Condensation Products of Acetaldehyde and Derivatives

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PURDUE UNIVERSITY

T H IS IS TO C E R T IF Y TH A T T H E T H E S IS P R E P A R E D U N D E R MY S U P E R V IS IO N

by

Thomas H, Stoudfr

EN T IT L E D _________

COSIDBMSATION PBODÏÏCTS OF ACBTALDEHYDE

AND DERIVATIVES

C O M P L IE S W ITH T H E U N IV E R S IT Y R E G U L A T IO N S O N G R A D U A T IO N T H E S E S

A N D IS A P P R O V E D B Y M E A S F U L F IL L IN G T H IS P A R T O F T H E R E Q U IR E M E N T S

FO R THE DEG REE OF

D octor o f P h ilo so p h y

P

H

(v?

r o f e s s o r in

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o 19yy

TO T H E L IB R A R IA N :---IS T H IS T H E S IS m .-fjprair TO B E R E G A R D E D A S C O N F ID E ]

BBGISTHABFOBM10— 7-47— 2M

Charge

chool or

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of

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e s is

epartm ent

condensation :

Products

of acetaldehyde and d e r iv a t iv e s

A T h e s is S u b m itte d t o t h e F a c u lty of P u rd u e U n iv e r s ity

by

Thomas H, S to u d t

In P a r t i a l F u lfillm e n t o f th e R e q u ire m e n ts f o r t h e D egree

of D o c to r o f P h ilo s o p h y A u g u st, 1949

ProQuest Number: 27712232

All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is d e p e n d e n t upon the quality of the copy subm itted. In the unlikely e v e n t that the a u thor did not send a c o m p le te m anuscript and there are missing pages, these will be noted. Also, if m aterial had to be rem oved, a n o te will ind ica te the deletion.

uest ProQuest 27712232 Published by ProQuest LLC (2019). C opyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C o d e M icroform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106 - 1346

ACKNOWLEDGMENT The a u t h o r w ish e s t o e x p r e s s a p p r e c i a t i o n t o D r. Ed. F. D e g e rin g , D r. E. H i t c h , and D r. Geo. 01 M o rriso n o f Shawi n i g a n P r o d u c ts C o r p o r a tio n f o r t h e i r c o n t r i b u t i o n t o t h i s work i n t h e fo rm o f m ost a b le d i r e c t i o n .

The a u th o r w ish e s t o

e x p r e s s h i s g r a t i t u d e t o S h aw in ig an P r o d u c ts C o r p o r a tio n f o r t h e f i n a n c i a l s u p p o rt o f t h i s p r o j e c t th ro u g h t h e P u rd u e R e s e a rc h F o u n d a tio n .

TABLE OF CONTENTS

P age ABSTRACT ............................................................................................................

1

INTRODUCTION..................................................................................................

1

PART I .

THE CONDENSATION OF ACETALDEHYDE WITH ACETALDOL

I n t r o d u c t i o n ......................... D is c u s s io n E x p e rim e n ta l PART I I .

8

.................................................

10

......................................................................... 12

THE POLYMERIZATION OF ACETALDEHYDE

I n t r o d u c t i o n ................

18

D i s c u s s i o n .......................

24

E x p e rim e n ta l

24

PART I I I .

.....................................................

THE POLYMERIZATION OF CROTONALDEHYDE

I n t r o d u c t i o n ......................................................................................

32

D i s c u s s i o n ........................................................................................... 34 E x p e rim e n ta l

...............................................................................

APPENDIX A.................................................................................

38

42

BIBLIOGRAPHY.................................................................................................. 4 5 V IT A ....................................................................................................................

LIST OF TABLES

T a b le 1.

Page E f f e c t o f T e m p e ra tu re on t h e T r1e th y la m in e C a ta ly z e d P o ly m e r iz a tio n o f

2.

A c e ta ld e h y d e .......................

28

The P o ly m e r iz a tio n o f C ro to n a Id e h y d e w ith T r l e t h y la m in e .......................................................................................

40

i

CONDENSATION PRODUCTS OF ACETALDEHYDE AND DERIVATIVES1 by Ed. F . D eg e rin g and Thomas H. S to u d t P u rd u e U n i v e r s i t y , L a f a y e t t e , I n d ia n a AN ABSTRACT: 1.

A b s tr a c te d fro m t h e t h e s i s o f T. H. S to u d t s u b m itte d t o

th e F a c u lty o f t h e G ra d u a te S c h o o l o f P u rd u e U n i v e r s it y i n p a r t i a l f u l f i l l m e n t o f t h e r e q u ire m e n ts f o r t h e d e g re e o f D o c to r o f P h ilo s o p h y , A u g u s t, 1949. The p o ly m e r iz a tio n o f a c e ta ld e h y d e h a s b e e n d e s c r ib e d w ith t h e u s e o f a g r e a t many d i f f e r e n t c a t a l y s t s .

A c e t-

a l d o l i s u s u a l l y p r e p a r e d by t h e a l k a l i c a t a ly z e d a l d o l con­ d e n s a t io n w h ile a g r e a t many h i g h e r p o ly m ers a r e d e s c r i b e d w hich h av e b e e n p r e p a r e d u n d e r a w ide ra n g e o f c o n d itio n s by t h e u s e o f b o th b a s i c and a c i d c a t a l y s t s . P o ly m ers h i g h e r t h a n a c e t a l d o l h av e n o t b e e n i s o l a t e d as t h e p o ly h y d ro x y a ld e h y d e s , b u t h a v e b e e n i d e n t i f i e d a s t h e d e h y d ra te d p r o d u c ts o r d e r i v a t i v e s o f th e d e h y d ra te d p r o d u c ts . The c o m p le x ity o f t h e h i g h e r p o ly m ers i s r e f l e c t e d i n s t r u c ­ t u r e s t u d i e s on a c e t a l d o l .

OWen h a s shown by c r y o s c o p ic

d e te r m in a tio n s t h a t a c e t a l d o l d im e r iz e s c o m p le te ly i n s e v e r a l h o u rs a f t e r d i s t i l l a t i o n ^ . 2.

S p a th and L o ren z h a v e p o s t u l a t e d

Owen, L. N ., J . Chem. S o c. , 1 9 4 3 . 44 5 .

t h i s d im e r t o b e p a r a l d o l w ith t h e f o llo w in g s t r u c t u r e

il

/O-GHH© GHttCHGH*GHp • GH

3*

S p a th , E. an d L o re n z , R . , B e r. , 75B , 1029 (194*2).

S a u n d e rs an d M urray h a v e shown by means o f Raman s p e c t r a t h a t f r e s h l y d i s t i l l e d a c e t a l d o l and p r o p io n a ld o l h a v e no c a rb o n y l g r o u p .

B u tyr a l d o l , on t h e o th e r h a n d , e x h i b i t e d

t h e n o rm al c a rb o n y l s p e c tru m 4.

S a u n d e r s , R. H. and M u rray , M. J . , J . Am. Chem. S o c. .

6 £ , 1309 (1 9 4 3 ).

A f r e q u e n t l y o b s e rv e d f a c t i s t h a t a c e ta ld e h y d e a p p ro a c h e s a maximum o f 66 2 /3 $ c o n v e r s io n t o a c e t a l d o l .

S au n d ers, in

s tu d y in g t h e compound fo rm a tio n b etw e e n a c e ta ld e h y d e and a c e t a l d o l , i n v e s t i g a t e d th e c a s e o f is o b u ty r a ld é h y d e .

Iso ­

b u t y r a l d o l i s q u i t e c o n v e n ie n t t o work w ith b e c a u s e o f i t s c o m p a r a tiv e ly h ig h s t a b i l i t y t o d e h y d r a tio n .

I n a l l a tte m p te d

c o n d e n s a tio n s u n d e r n e u t r a l and b a s ic c o n d i t i o n s , o n ly a s i n g l e t r i m e r was o b t a i n e d , t h e s t r u c t u r e o f w hich was d e t e r ­ m ined by i n f r a r e d s p e c t r a t o be t h e f o llo w in g ^ : (CH,)„CH-dH NCH OH(OH3 ) 2 C(H)0H 5»

S a u n d e r s , R. H. and M urray, M. J . , I b i d . , 6 9 . 1714 (1 9 4 3 ).

Usherwood h a s s tu d i e d t h e 1 s o b u t y r a ld o l - i s o b u ty r a ld e h y d e

ill

e q u i l i b r i u m an d h a s fo u n d t h a t u n d e r a l l c o n d itio n s t h e e q u i l i b r i u m a p p ro a c h e s e q u im o la r q u a n t i t i e s o f e a c h ^ . 6.

U sherw ood, E. H*, J . Chem* S o c » , 1 2 5 » 1717 (1 9 2 3 )•

A c e ta ld e h y d e and a c e t a l d o l would b e e x p e c te d t o p ro d u c e a s im ila r trim e r . I t h a s b e e n fo u n d t h a t a c e ta ld e h y d e ca n b e co n d en sed w ith a c e t a l d o l by means o f t r i e t h y l a m i n e .

The c o n d e n s a tio n

was fo u n d t o y i e l d f o u r m o le c u le s o f t h e b r a n c h - c h a in e d p o ly m er t o e a c h one o f th e s t r a i g h t - c h a i n e d ty p e .

The a l k a l i

c a ta ly z e d r e a c t i o n i s r e c o g n iz e d a s y i e l d i n g p r e d o m in a n tly t h e b r a n c h - c h a in e d v a r i e t y a lth o u g h no r e l a t i v e f i g u r e s a r e a v a ila b le .

S t e r i c e f f e c t s a r e p ro b a b ly q u i t e im p o rta n t h e r e ,

a s t h e a ld e h y d e g ro u p o f th e a c e ta ld e h y d e i s c e r t a i n l y more a v a ila b le f o r re a c tio n . I n t h e c a s e o f h i g h e r p o ly m e rs , B i l l i g c la im s t h e p r e ­ p a r a t i o n o f p o ly a l d o l s and r e s i n s by t h e u s e o f d ie th y la m ln e ? . 7-

B i l l i g , K. , G-er. P a t e n t 63 9 ,2 9 1 (D ec. 2 , 1 9 3 6 ).

P i p e r i d i n e h a s b e e n d e s c r ib e d by M atui a s a p o ly m e riz in g p a g e n t . A g r e a t many s e c o n d a ry am ines h av e b e e n d e s c r ib e d 8.

M a tu i, K. , J . Ghent. S o c. J a p a n , 6 1 , 712 ( 1941 ) .

a s p ro d u c in g s u i t a b l e m a t e r i a l s f o r la c q u e r s u b s t i t u t e s , e l e c t r i c a l i n s u l a t i o n , and p o l i s h e s ^ . 9*

In a d d itio n , a la rg e

F ra n k e rib u rg e r, W. and H am m erschm idt, H. , U .S. P a t e n t

2 ,1 9 0 ,1 8 4 (F eb . 1 3 , 1 9 4 0 ).

iv

v a r i e t y o f a f t e r t r e a t m e n ts h av e b e e n u s e d t o p ro d u c e p r o ­ d u c ts o f d e s i r a b l e p r o p e r t i e s . A dkins d e s c r i b e s t h e u s e o f a l a r g e num ber o f m e ta l o x id e s i n p ro d u c in g a c e ta ld e h y d e p o l y m e r s ^ * 10.

Tem per-

A d k in s , H. and K in s e y , M. E. , I n d . E ng. Chem ., 2 2 ,

1046 (1 9 3 0 ). 11.

A d k in s, H. and K in s e y , M. E . , I b i d . . 2 4 , 3141 (1 9 3 2 ).

a t u r e s o f 2 8 0-300°C . and p r e s s u r e s o f 5 * 0 0 0 -6 ,0 0 0 a tm o sp h e re s i s r e p o r t e d t o c a u se t h e r a p i d p o ly m e r iz a tio n o f a c e ta ld e h y d e t o a re d -b ro w n m a s s ^ . 12.

A B r i t i s h p a t e n t c o v e rs t h e u s e o f

L e i p u n s k i i , 0 . I . and R e in o v , V. M ., Compt. r e n d , a c a d .

s c i . ( tJ - l- S .R . ) , 2 0 , 624 (1941) ( i n E n g l i s h ) . ammonium s a l t s a s p o ly m e riz in g a g e n ts 13 •

13

.

F is c h e r h as in t r o -

B o z e l, M ., B r i t . P a te n t 5 9 7,128 ( J a n . 1 9 , 1 9 4 8 ).

d uced t h e u s e o f amino a c id s i n c a t a l y z i n g t h e a l d o l co n ­ d e n s a t io n o f a c e t a l d e h y d e ^ .

The u s e o f u l t r a s o n i c w aves’^

14.

F i s c h e r , F. (r. and M a r s c h a ll, A . , B e r. . 64B, 2825 (1931) •

15.

Demann, W. an d A sb ach , H. R . , T ech . M i t t . Knuoo F o r -

a c h u n g s h e r. 2 , 12 (1 9 4 0 ). and u l t r a v i o l e t l i g h t ^ ^ h a v e b e e n i n v e s t i g a t e d a s t o t h e i r 16.

B e r t h e l o t , Compt. r e n d . . 1 5 6 , 233 (1 9 1 2 ).

e f f e c t : o n t h e p o ly m e r iz a tio n o f a c e ta ld e h y d e .

V

T r ie th y la m in e h a s b e e n u s e d t o p o ly m e riz e a c e ta ld e h y d e t o h ig h p o ly m e rs a t te m p e r a tu r e s o f 9 0 - l6 0 oC.

T r ie th y la m in e ,

d ie th y la m in e , t r i p r o p y l a m i n e , and tr ia m y la m in e h av e b e e n u s e d under s im ila r c o n d itio n s .

The p o ly m ers w ere fo u n d t o h a v e

m o le c u la r w e ig h t o f a b o u t 350.

I n i t i a l t e s t s in d ic a te th e

p r e s e n c e o f d e s i r a b l e film - fo r m in g p r o p e r t i e s .

R e d u c tio n

o f t h e p o ly m e rs p ro d u c e d c l e a r am ber r e s i n s . A ls o , t h e p o ly m e r iz a tio n o f c r o to n a ld e h y d e h a s b e e n s tu d i e d i n t h e p r e s e n c e o f a g r e a t v a r i e t y o f c a t a l y s t s . B ern h a u e r h a s u s e d p i p e r i d i n e , d im e th y la m in e , d ie th y la m in e , sodium c a r b o n a t e , p o ta s s iu m c a r b o n a te , ammonium h y d r o x id e , sodium h y d r o x id e , b a riu m h y d r o x id e , d iso d iu m p h o s p h a te , h y d r o c h lo r ic a c i d and s u l f u r i c a c i d a s p o ly m e riz in g a g e n ts . The p r o d u c ts w ere o x id iz e d w ith s i l v e r o x id e t o t h e c o r ­ re s p o n d in g a c i d s an d i d e n t i f i e d .

The o r g a n ic b a s e s p ro d u c e d

a l a r g e num ber o f a c i d s in c lu d in g d i h y d r o - o - t o l u i c a c i d , p - t o l u i c a c i d , o c t a t r i e n i c a c i d , d i c r o t o n l c a c i d , and o i l y a c id s .

The p r o d u c ts o f th e in o r g a n ic b a s e s in c lu d e d s o r b ic

a c i d , d i c r o t o n l c a c i d , and o i l y a c i d s .

H y d ro c h lo ric a c id

and s u l f u r i c a c i d p ro d u c e d o c t a t r i e n i c a c i d , d i c r o t o n l c a c i d , a c r o t o n i e a c i d t r i m e r , and o i l y a c i d s '^ * 17.

B e rn h a u e r,

K. and N eu b au er, G-., Bio chem. Z . , 2 5 1 .

173 (1 9 3 2 ). 18.

B e rn h a u e r,

K. and In g a n g , K ., I b i d . , 2 5 4 . 434 (1 9 3 2 ).

19*

B e rn h a u e r,

K. and D ro b n ic k , R . , I b i d . , 2 6 6 , 197 (1 9 3 3 )•

20.

B e rn h a u e r an d In g a n g , K ., Ann. . 5 2 5 . 43 (1 9 3 6 ). I t h a s b ee n fo u n d t h a t t r i e t h y l a m i n e p ro d u c e s p o ly m e rs

vi

from c r o t o n a ld e h y d e s i m i l a r t o th o s e o f a c e ta ld e h y d e u n d e r s im ila r c o n d itio n s ♦

The p o ly m e rs h a d s i m i l a r p h y s i c a l and

ch e m ic a l p r o p e r t i e s and th e re d u c e d p r o d u c t was a l s o a c l e a r am ber r e s i n .

Re f lu x i n g t r i e t h y l a m i n e and c r o t o n ald e h y d e f o r

t h r e e d ay s p ro d u c e d c o m p lete p o ly m e r iz a tio n o f t h e c r o t on­ a ld e h y d e .

The p o ly m e rs w ere re d u c e d and n - o c t a n o l was

i d e n t i f i e d a s one o f t h e p r o d u c ts . E x p e rim e n ta l C o n d e n s a tio n o f a c e ta ld e h y d e w ith a c e t a l d o l .

The conden­

s a t i o n s w ere a l l p e rfo rm e d u n d e r an h y d ro u s c o n d i t i o n s . R e a g e n ts w ere d r i e d and d i s t i l l e d b e f o r e u s e .

To a s o l u t i o n

o f 88 g . o f a c e t a l d o l and 200 m l. o f c h lo ro fo rm was added a s o l u t i o n c o n ta in in g 44 g . o f a c e ta ld e h y d e , 10 g . o f t r i ­ e th y la m in e , and 500 m l. o f c h lo ro fo rm .

The a d d i t i o n was

c a r r i e d o u t o v e r a n e i g h t - h o u r p e r io d a t 50°C. w ith h ig h ­ sp eed s t i r r i n g .

The a c e ta ld e h y d e , t r i e t h y l a m i n e , and a c e t ­

a l d o l w ere rem oved a t re d u c e d p r e s s u r e s .

The n o n - v o l a t i l e

m a t e r i a l was d i s t i l l e d w ith d e c o m p o s itio n y i e l d i n g 44 g . o f p r o d u c t.

F r a c t i o n a l d i s t i l l a t i o n y i e l d e d 21 g . o f

v in y lc r o to n a ld e h y d e an d 5 6 » o f s o r b ic a ld e h y d e . The se m ic a rb a z o n e s were p r e p a r e d and r e c r y s t a l l z e d t o a c o n s ta n t m e ltin g p o i n t ; se m ic a rb a z o n e o f s o r b i c a ld e h y d e , m .p. = 205 ° 0 « » se m ic a rb a z o n e o f

- v in y lc r o t o n a l d e h y d e ,

m .p. - 1 9 6 °G. P o ly m e r ! z a tio n o f a c e t a ld e h y d e .

A ll t h e e x p e rim e n ts w ere

p e rfo rm e d by a d d in g t h e a c e ta ld e h y d e and t h e c a t a l y s t t o

v il

O ar l u s t u b e s , f l u s h i n g w e ll w ith n i t r o g e n , and f i n a l l y s e a lin g .

The t u b e s w ere m a in ta in e d a t te m p e r a tu r e s ra n g in g

from 9 0 - l6 0 GC*

The a l k y l a m in e s , t r i e t h y l a m i n e , t r i m e t h y 1 -

am in e, d ie th y la m in e , t r i - n - p r o p y la m in e , and tr ia m y la m ine w ere u se d a s c a t a l y s t s .

I t h a s b e e n fo u n d t h a t t h e m ost s a t i s ­

f a c t o r y p o ly m ers a r e p ro d u c e d by h e a t i n g a t 110-120°G . f o r n i n e t y - s i x h o u r s w ith 5 % by volum e o f c a t a l y s t .

F ilm -fo rm in g

t e s t s y i e l d e d t a c t - f r e e f ilm s o f a d e s i r a b l e n a t u r e i n l e s s th a n f i v e h o u r s e x c e p t f o r t h e p o ly m er p ro d u c e d by t r i a m y l am ine.

The l a t t e r p o ly m er r e q u i r e d s i x t e e n h o u rs f o r d r y in g

and r e s u l t e d i n a n u n d e s ir a b le f ilm . M o le c u la r w eig h t d e te r m in a tio n s by means o f t h e cam phorm e ltin g - p o in t d e p r e s s i o n m ethod y ie ld e d d e te r m in a tio n s a ro u n d 350 i n a l l e a s e s .

C a t a l y t i c r e d u c ti o n o f t h e p o ly m e rs w ith

Raney n i c k e l i n h ig h p r e s s u r e equipm ent y ie ld e d c l e a r am ber re s in s . The P o ly m e r iz a tio n o f C ro to n a ld e h y d e .

C ro to n a ld e h y d e , p u r i f i e d

by d i s t i l l i n g u n d e r n i t r o g e n , was p o ly m e riz e d i n a s i m i l a r m anner i n s e a l e d t u b e s .

P olym ers w ere o b ta in e d w ith s i m i l a r

p h y s ic a l and c h e m ic a l p r o p e r t i e s t o th o s e p ro d u c e d by a c e t ­ a ld e h y d e u n d e r s i m i l a r c o n d i tio n s .

The p o ly m ers a l s o w ere

fo u n d t o p o s s e s s d e s i r a b l e f ilm -fo rm in g p r o p e r t i e s .

R educ­

t i o n o f t h e p o ly m e rs y i e l d e d a r e s i n s i m i l a r t o t h a t o f th e re d u c e d a c e ta ld e h y d e p o ly m er. C ro to n a ld e h y d e was a l s o p o ly m e riz e d by r e f l u x i n g w ith 5% (by volum e ) t r i e t h y l a m i n e .

I n s e v e n ty -tw o h o u r s t h e

c r o t o n a ld e h y d e i s c o m p le te ly p o ly m e riz e d .

C a ta ly tic re d u c tio n

v iii

o f t h e p ro d u c t fo llo w e d by f r a c t i o n a t i o n y i e l d e d a f r a c t i o n i d e n tif ie d as n -o c ta n o l.

The f r a c t i o n w a s o b ta in e d a t

7 6 -7 7 °C I./lO mm. an d form ed a 3 *5 - d i n i t r o b e n z o a t e , m .p. 6l° C .

A lo w e r b o i l i n g f r a c t i o n 7 3 -7 4 ° C ./lO mm. c o u ld n o t

be i d e n t i f i e d . A cknow ledgm ent.

No lo w e r b o i l i n g m a t e r i a l was o b ta in e d . The a u th o r s a r e in d e b te d t o S h aw in ig an

P r o d u c ts C o r p o r a tio n , who f in a n c e d t h i s work th ro u g h t h e P u rd u e R e s e a rc h F o u n d a tio n . Summary A c e ta ld e h y d e was co n d en sed w ith a c e t a l d o l by means o f trie th y la m in e .

The c o n d e n s a tio n y i e l d i n g t h e b r a n c h -c h a in e d

p ro d u c t was fo u n d t o p re d o m in a te . A c e ta ld e h y d e was p o ly m e riz e d by means o f tr im e th y 1 am in e, t r i e t h y l a m i n e , d ie th y la m in e , t r ip r o p y l a m i n e , and t r i am ylam ine.

E x c ep t f o r t h e p o ly m er p ro d u ced by tr ia m y la m in e ,

th e p o ly m ers w ere fo u n d t o h av e d e s i r a b l e film -fo rm in g p ro p e rtie s . C ro to n a ld e h y d e was p o ly m e riz e d by means o f t r i e t h y l ­ am ine t o y i e l d p o ly m ers s i m i l a r t o th o s e p ro d u c e d from a c e t ­ a ld e h y d e u n d e r s i m i l a r c o n d iti o n s .

CONDENSATION PRODUCTS OF ACETALDEHYDE AND DERIVATIVES

INTRODUCTION T h is w ork was c a r r i e d o u t w ith t h e p u rp o s e o f d e te r m in ­ in g t h e p o s s i b i l i t i e s o f p ro d u c in g p o ly v in y l a lc o h o l ty p e o f p o ly m e rs fro m a c e ta ld e h y d e o r c o n d e n s a tio n p r o d u c ts o f a c e ta ld e h y d e .

I n r e c e n t y e a r s p o ly v in y l a lc o h o l h a s become

an im p o r ta n t p r o d u c t o f t h e c h e m ic a l i n d u s t r y w ith a n e v e r i n c r e a s i n g num ber o f a p p l i c a t i o n s b e in g fo u n d .

One o f t h e

c h i e f f a c t o r s i n i t s e v e r e x p an d in g m ark et i s t h e c o s t o f p r o d u c tio n .

Thus a c h e a p e r m ethod o f p r o d u c tio n would g r e a t ­

l y expand t h e a l r e a d y s i z e a b l e m a rk e t. The m ethod o f p r e p a r a t i o n b e in g u s e d a t p r e s e n t i s th ro u g h t h e h y d r o l y s i s o f p o ly v in y l a c e t a t e .

O b v io u s ly ,

t h i s i s q u i t e a c o s t l y p r o c e s s , s in c e a c o n s id e r a b le p o r t i o n o f t h e s t a r t i n g m a t e r i a l i s d e s ti n e d t o bd a b y - p ro d u c t i n t h e fo rm o f a c e t i c a c i d . M a rv e l, i n a s e r i e s o f e n d -g ro u p s t u d i e s h a s a r r i v e d a t t h e f o llo w in g s t r u c t u r e : HO*(OH2 *GHOH)n *OH2 *GHO. S e m ic a rb a z o n e s , and p h e n y lh y d ra z o n e s o f some p o ly v in y l a lc o h o l sam p le s a r e d e s c r ib e d a s w e ll a s a b s o r p t i o n s p e c t r a w hich a l s o v e r i f y t h e a ld e h y d e t e r m i n a l g ro u p ( 1 0 6 ) .

The

m o le c u la r w e ig h t i s , o f c o u r s e , d e p e n d e n t upon t h e v i n y l a c e ta te u sed in th e h y d r o ly s is .

A d d itio n a l e v id e n c e p r e -

2

s e n te d by M arvel I s t h e a p p a r e n t a l d o l c o n d e n s a tio n and r e ­ v e r s a l o f c o n d e n s a tio n i n a l k a l i s o lu tio n *

A c e ta ld e h y d e h a s

b e e n o b s e rv e d t o a p p e a r u n d e r c e r t a i n c o n d iti o n s w h ile u n d e r o t h e r s a p p a r e n t l y t h e r e i s c o n d e n s a tio n w hich p ro d u c e s h i g h e r m o le c u la r w e ig h t p o ly m e rs .

H y d ro c h lo ric a c i d h a s a l s o b e e n

d e s c r ib e d a s a c o n d e n sin g a g e n t i n s e v e r a l p a t e n t s ( 8 6 , 1 6 3 )• C o l l i e r , I n a r e c e n t r e v ie w , d e s c r ib e s t h e c h e m is tr y , f i l m fo rm in g p r o p e r t i e s , p h y s i o l o g i c a l p r o p e r t i e s , an d t h e s o l u ­ b i l i t y p r o p e r t i e s o f p o ly v in y l a lc o h o l ( 2 8 ) . On t h e b a s i s o f M a r v e l's p ro p o se d s t r u c t u r e , one w ould o b t a i n a s i m i l a r p o ly m er by t h e l i n e a r a l d o l c o n d e n s a tio n o f a c e ta ld e h y d e t o h ig h p o ly m e rs .

A p o ly m er o f t h i s ty p e c o u ld

be r e p r e s e n t e d a s : CHy (CH0H.CH2 )n *CH0. T h is p o ly m er w ould d i f f e r from t h e p ro p o se d s t r u c t u r e o f p o ly v in y l a l c o h o l i n t h a t one o f t h e t e r m i n a l g r o u p s , i n ­ s te a d o f b e in g a h y d ro x y l g r o u p , would be r e p la c e d by a h y d ro g e n . The a l d o l c o n d e n s a tio n o f a c e ta ld e h y d e t o a c e t a l d o l h a s b e e n known f o r many y e a r s .

H ow ever, t h e c o n d e n s a tio n t o

h i g h e r p o ly m e rs i s l i t t l e u n d e r s to o d .

The l i t e r a t u r e co n -

» t a i n s many d e s c r i p t i o n s o f p o ly m ers p ro d u c e d by t h e p o ly m er­ i z a t i o n o f a c e ta ld e h y d e o r a l d o l by v a r io u s c a t a l y s t s .

The

m ethod o f p ro d u c in g t h e s e p o ly m ers w i l l b e d is c u s s e d l a t e r . The s t r u c t u r e s o f t h e s e p o ly m ers a r e g e n e r a l l y unknown, b u t m ost l i k e l y c o n s i s t o f com plex m o le c u le s p ro d u c e d by

3

r e p e a t e d c o n d e n s a tio n o f ac e t a ld e h y d e i n s u c h a m anner a s t o p ro d u c e h i g h l y b ra n c h e d p o ly m ers •

C o n s id e ra b le c r o t o n i z a -

t i o n h a s alw a y s b e e n o b s e rv e d i n fo rm in g t h e s e h i g h e r p o ly ­ m ers.

By c r o t o n i z a t i o n i s m eant t h e d e h y d r a tio n o f t h e

h y d ro x y l compound form ed by t h e a l d o l c o n d e n s a tio n .

T h is

r e a c tio n w ill be re p e a te d ly r e f e r r e d to as c r o to n iz a tio n . The lo w e r p o ly e n e a ld e h y d e s h av e b e e n i s o l a t e d , b u t n e i t h e r o f t h e tw o c o n d e n s a tio n p r o d u c ts o f a c e t a l d o l and a c e t a l d e ­ h y d e , 3 , 5 - d ih y d r o x y - l- h e x a n a l o r 2 - ( 1 -h y d ro x y e th a n e ) - 3 h y d r o x y - l- b u tr y a ld e h y d e , h av e b e e n i s o l a t e d .

T h is f a c t i s

n o t s u r p r i s i n g , s in c e th e y w ould b e e x p e c te d t o be h ig h b o i l i n g compounds w hich w ould b e r e a d i l y d e h y d r a te d .

A

seco n d p o s s i b i l i t y c o u ld b e t h a t n e i t h e r d ih y d ro x y h e x a n a l r e a l l y i s fo rm ed a s su ch b u t t h a t d e h y d r a tio n o f a c e t a l d o l p r e c e d e s c o n d e n s a tio n . T h is l a t t e r p o s s i b i l i t y h a s some s u p p o rt i n t h e c a s e o f is o b u ty r a ld é h y d e .

I s o b u ty r a ld é h y d e r e a d i l y form s a n a l d o l

w hich i s q u i t e s t a b l e t o d e h y d r a tio n .

H ow ever, t h e conden­

s a t i o n o f 1 s o b u ty ra ld e h y d e w ith i t s a l d o l t o fo rm a l i n e a r trim e r h as n ev e r been re p o rte d .

S a u n d e rs i s o l a t e d a t r i m e r

b u t e v id e n c e p o i n t s t o t h e f o llo w in g c y c l i c s t r u c t u r e ( 1 2 9 ) i /Ox (CH^gHC-CH CH-GH(CH3 )2

‘ ' " V s ' v S , OH I s o b u t y r a l d o l h a s some i n t e r e s t i n g p r o p e r t i e s .

I t is

s t a b l e u n d e r 1 2 0 °C . an d i f h e a te d t o a h i g h e r te m p e r a tu r e slo w ly decom poses t o is o b u ty r a ld é h y d e .

S t a r t i n g w ith p u r e

4

i s o b u t y r a l d o l i p u r e I s o b u ty r a ld é h y d e , o r an y m ix tu re o f th e s e # a n e q u i l i b r i u m m ix tu re o f 66 2 / 3% i s o b u t y r a l d o l and 33 1/3% is o b u ty r a ld é h y d e i s alw ay s e s t a b l i s h e d (1 5 4 ).

The tim e

n e c e s s a r y f o r t h e e q u i l i b r iu m t o o c c u r i s d e p e n d e n t on t h e te m p e r a tu r e and t h e c a t a l y s t p r e s e n t , b e in g g r e a t l y a c c e l e r ­ a te d a t h i g h e r te m p e r a tu r e s and i n t h e p r e s e n c e o f s tr o n g b ases.

T h is i s o b s e rv e d w ith p u re is o b u ty r a ld é h y d e and i t s

a l d o l i n r e a g e n t b o t t l e s when a llo w e d t o s e t f o r lo n g p e r io d s o f tim e .

On d i s t i l l a t i o n o f a n e q u il ib r iu m m ix tu re a t r e ­

duced p r e s s u r e s a t r i m e r i s o b ta in e d , t h e s t r u c t u r e o f w hich i s p ro p o se d a b o v e .

S a u n d e rs o b ta in e d t h i s t r i m e r i n h i s

a tte m p ts t o co n d en se is o b u ty r a ld é h y d e and 1 s o b u ty r a l d o l i n a l i n e a r m anner.

T h is a ld e h y d e and a l d o l a r e u n iq u e i n t h a t

an a l d o l c o n d e n s a tio n c o u ld y i e l d o n ly one p r o d u c t.

H ow ever,

a l l a tte m p ts t o c a u s e t h i s c o n d e n s a tio n y i e l d e d t h e c y c l i c s tru c tu re .

Even i n n e u t r a l s o l u t i o n t h i s r e a c t i o n t o form

t h e c y c l i c s t r u c t u r e was o b s e rv e d t o go t o c o m p le tio n i n tw o w eeks.

Raman s p e c t r a w ere u s e d t o d e te rm in e s t r u c t u r e and

f o llo w t h e r e a c t i o n ( 1 2 9 ) . I n t h e c a s e o f a c e ta ld e h y d e and a c e t a l d o l , a s i m i l a r t r i m e r p r o b a b ly e x i s t s .

I n s u p p o rt i s t h e f r e q u e n t l y ob­

s e rv e d e x p e r im e n ta l r e s u l t t h a t t h e l i m i t o f t h e c o n v e r s io n o f a c e ta ld e h y d e t o a c e t a l d o l seems t o a p p ro a c h a c o n v e r s io n o f t w o - t h i r d s o f t h e a c e ta ld e h y d e .

The c y c l i c t r i m e r would

be e x p e c te d t o b e q u i t e s t a b l e i n b a s i c o r n e u t r a l s o l u t i o n and w ould p r e v e n t t h e a l d o l i s a t i o n o f a t h i r d o f t h e a c e t a l ­ d eh y d e.

The f i r s t p a r t o f t h e p r o j e c t d e s c r ib e d h e r e d e a l s

5

w ith t h i s p a r t i c u l a r problem * Q u ite e s s e n t i a l t o any work on t h e a l d o l c o n d e n s a tio n i s a n u n d e r s ta n d in g o f t h e m echanism o f t h e r e a c t i o n ( 1 6 4 ). C a rb o n y ls , i n g e n e r a l , a r e o b s e rv e d t o b e q u i t e a m p h o te ric i n n a tu re *

T h at i s , th e y f u n c t i o n a s a n a c i d o r a b a s e d e ­

p e n d in g on t h e i r e n v iro n m e n t.

On t r e a t i n g a c e ta ld e h y d e w ith

a s tr o n g b a s e , su c h a s h y d ro x id e o r e th o x ld e I o n s , t h e a ld e h y d e f u n c t io n s a s a n a c id *

I f t h e a c e ta ld e h y d e i s

t r e a t e d w ith alum inum c h l o r i d e t h e a ld e h y d e f u n c t io n s a s a base.

The f o llo w in g e q u a tio n s d e m o n s tr a te t h e s e ex am p le s: CHyCHO + OH ___ ^ CHyCHO + A1C15

CH2 -CH0

___ >

CHyC(H)e>-.AlCl3

I n t h e f i r s t exam ple t h e m echanism o f rem oving t h e p r o to n i s n o t known.

H ow ever, i t i s l i k e l y t h a t a c o o r d in a tio n

com plex i s f i r s t fo rm ed w hich th e n d i s s o c i a t e s .

The o v e r ­

a l l e f f e c t i s t h e rem o v al o f t h e p r o to n from a c e ta ld e h y d e y i e l d i n g t h e e n o l a t e io n .

T h is e n o l a te io n h a s t h e f o llo w ­

in g re s o n a n c e fo rm s: CH2 -C (H ):< r

CHj* C (H )-O 'A l(O E t

(2 )

C H y C (H ).O * A l(0 E t ) 3 + CHy CHO ___ »

CHy CH2 - 0 - AL(OEt ) 5 + + oh 5 » o :o

(3 )

— *■ CH3 *GH2 *0 + C H yC :0

> GH3 «GH2 *0(0)*G*CH 3

Kord h a s I n tr o d u c e d t h e u s e o f t h e f o llo w in g com plex a lk o x id e i Kfe [ a i ( 0 R)4] 2 (1 1 6 ,1 1 7 ) . T h is a lk o x ld e p ro d u c e s t h e g l y c o l e s t e r from a c e ta ld e h y d e , GH^• GHOH• GH2 • GH2 • O2 • 0 • OH3 .

T h is p ro d u c t c a n b e e x p la in e d by

f i r s t assu m in g a n a l d o l c o n d e n s a tio n p r o b a b ly c a ta ly z e d by t h e i o n , A l(O R)^ , f o llo w e d by a T isc h e n k o p o s s i b l y t h e i o n , Mg++ The seco n d p o r t i o n i z a t i o n o f a c e ta ld e h y d e

re a c tio n

in v o lv in g

o r H3 A1 ( 0 R)^T o f t h i s work d e a l s w ith t h e

a ld o l-

u n d e r a w ide ra n g e o f c o n d i t i o n s .

The

r e a c t i o n was c a r r i e d o u t o v e r a te m p e r a tu r e ra n g e o f - 25 ° t o 16000.

B a s ic c a t a l y s t s ra n g in g i n s t r e n g t h from p o ta s s iu m

7

a lk o x ld e t o t e r t i a r y am ines w ere u s e d t o d e te r m in e t h e i r r e s p e c t i v e e f f e c t i v e n e s s i n p ro m o tin g t h e a l d o l 1 z a t i o n o f ac e t a ld e h y d e . A n o th e r p o s s i b l e s o l u t i o n t o t h i s p ro b le m i s d e a l t w ith i n p a r t t h r e e .

The e x te n s iv e p o ly m e r iz a tio n o f c r o to n ­

a ld e h y d e i s e x p e c te d t o y i e l d lo n g p o ly e n e a ld e h y d e s a s e v id e n c e d by t h e i s o l a t i o n o f some o f t h e lo w e r members (1 1 , 1 2 , 1 3 , 1 4 ) .

H y d r a tio n o f t h e s e p o ly e n e a ld e h y d e s w ould

y i e l d p o l y v in y l a l c o h o l ty p e p o ly m e rs.

8

PART I THE CONDENSATION OF ACETALDEHYDE WITH ACETALDOL INTRODUCTION The p r e p a r a t i o n o f a l d o l from a c e ta ld e h y d e i s d e s c r ib e d i n a tre m e n d o u s num ber o f p a t e n t s .

A g r e a t v a r ie ty o f b a s ic

c a t a l y s t s a r e u s e d u n d e r a w ide ra n g e o f c o n d i t i o n s .

S il-

b e r r a d d e s c r i b e s t h e a d d i t i o n o f a c e ta ld e h y d e t o a b a riu m h y d ro x id e s lu d g e (139) w h ile E a r le u s e s c a lc iu m h y d ro x id e a s t h e c o n d e n sin g a g e n t (40 ) .

MSatheson, i n a n o th e r p a t e n t ,

d e s c r i b e s t h e u s e o f a l c o h o l i c p o ta s s iu m h y d ro x id e belo w 10°C. (1 0 7 )•

A lk a lin e and a l k a l i n e - e a r t h m e ta ls , a l l o y s

t h e r e o f , amalgams t h e r e o f , and compounds t h e r e o f , su ch a s a l c o h o l a t e s , h y d r o x id e s , c a r b i d e s , o x id e s , and c y a n id e s , a r e c o v e re d i n a num ber o f o t h e r p a t e n t s ( 3 0 , 31» 59, 6 0 , 6 1 , 6 2 , 6 3 , 7 5 )•

H ow ever, o f t h e c a t a l y s t s , t h e m ost w id e ly

u s e d to d a y i s t h e a l k a l i c a ta ly z e d r e a c t i o n .

V a rio u s m o d if­

i c a t i o n s , su c h a s r e a c t i o n te m p e r a tu r e , a l k a l i c o n c e n t r a t i o n , an d s o lv e n t a r e d e s c r ib e d i n a number o f p a t e n t s ( 4 1 , 4 8 , 4 9 , 5 0 , 7 4 , 7 9 , 8 1 , 1 1 1 , 1 1 4 ).

DuPont u s e s s o lv e n ts i n w hich

t h e a c e ta ld e h y d e i s s o lu b le and a l d o l s e p a r a t e s o u t ( 3 6 ) . G a s o lin e h a s b e e n u se d i n t h i s m anner ( 7 4 ) . The c o n c e n t r a t i o n o f th e c a t a l y s t u se d i s q u i t e v a r i a b l e , b u t ro u g h ly v a r i e s i n v e r s e l y w ith t h e s t r e n g t h o f i t s b a s i c p ro p e rtie s .

I n t h e e a s e o f a l k a l i , s o l u t i o n s o f aro u n d \%

a re g e n e ra lly used. A r e a c t i o n tim e o f 8 t o 10 h o u rs i s r e q u i r e d f o r co n -

9

v e r s i o n o f 5 0 -6 0 $ .

Of c o u r s e , h i g h e r te m p e r a tu r e s w i l l r e ­

q u ir e l e s s ti m e , b u t p ro d u c e more c r o t o n i z a t i o n .

T e m p e ra tu re s

a r e g e n e r a l l y m a in ta in e d b etw een 5-10°C . t o a v o id c r o t o n i z a ­ tio n . N e u tra liz a tio n o f th e b ase i s e s s e n tia l b e fo re d i s t i l l a ­ tio n o f th e a ld o l.

H y d r o c h lo r ic , p h o s p h o r ic , an d a c e t i c

a c i d a r e m ost g e n e r a l l y u s e d ( 8 1 , 1 0 7 , 1 3 9 )•

The f i n a l pH

s h o u ld be j u s t on t h e a c i d s id e o f n e u t r a l . D i s t i l l a t i o n o f t h e v o l a t i l e p r o d u c t s , a c e ta ld e h y d e , w a te r and c ro to n a ld e h y d e m ust be c a r r i e d o u t a t re d u c e d p r e s ­ su re .

A c e ta ld o l i s q u i t e s u s c e p t i b l e t o c r o t o n i z a t i o n above

8 0 ° C ., t h u s t h e p o t i s u s u a l l y m a in ta in e d below t h i s te m p e r­ a tu re .

A c e ta ld o l i s u s u a l l y d i s t i l l e d a t one t o t h r e e

m illim e te rs p r e s s u re . F r e s h ly d i s t i l l e d a c e t a l d o l i s o n ly s l i g h t l y v is c o u s b u t h a s b e e n o b s e rv e d t o i n c r e a s e i t s v i s c o s i t y c o n s id e r a b ly on s ta n d i n g .

Owen, by means o f c r y o s c o p ic d e te r m in a tio n s ,

showed t h a t f r e s h l y d i s t i l l e d a c e t a l d o l d im e riz e s c o m p le te ly w i t h i n s e v e r a l h o u rs ( 1 2 1 ).

H o ri h a s p ro p o se d t h a t t h e

d im e r, p a r a l d o l , h a s t h e f o llo w in g s t r u c t u r e (77)$ CHOH-O-CHMe

GH‘ Me«OGHOH S p a th an d L o ren z h a v e done e x te n s iv e work on t h e c o n s t i t u t i o n o f a l d o l and th e y m a in ta in i t e x i s t s i n t h e f o llo w in g t h r e e form s :

(l)

m onomeric fo rm , (2 )

a t h i c k o i l t o w hich t h e

10

monomer c o n v e r t s , and ( 3 ) p a r a l d o l w ith th e f o llo w in g s t r u c t u r e (143)

GH3 *0H0H«0H2 *( O'GHOH S au n d ers an d M urray to o k Raman s p e c t r a o f f r e s h l y d i s t i l l e d a c e t a l d o l , p r o p i o n a l d o l , and b u t y r a l d o l .

In th e case o f

a c e t a l d o l and p r o p i o n a l d o l , no c a rb o n y l g ro u p was fo u n d t o e x is t.

B u ty r a ld o l e x h i b i t e d t h e n o rm al c a rb o n y l s p e c tru m

( 1 2 8 ).

On t h e b a s i s o f t h e above w ork, i t seems r a t h e r s a f e

t o assum e t h a t a c e t a l d o l ca n n o t b e t r e a t e d a s d e s ig n a te d by i t s s im p le fo rm u la . DISCUSSION I n t h e o r d in a r y a l k a l i c a ta ly z e d c o n d e n s a tio n o f a c e ta ld e h y d e w ith a c e t a l d o l , a s e v id e n c e d by t h e d e h y d ra te d p r o d u c t s , t h e c o n d e n s a tio n c a n b e e f f e c t e d so a s t o o b t a i n two p r o d u c ts w hich a r e i l l u s t r a t e d below : (1 )

O H y O H O + CH3 « G H ( 0 H ) » C H 2 .G H 0

____ »

o h 3 » g h (o h )« o h 2 .o h (o h )« g h 2 -gho (2)

OHyCHO

+ C H ^-G H fO H )

•OHg'CHO

____ >

G H y OH ( OH ) • GH ( GHOH • GH^ ) • GHO

(3)

0H3 *CH(O H )-OHg-O H (O H )«OHg»GHO

___ >

O H y C H : O H « O H : C H 'O H O

S o r b ic a ld e h y d e

11

(4 )

OH^ • OH ( OH ) • CH ( OHOH. CH^ ) • OHO

___ ^

OH3 «O H :G (C H :O H 2 )*OHO 2 - v ln .y lc r o t onaldehyd©

T hese u n s a t u r a t e d a ld e h y d e s a r e u s u a l l y n o t I s o l a t e d a s s u c h , b u t a s t h e h y d ro g e n a te d p r o d u c t s , n - h e x a n o l an d 2 - e t h y l - l b u ta n o l.

The c o n d e n s a tio n , a s I l l u s t r a t e d I n e q u a tio n ( 2 ) ,

I s g r e a t l y fa v o re d I n t h e a l k a l i c a ta l y z e d r e a c t i o n .

Thus

on c o n tin u e d c o n d e n s a tio n o f ac e t a ld e h y d e w ith t h e p o ly m e r, one o b t a i n s p r a c t i c a l l y none o f t h e h ig h e r p o ly m er I n t h e l i n e a r fo rm .

I t I s a t t h i s c r i t i c a l p o in t th a t t h i s p a r t o f

t h e work was aim ed.

I f c o n d itio n s w ere a d j u s t e d so a s t o

o b t a i n l a r g e am ounts o f a l i n e a r t r i m e r o f t h e ac e t a ld e h y d e a c e t a l d o l c o n d e n s a tio n , i t w ould b e e x p e c te d t h a t h ig h e r l i n e a r p o ly m e rs o f t h e p o ly v in y l a lc o h o l ty p e o f polym er c o u ld be o b ta in e d .

The o b s e rv e d c o n d e n s a tio n o f a c e t a l d e -

hyde w ith p o l y v in y l a l c o h o l i s i n d i c a t i v e o f t h e f a c t t h a t h i g h e r p o ly m e rs do co n d en se i n a l i n e a r m anner and t h a t p o s s i b l y t h e r e i s a c r i t i c a l p o i n t i n m o le c u la r w e ig h t above w hich t h e d e s i r e d ty p e o f c o n d e n s a tio n i s e f f e c t e d w ith a lk a li. I n t h e c o n d e n s a tio n o f ac e t a ld e h y d e w ith a c e t a l d o l , t h e r e f o r e , t h e a ld e h y d e g ro u p o f t h e a c e ta ld e h y d e and t h e ^ -h y d ro g e n o f t h e a c e t a l d o l a r e in v o lv e d i n th e m ain r e a c t i o n . As t o t h e r e l a t i v e a c i d i t y o f th e expect th e

^ - h y d ro g e n s , one would

^ -h y d ro g e n o f a c e t a l d o l t o b e more a c i d i c on t h e

b a s i s o f b e in g

X - to b o th a c a rb o n y l and a h y d ro x y g ro u p .

12

T h is i s p a r t i a l l y o f f s e t , h o w e v e r, by s t a t i s t i c s , s in c e a c e ta ld e h y d e h a s t h r e e tw o .

%-h y d ro g e n s w h ile a c e t a l d o l h a s b u t

As t o s t e r i c c o n s i d e r a t i o n s , t h e c a r b o n y l g ro u p o f

a c e ta ld e h y d e o b v io u s ly i s more a v a i l a b l e f o r c o n d e n s a tio n . T h u s, on t h e b a s i s o f t h e above t h e o r e t i c a l c o n s i d e r a t i o n s , t h e m ain c o u r s e o f t h e r e a c t i o n c a n be p r e d i c t e d . R e c a l li n g t h e m echanism o f t h e a l d o l c o n d e n s a tio n d i s ­ c u s se d p r e v i o u s l y , i t would b e e x p e c te d t h a t i n t h e b a s e p r o to n , c o o r d i n a t i o n s , s t e r i c e f f e c t s c o u ld change t h e c o u rs e o f th e r e a c tio n .

I n t h e u s e o f a l k a l i , one would e x p e c t no

n o t i c e a b l e s t e r i c e f f e c t i n rem oving a p r o to n from a c e t a ld e h y d e o r a c e t a l d o l b e c a u s e o f th e r e l a t i v e l y s m a ll s i z e o f t h e b a s i c g ro u p .

I n t h i s f i r s t p a r t o f th e work t r i ­

e t h y l am ine was s e l e c t e d a s r e p r e s e n t i n g a b a s e o f s u f f i c i e n t b a s c i t y t o prom ote t h e a c e ta ld e h y d e - a c e t a l d o l c o n d e n s a tio n , b u t o f s u f f i c i e n t s i z e t o i n v e r t t h e n o rm a l r e l a t i v e a c i d i t i e s of t h e i r re s p e c tiv e

"^-hydrogens.

S in c e th e e n o l f o rm a tio n

i s t h e f i r s t s te p i n t h e p ro p o se d m echanism , t h e w hole c o u rs e o f t h e c o n d e n s a tio n s h o u ld b e a b le t o be c o n t r o l l e d h e r e . T h is ty p e o f r e v e r s a l o f a c i d i t y by t h e u s e o f t h e s t e r i c e f f e c t o f t h e b a s e h a s b e e n d e m o n s tra te d by Brown ( 2 3 ,2 4 ) . EXPERIMENTAL A l l t h e e x p e rim e n ts d e s c r ib e d b elo w w ere r u n u n d e r a n ­ h y d ro u s c o n d i t i o n s . b e fo re u se .

A ll r e a g e n t s w ere d r i e d and d i s t i l l e d

A n i t r o g e n a tm o s p h e re , d r i e d by p a s s in g th ro u g h

a tu b e o f m agnesium p e r c h l o r a t e , was alw ay s u s e d .

A ll g l a s s

13

eq u ip m en t was d r i e d by fla m in g and f lu s h i n g tw ic e w ith d ry n itro g e n .

W ater i s t o be a v o id e d t o p r e v e n t h y d ro x id e io n

c a t a l y s i s o f t h e c o n d e n s a tio n . R e a c tio n s w ere p e rfo rm e d i n M orton f l a s k s f i t t e d w ith a h ig h - s p e e d M orton s t i r r e r (1 1 2 , 1 1 3 )•

The a d v a n ta g e s o f

h ig h - s p e e d s t i r r i n g a r e f u l l y d is c u s s e d i n t h e r e f e r e n c e s . C h lo ro fo rm was f i r s t u s e d a s a s o lv e n t f o r t h e r e a c t i o n . I t was d r i e d f o r f o r t y - e i g h t h o u r s o v e r D r i e r l t e and t h e f r a c t i o n a t 6 l° C . c o l l e c t e d .

The t r i e t h y la m in e was d r i e d f o r

tw e n ty - f o u r h o u rs o v e r p o ta s s iu m h y d ro x id e p e l l e t s and d i s ­ t i l l e d w ith t h e f r a c t i o n a t 89«5°C . b e in g c o l l e c t e d .

A c e t­

a l d o l was d r i e d , o v e r D r i e r l t e , f o r tw e n ty - f o u r h o u r s and d i s t i l l e d a t 54~55°C. a t 6 mm. t i l l e d ju s t b e fo re u se .

The a c e t a l d o l was alw ay s d i s ­

A cet a ld e h y d e was found t o be s a t i s ­

f a c t o r y and was u s e d d i r e c t from t h e r e a g e n t b o t t l e . P h y s i c a l c o n s ta n ts o f r e a g e n t s : C h lo ro fo rm

b .p .

6l ° C . ,

n 20°

* ! • 44-59

T r ie th y la m in e

b .p .

8 9 .5 ° C .,

n 2Q0

s 1 .3 9 8 2

A c e ta ld o l

b .p .

54—5 5 ° C ./ 6 mm.

I n a p r e l im i n a r y r u n , t o a s o l u t i o n o f 88 g . (1 m ole) o f a c e t a l d o l and 200 m l. o f c h lo ro fo rm was added a s o l u t i o n o f 44 g .

(1 m ole) o f a c e ta ld e h y d e , 10 g .

e th y la m in e , and 500 m l. o f c h lo ro fo rm .

( 0 .1 0 m ole) o f t r i ­ The a d d i t i o n was made

o v e r a n e i g h t h o u r p e r i o d w ith h ig h - s p e e d s t i r r i n g and th e s o l u t i o n m a in ta in e d a t r e f l u x (a p p ro x . 6 5 ° C .).

T hese con­

d i t i o n s a r e co m p arab le t o c o n d itio n s u s e d by Langeribeck i n u s in g s e c o n d a ry amino a c i d s t o c a t a l y z e t h e a l d o l conden-

u

s a t io n (9 3 ).

H ow ever, w it h i n a n h o u r , t h e r e a c t i o n m ix tu re

h a d become a d a r k b ro w n , i n d i c a t i n g c o n s id e r a b le c r o t o n i z a tio n . The r u n was r e p e a t e d i n a s i m i l a r m anner a t 5 0 °0 .

The

r e a c t i o n m ix tu re t u r n e d t o a v e r y l i g h t y e llo w a f t e r t h e e ig h t h o u r a d d itio n .

The t r i e t h y l a m i n e , c h lo r o fo r m , a c e t ­

a ld e h y d e an d a c e t a l d o l w ere rem oved a t re d u c e d p r e s s u r e s . The re m a in in g m a t e r i a l was d i s t i l l e d w ith d e c o m p o s itio n a t 5 mm.

A t o t a l o f 4 4 g . o f m a t e r i a l was c o l l e c t e d a t 4 4 -5 8 ° 0 .

w ith t h e p o t ra n g in g from 90-135°C . On f r a c t i o n a t i n g t h e above p r o d u c t , t h e f o llo w in g f r a c ­ t i o n s were c o l l e c t e d :

6 g . b elo w 1 0 0 ° 0 ., 21 g . a t 1 4 2 -1 4 6 ° C .,

5 S* fro m 1 7 2 -1 7 6 ° G ., and 3 6» a t 1 9 6 -2 1 0 °0 .

S e m icarb azo n es

were p r e p a r e d o f t h e f r a c t i o n s 1 4 2 -1 4 6 °0 . and 1 7 2 - 1 7 6 ° 0 ., r e s p e c t i v e l y , a s d e s c r i b e d by S h r in e r and F uson*.

B oth

d e r i v a t i v e s w ere r e c r y s t a l l z e d from a 50 $ e t h a n o l- w a te r s o l u t i o n u n t i l a c o n s ta n t m e ltin g p o in t was o b ta in e d .

The

f o llo w in g r e s u l t s w ere o b ta in e d : R e p o rte d ( l)

*

F r a c t i o n 142-6°G ,

2. - v i n y l c r o to n a ld e h y d e b .p . l4 l° C . (1 62)

S em ica rb az o n e m .p. 196 °C.

no d e r i v a t i v e r e p o r t e d

S h r in e r and F u so n , 11I d e n t i f i c a t i o n o f O rg a n ic Compounds1'.

15

R e p o rte d (2 )

F r a c tio n 172- 6°

s o r b i c a ld e h y d e

Semi c a r b a zone m .p. 205 °C .

b . p . 1 7 3 -4 ° C .* s e m ic a rb a z o n e m .p. 2 0 5 °C .*

On t h e b a s i s o f t h e above e v id e n c e t h e f r a c t i o n s a r e i d e n t i ­ fie d as

1 - v i n y l c r o to n a ld e h y d e an d s o r b i c a ld e h y d e .

A s i m i l a r r e a c t i o n was r u n a t 4 5 °0 .

U sing 93 g . o f

a c e t a l d o l and 4 6 .5 g* o f a c e ta ld e h y d e , a t o t a l o f 60 g . o f n o n - v o l a t i l e m a t e r i a l was r e c o v e r e d .

Of t h e n o n - v o l a t i l e

m a t e r i a l 40 g . was a c e t a l d o l w h ile t h e re m a in d e r was i d e n t i ­ f i e d by t h e d e h y d r a tio n p r o d u c t s .

Ten gram s o f s o r b i c a l d e ­

hyde was o b ta in e d w h ile 10 g . o f b la c k r e s i d u e re m a in . C arbon t e t r a c h l o r i d e and n - p r o p y l c h l o r i d e w ere u s e d a s s o lv e n t s i n t h i s c o n d e n s a tio n y i e l d i n g s u b s t a n t i a l l y t h e same r e s u l t s .

T hese s o lv e n t s were d r i e d o v e r D r i e r l t e f o r

tw e n ty - f o u r h o u rs and d i s t i l l e d .

The f o llo w in g p h y s ic a l

c o n s ta n ts w ere o b ta in e d : C arbon t e t r a c h l o r i d e , b . p . 7 6 ° G ., n 2o n - p r o p y l c h l o r i d e , b . p . 4 7 ° C ., n2o

1*4629

1*3882

A r u n was made u s in g a b a s i c io n -e x c h a n g e r e s i n , known a s ,fDowex 50rt, a s t h e c a t a l y s t f o r t h e c o n d e n s a tio n .

The

r e s i n was p r e p a r e d f o r u s e by a c t i v a t i n g w ith 5% sodium h y d ro x id e s o l u t i o n , w ashing w e ll w ith d i s t i l l e d w a te r , and d r y in g a t 110°C. f o r tw e n ty - f o u r h o u r s .

Tw elve gram s o f th e

r e s i n was su sp e n d e d i n 108 g . o f a c e t a l d o l . *

F i f t y - f o u r gram s

H e llb r o n , “D ic tio n a r y o f O rg an ic Compounds", V o l. I l l , p . 633*

16

o f a c e ta ld e h y d e was added o v e r a tw e lv e h o u r p e r io d w ith h ig h - s p e e d s t i r r i n g and t h e te m p e r a tu r e m a in ta in e d a t 25°G. A t o t a l o f 120 g . o f a c e t a l d o l was d i s t i l l e d from t h e r e a c t i o n m ix tu re w ith no a p p r e c i a b le am ounts o f h i g h e r p r o d u c ts form ed. A p p a re n tly t h e b a s i c Io n -e x c h a n g e r e s i n d o e s n o t p r o ­ duce a p p r e c i a b l e a c e t a l d o l - a c e t a l d e h y d e c o n d e n s a tio n u n d e r t h e c o n d itio n s d e s c r i b e d , b u t a p p r e c i a b l e c o n d e n s a tio n o f a c e ta ld e h y d e t o a c e t a l d o l i s o b s e rv e d .

The a c t u a l amount

I s d i f f i c u l t t o e s ti m a t e b e c a u s e o f th e h ig h o r d e r o f th e r e v e r s i b i l it y o f th e re a c tio n .

D epending on t h e p r e s s u r e

u se d and r a t e o f d i s t i l l a t i o n , q u i t e a p p r e c ia b le am ounts o f a c e t a l d o l a r e alw ay s l o s t i n d i s t i l l a t i o n .

The l o s s i s , o f

c o u r s e , r e a l i z e d i n t h e form o f a c e ta ld e h y d e .

T h is same

r e v e r s i b i l i t y i s p r o b a b ly e x p e r ie n c e d i n d e a li n g w ith t h e h i g h e r r e a c t i o n p r o d u c ts .

F o r t h i s r e a s o n , i n a l l t h e above

r e a c t i o n s , t h e a c t u a l c o n v e r s io n t o h ig h c o n d e n s a tio n p r o ­ d u c ts i s p r o b a b ly h i g h e r th a n o b s e rv e d .

T h is r e v e r s i b i l i t y

h a s b e e n o b s e rv e d i n t h e c a s e o f a c e t a l d o l e v en a f t e r r e p e a t e d d is tilla tio n .

E i t h e r t h e b a s e i n th e g l a s s equ ip m en t may

be s u f f i c i e n t t o c a t a l y z e t h e r e v e r s e a l d o l i z a t i o n o r no c a ta ly s t i s re q u ire d . I t i s a p p a r e n t t h a t th e u s e o f t r i e t h y l a m i n e d id n o t c a t a l y z e p re d o m in a n t fo rm a tio n o f 3 , 5 - d ih y d ro x y - 1 - h e x a n a l . S in c e t h i s i s t h e c r i t i c a l p o in t i n fo rm in g p o ly v in y l a l c o h o l ty p e p o ly m e rs , i t i s p r e d i c t e d t h a t t r i e t h y l a m i n e , l i k e a l k a l i , c a n n o t c a t a l y z e t h e p o ly m e r iz a tio n o f a c e ta ld e h y d e t o p o ly v in y l a l c o h o l - ty p e p o ly m e rs .

As d e te rm in e d u n d e r th e

17

above c o n d i t i o n s , t h e c o n d e n s a tio n o f a c e ta ld e h y d e w ith a c e t a l d o l y i e l d s a b o u t f o u r m o le c u le s o f t h e b r a n c h ^ c h a in e d p r o d u c t t o one o f t h e s t r a i g h t - c h a i n e d v a r i e t y .

T h ese f i g ­

u r e s a r e n o t s t r i c t l y t r u e , s in c e t h e r e l a t i v e r e a c t i v i t y o f t h e tw o c o n d e n s a tio n p r o d u c ts may be v e ry d i f f e r e n t . The p r o d u c t w ith t h e h i g h e r r a t e o f r e a c t i v i t y w ould a p p e a r I n s m a lle r r e l a t i v e am ounts t h a n i s r e a l l y i n d i c a t i v e o f t h e r a t e o f f o r m a tio n .

T h is c r i t i c i s m i s r a t h e r l i m i t e d h e re o

b e c a u s e o f t h e s m a ll am ounts o f c o n d e n s a tio n p r o d u c ts form ed w hich a r e h i g h e r t h a n t h e t r i m e r o f a c e ta ld e h y d e . No r e l a t i v e f i g u r e s a r e a v a i l a b l e f o r t h e a l k a l i c a t a ly z e d c o n d e n s a tio n .

Thus no c o n c lu s io n s can b e draw n on t h e

c o m p a ra tiv e e f f e c t o f t h e u s e o f t r i e t h y l a m i n e i n c a t a l y z i n g th e a l d o l c o n d e n s a tio n o f a c e ta ld e h y d e w ith a c e t a l d o l .

How­

e v e r , t r i e t h y l a m i n e w i l l c a t a l y z e t h e c o n d e n s a tio n o f a c e t ­ a ld e h y d e w ith a c e t a l d o l .

18

PART I I THE POLYMERIZATION OF ACETALDEHYDE INTRODUCTION C a ta ly s ts .

A g r e a t v a r i e t y o f c o n d itio n s h a v e b e e n u s e d i n

t h e p o ly m e r i z a ti o n o f a c e ta ld e h y d e .

The p r e p a r a t i o n s o f

a c e t a l d o l m ost commonly u s e d a r e d is c u s s e d i n t h e p r e v io u s p a rt.

H ow ever, i n a d d i t i o n t o t h e c a t a l y s t s c o v e re d t h e r e ,

many o t h e r s h a v e b e e n s tu d i e d i n t h e p r o d u c tio n o f a c e t a l d o l and h i g h e r p o ly m e rs o f a c e ta ld e h y d e u n d e r a w ide ra n g e o f c o n d itio n s .

A b r i e f re v ie w o f t h e c a t a l y s t s an d p h y s ic a l

a g e n ts u s e d t o p ro m o te th e a l d o l c o n d e n s a tio n w i l l b e d i s ­ cu ssed . F i s c h e r r e p o r t s am ino a c id s a s g r e a t l y a c c e l e r a t i n g t h e a l d o l c o n d e n s a tio n o f a c e ta ld e h y d e t o a c e t a l d o l and h i g h e r p o ly m e rs .

The a c t i o n was fo u n d m ost p ro n o u n ced b etw e e n a

pH 7 -8 i n a h i g h l y b u f f e r e d p h o s p h a te s o l u t i o n ( 5 2 ) .

L angen-

b e ck fo u n d t h a t o f a lo n g s e r i e s o f am ino a c id s w hich c a t a l y z e t h e a l d o l c o n d e n s a tio n , t h e s e c o n d a ry am ino a c id s a r c o s in e was t h e m ost e f f e c t i v e (9 3 )•

B u d n its k a y a h a s a l s o found

many am ino a c i d s and egg alb u m in c a p a b le o f c a t a l y z i n g th e a l d o l c o n d e n s a tio n ( 2 3 )• B i l l i g , i n a German p a t e n t , c la im s t h e u s e o f am ines i n p ro d u c in g a c e t a l d o l , p o l y a e e t a l d o l s , and r e s i n s . u s e s f o r m a lin t o a c c e l e r a t e t h e r e a c t i o n ( 1 6 ) .

He

The a tte m p te d

r e p r o d u c t i o n o f t h i s p a t e n t i s c o v e re d i n th e e x p e r im e n ta l s e c t i o n u n d e r t h i s p a r t o f t h e w ork.

19

A r e c e n t B r i t i s h p a t e n t c o v e rs t h e u s e o f n e u t r a l ammonium s a l t s a s t h e c o n d e n sin g a g e n ts w ith exam ples ammon­ ium c h l o r i d e , ammonium o x a l a t e , and an ammonium s u l f a t e c i t e d . The r a t i o o f 0 . 2 - 0 . 5 6 « o f t h e s a l t i s u s e d f o r e a c h gram m ole o f a c e ta ld e h y d e ( 2 1 ) . M atui h a s d e s c r ib e d th e u s e o f p i p e r i d i n e i n p o ly m e riz ­ in g a c e ta ld e h y d e .

He h y d ro g e n a te d t h e p o ly m ers and a tte m p te d

an a n a l y s i s t h e r e o f ( 1 1 0 ) ^

L angehbeck s i m i l a r l y d e s c r i b e s

t h e u s e o f p i p e r i d i n e i n p o ly m e riz in g a c e ta ld e h y d e a s w e ll a s fo rm ald eh y d e and c r o t o n a ld e h y d e .

I t was p o in te d o u t t h a t

p i p e r i d i n e m ust be ad d ed c o n tin u o u s ly , a s i t i s consumed i n t h e r e a c t i o n ( 9 4 ). A p a t e n t i s s u e d t o F ra n k e rib u rg e r c o v e rs th e u s e o f p rim a ry o r s e c o n d a ry a l i p h a t i c am ines and h e t e r o c y c l i c s e c o n d a ry am in es a s c a t a l y s t s t o p o ly m e riz e a c e ta ld e h y d e , a c e t a l d o l , o r c r o t o n ald eh y d e t o r e s i n s (55)*

A ls o , I . G-.

F a r v e n i n d u s t r ie h a s a p a t e n t on t h e u se o f se c o n d a ry am ines t o p o ly m e riz e a c e t a l d o l t o r e s i n s .

The p r o d u c ts w ere su b ­

j e c t e d t o th e r m a l tr e a t m e n ts o f 160-190°C , ( 5 1 ). I t i s r e p o r t e d t h a t te m p e r a tu r e s o f 2 8 0 -5 2 0 °0 . and p r e s s u r e s o f 5 ,0 0 0 -6 ,0 0 0 atm o sp h e re s p o ly m e riz e a c e t a l d e ­ h y d e r a p i d l y t o a re d -b ro w n mass ( 9 6 ) .

A C an a d ia n p a t e n t

d e s c r i b e s t h e u s e o f a c i d t o p o ly m e riz e a c e t a l d o l t o p o ly a l d o l s ( 7 0 ). Adkins d e s c r ib e s th e r e a c t io n o f a ceta ld eh y d e o v er v a r io u s o x id e c a t a l y s t s c o n s is t in g o f chromium a lo n e or w ith co p p er, cadmium, s i l v e r , c o b a lt , z in c , magnesium, ir o n .

20

m anganese n i c k l e ; c o p p e r w ith vanadium o r molybdenum and c o p p e r w ith b a riu m and chromium.

The r e a c t i o n s w ere c a r r i e d

o u t i n e th a n o l a t 360 ° 0 . an d u n d e r 20 0 a tm o sp h e re s o f p r e s ­ su re .

I n a l l c a s e s b u t a n o l , c a p r o ic a c i d , and h i g h e r a l ­

c o h o ls and a c i d s w ere o b ta in e d ( 1 , 2 ) . S a b a t i e r r e p o r t s t h a t a c e ta ld e h y d e p a s s e d o v e r u ran iu m o x id e , th o riu m o x id e , o r t i t a n i u m o x id e i s c o n v e r te d i n p a r t t o c ro to n a ld e h y d e and r e d u c t i o n o f t h e p o ly m e riz e d p r o d u c ts y i e l d s b u t a n o l , h e x a n o l, some h ig h e r a l c o h o l s , and p h e n o lic compounds ( 1 2 7 ) . The e f f e c t o f u l t r a s o n i c waves on t h e a l d o l c o n d e n s a tio n was s t u d i e d .

Demann fo u n d t h a t th e y d i d i n c r e a s e t h e r a t e

o f r e a c t i o n b u t d i d n o t change th e d i r e c t i o n ( 33) •

B e r th e -

l o t fo u n d t h a t t h e p o ly m e r iz a tio n o f a c e ta ld e h y d e i s f a v o re d by u l t r a v i o l e t r a y s and t h a t r a y s o f s h o r t an d medium wave l e n g t h f a v o r r e s i n f o rm a tio n .

W ater was found t o b e a n

in h ib ito r to th e a c tio n o f u ltr a v io le t (15) . The S t r u c t u r e o f A c e ta ld e h y d e .

The s t r u c t u r e o f a c e t a l d e ­

hyde h a s b e e n s t u d i e d by s e v e r a l i n v e s t i g a t i o n s .

S te v e n so n

h a s i n v e s t i g a t e d t h e s t r u c t u r e o f a c e ta ld e h y d e by e l e c t r o n d i f f r a c t i o n te c h n iq u e s . t o b e 1 .5 0 - 0 .0 2 & c o v a le n t b o n d .

The c a rb o n -c a rb o n d i s t a n c e was found

a s com pared t o 1 .5 4 A

f o r t h e n o rm al

T h is i s ta k e n t o i n d i c a t e a p a r t i a l d o u b le

bond c h a r a c t e r d u e i n p a r t t o t h e re s o n a n c e form s 0H3 -G (H ):O

CH2 :C (H ).Ô H+

CH2 î0H0 H-

21

and i n p a r t t o t h e fo rm a l c h a rg e e f f e c t r e s u l t i n g fro m re s o n a n c e 0H ^*0(H )«0 No a tte m p t i s made t o e s tim a te t h e r e l a t i v e c o n t r i b u t i o n o f e a c h fo rm ( 1 4 8 ). Evans h a s s tu d i e d t h e e f f e c t o f a l k a l i on t h e f o r m a tio n o f v i n y l a lc o h o l d e r i v a t i v e s .

I t i s shown t h a t v i n y l m ercury

o x y c h lo r id e i s o b ta in e d i n a l k a l i n e s o lu t i o n s o f a c e t a l d e ­ hyde I n p r o p o r t i o n t o t h e a l k a l i n i t y o f t h e s o l u t i o n .

It

i s p o s t u l a t e d t h a t a l k a l i c a ta ly z e s th e fo rm a tio n o f v i n y l a lc o h o l ( 4 2 ) .

Shou, by u s e o f a b s o r p t io n s p e c t r a , h a s

e s tim a te d t h a t a c e ta ld e h y d e , i n t h e p r e s e n c e o f 0.01N . sodium h y d r o x id e , i s l / 335 t h i n t h e e n o l fo rm , i n t h e p u re s t a t e one p a r t i n f i f t e e n th o u s a n d i s i n t h e e n o l fo rm , and i n t h e p r e s e n c e o f 0.01N h y d r o c h lo r ic a c id l / l 0 4 5 t h i s i n t h e form o f t h e e n o l (133» 1 3 4 ). A num ber o f o t h e r m is c e lla n e o u s p a p e r s h av e a p p e a re d w hich a r e o f i n t e r e s t .

Van d e r W erf h a s d is c u s s e d t h e a p ­

p l i c a t i o n o f t h e e l e c t r o n i c th e o r y t o th e a l d o l c o n d e n s a tio n (1 5 5 ). A r e v ie w a r t i c l e on a c e ta ld e h y d e by Bady h a s a p p e a re d (7 ).

B o d en d o rf h a s p o s t u l a t e d a m echanism f o r th e a l d o l

c o n d e n s a tio n (1 8 ) and H nizda h a s made u s e o f t h e e l e c t r o d e t o s tu d y t h e p o ly m e r iz a tio n o f a c e ta ld e h y d e ( 7 6 ).

A v o lu ­

m e tr ic d e t e r m in a ti o n o f c a rb o n y l compounds in c lu d in g a c e t ­ a ld e h y d e , a c e t a l d o l , and c r o to n a ld e h y d e i s r e p o r t e d by H ahnel ( 6 4 ).

22

P o ly m ers o f A c e ta ld e h y d e .

A num ber o f w o rk ers h a v e r e p o r t e d

lo w -te n rp e ra tu re p o ly m e r iz a tio n o f a c e ta ld e h y d e .

T ra v e rs,

I n 1 9 3 6 , r e p o r t e d t h e p r e p a r a t i o n o f a lo w - te m p e ra tu r e p o ly m er (1 5 1 ).

L e t o r t o b s e rv e d t h a t d i s t i l l i n g a c e t a l d e ­

hyde I n a tu b e c o o le d w ith l i q u i d a i r I n a n e v a c u a te d s y ste m p ro d u c e s a p o ly m e r. t e m p e r a tu r e s ( 9 8 ) .

The p o ly m er I s a s t i c k y s o l i d a t room No c a t a l y s t was found t o e f f e c t t h i s

p o ly m e r iz a tio n , t h u s I t became known a s a sp o n ta n e o u s p o ly ­ m e r iz a tio n (9 9 )•

L e t o r t a l s o o b s e rv e d t h e f o rm a tio n o f a

p o ly m er a t t h e c r y s t a l l z a t l o n p o in t o f t h e a c e ta ld e h y d e ( 1 0 0 ) . I n f r a r e d s p e c t r a o f t h e s e p o ly m ers I n d i c a t e t h e f o llo w in g s t r u c t u r e ( 1 4 9 ): Me

Me

* 0 - 0 - 0

H

Me

,w 0 w Q — 0 ^

H

H

R e c e n tly , R igby and H lnshelw ood h a v e r e p o r t e d on work on t h e low te m p e r a tu r e po ly m er o f a c e ta ld e h y d e .

The p o ly ­

m e r iz a t io n o c c u rs o n ly d u r in g c r y s t a l l z a t l o n , t h e maximum p o ly m e r iz a tio n o c c u r r in g n e a r t h e f r e e z in g p o i n t .

The

po ly m er i s p o s t u l a t e d t o be lo n g m eth y l polyoxym ethy 1 ene c h a in s w hich d e p o ly m e riz e r e a d i l y a t room te m p e r a tu r e . O rg an ic s u b s ta n c e s su ch a s a c e to n e and c h lo ro fo rm were found t o I n h i b i t t h e p o ly m e r iz a tio n i n p r o p o r tio n t o t h e i r m o lar c o n c e n t r a t i o n ( 1 2 4 ). Somewhat o f a s t a t e o f c o n f u s io n e x i s t s a s t o w h e th e r t h e r e I s one o r more t h a n one lo w -te m p e ra tu re p o ly m e rs. T h ere I s a g ree m en t on t h e u n s ta b l e m eth y l p o ly o x y m eth y len e c h a in ty p e o f s t r u c t u r e p ro d u c e d a t t h e c r y s t a l l z a t l o n p o i n t

23

o f a c e ta ld e h y d e .

H ow ever, T r a v e r s and L e t o r t h a v e r e p o r t e d

lo w - te m p e ra tu r e p o ly m e rs form ed a t h ig h e r te m p e r a tu r e s and L e t o r t 1s p o ly m er was s t a b l e a t room te m p e r a tu r e . U shakov h a s d e s c r ib e d t h e p r o d u c tio n o f s o f t t a r s by t r e a t i n g a c e ta ld e h y d e w ith v a r y in g am ounts o f 1 0 -2 0 $ sodium h y d ro x id e s o l u t i o n . d a rk e r p ro d u c ts .

H ig h e r a l k a l i c o n c e n tr a t io n s y i e l d

H e a tin g o f th e t a r s a t 1 8 0 -2 0 0 ° y i e l d e d

p r o d u c ts o f h i g h e r m e ltin g p o in t and a lo w e r s o l u b i l i t y (1 5 2 ). A B r i t i s h p a t e n t c o v e rs t h e p r o d u c tio n o f u n s a tu r a t e d a ld e h y d e s from a c e ta ld e h y d e p o ly m e riz e d by a l k a l i .

T hese

u n s a tu r a t e d a ld e h y d e s c a n b e c o n v e rte d t o w e ttin g a g e n ts on h y d r o g e n a tio n fo llo w e d by s u l f a t i o n ( 2 2 ) .

C o n n o lly i s o l a t e d

two h e x a d ie n a ls and one o c t a t r i e n a l from a po ly m er form ed by t r e a t i n g a c e ta ld e h y d e w ith a l k a l i fo llo w e d by a tr e a tm e n t w ith 0 .5 $ c a lc iu m h y d ro x id e and f i n a l l y d i s t i l l i n g

from

d i l u t e m in e ra l a c i d (2 9 )• V o y a tz a k is p o ly m e riz e d s m a ll q u a n t i t i e s o f a c e ta ld e h y d e by a llo w in g i t t o s ta n d i n c o n ta c t w ith c a lc iu m o x id e f o r a p e r io d o f e i g h t d a y s (1 5 6 ).

M atsui u s e d b a riu m h y d ro x id e i n

s tu d y in g t h e p o ly m e r iz a tio n o f a c e ta ld e h y d e (1 0 9 )• A num ber o f p a t e n t s c o v e r v a r i a t i o n s i n a l k a l i t r e a t ­ ment o f a c e ta ld e h y d e t o form r e s i n s (26 , 2 7 $ 6 5 , 7 2 , 9 5 )• V a rio u s a f t e r - t r e a t m e n t s a r e g iv e n t h e p r o d u c ts su ch a s h y d r o g e n a tio n t o p ro d u c e u s a b le p r o d u c ts (2 6 , 2 7 , 9 5 ) . Seym our i n a p a t e n t p o ly m e riz e s a ld e h y d e s by t h e u s e o f s a l t s o f s e c o n d a ry a m in e s , u s u a l l y h e t e r o c y c l i c , w ith an

24

a f t e r trea tm en t c o n s is t in g o f h y d ro g en a tio n and th e a c t io n o f c h lo r o s u lf u r ic a c id t o y i e l d compounds w ith w e t t in g , d e t e r g e n t, and e m u ls ify in g p r o p e r t ie s (135)*

A French p a te n t

d e s c r ib e s p a s s in g a c eta ld eh y d e and hydrogen over b a s ic o x id e c a t a l y s t s t o y i e l d h ig h m o lecu la r w eigh t a lc o h o ls and e s t e r s ( 3 4 ). A c e ta ld e h y d e r e s i n s a r e d is c u s s e d by Osima i n a re v ie w a r t i c l e o f a n I n d ia n p u b l i c a t i o n (1 2 0 ). DISCUSSION The u s e o f a l k y l am ines c a t a l y s t s , e s p e c i a l l y t e r t i a r y a m in e s , i n t h e p o ly m e r iz a tio n o f a c e ta ld e h y d e h a s b e e n l i t t l e s tu d i e d an d w i l l b e c o v e re d i n t h i s p a r t .

A b a s ic i o n -

exchange r e s i n known a s Dowex 50 was u se d t o prom ote th e a l d o l c o n d e n s a tio n .

The u s e o f t r i e t h y l a m i n e , t r i m e t h y l -

am in e , t r i - n - p r o p y l a m i n e , and tria m y la m in e were u s e d a s c a t a l y s t s i n fo rm in g h ig h p o ly m ers o f a c e ta ld e h y d e .

P ro p er­

t i e s and s t r u c t u r e s t u d i e s o f t h e s e p o ly m ers a r e r e p o r t e d . EXPERIMENTAL Use o f b a s ic Io n -e x c h a n g e r e s i n .

I n a s e r i e s o f e x p e r im e n ts ,

a b a s i c io n -e x c h a n g e r e s i n , Dowex 5 0 , was u se d t o p o ly m e riz e a c e ta ld e h y d e .

The io n -e x c h a n g e r e s i n was p r e p a re d f o r u s e

by a c t i v a t i n g w ith 5% sodium h y d r o x id e , w ashing th o ro u g h ly w ith d i s t i l l e d w a te r , and d ry in g f o r t w e n ty - f o u r h o u r s a t 110°C. The r e s i n was p a c k e d i n an e ig h te e n - in c h 20 mm. tu b e

25

w ith a n o u t e r t u b e , w rapped w ith a n lch ro m e h e a t i n g e le m e n t, s u p p ly in g a n a i r j a c k e t .

The a c e ta ld e h y d e was p a s s e d down

th ro u g h t h e b e d o f c a t a l y s t by e v a p o r a tio n from a f l a s k . I n a r u n i n w hich t h e colum n was m a in ta in e d a t 6 0 ° G ., 15 ml# o f a c e t a ld e h y d e was p a s s e d i n t o t h e tu b e b e f o r e t h e colum n becam e c lo g g e d w ith v is c o u s r e a c t i o n p r o d u c ts .

An

e t h e r e x t r a c t i o n y i e l d e d 10 g . o f a brown v is c o u s m a t e r i a l , a l l o f w hich was d i s t i l l e d a t re d u c e d p r e s s u r e a s a c e t a l d o l . T h is r u n was r e p e a te d a t 8 0 °0 . and 20 m l. o f a c e t a l d e ­ hyde was p a s s e d i n t o t h e colum n b e f o r e becom ing c lo g g e d .

The

e t h e r e x t r a c t c o n ta in e d 15 g . o f h ig h b o i l i n g m a t e r i a l , 12 g . o f w hich w ere i d e n t i f i e d a s a c e t a l d o l .

A p p a r e n tly , n e g l i g i b l e

am ounts o f p o ly m e rs h i g h e r th a n a c e t a l d o l a r e o b t a in a b le by means o f t h i s c a t a l y s t .

S in c e a te m p e r a tu re o f 8 0 °0 . i s t h e

p o i n t a t w hich c r o t o n i s a t i o n i s o b s e rv e d , h ig h e r te m p e r a tu r e s would o n ly p ro d u c e l a r g e am ounts o f c r o to n iz e d p r o d u c ts . Use o f b u f f e r e d s o l u t i o n from oH 6 - 8 .

A s e rie s o f b u ffe rs

were p r e p a r e d from 0 .1 M. c i t r i c a c i d and 0 .2 M. d iso d iu m p h o s p h a te a s d e s c r ib e d i n M c lv a in e ’ s t a b l e o f t h e Handbook o f C h e m istry and P h y s ic s by t h e C hem ical R ubber Co.

B u ffe rs

w ere p r e p a r e d w ith 0 .2 pH u n i t in c re m e n ts from a pH o f 6 t o a pH o f 8 .

To 25 m l. o f each b u f f e r s o l u t i o n w ere added

50 m l. o f a c e ta ld e h y d e .

The s o lu t i o n s were s e t a s id e i n

s e a le d b o t t l e s a t room te m p e r a tu r e . A f t e r a m onth, no a p p r e c ia b le p o ly m e r iz a tio n o f a c e t ­ a ld e h y d e o c c u r re d i n any o f th e b u f f e r e d s o l u t i o n s ,

A c e t­

a ld e h y d e was r e c o v e re d a lm o st q u a n t i t a t i v e l y from a l l b u f f e r

26

s o lu tio n s . Use o f n o t a s alum t e r t - b u t o x id e .

A s o l u t i o n o f p o ta s s iu m

t e r t - b u t o x id e was p r e p a r e d by d i s s o l v i n g 1 .8 5 g* o f p o ta s s iu m i n 50 m l. o f t e r t - b u t y l a l c o h o l w hich was d i s t i l l e d a t 8 2 °0 . The s o l u t i o n was fo u n d t o b e 1.0N . by t i t r a t i o n w ith s ta n d a r d ­ i z e d h y d r o c h l o r i c a c i d u s in g p h e n o lp h th a le in a s a n i n d i c a t o r . One, tw o , t h r e e , f o u r , and f i v e m i l l i l i t e r s o f th e b u to x id e s o l u t i o n w ere added t o a s e r i e s o f f i v e f l a s k s con­ t a i n i n g 50 m l. o f a c e ta ld e h y d e a t 0°C. and a llo w e d t o s ta n d f o r tw o h o u r s . F iv e m i l l i l i t e r s p ro d u c e d r e s i n f o r m a tio n , f o u r m i l l i ­ l i t e r s p ro d u c e d l e s s t h a n 10 m l. o f a c e t a l d o l , w h ile t h e r e ­ m ain d e r p ro d u c e d e s s e n t i a l l y no p o ly m e r iz a tio n .

F o u r and a

h a l f m i l l i l i t e r s was fo und t o p o ly m e riz e a c e ta ld e h y d e t o a c e t a l d o l i n b e t t e r t h a n 50% y i e l d s w ith e s s e n t i a l l y no h i g h e r c o n d e n s a tio n p r o d u c ts .

Under th e c o n d itio n s s t u d i e d ,

p o ta s s iu m t e r t - b u t o x i d e y i e l d s no p o ly a ld o ls . Use o f 5M a l k a l i a t low te m p e r a tu r e s .

To 25 m l. o f a c e t ­

a ld e h y d e a t -2 5 °C . was added 1 m l. o f 5M. a l k a l i s o l u t i o n . A w h ite p o ly m er was q u ic k ly form ed w hich was s t a b l e up t o -1 0 G0 .

At room te m p e r a tu r e , t h e polym er q u ic k ly d is a p p e a r s

and a c e ta ld e h y d e I s re c o v e re d .

T h is p olym er i s form ed a t a

te m p e r a tu r e somewhat h i g h e r th a n p r e v io u s l y r e p o r t e d . Use o f d le th v la m ln e a s r e p o r te d i n G er. P a te n t 6 5 9 .2 9 1 ( 1 6 ). B i l l i g h a s r e p o r t e d th e u s e o f d ie th y la m in e a s a c a t a l y s t i n t h e f o r m a tio n o f w a te r - s o lu b le a c e ta ld e h y d e p o ly m e rs .

Form­

a ld e h y d e was u s e d t o i n c r e a s e t h e r a t e o f th e p o l y m e r iz a tio n .

27

S e v e r a l r u n s w ere made a s d e s c r ib e d i n t h e p a t e n t e x c e p t t h a t t h e s c a l e was c u t down by o n e - t e n t h o f t h a t d e s c r i b e d . O n e - h a lf gram o f d ie th y la m in e was added t o a w e l l - s t i r r e d s o l u t i o n o f 100 g . o f a c e ta ld e h y d e and 10 g . o f 35% f o r m a lin . The p a t e n t d e s c r i b e s t h e r e a c t i o n a s q u i t e v ig o ro u s and r e ­ q u i r i n g c o o lin g t o k eep belo w 54°G.

No r i s e i n te m p e r a tu r e

was o b s e rv e d and r e f l u x i n g f o r a w hole d ay d id n o t r a i s e t h e r e f l u x te m p e r a tu r e above 2 5 °0 .

The r e a c t i o n i s r e p o r t e d t o

go t o c o m p le tio n i n a few h o u r s .

I n t h e a tte m p te d r e p r o ­

d u c t i o n s , no a p p r e c i a b l e c o n d e n s a tio n p r o d u c ts were o b s e rv e d . The brow n c o l o r a t i o n o b s e rv e d on t h e a d d i t i o n o f t h e am ine i s a r e s u l t o f S c h i f f b a s e f o rm a tio n w ith t h e a ld e h y d e s . Use o f T e r t i a r y A lk v l A m ines.

I n t h e f o llo w in g work t h e

p o ly m e r iz a tio n o f a c e ta ld e h y d e was e f f e c t e d by t e r t i a r y a l k y l am in es a t v a r io u s te m p e r a tu r e s and o v e r v a r y in g p e r io d s o f tim e .

The r e a c t i o n s w ere a l l c a r r i e d o u t i n s e a le d tu b e s

p r e p a r e d by p la c in g t h e a c e ta ld e h y d e and am ine i n O a riu s t u b e s , f l u s h i n g w e ll w ith n i t r o g e n , and f i n a l l y s e a l i n g . The e f f e c t io n o f te m p e r a tu r e on t h e n a t u r e o f t h e p r o ­ d u c ts was s t u d i e d a t 9 0 , 1 1 0 , and 1 4 0 °0 , u s in g t r i e t h y l a m i n e as th e c a ta ly s t.

T a b le I c o n ta in s a summary o f t h e r e s u l t s :

The p o ly m e rs i n a l l th e above r e a c t i o n s a r e form ed on t h e b o tto m o f t h e r e a c t i o n tu b e b e in g c o v e re d by a w a te r la y e r.

The w a te r l a y e r was rem oved and t h e m a t e r ia l su b ­

j e c t e d t o a re d u c e d p r e s s u r e o f ab o u t 1 mm.

By h e a t in g t o

a b o u t 90°G. an d s u b j e c t i n g t o low p r e s s u r e s t h r e e ti m e s , a s o l i d am orphous m a t e r i a l i s o b ta in e d .

The m a t e r i a l i s a d a r k

28

TABLE I .

EFFECT OF TEMPERATQBB OH THE TRIETHYLAMINE CATALYZED POLYMERIZATION OF ACETALDEHYDE

Time

Temper­ a tu re

P e r c e n t M o le c u la r w e ig h t C a t a ly s t * D e te rm in a tio n s * *

N a tu re o f P ro d u c t

90°

96 h r s .

5

320

o ra n g e -re d s o lid

110°

96 h r s .

1

- ——

no a p p r e c i a b le p o ly m e r ! z a tI o n

110°

96 h r s .

5

341

o ra n g e -re d s o lid

140°

96 h r s .

5

318

o ra n g e -re d s o lid

*

P e r c e n t c a t a l y s t I s e x p re s s e d by volum e.

**

The m o le c u la r w e ig h ts were d e te rm in e d b y t h e camphor m e l t i n g - p o i n t d e p r e s s io n m ethod. The ch eck s w ere w it h i n 5$.

r e d i n c o l o r i n t h e r e a c t i o n t u b e , b u t on d r y in g becom es a re d -o ra n g e .

The s o l i d was found t o have a g r a d u a l s o f te n in g

p o in t aro u n d 7 5 - 9 0 °C . T hese p o ly m ers a r e a l l v e ry i n s o l u b l e i n w a te r b u t s o lu b le i n a c e to n e , d io x a n and e t h a n o l , w ith a low o r d e r o f s o l u b i l i t y i n e t h e r and p e tro le u m e t h e r .

A ttem p ts t o r e -

c r y s t a l i z e from e t h a n o l , d io x a n , a c e to n e , b e n z e n e , and e t h e r w ere a l l u n s u c c e s s f u l .

However, th e r e s i n i s r e p r e c i p i t a t e d

from d io x a n s o l u t i o n s by e t h e r .

The u s e o f p e tro le u m e t h e r

a s a p r e c i p i t a t i n g a g e n t c a u se s th e fo rm a tio n o f t a r s . The p o ly m e rs a l l a r e h ig h ly u n s a tu r a te d and add brom ine r e a d i l y a s w e ll a s d e c o l o r i z e p o ta s s iu m p e rm a n g a n a te .

A

29

p h e n y lh y d ra z o n e i s form ed r e a d i l y .

H ow ever, i t to o h a s a

s o f t e n i n g p o i n t and no m e ltin g p o i n t ev en a f t e r r e c r y s t a l iz a tio n . The m a t e r i a l o b ta in e d i n t h e 110®C. p o ly m e r iz a tio n was d i s s o l v e d i n 250 m l. o f e th a n o l and a gram o f R a n e y -n ic k e l ad d ed .

H igh p r e s s u r e h y d r o g e n a tio n a t 1300 l b s . p ro d u c e d no

a p p r e c i a b l e a b s o r p t i o n o f h y d ro g e n .

H e a tin g t o 1 1 0 °0 . was

n e c e s s a r y t o b e g in t h e h y d r o g e n a tio n . f o r 12 h o u r s .

S haking was c o n tin u e d

The R a n e y -n ic k e l was f i l t e r e d from t h e s o l u t i o n

and t h e a l c o h o l was rem oved a t re d u c e d p r e s s u r e s .

A c le a r

l i g h t - y e l l o w s o l i d r e s i n i s p ro d u c e d . The re d u c e d r e s i n m e lts a t 6 0 -6 5 °0 . and h a s t h e a p p e a r ­ an c e o f w axes.

I t i s s o lu b le i n a lc o h o l , a c e to n e , an d

d io x a n , b u t r a t h e r i n s o l u b l e i n e t h e r and p e tr o le u m e t h e r . The u n re d u c e d p o ly m er u se d h e r e h ad a m o le c u la r w eig h t o f 341 w h ile t h e re d u c e d polym er was 375* The re d u c e d p o ly m er e x h ib ite d no a d d i t i v e p r o p e r t i e s and id i i l e i t r e a c t e d w ith r e a g e n ts u s e d t o p r e p a r e a lc o h o l d e r i v ­ a t i v e s , no s o l i d d e r i v a t i v e s w ere o b ta in e d . A tte m p ts t o r e c r y s t a l i z e were u n s u c c e s s f u l i n a l c o h o l , a c e to n e , b e n z e n e , and d io x a n .

The re d u c e d p o ly m er I s r e -

p r e c i p i t a t e d i n d io x a n s o l u t i o n by e t h e r b u t form s a n o i l . P e tro le u m e t h e r a l s o p r e c i p i t a t e s an o i l from a c e to n e and d io x a n s o l u t i o n s . I n a n a tte m p t t o d e te rm in e t h e n a t u r e o f t h e p o ly m er p ro d u c e d , a p o ly m er p ro d u c e d by Vfo t r i e t h y l a m i n e a t 1 1 0 120°C . f o r s i x t y h o u rs was s u b je c te d t o f r a c t i o n a t i o n .

The

30

c a t a l y s t an d tim e o f r e a c t i o n w ere re d u c e d so t h a t lo w e r m o le c u la r w e ig h t p o ly m ers w ould he p ro d u c e d .

T h re e h u n d re d

gram s o f a c e ta ld e h y d e w ere p o ly m e riz e d a s d e s c r ib e d an d t h e p o ly m er re d u c e d a s d e s c r i b e d p r e v i o u s l y . y i e l d e d t h e f o llo w in g r e s u l t s : 1 .3 9 6 9 ; 10 g . a t 1 4 6 -1 4 7 ° C .,

A fra c tio n a tio n

5 g . a t 1 1 5 -1 1 6 ° C ., n 20 * - 1.41971 8 g . a t 1 5 2 ° C .,

ago = 1 .4 1 7 5 ; 5 g . a t 7 3 ° 0 ./2 » 5 mm., ngQ = 1 .4 5 1 3 ; 17 g . a t 1 2 5 - l4 0 ° 0 ./ 3 mm. ; 25 g . a t l4 0 -1 9 0 oc . / 3 mm.; and 30 g . a t 1 9 0 - 2 l 6 ° 0 ./ 3 mm.

I n t h e c a s e o f th e h i g h e r b o i l i n g m a te r­

i a l s , m o le c u la r w e ig h t d e te r m in a tio n s were c a r r i e d o u t w ith t h e f o llo w in g r e s u l t s :

f r a c t i o n a t 1 2 5 - l4 0 ° G ./3 mm., M.W.

= 2 3 9 » f r a c t i o n l4 0 - 1 9 0 ° C ./3 mm., M.W. s 2 8 2 , and th e f r a c ­ t i o n 1 9 0 - 2 l6 ° G ./3 mm., M.W. = 273. The f r a c t i o n a t i o n o f t h e re d u c e d p o ly m e riz e d m a t e r ia l i n d i c a t e s t h a t t h e p o ly m ers a r e p re d o m in a n tly o f th e b ra n c h c h a in e d v a r i e t y .

I n t h e e a se o f t h e h e x a n o ls p ro d u c e d , 2 -

e t h y l - 1 - b u t a n o l was p ro d u c e d i n s l i g h t l y h i g h e r am ounts th a n n - h e x a n o l.

I n t h e c a s e o f h ig h e r p r o d u c ts s m a ll am ounts o f

n - o c t a n o l w ere o b ta in e d b u t a p p a r e n tly no n -d o d e c a n o l.

How­

e v e r , t h i s i s n o t s u r p r i s i n g s in c e th e p o s s i b i l i t y o f p r o ­ d u c in g a s t r a i g h t - c h a i n e d m o lecu le i s l o s t a f t e r a s i n g l e b r a n c h - c h a in e d c o n d e n s a tio n . H ig h e r te m p e r a t u r e s , up t o 1 6 0 °G ., w ere u s e d i n t h e t r i ­ e th y la m in e p o ly m e r iz a tio n .

The p o ly m ers p ro d u c e d a t t h e s e

h i g h e r te m p e r a tu r e s a p p e a r t o h av e l e s s d e s i r a b l e p r o p e r t i e s t h a n t h o s e p ro d u c e d a t lo w e r te m p e r a tu r e s .

T e m p e ra tu re s lo w e r

31

th a n 90°G. p ro d u c e a v e r y slow p o ly m e r iz a tio n . The p o ly m e r p ro d u c e d by t r i e t h y l a m i n e a t 110° was u s e d i n a tte m p te d c o p o ly m e r iz a tio n s w ith s ty r e n e and v in y l a c e t a t e . Two gram s o f t h e p o ly m er w ere ad d ed t o ea c h o f two t u b e s , one c o n ta in in g 10 m l. o f v i n y l a c e t a t e and t h e o t h e r 10 m l. o f s ty re n e .

A c r y s t a l o f b e n z o y l p e r o x id e was added t o b o th

and t h e t u b e s s e a l e d .

B o th tu b e s a lo n g w ith c o n t r o l s o f

v i n y l a c e t a t e an d s t y r e n e , w ere s e t i n an oven a t 100°G. fo r e ig h t h o u rs.

In th e case o f v in y l a c e ta te , th e c o n tro l

p o ly m e riz e d w h ile t h e a c e ta ld e h y d e po ly m er a c t u a l l y i n h i b i t e d p o ly m er f o r m a tio n .

The s ty r e n e c o n t r o l p o ly m e riz e d a s w e ll

a s t h e one c o n ta in in g t h e a c e ta ld e h y d e p o ly m e r. was c l e a r b u t re m a in e d r e d i n c o l o r .

The p ro d u c t

I t i s q u e s tio n a b le

w h e th e r co p o ly m e r! z a t i o n o c c u r re d . P o ly m ers w ere p ro d u c e d by u s e o f t r i e t h y l a m i n e , t r i - n p ro p y la m in e , tr i - n - a m y la m in e , and d ie th y la m in e .

A te m p e r a tu r e

o f 110°G . was u s e d f o r n i n e t y - s i x h o u r s w ith r e s u l t s i n d i c a t ­ in g v e r y s i m i l a r ty p e o f p o ly m ers p ro d u c e d by a l l t h e s e am in es. The p o ly m e rs a p p e a r t o h av e d e s i r a b l e film - fo r m in g p r o ­ p e rtie s .

I n a s e r i e s o f film - fo r m in g t e s t s t h e p o ly m ers

p ro d u c e d by t rim e th y la m in e , t r i e t h y l a m i n e , d ie th y la m in e , and tr i p r o p y la m in e w ere fo u n d q u i t e d e s i r a b l e .

The f ilm s became

t a c t l e s s w i t h i n f i v e h o u r s form in g a m edium -hard f ilm .

The

f ilm o f t h e tr ia m y la m in e polym er r e q u i r e d s i x t e e n h o u r s t o become t a c t - f r e e .

The f i l m was q u i t e s o f t and u n d e s ir a b l e .

The u s e o f d r y in g c a t a l y s t s would p r o b a b ly Im prove t h e d r y in g p r o p e r t i e s o f t h e s e p o ly m e rs c o n s id e r a b ly .

32

PART I I I THE POLYMERIZATION OF GROTONALDEHYDE INTRODUCTION Sm edley i n 1912 o b s e rv e d c r o t o n a ld eh y d e t o y i e l d a y e llo w v i s c i d o i l when a llo w e d t o s ta n d f o r t h r e e d ay s i n t h e p r e s e n c e o f o n e - t e n th norm al p o ta s s iu m c a r b o n a te .

A f te r

o x id iz in g t h i s v i s c i d o i l and h y d r o g e n a tio n c o m p le te ly , n - o c t o i c a c i d was i s o l a t e d (1 4 0 ). I n 1932 B e rn h a u e r p u b lis h e d a s e r i e s o f p a p e r s on t h e p o ly m e r iz a tio n o f c r o t o n a ld e h y d e .

T h is work was done a s

p a r t o f t h e work on t h e s y n th e s i s o f t h e s id e c h a in o f V ita m in A.

The p a p e r s in c lu d e d t h e s tu d y o f p i p e r i d i n e , d im e th y l-

a m in e , d i e t h y l a m i n e , sodium c a r b o n a te , p o ta s s iu m c a r b o n a te , ammonium h y d r o x id e , sodium h y d r o x id e , b a riu m h y d r o x id e , d i ­ sodium p h o s p h a te , b a riu m o x id e , h y d ro g e n c h l o r i d e , and s u l ­ f u r i c a c i d a s p o ly m e riz in g a g e n ts .

The p r o d u c ts were e i t h e r

i d e n t i f i e d a s t h e u n s a t u r a t e d a ld e h y d e o r more g e n e r a l l y o x id iz e d w ith s i l v e r o x id e t o th e c o rre s p o n d in g a c i d .

A fte r

o x i d a t i o n w ith s i l v e r o x id e t h e p r o d u c ts i s o l a t e d from th e p o ly m e r iz a tio n s e f f e c t e d by th e o r g a n ic b a s e s a l l in c lu d e d d ih y d ro - o - to lu lc ; a c id , p -to lu ic a c id , o c ta tr ie n ic a c id , d i c r o t o n i c a c i d , an d o i l y a c i d s .

The p r o d u c ts o f t h e i n ­

o r g a n ic b a s e s in c lu d e d s o r b ic a c i d , d i c r o t o n i c a c i d , and o i l y a c i d s w h ile w ith s u l f u r i c a c id th e p r o d u c ts w ere o c t a ­ t r i e n i c a c i d , d i c r o t o n i c a c i d , a t r i m e r i c c r o t o n ic a c i d , and o i l a c id s .

The fo llo w in g e q u a tio n s i l l u s t r a t e t h e s o u rc e

33

o f t h e s e p r o d u c ts s

,0H3 OH

OHO

z

OHO

OH f

L

OHO

OH

d i c r o t o n ald eh y d e

/

OH3

H3

H

OH

OH

OH OHO

«

OHO

OH I OHO

. OHO

o c ta trie n a l

d lh y d r o - o t o l y la l d e h y d e

f H3 OH

OH-

?H3

:H

OH

&

OH

OHO

I

f

OHO

OH

OH, I 5

OHOH

V

OHO

OHO d i h y d r o - p - t o ly l a ld e h y d e T h ese c o n d e n s a tio n s w ere c a r r i e d o u t by h e a t i n g from o n e -

34

h a l f h o u r t o tw o h o u r s on a ste a m b a th ( 1 1 , 1 2 , 1 3 , 1 4 ) . Kuhn h a s shown t h a t p i p e r i d i n e d o es n o t c a t a l y z e t h e c r o t o n a ld e h y d e p o ly m e r iz a tio n u n l e s s s u n l i g h t o r a n a c i d a r e p re s e n t. re a c tio n .

The s u n l i g h t c a u s e s a d d f o r m a tio n w hich s t a r t s t h e Thus i t i s n o t p i p e r i d i n e b u t p i p e r i d i n e s a l t s

w hich c a t a l y z e s t h e r e a c t i o n ( 8 7 )• F.

S. F i s h e r by u s e o f p i p e r i d i n e a c e t a t e h a s i s o l a t e d

dode c a - p e n t a e n a l an d a f t e r o x i d a t io n t e t ra d e cahexaeno i c a c i d . O c t a t r i e n a l and d i h y d r o - o - to ly l a ld e h y d e w ere a l s o i s o l a t e d (5 4 ).

P i p e r i d i n e a c e t a t e was f a r t h e r s t u d i e d i n t h i s p o ly ­

m e r iz a tio n i n t h e p r e s e n c e o f v a r io u s s o lv e n t s ( 3 5 ) . Badoche r e p o r t e d a t r i m e r i c c r o to n a ld e h y d e i s o l a t e d from a p o ly m e r iz a tio n u s in g h y d ro g e n c h lo r id e a s th e c a t a l y s t ( 6 ) . A German p a t e n t c o v e rs t h e p r o d u c tio n o f p o ly m ers o f c r o t o n a ld e h y d e b y means o f a l k a l i o r a l k a l i n e e a r t h h y d r o x id e s w hich a r e s u i t a b l e f o r d y in g o i l s ( 1 2 3 )• I n tw o o t h e r p a t e n t s Schm idt co n d en ses c ro to n a ld e h y d e by means o f a l k a l i a l c o h o l a t e s and th e n h y d r o g e n a te s c a t a l y t l c a l l y (1 3 1 , 1 3 2 ). DISCUSSION B e rn h a u e r d e s c r i b e s t h e u s e o f a g r e a t many c a t a l y s t s f o r t h e p o ly m e r iz a tio n o f c r o t o n a ld e h y d e .

H ow ever, h e d i s ­

c a rd s t r i e t h y l a m i n e and a l l t e r t i a r y am ines a s b e in g p o o r c a ta ly s ts .

U nder h i s c o n d itio n s o f h e a tin g th e m ix tu re o f

c ro to n a ld e h y d e and c a t a l y s t o v e r a steam b a th f o r h a l f a n h o u r t o tw o h o u r s , h e o b ta in e d v e ry l i t t l e

c o n d e n s a tio n

35

p r o d u e ts u s in g t r i e t h y l a m i n e .

He c o m p le te ly a v o id e d lo n g e r

r e a c t i o n tim e s o r h ig h te m p e r a tu r e s . I n t h i s work c r o t o n a ld eh y d e was t r e a t e d s i m i l a r t o th e s e a l e d tu b e r e a c t i o n s o f a c e ta ld e h y d e .

In a d d itio n , re a c tio n s

w ere c a r r i e d o u t a t t h e r e f l u x te m p e r a tu r e o f t h e c r o to n ­ a ld e h y d e , b u t o v e r e x te n d e d p e r io d s o f tim e .

I t h as been

shown t h a t t r i e t h y l a m i n e w i l l c a t a ly z e t h e c r o t o n a ld eh y d e p o ly m e r iz a tio n b u t a t a s lo w e r r a t e u n d e r co m p arab le c o n d i­ t i o n s t h a n d ie th y la m in e and p i p e r i d i n e a c e t a t e . The p o ly m e r iz a tio n o f c r o t o n ald eh y d e i s o f i n t e r e s t i n t h i s work i n r e f e r e n c e t o t h e p r e p a r a t i o n o f p o ly e n e a l d e ­ h y d es w hich may be s u i t a b l e f o r h y d r a t io n th u s m aking them w a te r s o l u b l e .

G ro to n a ld e h y d e i t s e l f i n t h e p r e s e n c e o f

p i p e r i d i n e a c e t a t e h a s b e e n shown t o h y d r a te t o a c e t a l d o l (9 2 ).

As a m a tte r o f f a c t , t h e e q u i lib r i u m a t v a r io u s tem ­

p e r a t u r e s u s in g v a r io u s in o r g a n ic a c id s h a s b e e n d e te rm in e d (l6 o ).

The p o ly m ers a r e n o t q u i t e a n a lo g o u s , h o w ev er, i n

t h a t th e y a r e n o t s o lu b le t o any a p p r e c ia b le e x te n t i n w a te r o r weak a c i d s .

They a r e r e a d i l y s o lu b le i n c o n c e n tr a te d

s u l f u r i c w ith r e a c t i o n j u s t a s o t h e r u n s a tu r a t e d compounds. The h y d r o l y s i s o f t h e s e s u l f a t e d compounds would y i e l d p o ly ­ h y d ro x y w a t e r - s o l u b l e compounds. The p r e p a r a t i o n o f p o ly e n e a ld e h y d e s h a s p ro v e n t o be q u i t e a com plex p ro b le m .

As m en tio n ed a b o v e , B e rn h a u e r h a s

i s o l a t e d b e s id e s o c t a t r i e n a l t h e c y c l i c compounds d lh y d r o - o t o l y l a l d e h y d e and d i h y d r o - p - to ly la ld e h y d e .

D ic r o to n ic a l d e ­

h y d e h a s a l s o b e e n d e m o n s tra te d w ith some e v id e n c e p o i n t i n g

36

t o t r l e o n t r o n l c a ld e h y d e b e in g p r e s e n t a l s o . I n t h e c a s e o f in o r g a n ic a c id c a t a l y s t s , B e rn h a u e r h a s shown s o r b i c a ld e h y d e t o be p ro d u c e d i n t h e c r o to n a ld e h y d e p o ly m e r iz a tio n .

T h is i s a c l e a r d e m o n s tr a tio n o f t h e r e -

v e r s a b i l i t y o f t h e d e h y d r a tio n o f a c e t a l d o l .

In a d d itio n

i t i l l u s t r a t e s t h e r e v e r s i b i l i t y o f t h e a c e t a ld e h y d e - a c e ta l d o l c o n d e n s a tio n e v e n u n d e r h ig h a c id c o n c e n t r a t i o n s .

A lso

t h e p r e s e n c e o f t h i s com plex e q u i lib r iu m opens t h e p a th f o r a w hole h o s t o f p r o d u c ts . B e rn h a u e r h a s d e m o n s tra te d a number o f p r o d u c ts form ed i n t h e c r o t o n a ld eh y d e p o ly m e r iz a tio n b u t many more i n a l l p r o b a b ilitie s a ls o e x i s t .

F o r ex am p le, t h e c ro to n a ld e h y d e

can co n d en se w ith t h e c y c l i c compound a s f o llo w s :

ch 5

6

+ \

OH OH

OHO

/

/OH

OHO OH

OH, f!W

+

P

OH

OHO OHO

OHO

37

S in c e t h e c r o t o n a l d e h y d e - a e e ta ld o l e q u ili b r iu m and t h e a c e t a l d o l - a c e t a l d e h y d e e q u ili b r iu m a p p e a rs t o b e p r e s e n t i n th e sy ste m t h e f o llo w in g r e a c t i o n s p r o d u c ts p r o b a b ly a l s o e x is t. 0H. P . , J . Am. Chem. S o c. . 5 6 . 53 0 , Ç. A ., 8 , 1577 (1 9 1 4 ).

92.

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93>

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94.

L an g en b eck , W., P e l U. K o h le . 40 . 206 ( 1 9 4 4 ), Ç. A ., 5 9 .

52

278 (1 9 4 5 ). 95»

L a v o rs k y , 8 . , B r i t . P a t e n t 5 1 5 ,8 9 4 , (D ec. 1 8 , 1 9 3 9 ), 0 . A ., 2 5 , 6019 (1 9 4 1 ).

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10 0 .

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103.

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104.

2216 (1 9 3 7 ).

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53

G. 108.

a. ,

a , 2795 (1 9 1 5 ).

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, U .S. P a te n t 1 ,4 5 0 ,9 8 4 ( A p r il 1 0 ,

1 9 2 3 ),

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(O sa k a ),

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5380 (1 9 3 8 ). 12 3 .

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55

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57

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VITA

Thomas H. S to u d t was b o r n i n T em ple, P e n n s y lv a n ia , A p r il 6 , 1922. He r e c e i v e d t h e d e g re e o f B a c h e lo r o f S c ie n c e from A lb r ig h t C o lle g e , a t R e a d in g , P e n n s y lv a n ia , A u g u st, 1943# and t h e d e g re e o f M a ste r o f S c ie n c e from R u tg e rs U n i v e r s i t y , Hew B ru n sw ic k , Hew J e r s e y , J u l y , 1944. He i s a member o f Sigma X i, P h i Lambda U p silo n » and A m erican C h em ical S o c ie ty .