limonene with maleic anhydride[J]. European Polymer Journal, 1981, 17 (9): 961-968.
[11]	MASLINSKA-SOLICH J, KUPKA T, KLUCZKA M. Optically active polymers (2): Copolymerization of limonene with maleic anhydride[J]. Macromol. Chem. Physics, 1994, 195 (5): 1843-1850.
[12]	AHMED A, BLANCHARS L P. Copolymerization of elemental sulfur with styrene[J]. Journal of Applied Polymer Science, 1984, 29 (4): 1225-1239.
[13]	SHARMA S, SRIVASTAVA A K. Synthesis and characterization of copolymers of limonene with styrene initiated by azobisisobutyronitrile[J]. European Polymer Journal, 2004, 40 (9): 2235-2240.
[14]	SHARMA S, SRIVASTAVA A K. Alternating copolymers of limonene with methyl methacrylate: kinetics and mechanism[J]. J. Macromol. Sci. A, 2003, 40 (6): 593-603.
[15]	REN S, TREVINO E, DUBE M A. Copolymerization of limonene with n-butyl acrylate[J]. Macromolecular Reaction Engineering, 2015, 9 (4): 339-349.
[16]	NORSTROM E. Terpenes as renewable monomers for biobased materials[D]. Stockholm: KTH, 2011.
[17]	DIRLAM P T, SIMMONDS A G, KLEINE T S, et al. Inverse vulcanization of elemental sulfur with 1, 4-diphenylbutadiyne for cathode materials in Li-S batteries[J]. RSC Advances, 2015, 5 (31): 24718-24722.
[18]	SUN Z J, XIAO M, WANG S J, et al. Sulfur-rich polymeric materials with semi-interpenetrating network structure as a novel lithium-sulfur cathode[J]. Journal of Materials Chemistry A, 2014, 2 (24): 9280-9286.
[19]	GRIEBEL J J, NAMNABAT S, KIM E T, et al. New infrared transmitting material via inverse vulcanization of elemental sulfur to prepare high refractive index polymers[J]. Advanced Materials, 2014, 26 (19): 3014-3018.
[20]	TROFIMOV B A, VASIL?TSOV A M, PETROVA O V, et al. Sulfurization of polymers (6): Poly(vinylene polysulfide), poly(thienothiophene), and related structures from polyacetylene and elemental sulfur[J]. Russ. Chem. Bull., 2002, 51 (9):1709-1714.
[21]	王荣杰, 沈本贤, 马健, 等. 基于密度泛函的硫磺 S8 开环裂解机理研究[J]. 化工学报, 2015, 66 (10): 3919-3924. DOI: 10.11949/j.issn.0438-1157.20150274. WANG R J, SHEN B X, MA J, et al. Ring-open reaction mechanism of sulfur S8 based on density functional theory[J]. CIESC Journal, 2015, 66 (10): 3919-3924. DOI: 10.11949/j.issn.0438-1157.20150274.