硅酸盐学报

液态聚碳硅烷的一步超声缩合制备及其表征

PDF下载

郭洪亮 , 王小宙

硅酸盐学报 | 聚合物先驱体陶瓷专题—研究论文 2024,52(9): 2800-2805

收起

硅酸盐学报 |聚合物先驱体陶瓷专题—研究论文 2024 , 52 (9) : 2800 -2805

液态聚碳硅烷的一步超声缩合制备及其表征

全屏

[Author(id=1322564580895736628, tenantId=1146029695717560320, journalId=1263187385517883426, articleId=1320098218701078612, orderNo=0, firstName=null, middleName=null, lastName=null, nameCn=null, orcid=null, stid=null, country=null, authorPic=null, dead=0, email=andrew_ghl@163.com, emailSecond=null, emailThird=null, correspondingAuthor=0, authorType=1, ext={EN=AuthorExt(id=1322564580979622710, tenantId=1146029695717560320, journalId=1263187385517883426, articleId=1320098218701078612, authorId=1322564580895736628, language=EN, stringName=Hongliang GUO, firstName=Hongliang, middleName=null, lastName=GUO, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=null, address=Science and Technology on Advanced Ceramic Fibers and Composites Laboratory, National University of Defense Technology, Changsha 410073, China, bio={"content":"

GUO Hongliang (1998-), male, Master candidate. E-mail: andrew_ghl@163.com

"}, bioImg=null, bioContent=

GUO Hongliang (1998-), male, Master candidate. E-mail: andrew_ghl@163.com

, aboutCorrespAuthor=null), CN=AuthorExt(id=1322564581046731575, tenantId=1146029695717560320, journalId=1263187385517883426, articleId=1320098218701078612, authorId=1322564580895736628, language=CN, stringName=郭洪亮, firstName=null, middleName=null, lastName=null, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=null, address=国防科技大学，新型陶瓷纤维及其复合材料重点实验室，长沙 410073, bio={"content":"

郭洪亮（1998—），男，硕士研究生。

"}, bioImg=null, bioContent=

郭洪亮（1998—），男，硕士研究生。

, aboutCorrespAuthor=null)}, companyList=[AuthorCompany(id=1322564580824433456, tenantId=1146029695717560320, journalId=1263187385517883426, articleId=1320098218701078612, xref=null, ext=[AuthorCompanyExt(id=1322564580832822065, tenantId=1146029695717560320, journalId=1263187385517883426, articleId=1320098218701078612, companyId=1322564580824433456, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=Science and Technology on Advanced Ceramic Fibers and Composites Laboratory, National University of Defense Technology, Changsha 410073, China), AuthorCompanyExt(id=1322564580841210674, tenantId=1146029695717560320, journalId=1263187385517883426, articleId=1320098218701078612, companyId=1322564580824433456, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=国防科技大学，新型陶瓷纤维及其复合材料重点实验室，长沙 410073)])]), Author(id=1322564581197726521, tenantId=1146029695717560320, journalId=1263187385517883426, articleId=1320098218701078612, orderNo=1, firstName=null, middleName=null, lastName=null, nameCn=null, orcid=null, stid=null, country=null, authorPic=null, dead=0, email=wangler2002@163.com, emailSecond=null, emailThird=null, correspondingAuthor=1, authorType=1, ext={EN=AuthorExt(id=1322564581269029691, tenantId=1146029695717560320, journalId=1263187385517883426, articleId=1320098218701078612, authorId=1322564581197726521, language=EN, stringName=Xiaozhou WANG, firstName=Xiaozhou, middleName=null, lastName=WANG, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=null, address=Science and Technology on Advanced Ceramic Fibers and Composites Laboratory, National University of Defense Technology, Changsha 410073, China, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null), CN=AuthorExt(id=1322564581331944252, tenantId=1146029695717560320, journalId=1263187385517883426, articleId=1320098218701078612, authorId=1322564581197726521, language=CN, stringName=王小宙, firstName=null, middleName=null, lastName=null, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=null, address=国防科技大学，新型陶瓷纤维及其复合材料重点实验室，长沙 410073, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null)}, companyList=[AuthorCompany(id=1322564580824433456, tenantId=1146029695717560320, journalId=1263187385517883426, articleId=1320098218701078612, xref=null, ext=[AuthorCompanyExt(id=1322564580832822065, tenantId=1146029695717560320, journalId=1263187385517883426, articleId=1320098218701078612, companyId=1322564580824433456, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=Science and Technology on Advanced Ceramic Fibers and Composites Laboratory, National University of Defense Technology, Changsha 410073, China), AuthorCompanyExt(id=1322564580841210674, tenantId=1146029695717560320, journalId=1263187385517883426, articleId=1320098218701078612, companyId=1322564580824433456, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=国防科技大学，新型陶瓷纤维及其复合材料重点实验室，长沙 410073)])])]

郭洪亮, 王小宙

作者信息

国防科技大学，新型陶瓷纤维及其复合材料重点实验室，长沙 410073

通讯作者:

王小宙（1984—），男，博士，副研究员。

作者简介:

郭洪亮（1998—），男，硕士研究生。

One-Step Ultrasonic Condensation Preparation and Characterization of Liquid Polycarbosilane

Hongliang GUO, Xiaozhou WANG

Affiliations

Science and Technology on Advanced Ceramic Fibers and Composites Laboratory, National University of Defense Technology, Changsha 410073, China

Corresponding Author:

WANG Xiaozhou (1984-), male, Ph.D., Associate Professor. E-mail: wangler2002@163.com

GUO Hongliang (1998-), male, Master candidate. E-mail: andrew_ghl@163.com

出版时间: 2024-09-20 doi: 10.14062/j.issn.0454-5648.20240170

文章导航

摘要

收起

液态聚碳硅烷（LPCS）是先驱体浸渍-裂解法（PIP）制备SiC陶瓷基复合材料的理想先驱体。以甲基氢二氯硅烷、甲基乙烯基二氯硅烷、二溴甲烷、金属钠为原料，经Wurtz缩合反应一步制备了含活性基团的LPCS。在超声波和醚助剂条件下，反应在40 ℃保温4 h即可完成，合成收率超过90%。采用Fourier变换红外光谱、核磁共振、紫外-可见光光谱、热重分析等对LPCS进行表征。结果表明：LPCS具有Si—C键的主链结构，同时形成了部分Si—Si键。所合成的LPCS含有丰富的Si—H、CH=CH₂等活性基团，1200 ℃以上热解后可转化为SiC，陶瓷产率最高为48.8%（质量分数）。

关键词

液态聚碳硅烷 / Wurtz反应 / 超声波 / 合成与表征

Abstract

收起

Introduction

SiC ceramic matrix composites have excellent mechanical properties and high-temperature resistance, and hence attracts increasing research attentions in aerospace and other fields. Precursor infiltration and pyrolysis (PIP) is one of the most common methods for the preparation of SiC ceramic matrix composites. The synthesis of organic precursors is the basis of the PIP process. Liquid polycarbosilane (LPCS) is an ideal precursor for the preparation of SiC ceramic matrix composites by PIP process. LPCS can be prepared using the Grignard coupling reaction, while this method suffers from the problem of long synthesis route and high cost. The Wurtz reaction, as another method for synthesizing LPCS, has a shorter route and less cost. However, it is difficult to directly synthesize LPCS containing active groups because of the severe reaction conditions. Ultrasound can significantly promote the effective contact between sodium and chlorosilanes and reduce the reaction conditions in the Wurtz reaction, and some ether additives can improve the activity of the reaction groups. Therefore, the introduction of ultrasound and ether additives is expected to realize the efficient synthesis of LPCS containing active groups. In this work, an active LPCS was prepared directly from chlorosilane monomer containing active groups by using ultrasonic and ether additives in Wurtz reaction. The basic structure of the product, ceramic yield and pyrolytic properties of the transformed ceramics were characterized.

Methods

CH₂Br₂, MeHSiCl₂ and ViMeSiCl₂ were used as raw materials, and mixed with the molar ratio of 2∶1∶1. Under the conditions of no ultrasonic or ether auxiliary agent, ether auxiliary agent only and ultrasonic together with ether auxiliary agent, the reaction was carried out at 40 ℃ for 4 h, and the excess Si—Cl was reacted by Me₃SiCl. The corresponding products were obtained by filtration and distillation. Diethylene glycol dimethyl ether (DGDME) or tetrahydrofuran (THF) was selected as ether auxiliary agent, and THF is easier to remove due to its lower boiling point, thus providing an advantage. On this basis, the molar ratio was adjusted to 3∶1∶1 and 4∶1∶1 to synthesize the products.

According to the ratio of actual yield to theoretical yield, the yield of each product was calculated. The basic structures and functional groups of the synthesized products under different conditions of ultrasonic and ether were characterized by Fourier transfer infrared spectroscopy (FT-IR) and nuclear magnetic resonance hydrogen spectroscopy (¹H-NMR). For the synthesized products with THF as ether auxiliary agent and the molar ratios of raw materials as 2∶1∶1, 3∶1∶1 and 4∶1∶1, the functional groups and structures were characterized and compared with FT-IR, and the existence of Si—Si bonds was determined and compared with UV-Vis spectroscopy. The mass change curves of the pyrolysis products at 900 ℃ were analyzed by thermogravimetric analyzer (TG). The crystal structures of the pyrolysis products prepared at 1 000, 1 200 ℃ and 1 400 ℃ were analyzed by X-ray diffractometer (XRD).

Results and discussion

For the precursors synthesized under different conditions of ultrasonic and ether, it was found that liquid products could not be obtained by Wurtz reaction at 40 ℃ without ultrasonic and ether. On the contrary, when ultrasonic is introduced, the reaction can take place to obtain the product, and when ultrasound and ether auxiliary agent are used simultaneously, the yield can be further improved. FT-IR and ¹H-NMR spectra show that Si—H, CH=CH₂ exist in all products, and Si—C—Si chain is formed, which proves that LPCS containing active groups can be successfully synthesized by this method. According to IR spectra, Si—CH₂—Si in the product is the most when the molar ratio of raw materials is 3∶1∶1, which indicates that proper increase of CH₂Br₂ content may promote polymerization, which may be due to CH₂Br₂ affecting the concentration of reactive free radicals in the reaction. The TG curves show that the mass loss of each precursor occurs at room temperature to 250 ℃ and 500-600 ℃, respectively, due to the volatilization of small molecular oligomers and the thermal crosslinking process dominated by active groups. When the molar ratio of raw materials is 3∶1∶1, the highest ceramic yield is obtained up to 48.8%. UV-Vis analysis shows that Si-Si bond exists in LPCS. XRD results shows that there is no obvious diffraction peak in the pyrolysis product curve at 1 000 ℃. With the temperature increasing to 1 200 ℃, diffraction peaks of the pyrolysis products appeared at 35.7°, 59. 9° and 71.7°, corresponding to the crystal structure of β-SiC. Further, at 1 400 ℃, the characteristic diffraction peaks of β-SiC were enhanced. All above indicate that LPCS can be partially transformed into β-SiC crystal after 1 200 ℃.

Conclusions

Through the introduction of ultrasonic and ether auxiliary agent, LPCS containing reactive groups can be rapidly synthesized using the Wurtz reaction at a temperature of 40 ℃ with a yield of more than 90%. The synthesized LPCS takes Si—C and Si—Si bonds as the main chain structure, and is rich in Si—H, CH=CH₂ active groups. When the molar ratio of CH₂Br₂, MeHSiCl₂, ViMeSiCl₂ is 3∶1∶1, the ceramic yield of the product reaches the highest value up to 48.8%. This study demonstrates that Wurtz reaction assisted by ultrasonic and ether auxiliary agent is simple in process, high efficient and low cost. It is an effective method to prepare liquid SiC ceramic precursors containing active groups.

Key words

liquid polycarbonsilane / Wurtz reaction / ultrasonic / synthesis and characterization

引用本文

郭洪亮, 王小宙. 液态聚碳硅烷的一步超声缩合制备及其表征. 硅酸盐学报, 2024 , 52 (9) : 2800 -2805 . DOI: 10.14062/j.issn.0454-5648.20240170

Hongliang GUO, Xiaozhou WANG. One-Step Ultrasonic Condensation Preparation and Characterization of Liquid Polycarbosilane[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (9) : 2800 -2805 . DOI: 10.14062/j.issn.0454-5648.20240170

基金

收起

国家自然科学基金(51872329)

参考文献

收起

文献

收起

参考文献引证文献

排序方式：

2024年第52卷第9期

PDF下载

引用本文

BibTeX

文章信息

doi: 10.14062/j.issn.0454-5648.20240170

接收时间：2024-02-29
首发时间：2026-10-22
出版时间：2024-09-20

补充材料

相关文章

文章信息

作者

出版历史

收稿日期：2024-02-29
修回日期：2024-04-07

基金

国家自然科学基金(51872329)

作者信息

国防科技大学，新型陶瓷纤维及其复合材料重点实验室，长沙 410073

通讯作者:

王小宙（1984—），男，博士，副研究员。

参考文献

分享链接

https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240170

分享至

全文二维码

扫描看全文

引用本文

BibTeX

本文的引用情况

2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

关闭全屏

BibTeX
EndNote
RefWorks
TxT