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Effects of pre-imidization on rheological behaviors of polyamic acid solution and thermal mechanical properties of polyimide film: an experiment and molecular dynamics simulation

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Abstract

A series of polyamic acid (PAA) solutions and corresponding polyimide (PI) films with different chemical structures were prepared through a partial pre-imidization process, and the rheological behavior of PAA solutions and thermal mechanical properties of PI films were investigated in detail. The FT-IR spectra indicate that the pre-imidization degree (pre-ID) of PI could be accurately controlled by adjusting the amount of dehydration reagents. The PI films with a certain pre-ID exhibit better mechanical properties and lower coefficient of thermal expansion. The viscosity curves of PAA solution with varying shear rate show that the PAA solutions with high pre-ID have low shear sensitivity, which exhibits a lower viscosity at the low shear rate, but retains almost the same viscosity at high shear rate. Chain conformation variations with pre-IDs and solvent content were investigated by molecular dynamic (MD) simulation. The MD results indicate that a sudden increase in cohesive energy density leads to gel at a certain pre-ID and the mobility of molecular chain decreases greatly with solvent volatilization. It is supposed that the molecular chain orientation induced by the pre-imidization will be preserved in the subsequent thermal imidization process. Therefore, the PI films with a certain pre-IDs exhibit more excellent thermal mechanical properties, especially for the PI with rigid-rod segments.

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References

  1. Okumura H, Takahagi T, Nagai N, Shingubara S (2003) Depth profile analysis of polyimide film treated by potassium hydroxide. J Polym Sci Part B: Polym Phys 41:2071–2078

    CAS  Google Scholar 

  2. Song G, Zhang X, Wang D, Zhao X, Zhou H, Chen C, Dang G (2014) Negative in-plane CTE of benzimidazole-based polyimide film and its thermal expansion behavior. Polymer 55:3242–3246

    CAS  Google Scholar 

  3. Liaw DJ, Wang KL, Huang YC, Lee KR, Lai JY, Ha CS (2012) Advanced polyimide materials: syntheses, physical properties and applications. Prog Polym Sci 37:907–974

    CAS  Google Scholar 

  4. Kreuz JA, Edman JR (1998) Polyimide films. Adv Mater 10:1229–1232

    CAS  Google Scholar 

  5. Kuznetov AA, Tsegelskaya AY, Belov MY (1998) Acid-catalyzed reactions in polyimide synthesis. Macromol Symp 128:203–219

    Google Scholar 

  6. Ali AAM, Ahmad Z (2007) The effect of curing conditions and aging on the thermo-mechanical properties of polyimide and polyimide-silica hybrids. J Mater Sci 42:8363–8369 https://doi.org/10.1007/s10853-006-1072-x

    CAS  Google Scholar 

  7. Saeed MB, Zhan MS (2006) Effects of monomer structure and imidization degree on mechanical properties and viscoelastic behavior of thermoplastic polyimide films. Eur Polym J 42:1844–1854

    CAS  Google Scholar 

  8. Zhou H, Lei HY, Wang JH, Qi SL, Tian GF, Wu DZ (2019) Breaking the mutual restraint between low permittivity and low thermal expansion in polyimide films via a branched crosslink structure. Polymer 162:116–120

    CAS  Google Scholar 

  9. Li XL, Lei HY, Guo JC, Wang JH, Qi SL, Tian GF, Wu DZ (2019) Composition design and properties investigation of BPDA/PDA/TFDB co-polyimide films with low dielectric permittivity. J Appl Polym Sci 47989.

  10. Park SJ, Cho KS, Kim SH (2004) A study on dielectric characteristics of fluorinated polyimide thin film. J Colloid Interf Sci 272:384–390

    CAS  Google Scholar 

  11. Li J, Zhang G, Zhu Q, Li J, Zhang H, Jing Z (2016) Synthesis and properties of ultralow dielectric constant porous polyimide films containing trifluoromethyl groups. J Appl Polym Sci 134:44494

    Google Scholar 

  12. Tong H, Hu CC, Yang SY, Ma YP, Guo HX, Fan L (2015) Preparation of fluorinated polyimides with bulky structure and their gas separation performance correlated with microstructure. Polymer 69:138–147

    CAS  Google Scholar 

  13. Lee C, Iyer NP, Han H (2004) Nanoindentation and optical properties of poly(4,4′-oxydiphenylene p-phenylene pyromellitimide) copolyimide thin films according to the p-phenylene diamine content. J Polym Sci Part B: Polym Phys 42:2202–2214

    CAS  Google Scholar 

  14. Kim Y, Ree M, Chang T, Ha CS, Nunes TL, Lin JS (1995) Rodlike/flexible polyimide composite films prepared from soluble poly(amic diethyl ester) precursors: Miscibility, structure, and properties. J Polym Sci Part B: Polym Phys 33:2075–2082

    CAS  Google Scholar 

  15. Khatua SC, Maiti S (2002) High performance polymer films 4. Mechanical behavior Eur Polym J 38:537–543

    CAS  Google Scholar 

  16. Hsiao BS, Kreuz JA, Cheng SZD (1996) Crystalline Homopolyimides and copolyimides derived from 3,3’,4,4’-biphenyltetracarboxylic dianhydride/1,3-bis(4-aminophenoxy)benzene /1,12-dodecanediamine. 2. crystallization, melting, and morphology. Macromolecules 29:135–142

    CAS  Google Scholar 

  17. Brandom DK, Wilkes GL (1995) Influence of thermal imidization on the crystallization and melting behaviour of the aromatic polyimide, LaRC CPI-2. Polymer 36:4083–4089

    CAS  Google Scholar 

  18. Brillhart MV, Cebe P (1995) Thermal expansion of the crystal lattice of novel thermoplastic polyimides. J Polym Sci Part B: Polym Phys 33:927–936

    CAS  Google Scholar 

  19. Hsu SC, Luo GW, Chen HT, Chuang SW (2005) Synthesis and characterization of novel aromatic poly (imide-benzoxazole) copolymers. J Polym Sci Part A: Polym Chem 43:6020–6027

    CAS  Google Scholar 

  20. Hsu SC, Chen HT, Tsai SJ (2004) Novel positive-working and aqueous-base-developable photosensitive poly(imide-benzoxazole) precursor. J Polym Sci Part A: Polym Chem 42:5990–5998

    CAS  Google Scholar 

  21. Musto P, Ragosta G, Scarinzi G, Mascia L (2004) Polyimide-silica nanocomposites: spectroscopic, morphological and mechanical investigations. Polymer 45:1697–1706

    CAS  Google Scholar 

  22. Gao H, Yorifuji D, Wakita J, Jiang ZH, Ando S (2010) In situ preparation of nano ZnO/hyperbranched polyimide hybrid film and their optical properties. Polymer 51:3173–3180

    CAS  Google Scholar 

  23. Chiang PC, Whang WT, Tsai MH, Wu SC (2004) Physical and mechanical properties of polyimide/titania hybrid films. Thin Solid Films 447:359–364

    Google Scholar 

  24. Chen D, Zhu H, Liu TX (2010) In situ thermal preparation of polyimide nanocomposite films containing functionalized graphene sheets. Appl Mater Interface 2:3702–3708

    CAS  Google Scholar 

  25. Lin DL, Liu YZ, Jia ZQ, Qi SL, Wu DZ (2020) Structural evolution of macromolecular chain during pre-imidization process and its effects on polyimide film properties. J Phys Chem B 124:7969–7978

    CAS  Google Scholar 

  26. Wang Y, Yang Y, Jia ZX, Qin JQ, Gu Y (2013) Effect of chemical structure and preparation process on the aggregation structure and properties of polyimide film. J Appl Polym Sci 4581–4587.

  27. Wang Y, Yang Y, Jia ZX, Qin JQ, Gu Y (2012) Effect of pre-imidization on the aggregation structure and properties of polyimide films. Polymer 53:4157–4163

    CAS  Google Scholar 

  28. Zhai Y, Yang Q, Zhu RQ, Gu Y (2008) The study on imidization degree of polyamic acid in solution and ordering degree of its polyimide film. J Mater Sci 43:338–344. https://doi.org/10.1007/s10853-007-1697-4

    Article  CAS  Google Scholar 

  29. Wang ZH, Chen X, Yang HX, Zhao J, Yang SY (2019) The in-plane orientation and thermal mechanical properties of the chemically imidized polyimide films. Chinese J Polym Sci 37:268–278

    CAS  Google Scholar 

  30. Hao FY, Wang JH, Qi SL, Tian GF, Wu DZ (2020) Structures and properties of polyimide with different pre-imidization degrees. Chinese J Polym Sci 38:840–846

    CAS  Google Scholar 

  31. Dabral M, Xia XY, Gerberich WW, Francis LF, Scriven LE (2011) Near-surface structure formation in chemically imidized polyimide films. J Polym Sci Part B: Polym Phys 39:1824–1838

    Google Scholar 

  32. Fang YT, Dong J, Zhang DB, Zhao X, Zhang QH (2019) Preparation of high-performance polyimide fibers via a partial pre-imidization process. J Mater Sci 54:3619–3631. https://doi.org/10.1007/s10853-018-3068-8

    Article  CAS  Google Scholar 

  33. Chang JJ, Ge QY, Zhang MY, Liu WW, Cao L, Niu HQ, Sui G, Wu DZ (2015) Effect of pre-imidization on the structures and properties of polyimide fibers. RSC Adv 5:69555

    CAS  Google Scholar 

  34. Young JA, Hinkley JA, Farmer BL (2000) Molecular simulations of the imidization of adsorbed polyamic acid. Macromolecules 33:4936–4944

    CAS  Google Scholar 

  35. Nishino T, Kotera M, Inayoshi N, Miki N, Nakamae K (2000) Residual stress and microstructures of aromatic polyimide with different imidization processes. Polymer 41:6913–6918

    CAS  Google Scholar 

  36. Kook HJ, Kim D (2000) In situ measurements and analysis of imidization extent, thickness, and stress during the curing of polyimide films. J Mater Sci 35:2949–2954. https://doi.org/10.1023/A:1004722609188

    Article  CAS  Google Scholar 

  37. Su JF, Chen L, Tang TT, Ren CB, Wang JJ, Qin CX, Dai LX (2011) Preparation and characterization of ternary copolyimide fibers via partly imidized method. High Perform Polym 23:273–280

    CAS  Google Scholar 

  38. Park SK, Farris RJ (2001) Dry-jet wet spinning of aromatic polyamic acid fiber using chemical imidization. Polymer 42:10087–10093

    CAS  Google Scholar 

  39. Kotera M, Nishino T, Nakamae K (2000) Imidization processes of aromatic polyimide by temperature modulated DSC. Polymer 41:3615–3619

    CAS  Google Scholar 

  40. Kim BH, Park HJ, Park HY, Moon DC (2013) Degree of imidization for polyimide films investigated by evolved gas analysis-mass spectrometry. Thermochim Acta 551:184–190

    CAS  Google Scholar 

  41. Ma XR, Zheng F, Sittert CGCE, Lu QH (2019) Role of Intrinsic factors of polyimides in glass transition temperature: an atomistic investigation. J Phys Chem B 123:8569–8579

    CAS  Google Scholar 

  42. Wang XY, in ’t Veld PJ, Lu Y, Freeman BD, Sanchez IC (2005) A molecular simulation study of cavity size distributions and diffusion in para and meta isomers. Polymer 46: 9155-9161

  43. Kang JW, Choi K, Jo WH, Hsu SL (1998) Structure-property relationships of polyimides: a molecular simulation approach. Polymer 39: 7079–7087.

  44. Lin DL, Li RY, Liu Y, Qi SL, Wu DZ (2021) Clarifying the effect of moisture absorption and high-temperature thermal aging on structure and properties of polyimide film at molecular dynamic level. Polymer 214:123251.

  45. Lin DL, Jiang M, Qi SL, Wu DZ (2020) Macromolecular structural evolution of polyimide chains during large-ratio uniaxial fiber orientation process revealed by molecular dynamics simulation. Chem Phys Lett 756: 137847.

  46. Lei HY, Qi SL, Wu DZ Hierarchical multiscale analysis of polyimide films by molecular dynamics simulation: Investigation of thermo-mechanical properties. Polymer 179: 121645.

  47. Lin DL, Li RY, Li TF, Xu SQ, Qi SL, Wu DZ (2021) Sol-gel transition of polyamic acid solution during chemical imidization and its effect on the drawing behavior of polyimide films. Polymer. https://doi.org/10.1016/j.polymer.2021.123842

    Article  Google Scholar 

  48. Spenley NA, Cates ME (1994) Pipe models for entangled fluids under strong shear. Macromolecules 27:3850–3858

    CAS  Google Scholar 

  49. Liu XX, Qian LY, Shu T, Tong Z (2003) Rheology characterization of sol–gel transition in aqueous alginate solutions induced by calcium cations through in situ release. Polymer 44:407–412

    CAS  Google Scholar 

  50. Yin CQ, Dong J, Zhang ZX, Zhang QH (2014) Rheological behaviour of polyamic acid spinning solutions containing heterocycle. Mater Res Innov 18:803–807

    Google Scholar 

  51. Dikshit AK (2012) Rheological behaviours of polyimide precursor in organic solvents for coating on silica optical fibre. Polym-Plast Technol 51:707–715

    CAS  Google Scholar 

  52. Zhang MY, Niu HQ, Lin ZW, Qi SL, Chang JJ, Ge QY, Wu DZ (2015) Preparation of high performance copolyimide fibers via increasing draw ratios. Macromol Mater Eng 300:1096–1107

    CAS  Google Scholar 

Download references

Acknowledgements

The authors thank the financial support from the National Natural Science Foundation of China [Grant No. 51790501, 51673017, 21404005], the Fundamental Research Funds for the Central Universities (XK1802-2), the National Key Basic Research Program of China [973 program, grant number 2014CB643604, 2014CB643606] and the Natural Science Foundation for Distinguished Young Scholars of Jiangsu Province [Grant No. BK20140006].

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Authors and Affiliations

  1. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, 100029, China

    Daolei Lin, Runyue Li, Tengfei Li, Yucheng Zi, Shengli Qi & Dezhen Wu

  2. Changzhou Institute of Advanced Materials, Beijing University of Chemical Technology, Changzhou, 213164, Jiangsu, China

    Shengli Qi & Dezhen Wu

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  1. Daolei Lin
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Lin, D., Li, R., Li, T. et al. Effects of pre-imidization on rheological behaviors of polyamic acid solution and thermal mechanical properties of polyimide film: an experiment and molecular dynamics simulation. J Mater Sci 56, 14518–14530 (2021). https://doi.org/10.1007/s10853-021-06241-1

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