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CONTINUOUS PRODUCTION OFn -BU TYLACRYLATE FREE FROMDIBUTYLETIIERI n v e n t o r s : Heinz Erpenbach, S u r t h n e a rC o l o g n e ; K l a u s G e h r m a n n ,

E r f t s t a d t - L e c h e n i c h ; H e r b e r t J o e s t ,E r f t s t a d t - L i b l a r ; P ete r Zerres,E r f t s t a d t - F r i e s h e i m , a l l o f GermanyH o e c h s t A k t i e n g e s e l l s c h a f t ,F r a n k f u r t a m M a i n , Germany

F i l e d : O c t . 1 4 , 1 9 7 5A p p l . N o . : 6 2 2 , 2 6 3

F o r e i g n A p p l i c a t i o n P r i o r i t y D a t aOct. 19, 1974 Germany . . . . . . . . . . . . . . . . . . . . . . . . 2449811US. Cl. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260/486 RI n t . Cl.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C07C 69/54Field of S e a r c h . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260/486 R

R e f e r e n c e s C i t e dUNITED STATES PATENTS10/1966 Baker et a l . . . . . . . . . . . . . . . . . . . 260/486 R

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FOREIGN P ATENTS OR APPLICATIONS841,521 7/1960 United K ing do m . . . . . . . . . . . . . . 260/4861,003,007 9/1965 United Kingdom . . . . . . . . . . . . . . . 260/486

OTHER PUBLICATIONSL e v e s q u e , C . L . e t a 1 , I n d u s t r i a l a n d E n g i n e e r i n gChem., v o l . 4 0 , No. 1 , p p . 96-99, J a n . 1 9 4 8 .P r i m a r y E x a m i n e r - P a u l J . K i l l o sA t t o r n e y , A g e n t , o r F i r m - C o n n o l l y a n d H u t z[ 5 7 ] ABSTRACTn - B u t y l a c r y l a t e i s p r o d u c e d b y r e a c t i n g a c r y l i c a c i dw i t h n - b u t a n o l i n l i q u i d p h a s e i n c o n t a c t w i t h a n a c i dc a t i o n exchanger a s a c a t a l y s t .To h i s e n d , t h e a c r y l i c a c i d a n d b u t a n o l a r e r e a c t e d i na molar r a t i o from 1 : 1 t o 1 : 2 5 , a t 8 0 t o 1 3 0 C , undera p r e s s u r e f r o m 3 t o 1 5 atmospheres g a u g e , and f o r 20 90 m i n u t e s .

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( a c r y l i c a c i d n - b u t y l e s t e r ) , w h e r e i n a c r y l i c a c i d i s r ea c t e d w i t h n - b u t a no l i n l i q u i d p h a s e , a t e l e v a t e d temp e r a t u r e and i n t h e p r e s e n c e o f an a c i d c a t i o n e xc h a n g e r a s a c a t a l y s t have a l r e a d y been d e s c r i b e d i nt h e a r t , e . g . i n G e r m a n P a t e n t S p e c i ? c a t i o n O f f e nl e g u n g s s c h r i f t No. 2 226 8 2 9 . These p r o c e s s e s a r emore p a r t i c u l a r l y concerned w i t h e q u i l i b r i u m r e a ct i o n s , w h e r e i n t h e e q u i l i b r i u m c o n s t a n t i s t h e f a c t o rwhich c r i t i c a l l y d e t e r m i n e s t h e c o n v e r s i o n r a t e o f t h ea c i d or a l c o h o l t o t h e e s t e r . As a r e s u l t , i t i s n e c e s s a r yf o r u n r e a c t e d s t a r t i n g m a t e r i a l t o b e s e p a r a t e d f r o m t h ee s t e r produced and t o be r e c y c l e d t o t h e r e a c t i o n z o n e .T h i s i s a n o p e r a t i o n which e n t a i l s c o n s i d e r a b l e d i f ? c u lt i e s i n r e d u c i n g t h e p r o c e s s t o p r a c t i c e .To i n c r e a s e t h e a c r y l i c a c i d c o n v e r s i o n t o t h e e s t e r , i th a s been p r o p o s e d , f o r e x a m p l e , t o u s e b u t a n o l i n a

l a r g e e x c e s s w i t h r e s p e c t t o a c r y l i c a c i d , or t o r e m o v et h e r e a c t i o n water by a z e o t r o p i c d i s t i l l a t i o n o r t o e xt r a c t t h e e s t e r w i t h a s o l v e n t d u r i n g t h e r e a c t i o n . T h i si s , however, n o t s a t i s f a c t o r y a s i t i s n e c e s s a r y f o r a ni m p o r t a n t e x c e s s o f b u t a n o l t o be r e c o v e r e d , o r f o r t h ed i s t i l l a t i o n a i d o r t h e s o l v e n t e x t r a c t a n t t o be separ a t e d . I n a d d i t i o n t o t h i s , a c o n s i d e r a b l e q u a n t i t y o fu n d e s i r a b l e d i b u t y l e t h e r b y - p r o d u c t , w h i c h h a s t h esam e b o i l i n g p o i n t a s t h e b u t y l e s t e r , i s o b t a i n e d .The p r e s e n t i n v e n t i o n n o w p r o v i d e s a p r o c e s s whichi s f r e e from t h e d i s a d v a n t a g e s d e s c r i b e d h e r e i n a b o v ea n d w h i c h c o m p r i s e s r e a c t i n g a c r y l i c a c i d a n d b u t a n o li n a molar r a t i o w i t h i n t h e r a n g e 1 : 1 and 1 : 2 5 , a t t e mp e r a t u r e s w i t h i n t h e r a n g e 8 0 and 1 3 0 C , u n d e r ap r e s s u r e w i t h i n t h e r a n g e 3 a n d 1 5 a t m o s p h e r e s g a u g e ,a n d f o r p e r i o d s w i t h i n t h e r a n g e 20 and 9 0 m i n u t e s .A r e f e r r e d em b o dim ent o f t h e p r e s e n t p r o c e s s c o mp r i s e s : i n t r o d u c i n g c o n t i n u o u s l y a c r y l i c a c i d a n d nb u t a n o l i n t o a r e a c t i o n zone b e i n g ? l l e d w i t h an a c i dc a t i o n e x c h a n g e r ; d e l i v e r i n g t h e r e s u l t i n g e s t e r i ? c a t i o nmixture t o a ? r s t d i s t i l l a t i o n z o n e , d i s t i l l i n g o f f nea r thehead of t h e ? r s t d i s t i l l a t i o n zone a t e r n a r y mixturec o n s i s t i n g o f b u t y l a c r y l a t e , b u t a n o l and w a t e r , c o nd e n s i n g t h e m i x t u r e a n d s e p a r a t i n g i t i n t o a n o r g a n i cp h a s e and an a q u e o u s p h a s e , r e c y c l i n g t h e b u l k o f t h eaqueous phase t o t h e head o f t h e ? r s t d i s t i l l a t i o n zonea n d r e m o v i n g t h e a q u e o u s p h a s e b a l a n c e p o r t i o n ; r em o v i n g c o n c e n t r a t e d a c r y l i c a c i d f r o m t h e b o t t o mp o r t i o n o f t h e ? r s t d i s t i l l a t i o n z o n e , d i s t i l l i n g o f f h i g h e rb o i l i n g f r a c t i o n s a n d r e c y c l i n g t h e a c r y l i c a c i d t o t h er e a c t i o n z o n e ; d e l i v e r i n g t h e o r g a n i c p h a s e r e c o v e r e dfrom d i s t i l l a t e o f t h e ? r s t d i s t i l l a t i o n zone t o a secondd i s t i l l a t i o n z o n e , d i s t i l l i n g o f f near t h e h e a d of t h e s e co nd d i s t i l l a t i o n zone a t e r n a r y mixture c o n s i s t i n g ofb u t y l a c r y l a t e , b u t a n o l a n d w a t e r , c o n d e n s i n g t h e m i xt u r e and s e p a r a t i n g i t i n t o a n o r g a n i c p h a s e and ana q u e o u s p h a s e , r e c y c l i n g t h e o r g a n i c p h a s e t o t h e h e a do f t h e second d i s t i l l a t i o n zone and removing t h e aqueo u s p h a s e ; d e l i v e r i n g b a s e p r o d u c t o b t a i n e d i n t h es e c o n d d i s t i l l a t i o n z o n e and c o n s i s t i n g o f b u t y l a c r y l a t eand b u t a n o l t o a t h i r d d i s t i l l a t i o n z o n e , d i s t i l l i n g o f fnear t h e h e a d of t h e t h i r d d i s t i l l a t i o n z o n e a b u t a n o l /b u t y l a c r y l a t e - a z e o t r o p e , c o n d e n s i n g t h e a z e o t r o p e a n dr e c y c l i n g i t t o t h e r e a c t i o n z o n e , and r e m o v i n g p u r en - b u t y l a c r y l a t e t h r o u g h t h e b o t t o m p o r t i o n o f t h e t h i r dd i s t i l l a t i o n zone.

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b e u s e d i s a p o l y s t y r e n e / s u l f o n i c a c i d b a s e d c a t i o ne x c h a n g e r r e s i n .With r e s p e c t t o t h e e s t e r i ? c a t i o n r e a c t i o n , i t i s a dv a n t a g e o u s f o r i t t o b e e f f e c t e d a t t e m p e r a t u r e s w i t h i nt h e r a n g e 8 5 a n d 1 2 5 C . H i g h e r t e m p e r a t u r e s h a v ebeen found t o promote t h e f o r m a t i o n o f d i b u t y l e t h e ra n d p o l y m e r i z a t i o n a n d t h e r e b y t o a f f e c t t h e c a t a l y s tp e r f o r m a n c e , w h i l s t l o w e r t e m p e r a t u r e s e f f e c t a cons i d e r a b l e r e d u c t i o n o f t h e r e a c t i o n v e l o c i t y .The r e a c t i o n s h o u l d p r e f e r a b l y b e e f f e c t e d u n d e r t h ep r e s s u r e n e c e s s a r y t o m a i n t a i n t h e l i q u i d p h a s e u n d e rt h e r e a c t i o n c o n d i t i o n s s e l e c t e d . A e a c t i o n p r e s s u r ew i t h i n t h e r a n g e 5 and 1 0 a t m o s p h e r e s g a u g e h a s v e r yb e n e ? c i a l e f f e c t s on t h e c a t a l y s t p e r f o r m a n c e .The e s t e r i ? c a t i o n r e a c t i o n a n d d i s t i l l a t i v e s e p a r a t i o ns h o u l d c o n v e n i e n t l y b e e f f e c t e d i n t h e p r e s e nc e o f as u i t a b l e p o l y m e r i z a t i o n i n h i b i t o r , which m ay b e s el e c t e d , f o r e x a m p l e , f r o m h y d r o q u i n o n e , h yd r o q u i n o n e m o n o m e t h y l e t h e r , p - b e n z o q u i n o n e , p h e n ot h i a z i n e o r m e t h y l e n e B l u e , and u s e d i n a d m i x t u r e w i t ha i r , i f d e s i r e d .With r e s p e c t t o t h e b u t a n o l s t a r t i n g m a t e r i a l , i t i sa l l o w a b l e f o r i t t o c o n t a i n s o m e water or b u t y l a c r y l a t e .The c r y l i c a c i d a n d b u t a n o l a r e , h o w e v e r , r e q u i r e d t obe p r e s e n t i n t h e r e a c t i o n zone i n a molar r a t i o w i t h i nt h e r a n g e 1 : 1 a n d 1 1 2 . 5 , p r e f e r a b l y 1 1 1 . 3 and 1 : 2 .Lower r a t i o s e f f e c t a r e d u c t i o n o f t h e r e a c t i o n v e l o c i t ya n d o f t h e c o n v e r s i o n , w h i l e h i g h e r r a t i o s e f f e c t t h ef o r m a t i o n o f u n d e s i r a b l e d i b u t y l e t h e r .A r e f e r r e d em b o dim ent o f t h e p r o c e s s w i l l n o w bed e s c r i b e d b y way o f e x a m p l e w i t h r e f e r e n c e t o t h ea c c o m p a n y i n g ?ow s c h e m e .As c a n b e s e e n , a r e a c t o r 2 having t h e c a t a l y s t s ec u r e d t h e r e i n i s s u p p l i e d w i t h a c r y l i c a c i d a n d nb u t a n o l t h r o u g h l i n e 1 . The q u a n t i t y o f s t a r t i n g m a t e -r i a l s u p p l i e d d e t e r m i n e d t h e q u a n t i t y o f r e s u l t i n g e s t e ri ? c a t i o n m i x t u r e , w h i c h f l o w s t h r o u g h a p r e s s u r er e t a i n i n g v a l v e 3 and w h i c h i s d e l i v e r e d t h r o u g h l i n e 4t o ? r s t d i s t i l l a t i o n c olum n 5 . A e r n a r y m i x t u r e c o n s i s ti n g o f b u t y l a c r y l a t e , b u t a n o l a n d w a t e r i s t h e d i s t i l l a t et r a v e l l i n g t h r o u g h l i n e 6 a t t h e h e a d o f c o l u m n 5 , w h i c hi s operated under a p r e s s u r e o f 100-7 60 mm g nd a ta t e m p e r a t u r e o f 4 6 9 2 C . The i s t i l l a t e i s condensedi n c o n d e n s e r 7 and s e p a r a t e d i n s e p a r a t o r 8 i n t o ano r g a n i c p h a s e a n d a n a q u e o u s p h a s e , o f w h i c h a b o u t97 i s p r e f e r a b l y r e c y c l e d t o t h e h e a d o f column 5 ,t h r o u g h l i n e 9 , a n d o f w h i c h a b o u t 3 i s p r e f e r a b l yr e m o v e d , t h r o u g h l i n e 2 1 . The b a s e o f c o l u m n 5 , w h i c hi s o p e r a t e d under a p r e s s u r e o f 100-760 mm g t at e m p e r a t u r e o f 6 5 _ l 4 0 C , c o n t a i n s a c r y l i c a c i d o fa b o u t 8 5 w e i g h t t r e n g t h . The a c i d i s d i s t i l l a t i v e l yf r e e d l f r o m h i g h e r b o i l i n g f r a c t i o n s i n a n e v a p o r a t o r 2 2 ,w h i c h i s o p e r a t e d u n d e r a p r e s s u r e o f 20-200mm H gand a t a t e m p e r a t u r e o f 4 0 9 5 C , and r e c y c l e d t or e a c t o r 2 , t h r o u g h l i n e 10 and l .The o r g a n i c p h a s e , w h i c h c o n s i s t s o f b u t y l a c r y l a t e ,b u t a n o l and a b o u t 6 w e i g h t f w a t e r and a c c u m ul t e s i n s e p a r a t o r 8 , i s d e l i v e r e d t o second d i s t i l l a t i o ncolumn 1 2 , t h r o u g h l i n e 1 1 . A t e r n a r y m i x t u r e o fb u t y l a c r y l a t e , b u t a n o l and w a t e r i s removed a t t h e heado f c olum n 1 2 u n d e r a p r e s s u r e o f 100-760 mm g a n da t a temperature of 4692 C . The mixture i s c o nd e n s e d i n c o n d e n s e r 1 3 and s e p a r a t e d i n t o two p h a s e si n s e p a r a t o r 1 4 , o f w h i c h t h e o r g a n i c p h a s e i s r e ? u x e dt o column 1 2 , w h e r e a s t h e a q u e o u s p h a s e i s r e m o v e d ,t h r o u g h l i n e 1 5 . A n h y d r o u s b a s e p r o d u c t c o n s i s t i n g o fb u t y l a c r y l a t e a n d b u t a n o l i s removed u n d e r a p r e s s u r e


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4 , 0 1 2 , 4 3 93o f 100-760 mm g a n d a t a t e m p e r a t u r e o f 65-l40 Cfrom t h e b a s e o f column 1 2 and d e l i v e r e d t o t h i r dd i s t i l l a t i o n column 1 7 , t h r o u g h l i n e 1 6 . Column 1 7 i soperated u n d e r a pressure of 20-760 mm g, a t a h e a dtem per a tu re of 3 9 l 1 7 C and a base temperature of4 5 ~ 4 7 C , and u s e d t o e f f e c t s e p a r a t i o n t h e r e i n i n t o ab u t a n o l / b u t y l a c r y l a t e - a z e o t r o p e ( h e a d p r o d u c t ) ,which i s condensed i n c o n d e n s e r 1 8 and r e c y c l e d t oe s t e r i ? c a t i o n r e a c t o r 2 , t h r o u g h l i n e s 1 9 a n d 1 , a n di n t o p u r e b u t y l a c r y l a t e ( b a s e p r o d u c t ) w h i c h i s d i sc h a r g e d t h r o u g h l i n e 2 0 .

P o l y m e r i z a t i o n o f t h e m a t e r i a l i n t h e t h r e e columns si n h i b i t e d by means o f a p o l y m e r i z a t i o n i n h i b i t o r whichi s added t h e r e t o .

EXAMPLEThe r e a c t o r 2 w a s a c y l i n d r i c a l j a c k e t e d s t a i n l e s s

s t e e l r e a c t o r . I t h a d a n i n t e r n a l diameter of 25 mm, vl e n g t h o f 850 mm nd w a s s t e a m - h e a t e d . Placed i n t h ei n t e r i o r of the r e a c t o r w a s 250 cc 155 g ) of a c o m m e r ~c i a l l y a v a i l a b l e a c i d c a t i o n e x c h a n g e r (AMBERLYST1 5 , a product o f Rohm a n d Haas) a s a c a t a l y s t .The r e a c t o r was s u p pl i e d w i t h t h e s t a r t i n g m a te r i a l s ,which were i n t r o d u c e d f rom below and t r a v e l l e d u pw a r d l y t h e r e i n . P r e s s u r e - r e t a i n i n g v a l v e 3 a t t h e r e a ct o r o u t l e t w a s used t o e s t a b l i s h t h e working p r e s s u r e .The s y s t e m was s u p p l i e d p e r hour w i t h 83 g ( 1 . 1 5 m o l )o f f r e s h a c r y l i c a c i d , 8 5 g 1 . 1 5 m o l ) o f f r e s h n - b u t a n o la n d w i t h u n r e a c t e d r e c y c l e p r o d u c t , which t r a v e l l e dt h r o u g h l i n e 1 . I n o t h e r w o r d s , r e a c t o r 2 was c h a r g e dp e r hour w i t h a l t o g e t h e r 300 g o f a m i x t u r e c o n s i s t i n go f 9 8 . 5 g ( 3 2 . 8 w e i g h t ) o f a c r y l i c a c i d ( 1 . 3 7 m o l ) ,1 7 2 g ( 5 7 . 3 w e i g h t ) o f n - b u ta n o l ( 2 . 3 3 m o l ) a n d2 9 . 5 g ( 9 . 9 w e i g h t ) o f n - b u t y l a c r y l a t e ( a c r y l i c a c i dn - b u t y l e s t e r ; 0 . 2 3 m o l ) . The m o l a r r a t i o o f a c r y l i c a c i dt o n - b u t a n o l a c c o r d i n g l y w a s 1 1 1 . 7 . 84.3 of t h ea c r y l i c a c i d w as converted i n r e a c t o r 2 a t a r e a c t i o nt e m p e r a t u r e o f 1 2 0 C , under a p r e s s u r e o f 7 a t m os p h e r e s gauge and w i t h i n 45 m i n u t e s . 300 g / h o f r e a ct i o n p r o d u c t c o n t a i n i n g 1 7 4 . 5 g ( 1 . 3 6 4 m o l ) o f nb u t y l a c r y l a t e , 1 5 . 5 g ( 0 . 2 1 5 m o l ) o f a c r y l i c a c i d , 8 7 g( 1 . 1 7 5 mol) o f b u t a n o l and 20 g ( 1 . 1 3 4 m o l ) o f w a t e ra s w e l l a s 3 g of r e s i d u e w a s r e m o v e d through p r e s s u r er e t a i n i n g v a l v e 3 and i n t r o d u c e d t h r o u g h l i n e 4 a p p r o xi m a t e l y i n t o t h e c e n t e r p o r t i o n o f ? r s t d i s t i l l a t i o n c o lumn 5 , w h i c h w a s oper a ted u n d e r a p r e s s u r e of 200mm g a n d a t a temperature of 8 8 C . 1 8 . 5 g / h of b a s ep r o d u c t c o n t a i n i n g 8 4 w e i g h t f a c r y l i c a c i d a n d 4w e i g h t o f w a t e r was r e m o v e d , d i s t i l l a t i v e l y f r e e d. f r o m r e s i d u e i n e v a p o r a t o r 2 2 under a p r e s s u r e o f 50mm g and a t 5 6 C , and r e c y c l e d t o r e a c t o r 2 t h r o u g hl i n e 1 0 . The head product obtained a t 63 C w a s a. t e m a r y m i x t u r e o f b u t y l a c r y l a t e , b u t a n o l a n d w a t e r ,which was condensed and s e p a r a t e d i n t o two p h a s e s .97 ( = 1 0 0 g / h ) o f t h e a q u e o u s p h a s e w a s r e c y c l e dt h r o u g h l i n e 9 t o column 5 t o e f f e c t f o r m a t i o n o f t h et e r n a r y m i x t u r e t h e r e i n , and 3 (= 3 . 5 g / h ) was r emoved f r o m t h e s y s t e m t h r o u g h l i n e 2 1 . 2 7 8 g / h o fo r g a n i c p h a s e , w h i c h was f r e e f r o m a c r y l i c a c i d a n dc o n t a i n e d 6 2 . 7 w e i g h t f b u t y l a c r y l a t e , 3 1 . 3 w e i g h t

f b u t a n o l and 6 w e i g h t f w a t e r , w a s i n t r o d u c e dt h r o u g h l i n e 1 1 a p p r o x i m a t e l y i n t o t h e c e n t e r p o r t i o no f s e c o n d d i s t i l l a t i o n c ol u m n 1 2 . The t e r n a r y m i x t u r e

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w h i c h w e n t o v e r a t a h e a d t e m p e r a t u r e o f 62 C n d e ra p r e s s u r e o f 150 mm g w a s c o n d e n s e d a n d gave t w op h a s e s , o f w h i c h t h e o r g a n i c p h a s e ( f r o m c o l u m n 1 2 )was r e ? u x e d , a n d o f w h i c h t h e a q u e o u s p h a s e ( 1 6 . 5 g )was r em o ved t h r o u g h l i n e 1 5 . 2 6 1 . 5 g o f a n h y d r o u s

65

4b a s e p r o d u c t was d i s c h a r g e d a t 8 3 C and i n t r o d u c e dt h r o u g h l i n e 1 6 a p p r o x i m a t e l y i n t o t h e c e n t e r p o r t i o no f t h i r d d i s t i l l a t i o n column 1 7 . 1 1 6 . 5 g / h o f a n a z e ot r o p i c m i x t u r e o f 7 4 . 5 w e i g h t f b u t a n o l and 2 5 . 5weight f b u t y l a c r y l a t e w a s obtained a s t h e h e a dproduct a t 53 C nder a p r e s s u r e of 50 mm g. I t w a sr e c y c l e d t o r e a c t o r 2 t h r o u g h l i n e s 1 9 a n d l . The c o lu m n b a s e p r o d u c t , which was n - b u t y l a c r y l a t e f r e e fromd i b u t y l e t h e r , was o b t a i n e d a t 8 3 C t a h o u r l y r a t e of1 4 3 g ( 1 . 1 2 m o l ) . T h i s c o r r e s p o n d e d t o a y i e l d o f9 7 . 4 % , b a s e d on t h e a c r y l i c a c i d which underwentc o n v e r s i o n . The c a t a l y s t p e r f o r m a n c e was 9 2 3 g o fn - b u t y l a c r y l a t e p e r k g o f c a t a l y s t p e r h o u r . T h e m a t er i a l i n each o f t h e t h r e e columns w as s t a b i l i z e d bym e a n s o f 0 . 1 w e i g h t f h y d r o q u i n o n e , b a s e d on t h ew e i g h t o f t h e l i q u i d p h a s e . The g a s p h a s e w a s s t a b i l i z e da d d i t i o n a l l y i n e a c h o f t h e columns by means o f a i r .

EXAMPLE 2T h e apparatus w a s the s a m e a s t h a t described i nEx am p l e 1 . The p r e s s u r e w a s reduced d o w n t o 3 a t m o

s p h e r e s g a u g e w h i l e t h e o t h e r p a r a m e t e r s , n a m e l y t h e1 2 0 C r e a c t i o n t e m p e r a t u r e and t h e a c r y l i c a c i d t on - b u t a n o l m o l a r r a t i o o f 1 : 1 . 7 r e m a i n e d u n c h a n g e d .290 g o f a m i x t u r e c o n s i s t i n g o f 57 w e i g h t f nb u t a n o l , 3 2 . 6 w e i g h t f c r y l i c - a c i d a n d 1 0 . 4 w e i g h to f n - b u t y l a c r y l a t e w as p u t t h r o u g h i n r e a c t o r 2 .81.4 o f t h e a c r y l i c a c i d u n d e r w e n t c o n v e r s i o n . 290g / h o f r e a c t i o n p r o d u c t c o n t a i n i n g 5 5 . 8 w e i g h t fb u t y l a c r y l a t e , 2 9 . 9 w e i g h t f b u t an o l , 6 . 5 5 w e i g h to f w a t e r, 6 . 0 5 w e i g h t f a c r y l i c a c i d a n d 1 . 7 w e i g h t

f r e s i d u e was d i s c h a r g e d from r e a c t o r 2 . 1 3 0 g / h o fp u r e b u t y l a c r y l a t e was o b t a i n e d . T h i s corresponded t oa y i e l d o f 95 , b a s e d on t h e a c r y l i c a c i d which underwent c o n v e r s i o n . The c a t a l y s t performance was 838 go f b u t y l a c r y l a t e p e r k g o f c a t a l y s t p e r h o u r .

EXAMPLEThe apparatus w a s the s a m e a s t h a t described i nExample 1 . The r e a c t i o n t e m p e r a t u r e w as 1 2 0 C , t h e

a c r y l i c a c i d t o n - b u t a n o l molar r a t i o w a s 1 2 1 . 7 a n d t h eworking p r e s s u r e was i n c r e a s e d t o 1 5 atmospheresg a u g e . 280 g / h o f a m i x t u r e c o n s i s t i n g o f 3 2 . 8 w e i g h to f c r y l i c a c i d , 5 7 . 3 w e i g h t f b u t a n o l a n d 9 . 9 w e i g h tf b u t y l a c r y l a t e w as p u t t h r o u g h i n r e a c t o r 2 . Thea c r y l i c a c i d c o n v e r s i o n r a t e was 8 4 . 7 % . 280 g / h o fr e a c t i o n p r o d u c t ( t h i s c o r r e s p o n d e d t o t h e q u a n t i t y o fs t a r t i n g m a t e r i a l u s e d ) c o n t a i n i n g 5 7 . 8 w e i g h t o fb u t y l a c r y l a t e , 5 w e i g h t f c r y l i c a c i d , 2 8 . 9 w e i g h to f n - b u t a n o l , 6 . 8 w e i g h t f w a t e r and 1 . 4 w e i g h t fr e s i d u e , w a s removed. Th e m a t e r i a l w a s w o r k e d u p a n d134 g of pure n - b u t y l a c r y l a t e w a s o b t a i n e d . T h i s c o r r esponded t o a y i e l d o f 9 6 . 4 % , b a s e d on t h e a c r y l i c a c i dw h i c h u n d e r w e n t c o n v e r s i o n . The c a t a l y s t p e r f o r ma n c e wa s 866 g o f b u t y l a c r y l a t e p e r kg o f c a t a l y s t p e rh o u r .

EXAMPLE 4T h e conditions w e r e the s a m e a s those described i nExample 1 , b u t t h e r e a c t i o n t e m p e r a t u r e was i n c r e a s e dfrom 1 2 0 t o 1 3 0 C . The r e a c t o r w a s charged w i t h 3 l 0

g / h o f a m i x t u r e c o n s i s t i n g o f 3 2 . 7 w e i g h t f a c r y l i ca c i d , 5 7 . 2 w e i g h t f n - b u t a n o l a n d 1 0 . 1 w e i g h t fb u t y l a c r y l a t e . 8 3 . 2 % o f t h e a c r y l i c a c i d u n d e r w e n tc o n v e r s i o n . 3 1 0 g o f r e a c t i o n p r o d u c t c o n s i s t i n g o f 1 7 5g o f b u t y l a c r y l a t e , 90 g o f n - b u t a n o l , 2 1 g o f w a t e r , 1 7g o f a c r y l i c a c i d and 7 g o f r e s i d u e was d i s c h a r g e d . 1 4 3g / h o f p u r e b u t y l a c r y l a t e f r e e f r o m d i b u t y l e t h e r was


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4 , 0 1 2 , 4 3 95o b t a i n e d . T h i s c o r r e s p o n d e d t o ' a y i e l d o f 9 5 . 7 % , b a s e don t h e a c r y l i c a c i d w h i c h u n d e r w e n t - c o n v e r s i o n i l T h ec a t a l y s t p e r f o r m a n c e w a s 9 2 3 g o f b u t y l a c r y l a t e p e r k go f catalyst p r hour.

EXAMPLEThe c o n d i t i o n s were t h e sam e a s t h o s e d e s c r i b e d i nE x a m p l e 1 , b u t t h e r e a c t i o n t e m p e r a t u r e w a s r e d u c e dfrom 1 2 0 C d o w n t o 8 5 C . The r e a c t o r w a s charged

w i t h 316 g / h o f a m i x t u r e c o n s i s t i n g o f 1 0 0 g o f a c r y l i ca c i d , 1 7 5 g o f n - b u t a n o l and 4 1 g o f n - b u t y l a c r y l a t e . Ani d e n t i c a l q u a n t i t y o f r e a c t i o n p r o d u c t c o n s i s t i n g o f 1 3 6g o f b u t y l a c r y l a t e , 4 6 g o f a c r y l i c a c i d , 1 2 0 g o f nb u t a n o l , 1 3 g o f water and 1 g o f r e s i d u e w as o b t a i n e d .5 4 g o f t h e a c r y l i c a c i d u n d e r w e n t c o n v e r s i o n . 9 3 g / h o fp u r e b u t y l a c r y l a t e f r e e f r o m d i b u t y l e t h e r w a s o b t a i n e d .T h i s c o r r e s p o n d e d t o a y i e l d o f 97 , b a s e d on t h ea c r y l i c a c i d w h i c h u n d e r w e n t c o n v e r s i o n . The a t a l y s tp e r f o r m a n c e wa s 600 g o f b u t y l a c r y l a t e p e r kg o f c a t al y s t p e r hour.

EXAMPLEThe c o n d i t i o n s w e r e t h e s a m e a s those d e s c r i b e d i nE x a m p l e 1 , b u t a c r y l i c a c i d a n d n - b u t a n o l w e r e u s e d i n

t h e molar r a t i o o f 1 : 1 . The r e a c t o r was s u p p l i e d w i t h2 9 7 g / h o f a m i x t u r e c o n s i s t i n g o f 1 3 8 g o f a c r y l i c ac i d ,1 4 2 g o f n - b u t a n o l and 1 7 g o f b u t y l a c r y l a t e . An i d e n t ic a l q u a n t i t y o f r e a c t i o n p r o d u c t c o n s i s t i n g o f 1 7 3 g o fb u t y l a c r y l a t e , 4 6 g o f a c r y l i c a c i d , 5 0 g o f b u t a n o l , 2 2g o f water and 6 g of r e s i d u e w as d i s c h a r g e d . 66.7 oft h e a c r y l i c a c i d u n d e r w e n t c o n v e r s i o n . 1 5 4 g / h o f p u r eb u t y l a c r y l a t e f r e e f r o m d i b u t y l e t h e r w a s o b t a i n e d . T h i sc o r r e s p o n d e d t o a y i e l d o f 9 4 . 1 % , b a s e d on t h e a c r y l i ca c i d c o n v e r t e d . The c a t a l y s t p e r f o r m a n c e w a s 9 3 3 g o fb u t y l a c r y l a t e p e r k g o f c a t a l y s t p e r h o u r .EXAMPLE

T h e conditions w e r e the s a m e a s those described i nE x a m p l e 1 , b u t a c r y l i c a c i d a n d n - b u t a n o l w e r e u s e d i nt h e m o l a r r a t i o o f 1 : 2 5 . The c a t a l y s t zone was f e d w i t h3 2 5 g / h o f a m i x t u r e c o n s i s t i n g o f 7 8 g o f a c r y l i c a c i d ,202 g o f n - b u t a n o l and 4 5 g o f b u t y l a c r y l a t e . 325 g o fr e a c t i o n p r o d u c t c o n t a i n i n g 1 6 3 g o f b u t y l a c r y l a t e , 1 0g o f a c r y l i c a c i d , 1 3 2 g o f b u t a n o l , 1 7 g o f w a t e r and 3g o f r e s i d u e was o b t a i n e d . 87.3 o f t h e a c r y l i c a c i dunderwent c o n v e r s i o n . The m a t e r i a l w a s w o rk e d u pa n d 1 1 6 g / h o f p u r e b u t y l a c r y l a t e f r e e from d i b ut y l e t h e r was o b t a i n e d . T h i s c o r r e s p o n d e d t o a y i e l d o f9 6 . 1 % , b a s e d on t h e a c r y l i c a c i d c o n v e r t e d . The c a t al y s t p e r f o r m a n c e was 7 4 9 g o f b u t y l a c r y l a t e p e r k g o fc a t a l y s t p er hour.

COMPARATIVE EXAMPLE AThe r e a c t i o n temperature w as i n c r e a s e d t o 1 4 0 Cand was a c c o r d i n g l y o u t s i d e t h e t e m p e r a t u r e r a n g e

d e s c r i b e d h e r e i n . The m o l a r r a t i o o f a c r y l i c a c i d t on - b u t a n o l o f 1 : 1 . 7 and t h e w o r k i n g p r e s s u r e o f 7 atmos p h e r e s g a u g e u s e d i n E x a m p l e I r e m a i n e d u n c h a n g e d .1 0 2 g o f a c r y l i c a c i d and 1 7 8 g o f n - b u t a n o l werep a s s e d p e r h o u r t h r o u g h t h e r e a c t o r . The a c r y l i c a c i dc o n v e r s i o n r a t e was 8 5 . 1 % . 280 g o f r e a c t i o n p r o d u c tc o n t a i n i n g 5 2 . 9 w e i g h t f b u t y l a c r y l a t e , 5 . 3 5 w e i g h t

f a c r y l i c a c i d , 3 1 . 4 5 w e i g h t f n - b u t a n o l , 7 . 8 5w e i g h t f w a t e r , 0 . 3 5 w e i g h t f d i b u t y l e t h e r a n d2 . 1 w e i g h t f r e s i d u e was o b t a i n e d . The b u t a n o l /b u t y l a c r y l a t e - a z e o t r o p e o b t a i n e d a t t h e h e a d o f t h i r dd i s t i l l a t i o n column 1 7 c o n t a i n e d 0 . 5 w e i g h t f d i b ut y l e t h e r and w a s , t h e r e f o r e , n o t r e c y c l e d t o t h e r e a c t o r ,

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61 4 6 . , g / h , i n c l u d i n g t h e b u t y l a c r y l a t e f r a c t i o n c o n t a i n e di n t h e s ' a z e o t r o p e , o f b u t y l a c r y l a t e c o n t a m i n a t e d w i t h0 . 3 w e i g h t f d i b u t y l e t h e r was o b t a i n e d . T h i s c o r r es p o n d e d t o y i e l d o f 9 4 . 4 % , b a s e d o n t h e a c r y l i c a c i dc o n v e r t e d . The c a t a l y s t p e r f o r m a n c e was 9 4 2 g o fb u t y l a c r y l a t e p e r k g o f c a t a l y s t p e r h o u r .As can be s e e n , d i b u t y l e t h e r i s o b t a i n e d a s a n u n d es i r a b l e b y - p r o d u c t i f t h e r e a c t i o n i s c a r r i e d o u t a t at e m p e r a t u r e o u t s i d e t h e t e m p e r a t u r e r a n g e o f t h e p r es e n t i n v e n t i o n .

COMPARATIVE EXAMPLE BA c r y l i c a c i d and n - b u t a n o l were u s e d i n a molar r a t i o

of 1 : 3 so a s t o b e o u t s i d e t h e mola r r a t i o describedh e r e i n . The w o r k i n g p r e s s u r e w a s 7 a t m o s p h e r e s a b s ol u t e and t h e r e a c t i o n t e m p e r a t u r e was 1 2 0 C . Ther e a c t o r was s u p p l i e d w i t h 280 g / h - o f a f e e d m i x t u r ec o n s i s t i n g o f 2 4 . 5 w e i g h t f a c r y l i c a c i d a n d 7 5 . 5w e i g h t f n - b u t a n o l . The a c r y l i c a c i d c o n v e r s i o n r a t ew a s 9 1 . 3 % . 2 8 0 g / h o f r e a c t i o n p r o d u c t c o n t a i n i n g 3 7 . 8w e i g h t f b u t y l a c r y l a t e , 2 . 1 w e i g h t f c r y l i c a c i d ,5 2 . 1 w e i g h t f n - b u t a n o l , 5 . 7 w e i g h t f w a t e r , 0 . 4w e i g h t f d i b u t y l e t h e r a n d 1 . 8 w e i g h t f r e s i d u ewas o b t a i n e d . The b u t y l a c r y l a t e / b u t a n o l - a z e o t r o p ecoming from t h e t h i r d d i s t i l l a t i o n column 1 7 c o n t a i n e d0 . 4 w e i g h t f d i b u t y l e t h e r and w a s , t h e r e f o r e , n o tr e c y c l e d . 1 0 5 g / h , i n c l u d i n g t h e b u t y l a c r y l a t e f r a c t i o ni n t h e a z e o t r o p e , o f b u t y l a c r y l a t e c o n t a m i n a t e d w i t h0 . 4 w e i g h t f d i b u t y l e t h e r was o b t a i n e d . T h i s c o r r esponded t o a y i e l d o f 94 , b a s e d on t h e a c r y l i c a c i dc o n v e r t e d . The c a t a l y s t p e r f o r m a n c e was 678 g o fb u t y l a c r y l a t e p e r k g o f c a t a l y s t p e r h o u r .As c a n be s e e n , d i b u t y l e t h e r i s obtained a s a n u n d es i r a b l e b y - p r o d u c t a n d t h e c a t a l y s t p e r f o r m a n c e i s i mp a i r e d b y u s i n g n - b u t a n o l i n a m o l a r e x c e s s b e y o n d t h eu p p e r l i m i t i n g v a l u e i n t h e m o l a r r a t i o d e s c r i b e dh e r e i n .We l a i m :1 . I n t h e p r o c e s s f o r m a k i n g n - b u t y l a c r y l a t e b y r e a c ti n g a c r y l i c a c i d w i t h n - b u t a n o l i n l i q u i d p h a s e i nc o n t a c t w i t h an a c i d c a t i o n exchanger a s a c a t a l y s t , t h ei m p r o v e m e n t , w h i c h c o m p r i s e s c o n t i n u o u s l y i n t r o d u ci n g i n t o , a n d r e a c t i n g i n , a r e a c t i o n z o n e a c r y l i c a c i dand n - b u t a n o l i n a molar r a t i o w i t h i n t h e r a n g e 1 2 1 and1 2 . 5 , a t t e m p e r a t u r e s w i t h i n t h e r a n g e 8 0 and 1 3 0 C ,under a p r e s s u r e w i t h i n t h e range 3 and 1 5 a t m os p h e r e s g a u g e , a n d f o r r e a c t i o n p e r i o d s w i t h i n t h er a n g e 20 and 90 m i n u t e s , t h e r e a c t i o n z o n e b e i n g ? l l e dw i t h a n a c i d c a t i o n e x c h a n g e r ; d e l i v e r i n g t h e r e s u l t i n ge s t e r i ? c a t i o n mixture t o a ? r s t d i s t i l l a t i o n z o n e , d i s t i l li n g o f f nea r t h e h e a d o f t h e ? r s t d i s t i l l a t i o n zone at e r n a r y m i x t u r e c o n s i s t i n g o f b u t y l a c r y l a t e , b u t a n o la n d w a t e r , c o n d e n s i n g t h e m i x t u r e a n d s e p a r a t i n g i ti n t o a n o r g a n i c p h a s e and a n a q u e o u s p h a s e , r e c y c l i n gt h e b u l k o f t h e aqueous phase t o t h e head of t h e ? r s td i s t i l l a t i o n z o n e a n d r e m o v i n g t h e a q u e o u s p h a s e b a la n c e p o r t i o n ; r e m o v i n g c o n c e n t r a t e d a c r y l i c a c i d f r o mt h e bottom p o r t i o n o f t h e ? r s t d i s t i l l a t i o n z o n e , d i s t i l li n g o f f h i g h e r b o i l i n g f r a c t i o n s a n d r e c y c l i n g t h e a c r y l i ca c i d t o t h e r e a c t i o n z o n e ; d e l i v e r i n g t h e o r g a n i c p h a s er e c o v e r e d from d i s t i l l a t e o f t h e ? r s t d i s t i l l a t i o n zone t oa second d i s t i l l a t i o n z o n e , d i s t i l l i n g o f f near t h e h e a d ofthe s e c o n d d i s t i l l a t i o n z o n e a t e r n a r y mi xt ure c o n s i s t i n g o f b u t y l a c r y l a t e , b u t a n o l a n d w a t e r , c o n d e n s i n g t h em i x t u r e a n d s e p a r a t i n g i t i n t o a n o r g a n i c p h a s e a n d a na q u e o u s p h a s e , r e c y c l i n g t h e o r g a n i c p h a s e t o t h e h e a do f t h e second d i s t i l l a t i o n z o n e and r emoving t h e aqueo u s p h a s e ; d e l i v e r i n g b a s e p r o d u c t o b t a i n e d i n t h e


6/6

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