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Low-Melting Organosilicon Monomers of High Molecular Weight David Harry Miles Iowa State College

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Low-Melting Organosilicon Monomers of High Molecular Weight David Harry Miles Iowa State College Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1957 Low-melting organosilicon monomers of high molecular weight David Harry Miles Iowa State College Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Miles, David Harry, "Low-melting organosilicon monomers of high molecular weight " (1957). Retrospective Theses and Dissertations. 1342. https://lib.dr.iastate.edu/rtd/1342 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. L0W-45ELTHQ ORGMOSILICQn MCMOMERS OF HIGH MOLECULAR "WEIGHT ^7 David Harry Miles A Dissertation. Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Major Subject: Organic Chemistry Approved: Signature was redacted for privacy. In Charge of Major Work Signature was redacted for privacy. Signature was redacted for privacy. Iowa. State College 1957 il TABLE OF CONTENTS Page INTRODUCTION 1 HISTORICAL k Qrganosilicon Compounds Prepared in This Laboratory 5 Division of the compounds into tables 6 Explanation of the columns in Tables 1-16 11 Compound 11 M.p. or b.p. 11 Thermal screening 12 Investigators 13 References lit Bibliography on Qrganosilicon Compounds Prepared in This Laboratory 100 References appearing in Tables 1-16 100 Alphabetical list of Ph.D. and M.S. Theses containing material on Qrganosilicon compounds which were pre­ pared in This Laboratory 10U Publications from. This Laboratory having material on Qrganosilicon compounds, but not cited in Tables 1-16 105 A Brief Review of the Recent Literature 106 Tetraorganosilanes containing long-chained n-alkyl groups 106 Tetraorganosilanes containing aralkyl groups 107 Tetraorganosilanes containing fluoro- or chloro- phenyl groups 109 Tetraorganosilanes containing ( oxydiphenylene ) or phenoxyphenyl groups 110 Tetraorganosilanes containing tolyl groups 111 Tetraorganosilanes containing biphenylene or biphenylyl groups 113 Steric hindrance in tetraorganosilanes containing cyclohexyl groups 115 EXPERIMENTAL 118 General Procedure 118 Reagents 118 iii TABT.Fi OF CONTENTS (continued) Page Solvents 118 Organic halides 118 Lithium. 218 Magnesium. 119 Chlorosilanes 119 Silan.es 119 Apparatus 119 Reaction set-ups 119 Distillation apparatus 120 Inert atmosphere 120 Isolation procedure 121 Physical property determination 121 Melting points and thermal screenings 121 Densities, indexes of refraction and molar refractions 121 Analyses 122 Organolithium and Organcmagnesium Compounds 122 Qrganosilicon Compounds 123 Tetraalkylsilanes 123 Tetra-n-dodecylsilane 123 Tetr a-n-tetrade cylsilane 125 TetrakLs(/3 -phecylethyl )- and tetrak±s(zf- phenylpropyl) silane 126 Qyclohexyltri-n-dodecylsilane (attempted) 126 n-Butyltri-n-hexadecylsilane 127 Benzyltri-n-o ctadecyl-, tribenzylçyclohexyl-, benzyltHT-n-dodecyl- and benzyltris( if- phenylpropyl) silane 127 Dibenzyldi-n-octadecjrlsilane 128 Di-n-octade cylbis( zf-phecylpropyl) silane 128 Trial fcylarylsilanes 129 (m-Br omophenyl )trimethylsilane 129 Tri-n-butylphenylsilane 129 2-Biphenylyltri-n-decylsilane. A. Ercm chlorotri- n-decylsilane ~ 130 B»~From. tri-n-decylsilane 130 iv TABLE OF CONTESTS (continued) Page 2-3iphenylyltri-n-butyl- and 2-biphenylyl- tri-n-hexadecylsilane (attempted) 131 2-Biphenylyltri-n-dodecylsilane (attempted) 131 2-Biphenylyltr i-n-hexade cylsilane 131 Tri-n-dodecylphenylsilane. A. From phenyllithium and chl or otri-n-dode cylsilane 132 B. From n-dodecylmagnesium brozd.de and tri- chlorophenylsilane 132 Tri-n-hexadecylphenylsilane. A. From tri-n- hexade cylsilane ~~ 133 B. From trichlorophenylsilane 133 £-Chlorophenyltri-n-hexadecylsilane 13k Tri-n-hexadecyl-g-phenoxyphenylsilane 13k U-Biphenylyltri-n-hexadecylsilane 135 T ribenzylphenyl-, tris(/S -phenylethyl )phenyl- and tris( îf"-phenylpropyl)phenylsilane 135 3-(3 r-Bromobiphenylyl )tri-n-butylsilane 135 3-(3'-Broniobiphenylyl)trimethyl- and 3-(3t- brcsaobiphenylyl )triphenylsilane 136 Dialkyldiarylsilanes* 137 Di-n-dodecylbis( oj-phenozyphenyl) silane 137 Bibenzyldiphenyl-, diphenylbis( jE> -phenylethyl )- and diphenylbis(d z-phenylpropyl)silane 11*2 Alkyltriaiylsilanes lii2 (Hethylsulf cnylmethyl )triphenylsilane 11*2 Qyclohexyltriphenylsilane. A. From trichloro- cyclohexylsilane and phenyl!i thium in ethyl ether 11*3 B. From trichlor ocyclohexylsilane and phenyl- lithium in t etrahydrofuran iWi C. From cycloheayl lithium and chlorotriphenyl- silane Uj5 D. From cyclohexene and triphenylsilane in the presence of benzoyl peroxide (attempted) 1U6 E. From cyclohexene and triphenylsilane in the presence of chloroplatinic acid (attempted) llt7 Other experiments on cyclohexyltriphenylsilane lli.8 n-Dodecyltri-m-tolylsilane 11*8 Tri.phenyl(^ -phenylethyl )- and triphenyl(5/ - phenylpr opyl )sllane H4.8 *See Tables 19 and 20 for other dxalkyldiarylsilanes. V TABLE OF CONTENTS (continued) Page Phenozasilin compounds ll*9 10,10-Dibenzylphenoxasilin ll# 10,10-Di-n-dodecylphenoxasilin 1)|? Other phenoxasilin compounds 150 Ccmpounds containing two or more silicon atoms bonded cxily to carbon 150 1,10-(Decapiethylene )bis[triphenylsilane] 150 TribenzylLm-( trimethylsilyl )phenyl] silane 151 Tri-n-hexade qylpp-(trimethylsilyl)phenyï] - silane 152 Di-n-dodecylbid~p-(tiimethyIsilyl)phenyi] - silane 152 Phenyltris[m-(trimethylsilyl )phenyl]silane 153 n-Dodecyltrrj~m--( trimethylsilyl )phenyl1 silane 153 3,3 T-Biphenylenebis Jiri-n-butylsilanel 151* U,U 1 -Biphenylenebi s [tri-n-hexade cylsilane] 15Ù 3,3'-Biphenylenebisjtribehzylsilanej 155 U,UT -Biphenylenebisftribenzylsilanêj 156 3,31-Biphenylenebi^3>ris( Zf-phenylpropyl )- silanej (attempted) 156 1*,1* 1 -BiphenylenebisCtri'ohenylsilanë] 156 ( Oxydi-o-phenylene )bis[trimethylsilanel 157 ( Oxydi-g-phenylene )bi W_trimethylsilanéj 157 ( Oxydi-g-phenylene )bi q^tribenzylsilanej 158 Silanes, chlorosilanes and a disilane 159 Tri-n-butylsilane 159 Tri-n-decylsilane 159 Tri-n-hexadecylsilane 160 Tri-n-butylchlorosilane 160 Cfclcarotri-n-de cylsilane 16L Chlorotri-n-hexadeeylsilane 162 A. From trichloro-n-hexadecylsilane 162 B. From tri-n-hexade cylsilane 163 1,1,l-Tri-n-hexadecyl-2 ,2, 2-triphenylsilane 163 Infrared spectra 165 DISCUSSION 166 Preparation of the Compounds 166 v± TABLE OF CONTENTS (continued) Page Intermediates 166 Organ(metallic compounds 167 Chlor osilanes 167 Silane s 169 Compounds for testing 170 2-Biphenylyl compounds 171 Cydohexyltriphenylsilane 172 Correlations Between Structure and the Target Physical Properties 17U Melting point relationships 175 Compounds containing long-chained n-alkyl groups 175 Compounds containing aralkyl groups 176 Confounds containing halophenyl groups 177 Compounds containing phenoxyphenyl groups 178 Compounds containing tolyl groups 178 Compounds containing biphenylyl groups 179 Compounds containing m-(trimethylsilyl)phenyl groups 179 Compounds containing Eiphenylene and ( oxydiphenylene) groups 180 Summary 183 Thermal screening relationships 183 Compounds containing long-chained n-alkyl groups 183 Compounds containing aralkyl groups 187 Compounds containing aryl groups 188 Summary 190 Suggestions for Further Research 190 SUMMARY 193 ACKNOiSLEDGMENT 195 1 INTRODUCTION The chemistry of organosilicon compounds has been studied for almost one hundred years-*-. Until the discovery of industrial applications for the polymeric silicones, most of the research efforts were directed toward the preparation of organosilicon monomers. When it was found that the silicones had high thermal stability, small change in viscosity -with change in temperature and other desirable properties, the volume of research increased (especially in industrial laboratories) and was directed mainly toward the preparation of polymeric materials or of monomers suitable for polymerization. Because of the poor lubricating properties of the silicones, and because of the need for high-temperature thermally-stable and radiation-resistant lubricants and hydraulic fluids, studies -were initiated in This Laboratory (under the auspices of the U.S. Air Force) on the preparation and properties of high-molecular -weight organosilicon monomers. It was felt that such materials might be superior in some respects to the silicones or to other compounds for the previously described applications. Some of the early -work on this project has shown that thermally-stable organosilicon monomers can be prepared. However, most of the compounds which have been synthesized have been found to be relatively high-melting solids and therefore unsuitable for use as lubricants or hydraulic fluids. The study presented in this dissertation "was undertaken in an effort ^For some of the earliest work on organosilicon compounds, see C. Friedel and J. M. Crafts, Ann., 127, 28 (1863) and A. Ladenburg, Ann., 162, 300 (1872). 2 to produce high-molecular weight organosilicon mraaomers with, low melting points which retained the thermal-stability of the previously synthezised compounds. Two similar approaches were made to the problem. A recent study^ has shown that organosilicon compounds which contain long-chained n-alkyl groups are quite thermally-stable and that such groups tend to lower the melting points of the organosilicon compounds
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