Yheiselsel seislslelstel Salsa! se lalelals lal sSai sala lle lalelslaistal sels lalelsleiselse CATALYTIC HYDROFORMYLATION OF ALKENES AND POLYALKENES: NOVEL APPROACHES TO CATALYST SYNTHESIS, CHARACTERIZATION AND RECYCLING s SEBHRDMeu : BY JIMOH TIJANI A Dissertation Presented to the DEANSHIP OF GRADUATE STUDIES | KING FAHD UNIVERSITY OF PETROLEUM & MINERALS DHAHRAN, SAUDI ARABIA In Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY In CHEMISTRY May 2006 ©) be, Xaannnnam SERS PEEa y UMI Number: 3242245 INFORMATION TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion.
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Box 1346 Ann Arbor, MI 48106-1346 KING FAHD UNIVERSITY OF PETROLEUM AND MINERALS DHAHRAN 31261, SAUDI ARABIA DEANSHIP OF GRADUATE STUDIES This dissertation, written by Mr. JIMOH TIJANI under the direction of his dissertation advisor and approved by his dissertation committee, has been presented to and accepted by the Dean of Graduate Studies, in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY IN CHEMISTRY. Dissertation Committee Lee Prof. Ali Member Dr.
Zaki Shaker Seddigi _<7 s__ Department Chairman T—— Dr. Mohammed Fettouhi € +) Member _€ = 22el Dr. Mohammad Abdulaziz Al-Ohali aS + Dean of Graduate Studies Dr. Abu-Sharkh | Member an 7 [.
Date: S10 200 é DEDICATED TO MY WIFE & CHILDREN ili ACKNOWLEDGMENT Praise be to Allah Almighty, The all Knowing. Blessing and peace be upon our leader Muhammad, his family, his companions, and those that follow his guidance until the last day. I wish to express my sincere appreciation to my thesis advisor Prof. Bassam El Ali.
The completion of this work is credited to his tireless support and priceless ideas. I wish to also thank my dissertation committee members, Dr. Al-Arfaj and Dr. Abu-Sharkh for their constructive contribution toward the success of the work and Dr.
El-Ghannam whom I’m indebted to for his sincere help and un-quantifiable support. Also, I would like to thank Dr. Sidiggi, and Dr. Al-Thukair present and previous chairmen of the department, for their moral support.
My special thanks also go to all faculty members, for their support in one way or another, especially Dr. Perzanowski for his valuable advice in NMR. I wish to acknowledge the technical support of all departmental staff members especially, M. Al-Gushairi, Saleem, Baig, Ismail, I.
My sincere appreciation to the following brothers for their kindness and encouragement in the course of the work Dr. Yunus, Bashir, Dr. Abdulkarim, Ali, Dr. Shazali, Ma’az, Sa’id, Abdulhamid, Jarudi, Dr.
Azhahrani, Rami, and Ya’u etc. I am grateful to my mum, wife, children, brothers, sisters and friends for their love and encouragement. Finally, my deep recognition to King Fahd University of Petroleum & Minerals, for providing the sponsorship and the material support for the project. iv TABLE OF CONTENTS Contents Page List of Figures xii List of Tables XVI Abstract (English) XIX Abstract (Arabic) XX CHAPTER 1 1.0 Introduction and literature overview 1.1 Introduction to Hydroformylation 1.
Background on hydroformylation 1.3 Overview of the existing recycling concepts 1.1 Water-soluble ligands 1.2 Thermoregualated phase transfer catalysis 1.4 Heterogenized homogeneous catalysis 22 1.4 Hydroformylation of polybutadiene 27 1.0 Soluble Rhodium Catalyzed Homogeneous Hydroformylation of Alkenes 2.2 General procedure for homogenous hydroformylation of alkenes 36 2.3 Results and discussion 36 2.1 Homogeneous Hydroformylation of Aryl Alkenes by rhodium Catalyst 36 2.2 Hydroformylation of Styrene Catalyzed by Rhe(CO)16/HPA-W}2 Effect of the type of and the amount of heteropolyacids 37 2.3 Hydroformylation of Styrene Catalyzed by Rhe(CO)16/HPA-W 12. Effect of Temperature and the type of solvent 39 2.4 Hydroformylation of Styrene Catalyzed by Rhạ¿(CO)¡/HPA-WI¿. Effect of the ratio of CO /H¿ and the reaction time 41 2.5 Hydroformylation of Styrene Catalyzed by Rhe(CO)t¢. Improvement of the reaction time and selectivity 43 2.6 Effect of amount of phosphite ligand on the selectivity and the reaction time 45 2.7 Effect of the Temperature and ligands on the activity and selectivity 47 2.8 Hydroformylation of various Aryl alkenes by Rhạ(CO)¡z/ HPA-W)}2 [or P(OPh)3/CO/H2/THF] 49 2.9 Hydroformylation of various terminal Alkyl alkenes 51 2.10 Hydroformylation of 1-Octene Catalyzed by Rh(CO);(acac)- bulky phosphite (XXII): Effect of Temperature and the type of solvent 53 2.11 Hydroformylation of 1-Octene Catalyzed by Rh(CO)2(acac)- vi XXII: Effect of CO / Hz and the reaction time 56 2.12 Hydroformylation of 1-Octene Catalyzed by Rh(CO)2(acac)- XXII: Effect of amount of Ligand 59 2.13 Hydroformylation of 1-octene: Effect of type of Rhodium and other Ligands 61 2.14 Hydroformylation of 1-Octene Catalyzed by Rh(CO);(acac)- XXII: Effect of different substrates 63 2.0 Soluble Rhodium Catalyzed Biphasic Hydroformylation of Alkenes 72 3.1 Thermomorphic biphasic hydroformylation 73 3.2 Thermoregulated Phase transfer biphasic hydroformylation 74 3.2 General procedure for Thermomorphic biphasic Hydroformylation of Alkenes 76 3.
General procedure for Thermoregualated Phase Transfer Biphasic Hydroformylation of Alkenes 77 3.4 Preparation of N,N-dipolyethylene-substituted- 2-(diphenylphosphino) phenylamine (DPPPA-PEO 77 vii 3.6 Preparation of binaphtyl phosphite polyethylene oxide 79 3.3 Results and discussion 80 3.1 Thermomorphic Biphasic Hydroformylation : Effect of the type of polar solvents 80 3.2 Thermomorphic Biphasic Hydroformylation : Effect of the Rhodium complexes and ligands 83 3.3 Thermomorphic Biphasic Hydroformylation : Effect of the temperature 85 3.4 Thermomorphic Biphasic Hydroformylation : Effect of total pressure (CO:H) = 1:1) 87 3.5 Thermomorphic Biphasic Hydroformylation : Effect of partial pressures CO:H2 89 3.6 Thermomorphic Biphasic, Hydroformylation : Effect of ligand to catalyst ratio 91 3.7 Thermomorphic Biphasic Hydroformylation : Effect of different alkenes 91 3.8 Thermomorphic Biphasic Hydroformylation : Effect of the chain length of alkyl alkenes 95 3.9 Thermomorphic Biphasic Hydroformylation : Recycling of the catalyst 97 3.4 Results and discussion 101 3.1 Thermoregulated phase transfer hydroformylation 101 Vili 3.2 Thermoregulated phase transfer hydroformylation: Catalyst recycling 103 3.3 Thermoregulated phase-separable hydroformylation: Catalyst recycling.0 Supported Rhodium Catalyzed Hydroformylation of Aryl Alkenes 112 4.2 Preparation of MCM-41 114 4.3 Preparation and Characterization of Rhodium (ID) and Rhodium (III) Impregnated with and without heteropolyacids on MCM-41 114 4.4 Synthesis of 1-2% Rh() or Rh(HD/HPA/MCM-41 in methanol (M) or water (W) [Rh32WHPA10MCM-M (M) and [Rh12WHPA10MCM-W (W)] 115 4.5 Synthesis of 5 % Rh() or RhdID/HPA/MCM-41 in ethanol (E) [Rh32HPA10MCM-E] and [Rh15HPA10WMCM-E] 115 4.6 Impregnation of rhodium (I) or rhodium (IIT) with and without heteropolyacid on MCM-41 116 4.7 Characterization of supported catalyst 118 ix 4.3 *'P CP-MAS NMR 120 4.5 Nitrogen adsorption-desorption isotherms 121 4.8 Procedure for the heterogeneous hydroformylation of styrene 122 4.3 Results and discussion 123 4.1 Rhodium (III) supported catalyst in the heterogeneous hydroformylation of styrene 123 4.2 Rhodium (I) supported catalysts in the heterogeneous hydroformylation of styrene 126 4.3 Hydroformylation of styrene: Effect of amount of water on Rh(III) based catalyst 130 4.4 Hydroformylation of styrene: Effect of temperature with Rh(II) based catalyst 134 4.5 Hydroformylation of styrene: Effect of the type of solvent 134 4.6 Hydroformylation of styrene derivatives by the supported Rh(D) or Rh(HI) catalyst 136 4.7 Effect of the rhodium leaching on the hydroformylation of styrene 139 4.8 Recycling of the supported catalyst in the hydroformylation of styrene 145 4.0 Supported Rhodium Catalyzed Hydroformylation of Aryl Alkenes 154 5.2 General procedure for the heterogeneous hydroformylation 156 5.3 Results and discussion 157 5.1 Hydroformylation of 1-octene catalyzed by Rh-HPW¡¿- MCM-41. Effect of the type of the supported catalyst 157 5.2 Hydroformylation of 1-octene catalyzed by Rh-HPW)2- MCM. Effect of temperature 160 5. Hydroformylation of 1-octene by the supported catalyst.
Effect of the reaction time and temperature 164 5.4 Hydroformylation of 1-octene by supported catalyst. Effect of the type of solvent 167 5.5 Hydroformylation of various terminal alkyl alkenes by Rh®12W10MCM-E 170 5.6 Study of the catalyst recycling 172 5.7 Proposed reaction mechanism 177 5.0 Soluble Rhodium Catalyzed Homogeneous Hydroformylation of polyalkenes 180 6.2 General procedure for homogenous hydroformylation of polyalkenes 182 6.3 Results and discussion 183 6.1 NMR analysis of PBD 183 6.2 NMR analysis of PBD60%Ph hydroformylated products 185 6. NMR analysis of PBD86%1,2Pred hydroformylated products 188 6.4 NMR analysis of PBD72%1,2Pred hydroformylated products 190 6.5 NMR analysis of PBD99%Ph hydroformylated products 190 6.6 IR analysis of hydroformylated products 192 6.7 Effect of reaction parameters 192 6.8 Biphasic hydroformylation of PBD: recycling of the catalyst 197 6.0 Conclusion 200 References 204 Appendices 213 Abbreviations 230 Vita 232 xi List of Figures Figure page Figure 1.1 Recycling concepts Figure 1.2 Thermoregualated Phase Transfer Catalysis lãi Figure 1.3 Thermoregualated Phase-Separable Catalysis 14 Figure 1.4 Diagrammatic representation of Thermomorphic catalysis 17 Figure 2.1 Hydroformylation of styrene Catalyzed by Rh¿(CO)s: Effect of the amount of P(OPh)3 46 Figure 2.2 Hydroformylation of styrene Catalyzed by Rh (CO),(acac)-XXII: Effect of the amount of XXII 60 Figure 2.31 FTIR spectra of the reaction intermediates 68 Figure 2.311 FTIR Spectra of the reaction intermediates 68 Figure 3.1 Thermomorphic biphasic hydroformylation of 1-octene: Effect of temperature 86 Figure 3.2 Thermomorphic Biphasic Hydroformylation of 1-octene: Effect of CO / H2 Total Pressure 88 Figure 3.3 Thermomorphic biphasic hydroformylation of 1-octene: Effect of CO /Hạ Partial Pressure 90 Figure 3.4 Thermomorphic biphasic hydroformylation of 1-octene: Effect of Ligand to Catalyst Ratio 92 Figure 3.5 Thermomorphic biphasic hydroformylation of different Alkyl Alkenes 96 Figure 3.6 Thermomorphic biphasic hydroformylation: Recycling of the Catalyst 98 Xill Figure 3.7 Thermomorphic biphasic hydroformylation: Recycling of the Catalyst 99 Figure 3.8 Thermomorphic biphasic hydroformylation: Recycling of the Catalyst 100 Figure 3.9 FTIR spectra of the reaction intermediates 108 Figure 4.1 FTIR spectra of a) MCM-41 b) HPAW)2 c )HRhCO(PPha); d) MCM-41/HPW21 e) Rh®15W10MCM-E f) Recycled Rh®15W10MCM-E after 6 cycles 119 Figure 4.2 Hydroformylation of styrene: Effect of % loading of HPA-W}2 127 Figure 4.3 Hydroformylation of styrene: Effect of volume of water 133 Figure 4.4 Hydroformylation of styrene: Effect of the Temperature 135 Figure 4.5 Hydroformylation of styrene by Rh32W10MCM-M. Effect of type of Solvent 137 Figure 4.6 Hydroformylation of styrene by Rh“12W10MCM-M.
Effect of type of Solvent 138 Figure 4.7 Hydroformylation of styrene: The Recycling of the Catalyst Rh15Mo10MCM-E 147 Figure 4.8 Hydroformylation of styrene: The Recycling of the Catalyst Rh1S5MCM-E 148 Figure 4.9 Hydroformylation of styrene: The Recycling of the Catalyst Rh15W10MCM-E 149 Figure 4.10 Hydroformylation of styrene: The Recycling of the Catalyst Rh15SiW10MCM-E 150 Xiv Figure 4.11 Hydroformylation of styrene: The Recycling of the Catalyst Rh35W10MCM-E 151 Figure 5.1 Hydroformylation of 1-octene by Rh32W10MCM-M. Effect of temperature 161 Figure 5.2 Hydroformylation of 1-octene by Rh?12W10MCM-M. Effect of temperature 162 Figure 5.3 Hydroformylation of 1-octene by Rh?12W10MCM-M. Effect of temperature 163 Figure 5.4 Hydroformylation of 1-octene by Rh32W10MCM-M.
Effect of type of solvent 168 Figure 5.5 Hydroformylation of 1-octene by Rh?12W10MCM-M. Effect of type of solvent 169 Figure 5.6 X-ray diffraction patterns of recycled supported catalyst 176 Figure 6.1 A) 'NMR of PBD60%Ph B) 'NMR of PBD99%Ph 184 Figure 6.2 A) 'NMR of partially hydroformylated PBD60%Ph B) 'NMR of PBD60%Ph 187 Figure 6.3 A) 'NMR of partially hydroformylated PBD86%1,2-Pred B) 'NMR of PBD86%1,2-Pred 189 Figure 6.4 A) 'NMR of partially hydroformylated PBD72%1,4-Pred B) NMR of PBD72%1,4-Pred 191 Figure 6.5 A) IR spectrum of partially hydroformylated PBD72%1,4-Pred B) IR spectrum of PBD72%1,4-Pred 193 XV List of Tables Table page Table 2.1 Hydroformylation of styrene catalyzed by Rhe(CO)16/HPA-W) 2: Effect of amount and type of the heteropolyacids 38 Table 2.2 Hydroformylation of styrene catalyzed by Rhg(CO)16/HPA-W) 2: Effect of temperature and type of solvent 40 Table 2.3 Hydroformylation of styrene catalyzed by Rhg(CO)16/HPA-W 12: Effect of CO/Hp pressure and the reaction time 42 Table 2.4 Hydroformylation of styrene catalyzed by Rhg(CO)16/HPA-W 12: Effect of temperature 44 Table 2.5 Hydroformylation of styrene catalyzed by Rhg(CO)16/P(OPh)s3: Effect of temperature and type of ligand 48 Table 2.
