الفهرس 
IntroductionOnly 14 pages are availabe for public view
 |  | from | 341 |  |  |
| | | from | 341 | | |
Abstract
The present work includes three chapters: Chapter (I): INTRODUCTION: 1 The introduction contains all the preparation trials of benzylidene Motives homopolymers, their characterization by using different lytical tools and the applications of these types of polymers in research industry. Also, this part includes the thin layer chromatographic tion of polymers on the basis of their structures or molecular its, which have been discussed in the literature. Chapter (II): EXPERIMENTAL: LThis chapter comprises all the chemicals used in this work, lental methods of the preparation of the benzylidene derivatives onomers and polymers in general and the polymers-iron (II) complexes their characterization by different tools such as UV, IR, ’H-NMR icscopy, TGA, X-ray diffraction and thin layer chromatography. Also, methods of molecular orbital calculations are given. ter (III): RESULTS AND DISCUSSION: khapter includes Jour parts: In this part, the preparation of some nitrogen containing polymers some benzylidene derivatives such as para-methyl benzylidene nitrile (PMeBMN), para-methoxy benzylidene malononitrile BMN), para-methyl benzylidene ethyl cyanoacetate (PMeBECA) para-methoxy benzylidene ethyl cyanoacetate (PMeOBECA) are out. The homopolymers are prepared by anionic polymerization ue using dimethyl formamide (DMF) as a reaction medium and iperidine (pipi) as initiator at 100 °C for 12-16 hours. The chemical structures of the obtained homopolymers are investigated by elemental analysis, infrared, ultraviolet, ’H-NMR spectroscopy and X- ray diffraction. Part II: The TLC separations of the prepared polymers according to the nations of the specific viscosity values or according to their chemical fcuctures are achieved. The TLC separation of PBMN and PPMeOBMN ccording to the variation in specific viscosity values by using a mixture of eetone and petroleum ether (40:60 V/V) as a mobile phase. Also, the TLC separation according to the structure (using the same r|Sp-value) using single solvent (ethanol) as in case of poly para-benzylidene malononitrile derivatives; and by using binary solvent mixture of benzene and dimethyl fermamide (95:5 V/V) in case of poly para-benzylidene ethyl cyanoacetate jderivatives. In all TLC separations, silica gel (G60) layers of 0.5 mm mickness, are used as stationary phase using normal saturation system at He. it. Part III: The Fe (II) complexes of PBMN, PPCIBIVTN, PPMeRMN mid fPMeOBMN are prepared. The suggested chemical structures of the prepared iron (II) polymers complexes are confirmed by using: elemental analysis, infrared spectroscopic analysis and thermogravimetric analysis fIGA). All the iron (II) complexes are thermally stable as shown from the TGA pattern. The order of the thermal stability of the investigated Fe (II) complexes is as follows: PPCIBMN-Fe (II) complex > PPMeBMN-Fe (II) complex > PMeOBMN-Fe (II) complex > PBMN-Fe (II) complex. from the X-ray diffraction analysis, it is clear that all the prepared nonomers are crystalline, but all the prepared homopolymers or the ^spared iron (II) complexes of the polypara-benzylidene malononitrile Jmvatives are amorphous. Part IV: In this part, molecular orbital calculations, for the investigated onomers, dimers and also the proposed mechanism of the polymerization Eeaetion is confirmed. By drawing the density maps HOMO and LUMO for She dimers by different interaction possibilities (head - head, head - tail and tail - tail), and also by the total energy calculations, one can conclude fax the most stable structure is formed by (head - tail) interaction. The (Mai energy (ET), heat of formation (AHr), dipole moment (fj,, D), ionization potential (IP) for the investigated monomers, dimers, pipi-monomers and one unite of iron (II) complexes of para-substituted benzylidene Edononitrile are calculated. from the obtained data of the A.Os, percentage p different moieties of HOMO and LUMO for monomers, pipi- monomers »d pipi- dimers, il is clear Uml the charge density is concentrated on Bp=C) of the second monomeric moiety indicating the formation of newHive «nter of the polymerization reaction. This behavior confirms the SBEgested mechanism of the anionic polymerization reaction. ¡1 Also, the combination between the theoretical dipole moment data and the experimental Rf- values or a.c conductivity are given. The present work includes three chapters: Chapter (I): INTRODUCTION: 1 The introduction contains all the preparation trials of benzylidene Motives homopolymers, their characterization by using different lytical tools and the applications of these types of polymers in research industry. Also, this part includes the thin layer chromatographic tion of polymers on the basis of their structures or molecular its, which have been discussed in the literature. Chapter (II): EXPERIMENTAL: LThis chapter comprises all the chemicals used in this work, lental methods of the preparation of the benzylidene derivatives onomers and polymers in general and the polymers-iron (II) complexes their characterization by different tools such as UV, IR, ’H-NMR icscopy, TGA, X-ray diffraction and thin layer chromatography. Also, methods of molecular orbital calculations are given. ter (III): RESULTS AND DISCUSSION: khapter includes Jour parts: In this part, the preparation of some nitrogen containing polymers some benzylidene derivatives such as para-methyl benzylidene nitrile (PMeBMN), para-methoxy benzylidene malononitrile BMN), para-methyl benzylidene ethyl cyanoacetate (PMeBECA) para-methoxy benzylidene ethyl cyanoacetate (PMeOBECA) are out. The homopolymers are prepared by anionic polymerization ue using dimethyl formamide (DMF) as a reaction medium and iperidine (pipi) as initiator at 100 °C for 12-16 hours. The chemical structures of the obtained homopolymers are investigated by elemental analysis, infrared, ultraviolet, ’H-NMR spectroscopy and X- ray diffraction. Part II: The TLC separations of the prepared polymers according to the nations of the specific viscosity values or according to their chemical fcuctures are achieved. The TLC separation of PBMN and PPMeOBMN ccording to the variation in specific viscosity values by using a mixture of eetone and petroleum ether (40:60 V/V) as a mobile phase. Also, the TLC separation according to the structure (using the same r|Sp-value) using single solvent (ethanol) as in case of poly para-benzylidene malononitrile derivatives; and by using binary solvent mixture of benzene and dimethyl fermamide (95:5 V/V) in case of poly para-benzylidene ethyl cyanoacetate jderivatives. In all TLC separations, silica gel (G60) layers of 0.5 mm mickness, are used as stationary phase using normal saturation system at He. it. Part III: The Fe (II) complexes of PBMN, PPCIBIVTN, PPMeRMN mid fPMeOBMN are prepared. The suggested chemical structures of the prepared iron (II) polymers complexes are confirmed by using: elemental analysis, infrared spectroscopic analysis and thermogravimetric analysis fIGA). All the iron (II) complexes are thermally stable as shown from the TGA pattern. The order of the thermal stability of the investigated Fe (II) complexes is as follows: PPCIBMN-Fe (II) complex > PPMeBMN-Fe (II) complex > PMeOBMN-Fe (II) complex > PBMN-Fe (II) complex. from the X-ray diffraction analysis, it is clear that all the prepared nonomers are crystalline, but all the prepared homopolymers or the ^spared iron (II) complexes of the polypara-benzylidene malononitrile Jmvatives are amorphous. Part IV: In this part, molecular orbital calculations, for the investigated onomers, dimers and also the proposed mechanism of the polymerization Eeaetion is confirmed. By drawing the density maps HOMO and LUMO for She dimers by different interaction possibilities (head - head, head - tail and tail - tail), and also by the total energy calculations, one can conclude fax the most stable structure is formed by (head - tail) interaction. The (Mai energy (ET), heat of formation (AHr), dipole moment (fj,, D), ionization potential (IP) for the investigated monomers, dimers, pipi-monomers and one unite of iron (II) complexes of para-substituted benzylidene Edononitrile are calculated. from the obtained data of the A.Os, percentage p different moieties of HOMO and LUMO for monomers, pipi- monomers »d pipi- dimers, il is clear Uml the charge density is concentrated on Bp=C) of the second monomeric moiety indicating the formation of newHive «nter of the polymerization reaction. This behavior confirms the SBEgested mechanism of the anionic polymerization reaction. ¡1 Also, the combination between the theoretical dipole moment data and the experimental Rf- values or a.c conductivity are given.