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SUPERVISOR
Mehran Ghiaci,Mehdi Amirnasr
مهران غیاثی (استاد راهنما) مهدی امیرنصر (استاد مشاور)
 
STUDENT
Fatemeh Mollaee
فاطمه ملائی

FACULTY - DEPARTMENT

دانشکده شیمی
DEGREE
Master of Science (MSc)
YEAR
1385

TITLE

Synthesis and characterization of modified ormosil nanocatalyst with porphyrin and using it in oxidation of ethylbenzene
Aromatic ketones are important chemical intermediates used in the synthesis of various perfumes, drugs, and pharmaceuticals. The production of these ketones by Friedel–Crafts acylation of aromatic compounds along with the acyl halide or acid anhydride, leads to the formation of a high volume of toxic and corrosive waste. Nowadays, due to economic and ecologic reasons, heterogeneous catalysts are of considerable importance. The use of metalloporphyrins substituted with electron-withdrawing groups and the immobilization on inorganic supports has resulted in efficient and selective catalysts for the oxidation of hydrocarbon. Oxidation of alkylbenzenes is an important transformation in chemical synthesis generally performed with corrosive, toxic or carcinogenic materials. The desired products are usually obtained with low selectivity accompanied by ecologically dangerous by-products. In recent researches, the possibility of using of metalloporphyrins as a catalyst in oxidation of such substrates has been proposed by several groups. These products strongly dependent on conditions used (catalyst, co-catalyst, oxidising agent, and solvent). The central objective of this research is to carry out oxidation reaction of ethylbenzene and produce acetophenone as the main product, using heterogeneous catalyst. Thus, this projects aims to design a heterogeneous catalyst based on the immobilization of porphyrin on silica gel. In order to do this, the porphyrin containing steric functional group, entitled 5, 10, 15, 20- tetrakis (4-methoxycarbonyl phenyl) porphyrin, was synthesized and immobilized using amidation reaction on modified silica gel (containing amino functional group). Ultimately, immobilized porphyrin was transformed into Mn(III) complex. Different techniques such as UV-Vis, FT-IR, CHN, TG, and BET were used for the characterization of the catalysts called SF-ATPS-Mn(III)TMCPP. Eventually, this catalyst was used for oxidation of ethylbenzene. In order to raise the conversion percentage of ethylbenzene and selectivity of acetophenone as the main product, various reaction conditions such as temperature, solvent, reaction time, oxidant, and a molar ratio of ethylbenzene: oxidant, were optimized.
در این پروژه هدف اصلی انجام واکنش اکسایش اتیل بنزن و تولید استوفنون به عنوان محصول اصلی، با استفاده از کاتالیست ناهمگن بود در نتیجه بر آن شدیم کاتالیست ناهمگنی را بر پایه تثبیت پورفیرین بر روی سیلیکاژل طراحی کنیم. برای این منظور پورفیرینی را که دارای گروه عاملی استری بود به نام 5،10،15،20-تتراکیس (4-متوکسی کربونیل فنیل)پورفیرین را سنتز کرده و آن را با استفاده از واکنش تشکیل آمید بر روی سیلیکاژل اصلاح شده (حاوی گروه عاملی آمینی) تثبیت نمودیم و در نهایت پورفیرین تثبیت شده به صورت کمپلکس با منگنز(III) درآمد. برای تأیید سنتز کاتالیست فوق به نام SF-ATPS-Mn(III)TMCPP از تکنیک های FT-IR، UV-Vis جامد، CHN، TGA و BET استفاده شد. در نهایت از این کاتالیست برای اکسایش اتیل بنزن استفاده شد وسپس برای افزایش درصد تبدیل اتیل بنزن و گزینش پذیری استوفنون به عنوان محصول اصلی، شرایط مختلف واکنش از جمله دما، حلال، زمان واکنش، اکسنده، نسبت مولی اتیل بنزن:اکسنده بهینه گردید.

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