Preparation and Thermostability of Heat-resistant Poly(silylene acetylene) Resins with Different Side Groups

Xin-yue Xu; Shi-long Dong; Qiao-long Yuan

doi:10.11777/j.issn1000-3304.2024.24115

您当前的位置：

首页 >

文章列表页 >

Preparation and Thermostability of Heat-resistant Poly(silylene acetylene) Resins with Different Side Groups

Research Article | 更新时间：2024-12-24

- Preparation and Thermostability of Heat-resistant Poly(silylene acetylene) Resins with Different Side Groups
- Acta Polymerica Sinica Vol. 55, Issue 11, Pages: 1561-1574(2024)
- 作者机构：
  
  华东理工大学材料科学与工程学院特种功能高分子材料及相关技术教育部重点实验室上海 200237
- 作者简介：
  
  Qiao-long Yuan, E-mail: qlyuan@ecust.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2024.24115
  CLC：
- CSTR：32057.14.GFZXB.2024.7262
- Received：16 April 2024，
  
  Accepted：2024-05-31，
  
  Published Online：22 July 2024，
  
  Published：20 November 2024
- 稿件说明：
移动端阅览
徐欣玥, 董仕龙, 袁荞龙. 不同侧基耐热聚硅乙炔树脂的制备及其热性能. 高分子学报, 2024, 55(11), 1561-1574

Xu, X. Y.; Dong, S. L.; Yuan, Q. L. Preparation and thermostability of heat-resistant poly(silylene acetylene) resins with different side groups. Acta Polymerica Sinica, 2024, 55(11), 1561-1574
徐欣玥, 董仕龙, 袁荞龙. 不同侧基耐热聚硅乙炔树脂的制备及其热性能. 高分子学报, 2024, 55(11), 1561-1574 DOI： 10.11777/j.issn1000-3304.2024.24115. CSTR： 32057.14.GFZXB.2024.7262.

Xu, X. Y.; Dong, S. L.; Yuan, Q. L. Preparation and thermostability of heat-resistant poly(silylene acetylene) resins with different side groups. Acta Polymerica Sinica, 2024, 55(11), 1561-1574 DOI： 10.11777/j.issn1000-3304.2024.24115. CSTR： 32057.14.GFZXB.2024.7262.

摘要

利用格氏试剂法合成了5种含不同侧基的端乙炔基硅乙炔树脂(ETSA)，通过核磁共振氢谱(

H-NMR)和傅里叶转换红外光谱(FTIR)对其结构进行了表征，用体积排除色谱法测其分子量，利用示差扫描量热仪(DSC)研究了ETSA树脂的固化行为，通过热失重分析仪(TGA)研究了ETSA树脂固化物的热稳定性，并利用高分辨透射电镜(HRTEM)和小角X光散射(SAXS)研究了ETSA树脂固化物的微孔结构. 另外，使用2种镍系催化剂对ETSA树脂的固化反应进行催化，并通过DSC、FTIR和TGA研究了催化剂对ETSA固化的催化效果. 结果表明，ETSA树脂随主链中硅原子上侧基体积的增大，聚合度依次下降，固化放热峰峰值温度向高温方向移动，放热焓显著下降. ETSA固化树脂具有优异的热稳定性，氮气与空气中的5%热失重温度(

)都超450 ℃，800 ℃残留量(

r800

)分别超过80%和27%. ETSA固化树脂交联网络微孔随侧基体积增加而增大. 镍系催化剂对ETSA树脂的固化反应具有较好的催化效果，降低起始固化温度大于50 ℃，催化固化树脂的

r800

变化不大. ETSA树脂有望用作高耐热树脂基体和聚合物陶瓷前驱体.

Abstract

Five ethynyl-terminated poly(silylene acetylene) (ETSA) resins with different side groups at Si atom were synthesized using the Grignard reagent method. The structures of ETSA resins were characterized by proton nuclear magnetic resonance (

H-NMR) and Fourier transformation infrared (FTIR). The size exclusion chromatography was used to measure the molecular weight and distribution of ETSA resins. The curing behaviors of ETSA resins were investigated using differential scanning calorimetr

y (DSC). The thermal stability of cured ETSA resins were studied by thermogravimetric analysis (TGA). Furthermore

the microporous structure of cured ETSA resin was investigated using high resolution transmission electron microscopy (HRTEM) and small angle X-ray scattering (SAXS). Additionally

two nickel-based catalysts were used to catalyze the curing reaction of the ETSA resins

and the catalytic effect of the catalysts on the curing reaction of ETSA resins were evaluated by DSC

FTIR and TGA. The results show that the degree of polymerization of ETSA resin decreases with increase of the volume of side group at Si atom in the backbone of ETSA. The peak exothermic temperature of the ETSA moves to a high temperature during curing

and the exothermic enthalpy and curing degree of the ETSA decrease with the increase of the volume of side group. The cured ETSA resins display excellent thermal stability. The temperature of 5% weight loss (

) of the cured ETSA resins in nitrogen and air are higher than 450 ℃. The residual yield at 800 ℃ (

r800

) in nitrogen and air of the cured ETSA resins are larger than 80% and 27%

respectively. The microporous size in the cross-linked networks of ETSA increases with the increase of the volume of side group. The nickel-based catalysts exhibit the good catalytic effect on the curing reaction of ETSA. The inital temperature of catalyst-curing ETSA resins can drop over 50 ℃

but the

r800

of the catalyst-cured ETSA resins change not much. The ETSA resin is promising to be used as a highly heat-resistant resin matrix and a polymeric precursor.

关键词

Keywords

references

Katzman H. A. ; Mallon J. J. ; Barry W. T. Polyarylacetylene-matrix composites for solid rocket motor components . J. Adv. Mater. , 1995 , 26 ( 3 ), 21 - 27 .

Kwock E. W. ; Baird , T. Jr Miller , Synthesis and characterization of soluble, high-molecular-weight poly-(aromatic diacetylenes) . Macromolecules , 1993 , 26 ( 11 ), 2935 - 2940 . doi: 10.1021/ma00063a044 http://dx.doi.org/10.1021/ma00063a044

Jiang J. X. ; Su F. B. ; Trewin A. ; Wood C. D. ; Campbell N. L. ; Niu H. J. ; Dickinson C. ; Ganin A. Y. ; Rosseinsky M. J. ; Khimyak Y. Z. ; Cooper A. I. Conjugated microporous poly(aryleneethynylene) networks . Angew. Chem. Int. Ed , 2007 , 46 ( 45 ), 8574 - 8578 . doi: 10.1002/anie.200701595 http://dx.doi.org/10.1002/anie.200701595

Cooper A. I. Conjugated microporous polymers . Adv. Mater. , 2009 , 21 ( 12 ), 1291 - 1295 . doi: 10.1002/adma.200801971 http://dx.doi.org/10.1002/adma.200801971

Liu M. X. ; Gan L. H. ; Zhao F. Q. ; Fan X. Z. ; Xu H. X. ; Wu F. R. ; Xu Z. J. ; Hao Z. X. ; Chen L. W. Carbon foams with high compressive strength derived from polyarylacetylene resin . Carbon , 2007 , 45 ( 15 ), 3055 - 3057 . doi: 10.1016/j.carbon.2007.10.003 http://dx.doi.org/10.1016/j.carbon.2007.10.003

Itoh M. ; Inoue K. ; Iwata K. ; Mitsuzuka M. ; Kakigano T. New highly heat-resistant polymers containing silicon: poly-(silyleneethynylenephenyleneethynylene)s . Macromolecules , 1997 , 30 ( 4 ), 694 - 701 . doi: 10.1021/ma961081f http://dx.doi.org/10.1021/ma961081f

Itoh M. ; Iwata K. ; Ishikawa J. I. ; Sukawa H. ; Kimura H. ; Okita K. Various silicon-containing polymers with Si(H)－C≡C units . J. Polym. Sci. A Polym. Chem. , 2001 , 39 ( 15 ), 2658 - 2669 . doi: 10.1002/pola.1242 http://dx.doi.org/10.1002/pola.1242

Liu X. T. ; Lv S. K. ; Heng K. J. ; Qiao Z. Y. ; Tang J. K. ; Yuan Q. L. ; Huang F. R. Thermal and thermoxidative decomposition of a heat-resistant poly(dimethylsilylene ethynylenephenyleneethynylene) resin . J. Therm. Anal. Calorim. , 2023 , 148 ( 17 ), 8889 - 8901 . doi: 10.1007/s10973-023-12305-y http://dx.doi.org/10.1007/s10973-023-12305-y

Antolovich S. D. ; Busso E. P. ; Skelton P. ; Telesman J. High temperature materials for aerospace applications . Mater. High Temp. , 2016 , 33 ( 4-5 ), 289 - 290 . doi: 10.1080/09603409.2016.1206294 http://dx.doi.org/10.1080/09603409.2016.1206294

Ijadi-Maghsoodi S. ; Pang Y. ; Barton T. J. Efficient, "one-pot" synthesis of silylene-acetylene and disilylene-acetylene preceramic polymers from trichloroethylene . J. Polym. Sci. A Polym. Chem. , 1990 , 28 ( 5 ), 955 - 965 . doi: 10.1002/pola.1990.080280501 http://dx.doi.org/10.1002/pola.1990.080280501

Budy S. M. ; Son D. Y. Synthesis and properties of polymers with an organosilicon—acetylene backbone . J. Inorg. Organomet. Polym. Mater. , 2018 , 28 ( 5 ), 1673 - 1687 . doi: 10.1007/s10904-018-0854-3 http://dx.doi.org/10.1007/s10904-018-0854-3

Pang Y. ; Ijadi-Maghsoodi S. ; Barton T. J. Catalytic synthesis of silylene-vinylene preceramic polymers from ethynylsilanes . Macromolecules , 1993 , 26 ( 21 ), 5671 - 5675 . doi: 10.1021/ma00073a021 http://dx.doi.org/10.1021/ma00073a021

Kong L. ; Zuo X. B. ; Zhu S. P. ; Li Z. P. ; Shi J. J. ; Li L. ; Feng Z. H. ; Zhang D. H. ; Deng D. Y. ; Yu J. J. Novel carbon-poly(silacetylene) composites as advanced thermal protection material in aerospace applications . Compos. Sci. Technol. , 2018 , 162 , 163 - 169 . doi: 10.1016/j.compscitech.2018.04.038 http://dx.doi.org/10.1016/j.compscitech.2018.04.038

Chen M. F. ; Xiong P. L. ; Zhou Q. ; Ni L. Z. ; Wang G. C. Synthesis, curing behavior and thermal properties of silicon-containing hybrid polymers with Si－C≡C units: silicon-containing hybrid polymers . Polym. Int. , 2014 , 63 ( 8 ), 1531 - 1536 . doi: 10.1002/pi.4661 http://dx.doi.org/10.1002/pi.4661

Li G. Z. ; Luo Z. H. ; Han W. J. ; Luo Y. M. ; Xu C. H. ; Zhao T. Preparation and properties of novel hybrid resins based on acetylene-functional benzoxazine and polyvinylsilazane . J. Appl. Polym. Sci. , 2013 , 130 ( 5 ), 3794 - 3799 . doi: 10.1002/app.39642 http://dx.doi.org/10.1002/app.39642

Dong S. L. ; Hu X. Y. ; Yuan Q. L. ; Huang F. R. An easy-to-process poly(silylene-acetylene) terminated by reactive ethynylphenyl: synthesis, properties and composites . React. Funct. Polym. , 2022 , 170 , 105099 . doi: 10.1016/j.reactfunctpolym.2021.105099 http://dx.doi.org/10.1016/j.reactfunctpolym.2021.105099

Németh C. ; Szabó D. ; Gyarmati B. ; Gerasimov A. ; Varfolomeev M. ; Abdullin T. ; László K. ; Szilágyi A. Effect of side groups on the properties of cationic polyaspartamides . Eur. Polym. J. , 2017 , 93 , 805 - 814 . doi: 10.1016/j.eurpolymj.2017.02.024 http://dx.doi.org/10.1016/j.eurpolymj.2017.02.024

Liu X. T. ; Ma M. P. ; Li C. ; Tang J. K. ; Yuan Q. L. ; Huang F. R. Effect of side groups on the properties of silicon-containing arylacetylene resins . Polym. Eng. Sci. , 2022 , 62 ( 3 ), 793 - 801 . doi: 10.1002/pen.25885 http://dx.doi.org/10.1002/pen.25885

Ma M. P. ; Liu X. T. ; Li C. ; Qiao Z. Y. ; Yuan Q. L. ; Huang F. R. Effects of pendant side groups on the properties of the silicon-containing arylacetylene resins with 2 , 5 -diphenyl-‍[1, 3 , 4 ] moieties-oxadiazole. RSC Adv., 2021, 11 ( 32 ), 19656 - 19665 . doi: 10.1039/d1ra02184b http://dx.doi.org/10.1039/d1ra02184b

Yi L. ; Huang W. ; Yan D. Y. Polyimides with side groups: synthesis and effects of side groups on their properties . J. Polym. Sci. A Polym. Chem. , 2017 , 55 ( 4 ), 533 - 559 . doi: 10.1002/pola.28409 http://dx.doi.org/10.1002/pola.28409

Liang A. S. ; Zhou X. Y. ; Zhou W. Q. ; Wan T. ; Wang L. H. ; Pan C. J. ; Wang L. Side-chain effects on the thermoelectric properties of fluorene-based copolymers . Macromol. Rapid Commun. , 2017 , 38 ( 18 ), 1600817 . doi: 10.1002/marc.201600817 http://dx.doi.org/10.1002/marc.201600817

Hayashi M. ; Yano R. ; Takasu A. Synthesis of amorphous low T g polyesters with multiple COOH side groups and their utilization for elastomeric vitrimers based on post-polymerization cross-linking . Polym. Chem. , 2019 , 10 ( 16 ), 2047 - 2056 . doi: 10.1039/c9py00293f http://dx.doi.org/10.1039/c9py00293f

Guo K. K. ; Li P. ; Zhu Y. P. ; Wang F. ; Qi H. M. Thermal curing and degradation behaviour of silicon-containing arylacetylene resins . Polym. Degrad. Stabil. , 2016 , 131 , 98 - 105 . doi: 10.1016/j.polymdegradstab.2016.07.006 http://dx.doi.org/10.1016/j.polymdegradstab.2016.07.006

Guo L. H. ; Liu W. J. ; Chen C. L. Late transition metal catalyzed α -olefin polymerization and copolymerization with polar monomers . Mater. Chem. Front. , 2017 , 1 ( 12 ), 2487 - 2494 . doi: 10.1039/c7qm00321h http://dx.doi.org/10.1039/c7qm00321h

Khoshsefat M. ; Ma Y. P. ; Sun W. H. Multinuclear late transition metal catalysts for olefin polymerization . Coord. Chem. Rev. , 2021 , 434 , 213788 . doi: 10.1016/j.ccr.2021.213788 http://dx.doi.org/10.1016/j.ccr.2021.213788

Meriwether L. S. ; Colthup E. C. ; Kennerly G. W. ; Reusch R. N. The polymerization of acetylenes by nickel-carbonyl-phosphine complexes . I. Scope of the Reaction. J. Org. Chem. , 1961 , 26 ( 12 ), 5155 - 5163 . doi: 10.1021/jo01070a091 http://dx.doi.org/10.1021/jo01070a091

Shen Y. ; Yuan Q. ; Huang F. ; Du L. Effect of neutral nickel catalyst on cure process of silicon-containing polyarylacetylene . Thermochim. Acta , 2014 , 590 , 66 - 72 . doi: 10.1016/j.tca.2014.06.002 http://dx.doi.org/10.1016/j.tca.2014.06.002

Zhang J. ; Huang J. X. ; Wang C. F. ; Huang F. R. ; Du L. A new silicon-containing arylacetylene resin with amine groups as precursor to Si－C－N ceramic . J. Macromol. Sci. Part B , 2009 , 48 ( 5 ), 1001 - 1010 . doi: 10.1080/00222340903011916 http://dx.doi.org/10.1080/00222340903011916

Mukbaniani O. ; Tatrishvili T. ; Titvinidze G. ; Mukbaniani N. ; Lezhava L. ; Gogesashvili N. Hydrosilylation reaction of methylhydridesiloxane to phenylacetylene . J. Appl. Polym. Sci. , 2006 , 100 ( 3 ), 2511 - 2515 . doi: 10.1002/app.23664 http://dx.doi.org/10.1002/app.23664

Qian B. J. ; Cao B. W. ; Chu M. Y. ; Li Y. B. ; Ma H. Y. ; Guo R. Y. ; Wan L. Q. Curing reactions of liquid hydridopolycarbosilanes with vinyl or allyl groups . J. Appl. Polym. Sci. , 2023 , 140 ( 42 ), e 54565 . doi: 10.1002/app.54565 http://dx.doi.org/10.1002/app.54565

Yeung L. Y. ; Pennino M. J. ; Miller A. M. ; Elrod M. J. Kinetics and mechanistic studies of the atmospheric oxidation of alkynes . J. Phys. Chem. A , 2005 , 109 ( 9 ), 1879 - 1889 . doi: 10.1021/jp0454671 http://dx.doi.org/10.1021/jp0454671

Tanaka K. ; Nakajima K. ; Okada M. ; Yamabe T. ; Ishikawa M. Electronic structures of simplified polymeric organosilicon systems containing π -conjugated moieties . Organometallics , 1991 , 10 ( 8 ), 2679 - 2684 . doi: 10.1021/om00054a032 http://dx.doi.org/10.1021/om00054a032

Gao X. X. ; Liu H. C. ; Wei H. T. ; Zheng J. ; Huang G. S. Effect of incompletely condensed tri-silanol-phenyl-POSS on the thermal stability of silicone rubber . Polym. Bull. , 2019 , 76 ( 6 ), 2835 - 2850 . doi: 10.1007/s00289-018-2499-3 http://dx.doi.org/10.1007/s00289-018-2499-3

Pu C. Z. ; Lin D. L. ; Xu H. J. ; Liu F. Z. ; Gao H. ; Tian G. F. ; Qi S. L. ; Wu D. Z. Clarifying the effect of chemical structure on high-temperature resistance of polyimides based on DFT and ReaxFF based molecular dynamic simulation . Polymer , 2022 , 255 , 125119 . doi: 10.1016/j.polymer.2022.125119 http://dx.doi.org/10.1016/j.polymer.2022.125119

Jin C. E. ; Wang F. ; Zhu Y. P. ; Deng S. F. ; Qi H. M. ; Du L. Thermal oxidation behavior and mechanisms for silicon-containing arylacetylene resins: experimental and reactive force field molecular dynamics simulations . ACS Appl. Polym. Mater. , 2024 , 6 ( 3 ), 1962 - 1972 . doi: 10.1021/acsapm.3c02845 http://dx.doi.org/10.1021/acsapm.3c02845

Lee J. , S M. ; Cooper A. I. Advances in conjugated microporous polymers . Chem. Rev. , 2020 , 120 ( 4 ), 2171 - 2214 . doi: 10.1021/acs.chemrev.9b00399 http://dx.doi.org/10.1021/acs.chemrev.9b00399

Tian B. ; Heringa J. R. ; Bouwman W. G. Scattering from oriented objects analysed by the anisotropic Guinier-Porod model . Food Struct. , 2021 , 30 , 100221 . doi: 10.1016/j.foostr.2021.100221 http://dx.doi.org/10.1016/j.foostr.2021.100221

Views

297

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Effect of Amylose Derivatives on Thermal Properties of Poly(methyl methacrylate)

Thermogravimetric Analysis and Its Applications in Polymer Characterization

Study on the Abnormal High Temperature Thermal Stability of Polymer:Fullerene Photovoltaic Cells

Fabrication of a La-based Metal Organic Framework and Its Effect on Fire Safety and Thermal Stability of Polycarbonate

Related Author

Wei Zhao

Xiao Dai

Li-li Zhang

Jun Shen

Qi-yuan Xie

Dan-dan Chen

Yan-wei Ding

Wen-sheng Zhao

Related Institution

School of Civil and Resource Engineering, University of Science and Technology Beijing

College of Materials Science and Chemical Engineering, Harbin Engineering University

State Key Lab of Fire Science, University of Science and Technology of China

Instruments Center for Physical Science, University of Science and Technology of China

College of Textile Engineering, Taiyuan University of Technology

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