سنتز و خصوصیات فیلم های نانوکامپوزیت کوپلی ایمید-سیلیکا سولفونه شده جدید

ﻣﻮﻧﻮﻣﺮ دی آﻣﯿﻦ ﺣﺎوی زاﻧﺘﻦ در ﭼﻬﺎر ﻣﺮﺣﻠﻪ ﺑﻪ وﺳﯿﻠﻪ ﺗﺮاﮐﻢ ﺑﺘﺎ-ﻧﻔﺘﻮل و 4-ﻧﯿﺘﺮوﺑﻨﺰاﻟﺪﺋﯿﺪ در ﺣﻀﻮر ﮐﺎﺗﺎﻟﯿﺰور ﭘﺎرا-ﺗﻮﻟﻮﺋﻦ ﺳﻮﻟﻔﻮﻧﯿﮏ اﺳﯿﺪ، ﮐﺎﻫﺶ ﺗﺮﮐﯿﺐ دی ﻧﯿﺘﺮو، واﮐﻨﺶ ﺟﺎﻧﺸﯿﻨﯽ ﻧﻮﮐﻠﺌﻮﻓﯿﻠﯽ آﻣﯿﻦ و 5،3-دی ﻧﯿﺘﺮو ﺑﻨﺰوﺋﯿﻞ ﮐﻠﺮﯾﺪ و ﻣﺘﻌﺎﻗﺒﺎ ﮐﺎﻫﺶ ﺗﺮﮐﯿﺐ دی ﻧﯿﺘﺮو ﺳﻨﺘﺰ ﮔﺮدﯾﺪ. ﺳﭙﺲ ﯾﮏ ﺳﺮی ﻧﺎﻧﻮﮐﺎﻣﭙﻮزﯾﺖ ﻫﺎی ﮐﻮﭘﻠﯽ اﯾﻤﯿﺪ ﺳﻮﻟﻔﻮﻧﻪ / ﺳﯿﻠﯿﮑﺎ ﺟﺪﯾﺪ ﺑﺎ درﺻﺪﻫﺎی ﻣﺨﺘﻠﻒ ﺳﯿﻠﯿﮑﺎ ﺑﻪ ﻃﻮر ﻣﻮﻓﻘﯿﺖ آﻣﯿﺰی از ﻃﺮﯾﻖ ﺗﺸﮑﯿﻞ درﺟﺎی ﺳﯿﻠﯿﮑﺎ درون ﻣﺎﺗﺮﯾﺲ ﭘﻠﯿﻤﺮ ﺑﻪ روش ﺳﻞ-ژل ﺳﻨﺘﺰ ﺷﺪﻧﺪ. ﻣﺤﻠﻮل ﭘﻠﯽ)آﻣﯿﮏ اﺳﯿﺪ( از 8،5،4،1- ﻧﻔﺘﺎﻟﻦ ﺗﺘﺮاﮐﺮﺑﻮﮐﺴﯿﻠﯿﮏ دی اﻧﯿﺪرﯾﺪ، 4 '،4-دی آﻣﯿﻨﻮ دیﻓﻨﯿﻞ اﺗﺮ 2 '،2-دیﺳﻮﻟﻔﻮﻧﯿﮏ اﺳﯿﺪ و دی آﻣﯿﻦ ﺳﻮﻟﻔﻮﻧﻪ ﻧﺸﺪه 5،3-دی آﻣﯿﻨﻮﺑﻨﺰوﺋﯿﻞ آﻣﯿﻨﻮﻓﻨﯿﻞ-14 h-دی ﺑﻨﺰو]j، a [زاﻧﺘﻦ درﺣﻼل n -ﻣﺘﯿﻞ ﭘﯿﺮﻟﯿﺪون ﺗﻬﯿﻪ ﺷﺪﻧﺪ. در ﻧﻬﺎﯾﺖ، ﻓﯿﻠﻢ ﻫﺎی ﻫﯿﺒﺮﯾﺪی ﺑﻪ وﺳﯿﻠﻪ ﻫﯿﺪروﻟﯿﺰ-ﭘﻠﯿﻤﺮ ﺷﺪن ﺗﺮاﮐﻤﯽ ﭘﯿﺶ ﻣﺎدهﻫﺎی ﺳﯿﻠﯿﮑﺎ، )3-آﻣﯿﻨﻮﭘﺮوﭘﯿﻞ(ﺗﺮیاﺗﻮﮐﺴﯽ ﺳﯿﻼن و ﺗﺘﺮا اﺗﻮﮐﺴﯽ ﺳﯿﻼن در ﻣﺤﻠﻮل ﭘﻠﯽ(آﻣﯿﮏ-اﺳﯿﺪ) ﺗﻬﯿﻪ ﮔﺮدﯾﺪﻧﺪ و ﺳﭙﺲ ﺟﻬﺖ ﺗﻮﻟﯿﺪ ﻧﺎﻧﻮﮐﺎﻣﭙﻮزﯾﺖﻫﺎی ﭘﻠﯽاﯾﻤﯿﺪ ﺳﻮﻟﻔﻮﻧﻪ/ﺳﯿﻠﯿﮑﺎ ﺑﻪ ﻃﻮر ﮔﺮﻣﺎﯾﯽ اﯾﻤﯿﺪه ﺷﺪﻧﺪ. ﺳﺎﺧﺘﺎر ﺷﯿﻤﯿﺎﯾﯽ و ﻣﻮرﻓﻮﻟﻮژی ﻧﺎﻧﻮﮐﺎﻣﭙﻮزﯾﺖﻫﺎی ﻫﯿﺒﺮﯾﺪی ﺣﺎﺻﻞ ﺑﻪ وﺳﯿﻠﻪ ﻃﯿﻒﺳﻨﺠﯽ ﻣﺎدون ﻗﺮﻣﺰ ﺗﺒﺪﯾﻞ ﻓﻮرﯾﻪ، ﺗﻔﺮق اﺷﻌﻪ x و ﻣﯿﮑﺮوﺳﮑﻮپ اﻟﮑﺘﺮوﻧﯽ ﻋﺒﻮری (tem) ﺑﺮرﺳﯽ ﺷﺪﻧﺪ. ﻫﺪاﯾﺖ اﻟﮑﺘﺮﯾﮑﯽ ﻣﻮاد ﺑﻪ وﺳﯿﻠﻪ ﭘﺘﺎﻧﺴﯿﻮﻣﺘﺮ اﻧﺪازه ﮔﯿﺮی ﺷﺪ. ﻧﺘﺎﯾﺞ tem ﻧﺸﺎن داد ﮐﻪ ذرات ﺳﯿﻠﯿﮑﺎ ﺑﻪ ﺧﻮﺑﯽ ﺑﺎ اﻧﺪازه ذرات ﺑﯿﻦ 50 اﻟﯽ 70 ﻧﺎﻧﻮﻣﺘﺮ در ﻣﺎﺗﺮﯾﺲ ﭘﻠﯿﻤﺮ ﭘﺨﺶ ﺷﺪهاﻧﺪ. ﻧﺘﺎﯾﺞ آﻧﺎﻟﯿﺰ ﮔﺮﻣﺎﺳﻨﺠﯽ ﻧﺸﺎن داد ﮐﻪ اﻓﺰاﯾﺶ ﺳﯿﻠﯿﮑﺎ درون ﻣﺎﺗﺮﯾﺲ ﭘﻠﯽاﯾﻤﯿﺪ ﺳﻮﻟﻔﻮﻧﻪ، ﭘﺎﯾﺪاری ﺣﺮارﺗﯽ ﻧﺎﻧﻮﮐﺎﻣﭙﻮزﯾﺖﻫﺎی ﺗﻬﯿﻪ ﺷﺪه را ﺑﻪ دﻟﯿﻞ اﻓﺰاﯾﺶ ﺑﺮﻫﻤﮑﻨﺶ و ﭘﺨﺶ ﺧﻮب ﺳﯿﻠﯿﮑﺎ درون ﻣﺎﺗﺮﯾﺲ ﭘﻠﯽ اﯾﻤﯿﺪ اﻓﺰاﯾﺶ داد. ﭘﺎﯾﺪاری ﺣﺮارﺗﯽ ﻧﺎﻧﻮﮐﺎﻣﭙﻮزﯾﺖﻫﺎی ﺗﻬﯿﻪ ﺷﺪه ﺑﺎ اﻓﺰاﯾﺶ درﺻﺪ ﺳﯿﻠﯿﮑﺎ اﻓﺰاﯾﺶ ﭘﯿﺪا ﮐﺮد. ﻧﺎﻧﻮﮐﺎﻣﭙﻮزﯾﺖﻫﺎی ﺗﻬﯿﻪ ﺷﺪه ﭘﺎﯾﺪاری ﺧﻮب در ﺑﺮاﺑﺮ آب و ﻫﺪاﯾﺖ اﻟﮑﺘﺮﯾﮑﯽ ﺑﺎﻻﯾﯽ را ﻧﺸﺎن دادﻧﺪ.

Synthesis and properties of novel sulfonated copolyimide-silica nanocomposite films

4,4’Diaminodiphenyl ether2,2’disulfonic acid (ODADS) as a sulfonated diamine was fabricated by direct sulfonation of diamine, 4,4’diaminodiphenyl ether in the presence of fuming sulfuric acid as the sulfonating agent. Additionally, a xanthenecontaining diamine monomer was prepared in four steps, by the condensation of βnaphtol and 4nitrobenzaldehyde in the presence of ptoluenesulphonic acid catalyst, reduction of the nitro intermediate, the nucleophilic substitution reaction of amine and 3,5dinitrobenzoyl chloride, and subsequent reduction of the dinitro compound. The diamine monomer could be obtained in quantitative yield. Then, a series of new sulfonated polyimide/silica nanocomposites with different percentages of silica have been successfully synthesized through the in situ formation of silica within a polymer matrix via solgel process. Poly(amic acid) solution is prepared from 1,4,5,8naphthalenetetracarboxylic dianhydride, ODADS and nonsulfonated diamine, 3,5diamino benzoyl amino phenyl14Hdibenzo[a,j]xanthene in Nmethyl2pyrrolidinone solvent. Finally, the nanocomposites films were obtained by the hydrolysispolycondensation of silica precursors (3aminopropyl)triethoxysilane (APTES) and tetraethoxysilane (TEOS) in poly(amic acid) solution and then thermally imidized to form polyimide/silica nanocomposites. The chemical and morphological structure of the hybrid nanocomposites were characterized by Fourier transform infrared spectroscopy, Xray diffraction, and transmission electron microscopy. The electrical conduction of materials was measured by potentiometer. The results of TEM show that the silica particles are well dispersed in the copolyimide matrix with particle size between 50 and 70 nm in diameter. Thermogravimetric analysis results indicated that the addition of silica into the sulfonated polyimide matrix was increased the thermal stability of the resulted nanocomposites owing to the enhanced interaction and good dispersion the silica into the polyimide matrix. The prepared nanocomposites were exhibited good water stability as well as great electrical conduction.