Preparation and Properties of Amine-terminated Styrene-butadiene Liquid Rubber

Liang Zhu; Su-yun Jie; Er-yuan Fang; Bo-geng Li

doi:10.11777/j.issn1000-3304.2024.24117

您当前的位置：

首页 >

文章列表页 >

Preparation and Properties of Amine-terminated Styrene-butadiene Liquid Rubber

Research Article | 更新时间：2024-12-24

- Preparation and Properties of Amine-terminated Styrene-butadiene Liquid Rubber
- Acta Polymerica Sinica Vol. 55, Issue 11, Pages: 1495-1503(2024)
- 作者机构：
  
  浙江大学化学工程与生物工程学院化学工程联合国家重点实验室杭州 310058
- 作者简介：
  
  Su-yun Jie, E-mail: jiesy@zju.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2024.24117
  CLC：
- CSTR：32057.14.GFZXB.2024.7263
- Received：18 April 2024，
  
  Accepted：2024-05-31，
  
  Published Online：10 September 2024，
  
  Published：20 November 2024
- 稿件说明：
移动端阅览
朱亮, 介素云, 房尔园, 李伯耿. 端氨基丁苯液体橡胶的制备及性能研究. 高分子学报, 2024, 55(11), 1495-1503

Zhu, L.; Jie, S. Y.; Fang, E. Y.; Li, B. G. Preparation and properties of amine-terminated styrene-butadiene liquid rubber. Acta Polymerica Sinica, 2024, 55(11), 1495-1503
朱亮, 介素云, 房尔园, 李伯耿. 端氨基丁苯液体橡胶的制备及性能研究. 高分子学报, 2024, 55(11), 1495-1503 DOI： 10.11777/j.issn1000-3304.2024.24117. CSTR： 32057.14.GFZXB.2024.7263.

Zhu, L.; Jie, S. Y.; Fang, E. Y.; Li, B. G. Preparation and properties of amine-terminated styrene-butadiene liquid rubber. Acta Polymerica Sinica, 2024, 55(11), 1495-1503 DOI： 10.11777/j.issn1000-3304.2024.24117. CSTR： 32057.14.GFZXB.2024.7263.

摘要

以溶聚丁苯橡胶(SSBR)为原料，通过反应控制相转移催化法对其进行环氧化，进一步对环氧基团进行裂解反应制得端醛基丁苯液体橡胶(ATBS)，然后采用端基转化法改变端基基团，制得端肟基(OTBS)和端氨基丁苯液体橡胶(AmTBS). 采用核磁共振氢谱和碳谱以及红外光谱，对原料、中间产物以及端氨基丁苯液体橡胶的组成与结构进行了表征与分析；根据化学滴定法测定了端氨基丁苯橡胶的胺值，并计算了氨基官能度；通过热重分析、示差量热扫描法对产物的热性能进行了测试与分析. 端氨基丁苯橡胶的流变性能测试结果表明，其符合牛顿流体的特征，本体黏度在一定范围内对温度变化较为敏感. 降解法制备的端氨基丁苯液体橡胶可进一步拓宽丁苯液体橡胶的应用领域.

Abstract

Liquid rubber is a class of viscous oligomers with low molecular weight

fluidity at room temperature and good processing properties. Telechelic liquid rubber with one functional group at each terminal end could undergo crosslinking

chain extension and other reactions with other monomers or polymers

further expanding the application fields of liquid rubber. Liquid styrene-butadiene rubber (LSBR) is a low molecular-weight copolymer of butadiene and styrene

which has good compatibility with many rubbers. One of commonly used functionalized butadiene styrene liquid rubber is hydroxyl-terminated butadiene styrene rubber (HTBS)

which is usually produced

via

free

radical polymerization or anionic polymerization. In this study

taking solution-polymerized styrene-butadiene rubber (SSBR) as a starting material

aldehyde-terminated styrene-butadiene rubber (ATBS) was obtained by the reaction-controlled phase-transfer catalytic epoxidation and oxidative cleavage of epoxy groups. Then

the oxime- and amino-terminated butadiene-styrene rubbers (OTBS and AmTBS) were further obtained by the conversion of terminal groups. The composition and structure of materials

intermediate products and AmTBS were characterized and analyzed by proton and carbon nuclear magnetic resonance (

H- and

C-NMR)

and Fourier transform infrared (FTIR) spectroscopies. The results showed that AmTBS was successfully synthesized. The amine value of AmTBS was determined according to the chemical titration and the amino functionality was calculated to be approximately 2.0. The thermal properties of products were analyzed by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results of rheological properties of AmTBS indicated that they matched the characteristics of Newtonian fluids and their intrinsic viscosities were sensitive to the temperature in a certain range. The AmTBS prepared by the degradation method possessed superior properties and could further broaden the application fields of LSBR.

关键词

Keywords

references

马迎荷 , 潘笛远 , 乔亚威 , 郑浩帅 , 郭雪 , 潘广勤 . 官能化液体橡胶制备技术及应用 . 弹性体 , 2023 , 33 ( 2 ), 96 - 100 . doi: 10.3969/j.issn.1005-3174.2023.02.016 http://dx.doi.org/10.3969/j.issn.1005-3174.2023.02.016

Jiménez del Barco Carrión, A. ; Subhy A. ; Izquierdo Rodriguez M. A. ; Lo Presti D. Optimisation of liquid rubber modified bitumen for road pavements and roofing applications . Constr. Build. Mater. , 2020 , 249 , 118630 . doi: 10.1016/j.conbuildmat.2020.118630 http://dx.doi.org/10.1016/j.conbuildmat.2020.118630

梁滔 , 王洪山 , 高阳光 , 龚光碧 , 魏绪玲 . 液体橡胶的研究进展I . 发展概况与合成技术. 合成橡胶工业 , 2010 , 33 ( 6 ), 482 - 487 .

梁滔 , 魏绪玲 , 龚光碧 . 液体橡胶的研究进展Ⅲ . 液体丁腈橡胶、液体丁苯橡胶和液体异戊二烯橡胶. 合成橡胶工业 , 2011 , 34 ( 5 ), 398 - 404 .

梁滔 , 魏绪玲 , 龚光碧 , 吴江 . 液体橡胶的研究进展II . 端基聚丁二烯液体橡胶的合成. 合成橡胶工业 , 2011 , 34 ( 3 ), 234 - 238 .

梁滔 , 魏绪玲 , 张惠怡 , 刘栓祥 . 双烯类液体橡胶的研发进展 . 高分子通报 , 2012 , ( 4 ), 11 - 16 .

徐丽 , 周文英 , 龚莹 , 赵伟 , 邓皓南 . 液体端羟基丁苯橡胶改性环氧树脂研究 . 中国塑料 , 2016 , 30 ( 9 ), 35 - 40 .

Brosse J. C. ; Derouet D. ; Epaillard F. ; Soutif J. C. ; Legeay G. ; Dušek K. Hydroxyl-terminated polymers obtained by free radical polymerization—Synthesis, characterization, and applications . Catalytical and Radical Polymerization. Berlin/Heidelberg : Springer-Verlag , 2006 . 167 - 223 .

Mir Mohamad Sadeghi G. ; Morshedian J. ; Barikani M. The effect of solvent on the microstructure, nature of hydroxyl end groups and kinetics of polymerization reaction in synthesize of hydroxyl terminated polybutadiene . React. Funct. Polym. , 2006 , 66 ( 2 ), 255 - 266 . doi: 10.1016/j.reactfunctpolym.2005.08.001 http://dx.doi.org/10.1016/j.reactfunctpolym.2005.08.001

Mohamad Sadeghi G. M. ; Morshedian J. ; Barikani M. The effect of initiator-to-monomer ratio on the properties of the polybutadiene-ol synthesized by free radical solution polymerization of 1 , 3 -butadiene . Polym. Int., 2003, 52 ( 7 ), 1083 - 1087 . doi: 10.1002/pi.1172 http://dx.doi.org/10.1002/pi.1172

Min X. A novel synthetic strategy for hydroxyl-terminated polybutadiene containing high cis-1 , 4 contents based on a Ni(ii)-coordinated anionic initiating system . RSC Adv., 2019, 9 ( 67 ), 39037 - 39045 . doi: 10.1039/c9ra04531g http://dx.doi.org/10.1039/c9ra04531g

庞永新 , 王孟钟 . 阴离子聚合法合成端羟基液体丁苯橡胶的研究Ⅱ . 端羟基液体丁苯橡胶的合成与表征. 合成橡胶工业 , 1986 , 9 ( 3 ), 189 - 195 .

Chen J. M. ; Lu Z. J. ; Pan G. Q. ; Qi Y. X. ; Yi J. J. ; Bai H. J. Synthesis of hydroxyl-terminated polybutadiene possessing high content of 1 , 4 -units via anionic polymerization . Chinese J. Polym. Sci., 2010, 28 ( 5 ), 715 - 720 . doi: 10.1007/s10118-010-9121-y http://dx.doi.org/10.1007/s10118-010-9121-y

边慧娟 , 张兴英 . 四氢呋喃/醇化合物二元极性调节体系对负离子聚合端羟基聚丁二烯橡胶微观结构的影响 . 合成橡胶工业 , 2005 , 28 ( 3 ), 225 . doi: 10.3969/j.issn.1000-1255.2005.03.020 http://dx.doi.org/10.3969/j.issn.1000-1255.2005.03.020

Andler R. ; Vivod R. ; Steinbüchel A. Synthesis of polyhydroxyalkanoates through the biodegradation of poly(cis-1 , 4 -isoprene) rubber . J. Biosci. Bioeng., 2019, 127 ( 3 ), 360 - 365 . doi: 10.1016/j.jbiosc.2018.08.015 http://dx.doi.org/10.1016/j.jbiosc.2018.08.015

Bertrand A. ; Hillmyer M. A. Nanoporous poly(lactide) by olefin metathesis degradation . J. Am. Chem. Soc. , 2013 , 135 ( 30 ), 10918 - 10921 . doi: 10.1021/ja4050532 http://dx.doi.org/10.1021/ja4050532

Phinyocheep P. ; Phetphaisit C. W. ; Derouet D. ; Campistron I. ; Brosse J. C. Chemical degradation of epoxidized natural rubber using periodic acid: preparation of epoxidized liquid natural rubber . J. Appl. Polym. Sci. , 2005 , 95 ( 1 ), 6 - 15 . doi: 10.1002/app.20812 http://dx.doi.org/10.1002/app.20812

Dai L. ; Wang X. X. ; Bu Z. Y. ; Li B. G. ; Jie S. Y. Facile access to carboxyl-terminated polybutadiene and polyethylene from cis -polybutadiene rubber . J. Appl. Polym. Sci. , 2019 , 136 ( 2 ), 46934 . doi: 10.1002/app.46934 http://dx.doi.org/10.1002/app.46934

Zhou Q. Z. ; Jie S. Y. ; Li B. G. Preparation of hydroxyl-terminated polybutadiene with high cis-1 , 4 content . Ind. Eng. Chem. Res., 2014, 53 ( 46 ), 17884 - 17893 . doi: 10.1021/ie503652g http://dx.doi.org/10.1021/ie503652g

周勤灼 , 曹哲 , 介素云 , 李伯耿 . 胶液法制备高顺式端羟基聚丁二烯液体橡胶 . 高分子学报 , 2016 , ( 3 ), 293 - 299 . doi: 10.11777/j.issn1000-3304.2016.15199 http://dx.doi.org/10.11777/j.issn1000-3304.2016.15199

Xu L. ; Li B. G. ; Jie S. Y. ; Li Z. S. ; Bu Z. Y. 110 th Anniversary: the epoxidation of polybutadiene via reaction-controlled phase-transfer catalysis . Ind. Eng. Chem. Res. , 2019 , 58 ( 29 ), 13085 - 13092 . doi: 10.1021/acs.iecr.9b02371 http://dx.doi.org/10.1021/acs.iecr.9b02371

Xu L. ; Jie S. Y. ; Bu Z. Y. ; Li B. G. Preparation of primary amine-terminated polybutadiene from cis -polybutadiene . Eur. Polym. J. , 2021 , 152 , 110484 . doi: 10.1016/j.eurpolymj.2021.110484 http://dx.doi.org/10.1016/j.eurpolymj.2021.110484

闫波 . 溶聚丁苯橡胶市场进展与工艺技术分析 . 江西化工 , 2021 , 37 ( 4 ), 20 - 22 . doi: 10.3969/j.issn.1008-3103.2021.04.007 http://dx.doi.org/10.3969/j.issn.1008-3103.2021.04.007

熊瑜 . 溶聚丁苯橡胶中国专利技术分析及展望 . 橡胶工业 , 2023 , 70 ( 8 ), 633 - 639 . doi: 10.12136/j.issn.1000-890X.2023.08.0633 http://dx.doi.org/10.12136/j.issn.1000-890X.2023.08.0633

Views

296

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Effects of Dibenzocrown Ether and Diphenoxyethylene Diether Structural Units on the Properties of Degradable Polyhexahydrotriazine Thermosetting Resins

Preparation, Biological Properties and Degradation Studies on the Electrospun Membranes of Poly (p-dioxanone-co-trimethylene carbonate)

Metathetic Degradation of Polybutadiene and Formation of Telechelic Oligomers via Cross Metathesis

Related Author

Jian Wu

Chun Lu

Ying-ying Han

Wei-qing Rong

Yan Zhang

Shi-jing Yan

Yu Zheng

Shu-hui Liu

Related Institution

School of Materials and Environment

Key Laboratory of Chemistry and Engineering of Forest Products, State Ethnic Affairs Commission, Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, Guangxi Collaborative Innovation Center for Chemistry and Engineering of Forest Products

School of Chemistry and Chemical Engineering, Guangxi University for Nationalities

Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences

University of Chinese Academy of Sciences

Postal code：100190
Tel：010-62588927 Email：gfzxb@iccas.ac.cn
Technical support is provided by Beijing Founder electronics co., LTD 京ICP备05002797号-8 京公网安备11010802024621
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.

⁰