聚酰亚胺介电常数的定量构效关系研究及其低介电薄膜的分子结构设计

范振国; 陈文欣; 魏世洋; 刘腾; 刘四委; 池振国; 张艺; 许家瑞

doi:10.11777/j.issn1000-3304.2018.18183

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聚酰亚胺介电常数的定量构效关系研究及其低介电薄膜的分子结构设计

研究论文 | 更新时间：2021-01-26

- 聚酰亚胺介电常数的定量构效关系研究及其低介电薄膜的分子结构设计
- Quantitative Structure-Property Relationship Study on Dielectric Constant of Polyimide and Its Molecular Structure Design for Low Dielectric Films
- 高分子学报 2019年50卷第2期页码：179-188
- 作者机构：
  
  中山大学聚合物复合材料及功能材料教育部重点实验室高性能树脂基复合材料广东省重点实验室广东省高性能有机聚合物光电功能薄膜工程技术研究中心光电材料与技术国家重点实验室化学学院广州 510275
- 作者简介：
  
  E-mail: ceszy@mail.sysu.edu.cn ceszy@mail.sysu.edu.cn
  E-mail: xjr@mail.sysu.edu.cn Jia-rui Xu &Yi Zhang, E-mail: xjr@mail.sysu.edu.cn
- 基金信息：
  
  国家重点基础研究计划(973计划，项目号 2014CB643605)、国家自然科学基金(基金号 51873239, 51373204)、广东省“特支计划”科技创新领军人才项目(项目号 2016TX03C295)、广东省前沿与关键技术创新专项(项目号 2015B090915003, 2015B090913003)、中国博士后科学基金(基金号 2017M612801)和高等学校基本科研业务费(项目号 161gzd08)资助项目()
- DOI：10.11777/j.issn1000-3304.2018.18183
  中图分类号：
- 纸质出版日期：2019-2，
  
  网络出版日期：2018-10-18，
  
  收稿日期：2018-8-15，
  
  修回日期：2018-9-4，
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范振国, 陈文欣, 魏世洋, 刘腾, 刘四委, 池振国, 张艺, 许家瑞. 聚酰亚胺介电常数的定量构效关系研究及其低介电薄膜的分子结构设计[J]. 高分子学报, 2019,50(2):179-188.

Zhen-guo Fan, Wen-xin Chen, Shi-yang Wei, Teng Liu, Si-wei Liu, Zhen-guo Chi, Yi Zhang, Jia-rui Xu. Quantitative Structure-Property Relationship Study on Dielectric Constant of Polyimide and Its Molecular Structure Design for Low Dielectric Films[J]. Acta Polymerica Sinica, 2019,50(2):179-188.
范振国, 陈文欣, 魏世洋, 刘腾, 刘四委, 池振国, 张艺, 许家瑞. 聚酰亚胺介电常数的定量构效关系研究及其低介电薄膜的分子结构设计[J]. 高分子学报, 2019,50(2):179-188. DOI： 10.11777/j.issn1000-3304.2018.18183.

Zhen-guo Fan, Wen-xin Chen, Shi-yang Wei, Teng Liu, Si-wei Liu, Zhen-guo Chi, Yi Zhang, Jia-rui Xu. Quantitative Structure-Property Relationship Study on Dielectric Constant of Polyimide and Its Molecular Structure Design for Low Dielectric Films[J]. Acta Polymerica Sinica, 2019,50(2):179-188. DOI： 10.11777/j.issn1000-3304.2018.18183.

摘要

利用量子化学计算方法和基团贡献法，采集了61种聚酰亚胺分子结构模型单元的12种量子化学结构参数，并通过通径分析法筛选出5种影响该聚合物介电常数的主要因素；在此基础上，基于多元线性回归(MLR)和人工神经网络(ANN)方法构建了2种定量构效关系研究模型(QSPR)，分析了模型的稳定性及预测能力. 计算结果揭示了5种结构参数与材料介电常数之间的内在关系——含氟量的自然律

−

、偶极距

、溶度参数

与介电常数之间存在正相关关系，而最负原子净电荷

−

、侧基长度

则与介电常数则存在着负相关关系. MLR-QSPR模型具备较好的物理意义，ANN-QSPR则具有较好的精度，实验数据证明2种模型的平均误差均低于10%. 依据MLR-QSPR模型设计了5种不同含氟量的聚酰亚胺链节结构，结果显示含氟量的增加有利于降低材料的介电常数值，但当含氟量达到一定程度后，介电常数趋于稳定，与文献报道实验结果相一致；当含氟量为34%时(k-3)，材料的介电常数最低，为2.02.

Abstract

Using the quantum chemical calculation method and the group contribution method

12 kinds of quantum chemical structure parameters of 61 polyimide molecular structure model units were collected. In order to simplify the calculation process

a segment of the polymer chain was selected and saturated with methyl group

which was used as the model of the polyimide. Through the path analysis

5 main factors that affect the dielectric constant of the polyimide films were further screened. On this basis

the multiple linear regression (MLR) and artificial neural network (ANN) methods were constructed. Two quantitative structure-property relationship model (QSPR) were built

and the stability and prediction ability of the models were analyzed. The results revealed the intrinsic relationship between the 5 structural parameters and the dielectric constant

i.e.

the fluorine content

−

the dipole pitch

and the solubility parameter

of polyimide are positively correlated with the dielectric constant

while the most negative atomic net charge

−

and the side length

are negatively correlated with the dielectric constant. MLR-QSPR model has better physical significance and the ANN-QSPR has better accuracy. The accuracy of the models is validated by combining four structures: 6FDA-TriPMPDA

6FDA-TriPMMDA

6FDA-TPCF3PDA and 6FDA-TPCF3MDA in our lab. The experimental data show that the average error of the two models is lower than 10% under 1 kHz test condition. Five different fluorine-containing polyimide chain structures were designed according to MLR-QSPR model. The results show that the increase in fluorine content is beneficial to reduce the dielectric constant of the material

but when the fluorine content reaches a certain level

the dielectric constant tends to be stable

which are consistent with the experimental results reported in the literature. When the fluorine content is 34% (k-3)

the material possesses the lowest dielectric constant of 2.02. Based on the results of this study

it is believed that QSPR has a good application prospect and theoretical significance in designing new polyimide materials and predicting its properties.

关键词

聚酰亚胺介电常数定量构效关系多元线性回归人工神经网络

Keywords

PolyimideLow dielectric constantQuantitative structure-property relationshipMultiple linear regressionArtificial neural network

references

Liu Y, Zhou Z, Qu L, Zou B, Chen Z, Zhang Y, Liu S, Chi Z, Chen X, Xu J . Mater Chem Front , 2017 . 1 ( 2 ): 326 - 337 . DOI:10.1039/C6QM00027Dhttp://doi.org/10.1039/C6QM00027D .

Bei R, Qian C, Zhang Y, Chi Z, Liu S, Chen X, Xu J, Aldred M P . J Mater Chem C , 2017 . 5 ( 48 ): 12807 - 12815 . DOI:10.1039/C7TC04220Ehttp://doi.org/10.1039/C7TC04220E .

Zhou Z, Zhang Y, Liu S, Chi Z, Chen X, Xu J . J Mater Chem C , 2016 . 4 ( 44 ): 10509 - 10517 . DOI:10.1039/C6TC03889Ahttp://doi.org/10.1039/C6TC03889A .

Liu Y, Qian C, Qu L, Wu Y, Zhang Y, Wu X, Zou B, Chen W, Chen Z, Chi Z, Liu S, Chen X, Xu J . Chem Mater , 2015 . 27 6543 - 6549 . DOI:10.1021/acs.chemmater.5b01798http://doi.org/10.1021/acs.chemmater.5b01798 .

Yan W, Zhang Y, Sun H, Liu S, Chi Z, Chen X, Xu J . J Mater Chem A , 2014 . 2 ( 48 ): 20958 - 20965 . DOI:10.1039/C4TA04663Chttp://doi.org/10.1039/C4TA04663C .

Zhang Y, Xiao S, Wang Q, Liu S, Qiao Z, Chi Z, Xu J, Economy J . J Mater Chem , 2011 . 21 ( 38 ): 14563 - 14568 . DOI:10.1039/c1jm12450ahttp://doi.org/10.1039/c1jm12450a .

Yang Tinging(杨婷婷), Zhou Zhuxin(周竹欣), Zhang Yi(张艺), Liu Siwei(刘四委), Chi Zhenguo(池振国), Xu Jiarui(许家瑞) . 高分子学报 , Acta Polymerica Sinica , 2017 . ( 3 ): 411 - 428.

Li Yuhan(李玉邯), Jin Rizhe(金日哲), Gao Lianxun(高连勋) . 高分子学报 , Acta Polymerica Sinica , 2014 . ( 8 ): 1096 - 1102.

Liu Jingang(刘金刚), Li Zhuo(李卓), Gao Zhiqi(高志琪), Yang Haixia(杨海霞), Yang Shiyong(杨士勇) . 高分子学报 , Acta Polymerica Sinica , 2009 . ( 1 ): 11 - 16 . DOI:10.3321/j.issn:1000-3304.2009.01.003http://doi.org/10.3321/j.issn:1000-3304.2009.01.003 .

Liu Jingang(刘金刚), Li Zhuo(李卓), Yang Haixia(杨海霞), Yang Shiyong(杨士勇) . 高分子学报 , Acta Polymerica Sinica , 2008 . ( 5 ): 460 - 465 . DOI:10.3321/j.issn:1000-3304.2008.05.011http://doi.org/10.3321/j.issn:1000-3304.2008.05.011 .

Chen Yiwang(陈义旺), Nie Huarong(聂华荣), Chen Lie(谌烈), Kang Yangtang(康燕镗) . 高分子学报 , Acta Polymerica Sinica , 2005 . ( 6 ): 807 - 812 . DOI:10.3321/j.issn:1000-3304.2005.06.002http://doi.org/10.3321/j.issn:1000-3304.2005.06.002 .

Liu Jingang(刘金刚), Shang Yuming(尚玉明), Fan Lin(范琳), Yang Shiyong(杨士勇) . 高分子学报 , Acta Polymerica Sinica , 2003 . ( 4 ): 565 - 570 . DOI:10.3321/j.issn:1000-3304.2003.04.021http://doi.org/10.3321/j.issn:1000-3304.2003.04.021 .

Roy K, Mitra I, Kar S, Ojha P K, Das R N, Kabir H . J Chem Inf Model , 2012 . 52 ( 2 ): 396 - 408 . DOI:10.1021/ci200520ghttp://doi.org/10.1021/ci200520g .

Katritzky A R, Pacureanu L, Dobchev D, Karelson M . J Chem Inf Model , 2007 . 47 ( 3 ): 782 - 793 . DOI:10.1021/ci600462dhttp://doi.org/10.1021/ci600462d .

Fishtik I, Datta R . J Chem Inf Comput Sci , 2003 . 43 ( 4 ): 1259 - 1268 . DOI:10.1021/ci0340310http://doi.org/10.1021/ci0340310 .

Katritzky A R, Stoyanova-Slavova I B, Tämm K, Tamm T, Karelson M . J Phys Chem A , 2011 . 115 ( 15 ): 3475 - 3479 . DOI:10.1021/jp104287phttp://doi.org/10.1021/jp104287p .

Katritzky A R, Petrukhin R, Jain R, Karelson M . J Chem Inf Comput Sci , 2001 . 41 ( 6 ): 1521 - 1530 . DOI:10.1021/ci010043ehttp://doi.org/10.1021/ci010043e .

Cocchi M, Benedetti P G D, Seeber R, Tassi L, Ulrici A . J Chem Inf Comput Sci , 1999 . 39 ( 6 ): 1190 - 1203 . DOI:10.1021/ci9903298http://doi.org/10.1021/ci9903298 .

Lee A, Kim D, Kim K, Choi S, Choi K, Jung D H . J Mol Model , 2012 . 18 ( 1 ): 251 - 256 . DOI:10.1007/s00894-011-1067-7http://doi.org/10.1007/s00894-011-1067-7 .

Schweitzer R C, Morris J B . Anal Chim Acta , 1999 . 384 ( 3 ): 285 - 303 . DOI:10.1016/S0003-2670(98)00781-8http://doi.org/10.1016/S0003-2670(98)00781-8 .

Schweitzer R C, Morris J B . J Chem Inf Comput Sci , 2000 . 40 ( 5 ): 1253 - 1261 . DOI:10.1021/ci0000070http://doi.org/10.1021/ci0000070 .

Sild S, Karelson M . J Chem Inf Comput Sci , 2002 . 42 ( 2 ): 360 - 367 . DOI:10.1021/ci010335fhttp://doi.org/10.1021/ci010335f .

Findlay J A, Barnsley J E, Gordon K C, Crowley J D . Molecules , 2018 . 23 ( 8 ): 2037 DOI:10.3390/molecules23082037http://doi.org/10.3390/molecules23082037 .

Shariatinia Z . Phys Chem Res , 2017 . 6 ( 1 ): 15 - 29.

Small P A . J Appl Chem , 1953 . 3 ( 2 ): 71 - 80.

Banchero M, Manna L . Molecules , 2018 . 23 ( 6 ): 1379 DOI:10.3390/molecules23061379http://doi.org/10.3390/molecules23061379 .

Le T, Epa V C, Burden F R, Winkler D A . Chem Rev , 2012 . 112 ( 5 ): 2889 - 2919 . DOI:10.1021/cr200066hhttp://doi.org/10.1021/cr200066h .

Ding Mengxian(丁孟贤). Polyimides: Chemistry, Relationship between Structure and Properties Materials(聚酰亚胺 —化学、结构与性能的关系及材料). Beijing(北京): Science Press(科学出版社), 2006. 246-247

Maier G . Prog Polym Sci , 2001 . 26 ( 1 ): 3 - 65 . DOI:10.1016/S0079-6700(00)00043-5http://doi.org/10.1016/S0079-6700(00)00043-5 .

Liu Y, Zhang Y, Lan Q, Liu S, Qin Z, Chen L, Zhao C, Chi Z, Xu J, Economy J . Chem Mater , 2012 . 24 ( 6 ): 1212 - 1222 . DOI:10.1021/cm3003172http://doi.org/10.1021/cm3003172 .

Liu Y, Zhang Y, Lan Q, Qin Z, Liu S, Zhao C, Chi Z, Xu J . J Polym Sci, Part A: Polym Chem , 2013 . 51 ( 6 ): 1302 - 1314 . DOI:10.1002/pola.26498http://doi.org/10.1002/pola.26498 .

Chern Y, Tsai J . Macromolecules , 2008 . 41 ( 24 ): 9556 - 9564 . DOI:10.1021/ma802305qhttp://doi.org/10.1021/ma802305q .

Qian Z, Ge Z, Li Z, He M, Liu J, Pang Z, Fan L, Yang S . Polymer , 2002 . 43 6057 - 6063 . DOI:10.1016/S0032-3861(02)00494-9http://doi.org/10.1016/S0032-3861(02)00494-9 .

Jang W, Lee H, Lee S, Choi S, Shin D, Han H . Mater Chem Phys , 2007 . 104 ( 2-3 ): 342 - 349 . DOI:10.1016/j.matchemphys.2007.03.025http://doi.org/10.1016/j.matchemphys.2007.03.025 .

Yang C, Su Y, Wu K . J Polym Sci, Part A: Polym Chem , 2004 . 42 5424 - 5438 . DOI:10.1002/(ISSN)1099-0518http://doi.org/10.1002/(ISSN)1099-0518 .

Yang C, Chen R, Chen K . J Polym Sci, Part A: Polym Chem , 2003 . 41 922 - 938 . DOI:10.1002/(ISSN)1099-0518http://doi.org/10.1002/(ISSN)1099-0518 .

Yang C, Su Y, Chiang H . React Funct Polym , 2006 . 66 ( 7 ): 689 - 701 . DOI:10.1016/j.reactfunctpolym.2005.10.020http://doi.org/10.1016/j.reactfunctpolym.2005.10.020 .

Chen W, Zhou Z, Yang T, Bei R, Zhang Y, Liu S, Chi Z, Chen X, Xu J . React Funct Polym , 2016 . 108 71 - 77 . DOI:10.1016/j.reactfunctpolym.2016.04.011http://doi.org/10.1016/j.reactfunctpolym.2016.04.011 .

Sun Huawei(孙华伟). Synthesis and Optical Properties Studies on Novel Diamines and Their Polyimide Films(新型二胺单体及其聚酰亚胺的设计合成与光学特性研究). Doctoral Dissertation of Sun Yat-sen University(中山大学博士学位论文), 2014

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