Ring-Opening Polymerization by Takeo Saegusa and Eric Goethals (Eds.)

By Takeo Saegusa and Eric Goethals (Eds.)

content material: Cationic polymerization of cyclic amines / E.J. Goethals, E.H. Schacht, P. Bruggeman, and P. Bossaer --
New facets of the chemistry of dwelling tetrahydrofuran polymers initiated by way of trifluoromethane sulfonic anhydride / Samuel Smith, William J. Schultz, and Richard A. Newmark --
New advancements in graft copolymerization by way of oxonium ion mechanism / K.I. Lee and P. Dreyfuss --
Ring-opening polymerization with enlargement in quantity / William J. Bailey, Robert L. sunlight, Hirokazu Katsuki, Takeshi Endo, Hideaki Iwama, Rikio Tsushima, Kazuhide Saigou, and Michel M. Bitritto --
development in polymerization of cyclic acetals / Stanisław Penczek and Przemysław Kubisa --
Ring-opening polymerization of macrocyclic acetals / Rolf C. Schulz, ok. Albrecht, C. Rentsch, and Q.V. Tran Thi --
Macrocyclic formals / Yuya Yamashita and Yuhsuke Kawakami --
Stereoregularity as a functionality of facet chain measurement in perhaloacetaldehyde polymerization / D.W. Lipp and O. Vogl --
Mechanism of the cationic polymerization of lactams / M. Rothe and G. Bertalan --
Ring-opening copolymerization of a few cyclic compounds containing oxygen and nitrogen atoms / H.L. Hsieh --
Ring-opening polymerizations : mechanism of polymerization of [epsilon]-caprolactone / R.H. younger, M. Matzner, and L.A. Pilato --
New clients in homogeneous ring-opening polymerization of heterocyclic monomers / Ph. Teyssié, J.P. Bioul, A. Hamitou, J. Heuschen, L. Hocks, R. Jérôme, and T. Ouhadi --
Optically lively poly[oxy(1-alkyl)ethylene] / Teiji Tsuruta --
Stereoselective and stereoelective polymerization of oxiranes and thiiranes / Nicolas Spassky --
expense and stereochemistry of the anionic polymerization of [alpha], [alpha]-disubstituted-[beta]-propiolactones / Robert W. Lenz, Cristian G. D'Hondt, and Ebrahim Bigdeli --
particular interactions of lithium chloride within the anionic polymerization of lactams / Giorgio Bontá, Alberto Ciferri, and Saverio Russo --
Isomerization polymerization of lactams / H.K. Reimschuessel --
Copolymerization of [epsilon]-caprolactam with [beta]-(3,4-diaminophenyl) propionic acid / S.W. Shalaby and E.A. Turi --
Anionic polymerization of fluorocarbon epoxides / James T. Hill and John P. Erdman --
Ring-opening polymerization through C-C bond beginning / H.K. corridor, Jr., H. Tsuchiya, P. Ykman, J. Otton, S.C. Snider, and A. Deutschman, Jr. --
New polymers by way of ring-opening polymerization of norbornene derivatives with polar substituents / S. Matsumoto, ok. Komatsu, and okay. Igarashi --
Polymerization of aryl cyclic sulfonium zwitterions / D.L. Schmidt --
Spontaneous alternating copolymerization of cyclic phosphorus compounds through phosphonium zwitterion intermediates / Takeo Saegusa, Shiro Kobayashi, Yoshiharu Kimura, and Tsunenori Yokoyama.

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Example text

G r a f t copolymers have been p r e p a r e d from seve backbones poly(vinyl chloride) polychloroprene, chlorinate b r o m o b u t y l r u b b e r , c h l o r i n a t e d p o l y ( b u t a d i e n e ) , and c h l o r i n a t e d b u t a d i e n e - s t y r e n e copolymer. I n t h e most t h o r o u g h l y examined c a s e s w i t h p o l y t e t r a h y d r o f u r a n as t h e g r a f t e d copolymer and s i l v e r t r i f l a t e as t h e i n o r g a n i c s a l t , c u r r e n t d a t a i n d i c a t e t h a t no u n r e a c t e d backbone remains and no homopolymer forms.

E v i d e n c e t h a t t h e y do o c c u r was o b t a i n e d from uv s p e c t r o s c o p y . Figure 5 shows the uv s p e c t r a f o r t r e a t e d and u n t r e a t e d c h l o r o ­ b u t y l r u b b e r s . A s h o u l d e r from 220 t o 240 πιμ appears i n the polymer i s o l a t e d a f t e r the g r a f t i n g r e a c t i o n . This shoulder i s c o n s i s t e n t w i t h but not proof t h a t d i e n e s a r e b e i n g formed. Because the b r o m o b u t y l r u b ­ b e r uv spectrum a l r e a d y c o n t a i n e d a s i m i l a r a b s o r p t i o n b e f o r e the a t t e m p t e d g r a f t i n g , i t was d i f f i c u l t t o ob­ t a i n c o n v i n c i n g e v i d e n c e f o r an i n c r e a s e d d i e n e c o n ­ tent a f t e r grafting T h i s was e s p e c i a l l y d i f f i c u l t s i n c e a f t e r the g r a f t i n m a r k e d l y i n c r e a s e d t e n d e n c y t o g e l and samples r e p r e s e n t a t i v e o f the whole were n o t p o s s i b l e t o o b t a i n .

As i n d i c a t e d i n F i g u r e 2 the volume change t h a t occurred d u r i n g homop o l y m e r i z a t i o n was q u i t pansion i n volume occurred 70°, a 7% expansion i n volume occurred; a t 85 a 2% expansion took p l a c e and the expansion decreased u n t i l a t 115° no change i n volume took p l a c e d u r i n g p o l y m e r i z a t i o n ; above 115° a s l i g h t shrinkage occurred. I t i s obvious from these data t h a t the l a r g e expansion i n volume t h a t occurs below the m e l t i n g p o i n t i n v o l v e s not o n l y the i n c r e a s e i n volume due t o the double ring-opening, but a l s o a change i n volume o f 3-6% due t o the process o f going from a c r y s ­ t a l l i n e monomer t o a l i q u i d monomer.

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