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University Microfilms, Inc., Ann Arbor, Michigan PART I: ORGANOSILICON COMPOUNDS PART I: ORGANOSILICON COMPOUNDS PART II: BLOCK POLYMERIZATIONS Item Type text; Dissertation-Reproduction (electronic) Authors Gollmar, Herbert George, 1938- Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 29/09/2021 02:40:10 Link to Item http://hdl.handle.net/10150/288205 This dissertation has been microfilmed exactly as received 70-1676 GOLLMAR, Herbert George, 1938- PART I: ORGA-NOSELICON COMPOUNDS. PART H: BLOCK POLYMERIZATIONS. University of Arizona, Ph.D., 1969 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan PART I: ORGANOSILICON COMPOUNDS PART II: BLOCK POLYMERIZATIONS by Herbert George Gollmar A Dissertation Submitted to the Faculty of the DEPARTMENT OF CHEMISTRY In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY In the Graduate College THE UNIVERSITY OF ARIZONA 19 6 9 THE UNIVERSITY OF ARIZONA GRADUATE COLLEGE I hereby recommend that this dissertation prepared under my direction by Herbert George Gollmar entitled . PART I; ORGANOSILICON COMPOUNDS PART II: BLOCK POLYMERIZATIONS be accepted as fulfilling the dissertation requirement of the degree of Doctor of Philosophy lb / % ^ Dissertation Director f D^e ' After inspection of the final copy of the dissertation, the folloi7ing members of the Final Examination Committee concur in its approval and recommend its acceptance:" ^Vv^VC,\W vQju—J-v. This approval and acceptance is contingent on the candidate's adequate performance and defense of this dissertation at the final oral examination. The inclusion of this sheet bound into the library copy of the dissertation is evidence of satisfactory performance at the final examination. STATEMENT BY AUTHOR This dissertation has been submitted in partial fulfillment of requirements for an advanced degree at The University of Arizona and is deposited in the University Library to be made available to bor­ rowers utider rules of the Library. Brief quotations from this dissertation are allowable without special permission, provided that accurate acknowledgment of source is made. Requests for permission for extended quotation from or re­ production of this manuscript in whole or in part may be granted by the head of the major department or the Dean of the Graduate College •when in his judgment the proposed use of the material is in the in­ terests of scholarship. In all other instances, however, permission must be obtained from the author. SIGNED: J2x$wt/fc' J/, To My Mother and Father ACKNOWLEDGMENT The author wishes to thank Dr. James E. Mulvaney for his guidance and help during the course of this research, and the U. S. Army Research Office - Durham for their financial support for Part I of this work. iv TABLE OF CONTENTS Page LIST OF TABLES vii ABSTRACT . viii PART I: ORGANOSILICON COMPOUNDS 1 INTRODUCTION 2 RESULTS AND DISCUSSION 14 EXPERIMENTAL 25 General ......... ..... 25 Materials 25 Polymerization Procedure 27 Diethoxymethyl-o(-styrylsilane (28) 28 Copolymerization of Diethoxymethyl-rt-styrylsilane and Maleic Anhydride 29 Preparation of Cycli" Trimers and Tetramers (3^) of Diethoxymethyl-c<-styrylsilane (28) 29 Rate of Equilibration of Cyclic Trimers and Tetramers (33) of Diethoxymethyl-tf-styrylsilane .... 30 Equilibration of Cyclic Trimers and Tetramers (3J) of Diethoxymethyl-«-styrylsilane .... 30 Heptamethyl-c<-styrylcyclotetrasiloxane (£4) ....... 31 Attempted Equilibration of Heptamethyl-rf-styryl- cyclotetrasiloxane ....... 31 Ethoxydimethyl-«-styrylsilane (3!j) 32 Bis(dime thyl-<*~styryl)disiloxane (36) •••••••••• 32 l,3-Diacetoxy-2-phenylpropane 33 3-Acetoxy-2-phenylpropene (39) (Pyrolysis Method) .... 33 5-Phenallyl Bromide (37) 33 Diethoxymethyl-5-phenallylsilane (3§) . 34 Reaction of 0-Phenallyl Bromide V7ith Ammonia 35 Reaction of 3-Hydroxy-2-phenylpropene with Bromo- tripheny.lphosphonium Bromide (Wiley Reaction) 36 Attempted Polymerizations of Diethoxymethyl- <*-styrylsilane, Ethoxydimethyl-c<-styrylsilane, Bis-d ime thy 1- of- s tyry Id isi 1 oxane, and Diethoxymethyl-g-phenallylsilane ...... 36 v vi TABLE OF CONTENTS--Continued Page PART II: BLOCK POLYMERIZATIONS 39 INTRODUCTION 40 RESULTS AND DISCUSSION 49 EXPERIMENTAL 57 Materials ........... 57 Infrared Spectra 57 Elemental Analyses 58 Poly(styrene-co-vinylene Carbonate) (l^A) 58 Poly(styrene-co-vinylene Carbonate) (l^B.) 59 Poly(styrene-co-vinylene Carbonate) (l^jC) 59 Poly(styrene-co-vinylene Glycol) (lJ^A) 60 Poly(styrene-co-vinylene Glycol) (iJ^Ba) ........ 60 Poly(styrene-co-vinylene Glycol) (IJ-^Jj) •••••••• 60 Poly(styrene-co-vinylene Glycol) • • 61 Preparation of Aldehyde-terminated Polystyrene (l^A) • • 61 Preparation of Aldehyde-terminated Polystyrene (18^Bj.) • 61 Preparation of Aldehyde-terminated Polystyrene (l^BJ?) . 62 Preparation of Aldehyde-terminated Polystyrene (jj^ji) . 62 Preparation of Carboxyl-terminated Polystyrene(. 62 Preparation of Poly(N-vinylpyrrolidone-co-vinylene Carbonate) (20) 63 Preparation of Poly(N-vinylpyrrolidone-co-vinylene Glycol) (21) 63 Preparation of Aldehyde-terminated Poly(N-vinylpyrrolidone) (22) 64 Sulfuric Acid Catalyzed Coupling of Aldehyde-terminated Polystyrene (18^Ba) with Amine-terminated Polystyrene (23^A) . .......... 64 £-Toluenesulfonic Acid Catalyzed Coupling of Aldehyde-terminated Polystyrene (l|^J3tj) with Amine-terminated Polystyrene (23^IJ) .......... 64 Coupling of Aldehyde-terminated Polystyrene with £-Phenylenediamine . 65 Attempted Uncatalyzed Coupling of Aldehyde-terminated Polystyrene (18^^5) with Amine-terminated Polystyrene (23^A) 65 Attempted Coupling of Carboxyl-terminated . Polystyrene (19^) with Amine-terminated Polystyrene (23^A) Using Dicyclohexyl- carbodiimide 65 LIST OF REFERENCES 67 LIST OF TABLES Table Page 1.1 EQUILIBRATION OF CYCLIC TRIMERS AND TETRAMERS OF DIETHOXYMETHYL-C<-STYRYLSILANE WITH CESIUM HYDROXIDE-DIMETHYL SULFOXIDE AT 85° . 19 1.2 VINYL POLYMERIZATION CONDITIONS 37 11.1 VISCOSITIES OF A SERIES OF COPOLYMERS DERIVED FROM VINYLENE CARBONATE 51 11.2 MOL % VINYLENE CARBONATE IN STYRENE COPOLYMERS 52 vii ABSTRACT Part I: Organosilicon Compounds Diethoxymethy 1-tf-styrylsilane, bis(dimethy1 - ol- s ty r y 1)d is i 1oxane, ethoxymethyl-c*-styrylsilane, and ethoxydimethyl-5-phenallylsilane were synthesized in order to test their usage as monomers for "ladder" poly­ mer formation. Free radical, cationic, and anionic initiators were unsuccessful for vinyl homopolymerization attempts with these monomers. Cyclic trimers and tetramers of diethoxymethyl-fc-styrylsilane were synthesized and equilibrated with various basic catalysts. Low molecular weight polysiloxanes were formed. Part II: Block Polymerizations Copolymers of vinylene carbonate were prepared. These co­ polymers were hydrolyzed and then cleaved with periodic acid to form polymers with aldehyde endgroups. The feasibility of forming blocks from the aldehyde-terminated polymers was demonstrated by coupling them with £-phenylenedxamine and amine-terminated polystyrene. viii PART I: ORGANOSILICON COMPOUNDS 1 INTRODUCTION A great deal of attention has been given to preparing heat stable polymers of the so-called "ladder" type. "Ladder" polymers con­ sist of two chains which are regularly joined together in the same man­ ner as a ladder is joined by its rungs. The general structure for a "ladder" polymer is shown below, where A and B are monomer units and C is the joining "rung." In many cases C consists only of a chemical bond. /x^WA A A A A—v~v^ c c c c c — i — B ~~ B — Several.reviews on ladder polymers are available (De Winter 1967, Bailey 1968, Wright and Lee 1968). Ladder polymers are of special interest because two simultaneous breaks at strands bordered by the same two "rungs" are necessary to depolymerize these materials. This feature enables ladder polymers to retain properties, such as tensile strength and toughness, at elevated temperature which would degrade many single- strand polymers. Many examples of ladder polymers have been reported but few of these materials have complete ladder structures. Often the conditions employed during attempted ladder formation lead to precipitation of low molecular weight polymers. When reactions are forced to completion, cross linked products are often obtained. 2 3 Ladder polymers theoretically should be fusible and soluble in appropriate solvents. Often, however, the rigidity of the rings in ladder polymers leads to difficulty in dissolving these compounds. Re­ cently Bailey and Feinberg (1967) have reported, however, that large, flexible rings in ladder structures lead to readily soluble polymers. Probably the first polymer to be prepared which was later shown by Bircumshaw, Taylor, and Whiffen (1954) to possess a partial ladder structure was paracyanogen (1). Paracyanogen has been prepared by ,N V C I .c 'N n 1 /V heating oxalamide, mercury(ll) cyanide, or silver cyanide. Paracyano­ gen is soluble in conc. sulfuric acid and is stable to 450° in vacuum. However, 1^ is very brittle and its ladder structure is not perfect. Another polymer containing partial ladder sequences which has been known for some time is Orion Black (2) which has been prepared by both one- and two-step pyrolyses of polyacrylonitrile. The two-step procedure (Geiderikh e_t al. 1961) is shown below. NH, 2 rJ Orion Black has the advantage that
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