{"Affiliation":[{"label":"Affiliation","value":"Science, Faculty of","attrs":{"lang":"en","ns":"http:\/\/vivoweb.org\/ontology\/core#departmentOrSchool","classmap":"vivo:EducationalProcess","property":"vivo:departmentOrSchool"},"iri":"http:\/\/vivoweb.org\/ontology\/core#departmentOrSchool","explain":"VIVO-ISF Ontology V1.6 Property; The department or school name within institution; Not intended to be an institution name."},{"label":"Affiliation","value":"Chemistry, Department of","attrs":{"lang":"en","ns":"http:\/\/vivoweb.org\/ontology\/core#departmentOrSchool","classmap":"vivo:EducationalProcess","property":"vivo:departmentOrSchool"},"iri":"http:\/\/vivoweb.org\/ontology\/core#departmentOrSchool","explain":"VIVO-ISF Ontology V1.6 Property; The department or school name within institution; Not intended to be an institution name."}],"AggregatedSourceRepository":[{"label":"AggregatedSourceRepository","value":"DSpace","attrs":{"lang":"en","ns":"http:\/\/www.europeana.eu\/schemas\/edm\/dataProvider","classmap":"ore:Aggregation","property":"edm:dataProvider"},"iri":"http:\/\/www.europeana.eu\/schemas\/edm\/dataProvider","explain":"A Europeana Data Model Property; The name or identifier of the organization who contributes data indirectly to an aggregation service (e.g. Europeana)"}],"Campus":[{"label":"Campus","value":"UBCV","attrs":{"lang":"en","ns":"https:\/\/open.library.ubc.ca\/terms#degreeCampus","classmap":"oc:ThesisDescription","property":"oc:degreeCampus"},"iri":"https:\/\/open.library.ubc.ca\/terms#degreeCampus","explain":"UBC Open Collections Metadata Components; Local Field; Identifies the name of the campus from which the graduate completed their degree."}],"Creator":[{"label":"Creator","value":"Johnson, Arthur Lee","attrs":{"lang":"en","ns":"http:\/\/purl.org\/dc\/terms\/creator","classmap":"dpla:SourceResource","property":"dcterms:creator"},"iri":"http:\/\/purl.org\/dc\/terms\/creator","explain":"A Dublin Core Terms Property; An entity primarily responsible for making the resource.; Examples of a Contributor include a person, an organization, or a service."}],"DateAvailable":[{"label":"DateAvailable","value":"2012-03-15T19:57:55Z","attrs":{"lang":"en","ns":"http:\/\/purl.org\/dc\/terms\/issued","classmap":"edm:WebResource","property":"dcterms:issued"},"iri":"http:\/\/purl.org\/dc\/terms\/issued","explain":"A Dublin Core Terms Property; Date of formal issuance (e.g., publication) of the resource."}],"DateIssued":[{"label":"DateIssued","value":"1950","attrs":{"lang":"en","ns":"http:\/\/purl.org\/dc\/terms\/issued","classmap":"oc:SourceResource","property":"dcterms:issued"},"iri":"http:\/\/purl.org\/dc\/terms\/issued","explain":"A Dublin Core Terms Property; Date of formal issuance (e.g., publication) of the resource."}],"Degree":[{"label":"Degree","value":"Master of Arts - MA","attrs":{"lang":"en","ns":"http:\/\/vivoweb.org\/ontology\/core#relatedDegree","classmap":"vivo:ThesisDegree","property":"vivo:relatedDegree"},"iri":"http:\/\/vivoweb.org\/ontology\/core#relatedDegree","explain":"VIVO-ISF Ontology V1.6 Property; The thesis degree; Extended Property specified by UBC, as per https:\/\/wiki.duraspace.org\/display\/VIVO\/Ontology+Editor%27s+Guide"}],"DegreeGrantor":[{"label":"DegreeGrantor","value":"University of British Columbia","attrs":{"lang":"en","ns":"https:\/\/open.library.ubc.ca\/terms#degreeGrantor","classmap":"oc:ThesisDescription","property":"oc:degreeGrantor"},"iri":"https:\/\/open.library.ubc.ca\/terms#degreeGrantor","explain":"UBC Open Collections Metadata Components; Local Field; Indicates the institution where thesis was granted."}],"Description":[{"label":"Description","value":"The emulsion polymerization of isoprene has been produced by using as initiating agents various compounds which are known to dissociate to a certain extent in solution into free radicals.\r\nThe rate of thermal decomposition of some of the diazothio ethers employed as initiating agents have been measured by observing the rate of evolution of nitrogen from a solution of the compounds in butylphthalate.","attrs":{"lang":"en","ns":"http:\/\/purl.org\/dc\/terms\/description","classmap":"dpla:SourceResource","property":"dcterms:description"},"iri":"http:\/\/purl.org\/dc\/terms\/description","explain":"A Dublin Core Terms Property; An account of the resource.; Description may include but is not limited to: an abstract, a table of contents, a graphical representation, or a free-text account of the resource."}],"DigitalResourceOriginalRecord":[{"label":"DigitalResourceOriginalRecord","value":"https:\/\/circle.library.ubc.ca\/rest\/handle\/2429\/41433?expand=metadata","attrs":{"lang":"en","ns":"http:\/\/www.europeana.eu\/schemas\/edm\/aggregatedCHO","classmap":"ore:Aggregation","property":"edm:aggregatedCHO"},"iri":"http:\/\/www.europeana.eu\/schemas\/edm\/aggregatedCHO","explain":"A Europeana Data Model Property; The identifier of the source object, e.g. the Mona Lisa itself. This could be a full linked open date URI or an internal identifier"}],"FullText":[{"label":"FullText","value":"EMULSION POLYMERIZATION OF ISOPRENE BY A r t h u r Lee Johnson, Be\/A. A T h e s i s submitted In P a r t i a l F u l f i l m e n t o f The Requirements f o r the Degree of MASTER OF ARTS i n the Department of CHEMISTRY The U n i v e r s i t y of B r i t i s h Columbia A p r i l I9$0 ABSTRACT The e m u l s i o n p o l y m e r i z a t i o n o f i s o p r e n e h a s b e e n p r o d u c e d b y u s i n g a s i n i t i a t i n g a g e n t s v a r i o u s compounds w h i c h a r e known t o d i s s o c i a t e t o a c e r t a i n e x t e n t i n s o l u -t i o n i n t o f r e e r a d i c a l s . The r a t e o f t h e r m a l d e c o m p o s i t i o n o f some o f t h e d i a z o t h i o e t h e r s e m p l o y e d a s i n i t i a t i n g a g e n t s h a v e b e e n m e a s u r e d b y o b s e r v i n g t h e r a t e o f e v o l u t i o n o f n i t r o g e n f r o m a s o l u t i o n o f t h e compounds i n b u t y l p h t h a l a t e . ACKNOWLEDGEMENT I wish t o acknowledge the guidanoe and I n t e r e s t o f Dr.. R.H. C l a r k , who has su p e r v i s e d the work done on the p o l y m e r i z a t i o n of isoprene a t t h i s u n i v e r s i t y . Acknowledgement i s a l s o made of the h e l p of Dr.. J.8. Tapp, A s s i s t a n t D i r e o t o r of Research, Poylmer C o r p o r a t i o n of Canada, and the f i n a n c i a l support o f the Polymer C o r p o r a t i o n through g r a n t s from the N a t i o n a l Research C o u n c i l which made p o s s i b l e the c o n t i n u a t i o n o f t h i s work d u r i n g the summers of 1948 and 1949, Art h u r Lee Johnson TABLE QF CONTENTS HISTORY 1 THEORY ; . . . , 4 EXFERBffiNTAL PART I (aj p r e p a r a t i o n o f Mono and D i s u l p h i d e s 9 (b) R e s u l t s 12 PART I I (a) p r e p a r a t i o n s 14 (b) Decomposition of Diazo T h i o E t h e r s 17 (c) Graphs 21 (4) R e s u l t s o f p o l y m e r i z a t i o n 24 TECHNIQUES (a) Y i e l d s 25 (b) P r e p a r a t i o n of A n t i - o x i d a n t 25 (c) P r e c i p i t a t i o n o f Latex , 25 (d) Determination of G e l Co$$ent 26 CONCLUSIONS 28 EMULSION POLYMERIZATION OF ISOPRENE HISTORY . As e a r l y as 1835 attempts were made t o deduce the s t r u o t u r e of n a t u r a l rubber by p y r o g e n e t i c decomposition. H o w e v e r , i t was not u n t i l 1862,:that G r e y i l l e W i l l i a m s i s o l a t e d a hydrocarbon having.a b o i l i n g p o i n t o f 27-38\u00b0 C from the low b o i l i n g , f r a c t i o n o f the d i s t i l l a t e o f n a t u r a l rubber. T h i s hydrocarbon he named i s o p r e n e , ? but i t was twenty y e a r s l a t e r b efore T l l d e n proposed the present s t r u c t u r a l formula f o r Isoprene. W a l l a c h showed t h a t the h i g h e r b o i l i n g f r a c t i o n s of the d i s t i l l a t e from n a t u r a l rubber were e i t h e r dimers, t r i m e r s , o r o t h e r r e l a t e d homo-logues o f Isoprene, I t was a l s o soon observed t h a t i s o p r e n e on prolonged s t a n d i n g a g a i n formed r u b b e r l i k e p r o d u c t s . . I t appeared, t h e r e f o r e , t h a t i s o p r e n e and rubber were g e n e t i c a l l y , r e l a t e d . , I t was, o f course,, a l o n g step from the f i r s t o b s e r v a t i o n s t o the a c t u a l p r e p a r a t i o n o f syn-t h e t i c rubber from isoprene., From 1885 on r e s e a r c h i n the f i e l d of rubber I n c r e a s e d , and i n 1906, H a r r i e s , as a r e s u l t of e x t e n s i v e r e s e a r o h g r e a t l y extended the knowledge of the chemistry of rubber by means of ozone d e g r a d a t i o n o f n a t u r a l rubber. He found t h a t decomposition o f the ozonides w i t h hot water gave an almost q u a n t i t a t i v e y i e l d o f d e r i v a t i v e s o f t h e u n i t group GijHg, a . t h a t i s , l e v u l i n i o aldehyde, l e v u l i n i o a c i d , \u2022 and \"aevuiiini-d: \u2022 aldehyde p e r o x i d e i The presence of these compounds Oh d e g r a d a t i o n show t h a t the rubber molecule c o n t a i n s a r e c u r r i n g double bond a f t e r each f o u r t h carbon and c o u l d be r e p r e s e n t e d by the f o l l o w i n g s t r u c t u r e Along w i t h the study of the s t r u c t u r e of the rubber m o l e c u l e j and the d e t e r m i n a t i o n o f i s o p r e h e as t h e b u i l d i n g u n i t * were many attempts t o s y n t h e s i z e a r t i f i c i a l rubber from i s o p r e n e i Although a g r e a t many attempts were'made, i t cannot be s a i d t h a t any of these, attempts were v e r y s u o o e s s f u l y and In 19io due to the h i g h p r i c e o f n a t u r a l r u b b e r i r e s e a r c h was s t a r t e d t o i n v e s t i g a t e t h e p o s s i b i l i t y -of p o l y m e r i z i n g butadiene;. T h i s work r e s u l t e d i n the p r o d u c t i o n of the Buna rubbers, whioh had p r o p e r t i e s t h a t made them a f a i r l y s u i t a b l e s u b s t i t u t e f o r n a t u r a l rubber. D u r i n g World War I , German chemists had l i t t l e success w i t h t h e i r s y n t h e t i c r u b b e r s . D u r i n g World War I I , s u p p l i e s o f n a t u r a l rubber were almost completely l o s t t o the A l l i e d rubber i n d u s t r i e s , and I t was imperative t o develop immed-i a t e l y a s u i t a b l e s y n t h e t i c rubber. Most of the r e s e a r c h was d i r e c t e d towards the g o a l of p e r f e c t i n g and p u t t i n g i n t o l a r g e s c a l e p r o d u c t i o n , GR-S (emulsion polymerized buta-diene-styrene) w i t h the r e s u l t t h a t a s a t i s f a c t o r y s u b s t i t u t e 3. f o r n a t u r a l rubber f o r most purposes was o b t a i n e d . The work on isoprene d u r i n g t h i s time was n e g l i g i b l e . 4. THEORY \u20223 I t was shown i n 1932 by FIsoher & H a r k i n s t h a t the absorbed f i l m between a hydrocarbon o i l and a sodium o l e a t e s o l u t i o n a t o . l M c o n c e n t r a t i o n i s monomolecular, w i t h the p o l a r groups o r i e n t e d toward the water, and the hydrocarbon group toward the o i l . T h i s o r i e n t a t i o n i s accompanied by a decrease i n f r e e energy and t h e r e f o r e i s the more s t a b l e \" c o n d i t i o n . However, i t was found t h a t a t room temperature potassium l a u r a t e g i v e s a c l e a r s o l u t i o n i n water up t o 33% and potassium i a y r i s t a t e up t o 26%, These h i g h v a l u e s might be taken t o i n d i c a t e t h a t s o l i d soap may reduce I t s f r e e energy by going i n t o s o l u t i o n i n some other form than t h a t of s i n g l e molecules. In g e n e r a l , i t has been found t h a t most o f t h e soap d i s s o l v e d I s pre s e n t as aggregates, each o f which o o n t a l n a l a r g e number o f molecules. These aggregates are d e s i g n a t e d as soap inmtioelles. The g e n e r a l s t r u c t u r e of \/these soap m i c e l l e s c o n s i s t s of three double l a y e r s o f soap \u2022r molecules w i t h the p o l a r groups toward the water, and the o i l groups towards each o t h e r , w i t h a l a y e r of water between eaoh double l a y e r o f soap molecules . T h i s water l a y e r i s an I n t e g r a l p a r t o f the soap m i c e l l e r a t h e r than a s o l v e n t , and i s u s u a l l y r e f e r r e d t o as \"bound water\", i n c o n t r a s t t o the term f r e e water (water as a s o l v e n t ) . B e s i d e s b e i n g an e m u l s i f i e r , soap i s a l s o a s o l u b i l i z e r . i t has been f a i r l y c o n c l u s i v e l y shown t h a t when monomer i s added t o soap s o l u t i o n , t h a t i t i s s o l u b i l i z e d b e t w e e n t h e h y d r o c a r b o n e n d s o f t h e o r i e n t e d s o a p m o l e c u l e s . The soap m i c e l l e i s t h e p r o m i n e n t i n i t i a l l o c u s f o r p o l y -m e r i z a t i o n . H o w e v e r , i t i s n o t a l o c u s t h r o u g h o u t t h e p o l y m e r i z a t i o n s i n c e t h e p o l y m e r p a r t i c l e f o r m e d a d s o r b s a m o n o l a y e r o f s o a p m o l e c u l e s . T h i s c a u s e s a r a p i d d i s a p p e a r -a n c e o f t h e s o a p f r o m t h e m i c e l l e s , a n d h e n c e t h e m i c e l l e s t h e m s e l v e s seem t o c o m p l e t e l y d i s a p p e a r f r o m a f i v e p e r c e n t , s o l u t i o n a t a c o n v e r s i o n o f a b o u t t w e l v e p e r c e n t . A t l o w y i e l d s t h e p o l y m e r h a s b e e n shown t o c o n t a i n more monomer t h a n p o l y m e r a n d t h u s a f t e r t w e l v e p e r c e n t , y i e l d t h e m a i n l o c u s o f r e a c t i o n i s t h e polymer-monomer p a r t i c l e . The monomer d r o p l e t s w h i c h p e r s i s t a f t e r t h e soap m i c e l l e s h a v e d i s a p p e a r e d a r e n o t t h o u g h t t o a c t p r i m a r i l y a s l o c i o f r e a c t i o n , b u t r a t h e r a s r e s e r v o i r s o f monomer f r o m w h i c h monomer m o l e c u l e s d i f f u s e i n t o a l l o f t h e o t h e r l o c i . I n a f r e e r a d i c a l t y p e o f r e a c t i o n t h e m o l e c u l e s g r o w v e r y r a p i d l y \u2014 i n t h e o r d e r o f a f r a c t i o n o f a s e c o n d . I n o r d e r , t h e r e f o r e , t o e x e r t a n y c o n t r o l o v e r t h e s i z e o f t h e m o l e c u l e s i t m u s t be a p r o c e s s o f b a l a n c i n g c h a i n i n i t -i a t i o n s a n d c h a i n t e r m i n a t i o n . Many o f t h e m e r c a p t a n s w h i c h a r e e f f e c t i v e a s c h a i n i n i t i a t o r s a r e a l s o e f f e c t i v e i n c o n t r o l l i n g m o l e c u l a r w e i g h t t h r o u g h c h a i n t r a n s f e r , e . g . c h a i n i n i t i a t i o n R-5H + Ox-> R \u00a3 \u00b0 + HQ,0 R - S \u00b0 + C H A = p ^ C H = C H , - ^ R-S