Sains Malaysiana 54(10)(2025): 2467-2475

http://doi.org/10.17576/jsm-2025-5410-11

 

Effect of Heating Methods and Immersion Times on the Physicochemical Properties of Polyimide Based on 3,3′,4,4′-Benzophenone Tetracarboxylic Dianhydride and
4,4′-Methylene Diphenyl Diisocyanate (BTDA-MDI)

(Kesan Kaedah Pemanasan dan Masa Rendaman terhadap Sifat Fisikokimia Polimida Berdasarkan 3,3′,4,4′-Benzofenon Tetrakarboksilat Dianhidrida dan 4,4′-Metilena
Difenil Diisosianat (BTDA-MDI))

 

NUR SHAWALINA AZRAN¹, NAJAA MUSTAFFA² & NADHRATUN NAIIM MOBARAK^1,3,*

 

¹Department of Chemical Sciences, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia
²Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 Johor Bahru, Johor, Malaysia
³Polymer Research Center (PORCE), Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia

 

Received: 3 March 2025/Accepted: 12 September 2025

 

Abstract

Aromatic polyimides (PIs) derived from diisocyanates can be synthesized through one-step polycondensation process, either by stepwise heating with controlled temperature increments or by direct heating, in which the reaction mixture is exposed immediately to the final target temperature. However, the impact of these heating method on the resulting PIs properties remains underexplored. In this study, PIs were synthesized from the reaction of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA) and 4,4′-methylene diphenyl diisocyanate (MDI) using both heating methods. Additionally, the effect of longer and shorter immersion times in distilled water applied after the thermal reaction during the precipitation process was examined to determine their influence on polymer properties. The combined effects of heating protocol and immersion duration on precipitation behaviour, solubility, and thermal stability were evaluated. Structural characterization was performed using FTIR and NMR spectroscopy. Thermogravimetric analysis (TGA) confirmed high thermal stability, with degradation temperatures ranging from 574 °C to 585 °C. Solubility tests showed that all BTDA-MDI-based PIs were partially soluble in N-methyl-2-pyrrolidone (NMP), while a comparative PIs synthesized from 6FDA-MDI was fully soluble in various organic solvents. These findings suggest that monomer structure has a stronger influence on solubility than on thermal or crystalline properties. Overall, the study provides valuable insights into how synthesis and post-reaction conditions influence PIs characteristics, supporting their optimization for advanced material applications.

 

Keywords: Diisocyanate; direct heating; one-step polycondensation; polyimide; stepwise heating

 

Abstrak

Poliimida aromatik (PIs) terbitan diisosianat dapat disintesis melalui proses polikondensasi satu langkah, sama ada menerusi pemanasan berperingkat dengan peningkatan suhu terkawal atau pemanasan langsung pada suhu sasaran. Walau bagaimanapun, kesan cara pemanasan ini terhadap sifat PIs yang terhasil masih kurang dikaji. Dalam kajian ini, PI telah disintesis daripada 3,3′,4,4′-benzofenon tetrakarboksilat dianhidrida (BTDA) dan 4,4′-metilena difenil diisosianat (MDI) menggunakan kedua-dua kaedah pemanasan. Di samping itu, kesan tempoh rendaman yang berbeza (lama dan singkat) dalam air suling selepas tindak balas terma semasa proses pemendakan turut dikaji bagi menilai pengaruhnya terhadap sifat polimer. Kesan gabungan protokol pemanasan dan tempoh rendaman terhadap tingkah laku pemendakan, keterlarutan dan kestabilan terma telah dianalisis. Pencirian struktur dilakukan menggunakan spektroskopi FTIR dan NMR. Analisis termogravimetri (TGA) menunjukkan kestabilan terma yang tinggi dengan suhu penguraian antara 574 °C hingga 585 °C. Ujian keterlarutan menunjukkan bahawa semua PIs berasaskan BTDA-MDI adalah separa larut dalam N-metil-2-pirolidon (NMP) manakala PIs perbandingan yang disintesis daripada 6FDA-MDI menunjukkan keterlarutan penuh dalam pelbagai pelarut organik. Keputusan ini menunjukkan bahawa struktur monomer memberikan pengaruh yang lebih ketara terhadap keterlarutan berbanding sifat terma atau kekristalan. Secara keseluruhan, kajian ini memberikan keputusan penting mengenai pengaruh kaedah sintesis dan keadaan pasca-tindak balas terhadap ciri PIs, yang dapat menyokong pengoptimuman bahan ini untuk aplikasi berprestasi tinggi.

 

Kata kunci: Diisosianat; pemanasan berperingkat; pemanasan langsung; poliimida; satu langkah polikondensasi

 

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*Corresponding author; email: nadhratunnaiim@ukm.edu.my