P a t e n t e d F e b .

1 5 , 1 9 4 9
2 , 4 6 1 , 8 8 2
UNITED STATES P ATENT ; O F F IC E
2 , 4 6 1 , 8 8 2
F URF URYL ALC O HO L RESIN AND P RO C ESS
or MAKING THE SAME
Ed wa rd R. Di l l e h a y , Gl e n El l y n , a n d Rob e rt D.
Sc h u e t z , C h i c a g o, 1 1 1 . , a s s i g n ors t o Th e Ri c h
a rd s on C ompa n y , Loc k l a n d , O h i o, a t c orpora
t i on of O h i o
No Dra wi n g . Appl i c a t i on Ma rc h 2 4 , 1 9 4 5 ,
Se ri a l No. 5 8 4 , 72 '
1 C l a i ms . ( C l . e c u - 9 2 . 6 )
1
O u r i n v e n t i on re l a t e s
f u ry l a l c oh ol re s i n h a v i n g c e rt a i n prope rt i e s of
t o t h e prod u c t i on of f u r- .
d e s i ra b i l i t y i n v a ri ou s a rt s , s a me b e i n g t h e re s u l t '
of a n ov e l pra c t i c e of pre pa ra t i on of t h e s a me .
It h a s b e e n qu i t e g e n e ra l l y u n d e rs t ood t h a t a c i d '
re a c t i n g s u b s t a n c e s a re t h e re qu i re d pol y me ri z i n g
a g e n t s f or t h e ma k i n g of re s i n s f rom f u rf u ry l a l
c oh ol . Th u s ph os ph ori c a c i d a n d s u l ph u ri c a c i d
a re a c c e pt e d a c t i v a t i on c a t a l y s t s , a c i d re a c t i n g
a mi n e s a n d a c i d re a c t i n g me t a l l i c s a l t s .
In t h e ory t h e s e a c t i v a t i on a g e n t s prod u c e h y
d rog e n i on s or prot on s wh i c h a re re s pon s i b l e f or
t h e c a t a l y t i c e f f e c t i n t h e t ra n s f orma t i on of f u r
f u ry ' l a l c oh ol t o u s e f u l re s i n ou s prod u c t s of h i g h
pol y me ri c or re s i n ou s c h a ra c t e r, b u t wh i c h h a v e
a s t ru c t u re re s u l t i n g f rom i n t e rmol e c u l a r c on
d e n s a t i on of a re a c t i v e ol e ?n t y pe of s t ru c t u re .
We h a v e f ou n d t h a t e l e me n t a l s u l f u r wi l l a c t
a s a c a t a l y s t i n f ormi n g a re s i n ou s s u b s t a n c e wi t h
f u rf u ry l a l c oh ol , : b u t on e wh i c h d i f f e rs i n a mou n t -
of pol y me ri z a t i on , d u e t o t h e f a c t , a s we re g a rd
i t f rom t h e poi n t of v i e w of t h e ory , t h a t t h e
re s on a n c e of t h e ri n g c ompou n d i s n ot c om
pl e t e l y b rok e n d own .
Th e s u l f u r c a u s e s pol y me ri z a t i on , g i v e s a c on
t rol l a b l e ra t e of pol y me ri z a t i on d e pe n d i n g u pon
. t h e t e mpe ra t u re a n d t i me of t re a t me n t , a n d a b ov e
a l l g i v e s a n e u t ra l re s i n ou s ma t e ri a l e n t i re l y f re e
of t h e d e f e c t s of t h e a c i d i c re s i n s h i t h e rt o re s u l t
i n g f rom t h e a c c e pt e d t y pe s of pol y me ri z a t i on .
Two- s pe c i ?c e xa mpl e s wi l l b e g i v e n , on e i n
wh i c h n o pre s s u re wa s e mpl oy e d , a n d on e i n
wh i c h . t h e re a c t i on wa s c a u s e d t o t a k e pl a c e
u n d e r pre s s u re i n a n a u t oc l a v e .
Exa mpl e 1 . - - F re s h l y d i s t i l l e d f u rf u ry l a l c oh ol
wa s e mpl oy e d d i s t i l l e d u n d e r re d u c e d pre s s u re ( 2 4
i n c h e s of v a c u u m) wi t h a b oi l i n g ra n g e of d i s
t i l l a t e c ol l e c t e d b e i n g 1 6 7 t o 1 70 C . ( 3 3 2 t o 3 3 8
F . ) a t a t mos ph e ri c pre s s u re . '
In a n Erl e n me y e r ?a s k ?t t e d wi t h a re ?u x c on
d e n s e r wa s pl a c e d 5 0 0 c c . ( 5 6 5 g r. , 5 . 3 0 mol e s ) of
f u rf u ry l a l c oh ol ; C 4 Ha 0 C Hz O H. To t h i s wa s
a d d e d 5 0 0 c c . ( 2 7. 6 mol e s ) of wa t e r; H2 O . La s t l y
t h e c a t a l y s t s u l f u r wa s a d d e d , 5 g r. ( 0 . 1 5 6 mol e ) .
Th e mi xt u re wa s s t i rre d v i g orou s l y t o g e t a s g ood
a s u s pe n s i on a s pos s i b l e . Th e e n t i re mi xt u re wa s
. h e a t e d u n d e r re ?u x t e mpe ra t u re ( 2 1 2 F . ) f or a
pe ri od of e i g h t e e n h ou rs i n wh i c h t i me a d a rk
v i s c ou s ma t e ri a l h a d s e pa ra t e d ou t f rom t h e re
a c t i on me d i u m. Th e re a c t i on v e s s e l wa s a l l owe d
t o c ool . t o room t e mpe ra t u re a n d t h e t op or wa t e r
l a y e r wa s d e c a n t e d of f . Th e v i s c ou s ma t e ri a l wa s
f u rt h e r pol y me ri z e d b y h e a t i n g i n a n e l e c t ri c a l l y
h e a t e d ov e n a t 2 6 0 F . It s v i s c os i t y g ra d u a l l y i n
c re a s e d a n d a f t e r t we n t y - f ou r h ou rs i t h a d a
1 0
3 0
4 0
2 .
v e ry h e a v y v i s c ou s n a t u re , b e i n g a l mos t b l a c k i n
c ol or. 0 n a l l owi n g i t t o c ool t o room t e mpe ra t u re
i t wa s t ra n s f orme d i n t o a s of t s e mi - e l a s t i c t y pe
of ma t e ri a l .
It i s i mport a n t t o poi n t ou t h e re t h a t t h e wa t e r
u s e d a s a re a c t i on me d i u m mu s t b e n e u t ra l a n d
c on t a i n n o b a s i c t y pe s of s a l t s , a s t h e s e a c t a s
i n h i b i t ors i n t h e pol y me ri z a t i on of f u rf u ry l a l c o
h ol b y s u l f u r. Wh e n ord i n a ry t a p wa t e r i s u s e d
t h e pol y me ri z a t i on i s c ompl e t e l y a rre s t e d d u e t o
t h e s a l t s wh i c h l i t c on t a i n s . It h a s b e e n f ou n d
t h a t t h e b e s t s ol v e n t or re a c t i on me d i u m t o u s e
i s d i s t i l l e d wa t e r. Th e wa t e r h a s a t wof ol d pu r
pos e ; b e s i d e s b e i n g a me d i u m i n wh i c h t o c a rry
ou t t h e pol y me ri z a t i on i t promot e s t h e pol y me ri
z a t i on . Th i s promot i n g e f f e c t re s u l t s f rom t h e
f a c t t h a t s i n c e wa t e r i s a pol a r s ol v e n t i t c a u s e s
i n d u c e d d i pol e s t o b e s e t u p i n t h e f u rf u ry l a l oe -
h ol , wh i c h a c c e l e ra t e s t h e f orma t i on of s u l f on i u l n
c ompl e xe s , t h e a c t i v e i n t e rme d i a t e s re s u l t i n g f rom
t h e c a t a l y t i c a c t i on of t h e s u l f u r on t h e f u rf u ry l
a l c oh ol .
Exa mpl e II. As h a s b e e n s t a t e d a b ov e , t h e
pol y me ri z a t i on re a c t i on re qu i re d e i g h t e e n h ou rs
a t 2 1 2 F . In ord e r t o i n c re a s e t h e ra t e of pol y
me ri z a t i on a n d t h e re b y s h ort e n t h e t i me re qu i re d
t o prod u c e t h e re s i n , t h i s s a me re a c t i on wa s ru n
u n d e r h i g h pre s s u re s . - -
Th i s wa s a c c ompl i s h e d i n t h e f ol l owi n g ma n
n e r. Th e s a me qu a n t i t i e s of ma t e ri a l we re u s e d
a s d e s c ri b e d a b ov e a n d we re a g a i n pu t i n a n Er
l e n me y e r ?a s k . Th e v ?a s k c on t a i n i n g t h e re a c t i on
ma s s wa s t h e n pl a c e d i n a s t e a m ja c k e t e d a u t o
c l a v e a n d a s t e a m pre s s u re of s i xt y pou n d s pe r
s qu a re i n c h wa s a ppl i e d t o t h e ja c k e t . Th i s c a u s e d
s ome of t h e ma t e ri a l i n t h e re a c t i on c h a mb e r t o
v ol a t i l i z e a n d prod u c e a pre s s u re i n t h e re a c t i on
c h a mb e r of t h e a u t oc l a v e e qu a l t o t h e s t e a m
pre s s u re i n t h e a u t oc l a v e ja c k e t . In t h i s ma n
n e r t h e t e mpe ra t u re of t h e re a c t i on ma s s wa s
b rou g h t u p t o t h e t e mpe ra t u re c orre s pon d i n g t o
s i xt y pou n d s s t e a m pre s s u re . Un d e r t h i s e l e v a t e d
t e mpe ra t u re t h e pol y me ri z a t i on wh i c h re qu i re d
e i g h t e e n h ou rs wa s b rou g h t a b ou t i n on e h ou r.
As t h e pol y me ri z a t i on i s e xot h e rmi c a g re a t d e a l
of h e a t i s l i b e ra t e d b y t h e re a c t i on a n d on c e
pol y me ri z a t i on h a s s e t i n , wh i c h t a k e s a b ou t
t we n t y mi n u t e s , t h e s t e a m i n t h e ja c k e t wa s s h u t
of f a n d t h e h e a t l i b e ra t e d b y t h e re a c t i on ma i n
t a i n e d t h e t e mpe ra t u re of t h e re a c t i on ma s s .
Af t e r t h e pol y me ri z a t i on wa s c ompl e t e , c ol d
wa t e r wa s ru n t h rou g h t h e s t e a m ja c k e t t o re d u c e
t h e pre s s u re i n t h e re a c t i on c h a mb e r t o a t mos
ph e ri c pre s s u re , a f t e r wh i c h t h e a u t oc l a v e wa s
ope n e d a n d t h e re a c t i on v e s s e l re mov e d . Th e
2 , 4 8 1 , 8 8 8
8
re s u l t i n g re s i n c ou l d b e h a n d l e d i n t h e s a me ma n
n e r a s wa s d e s c ri b e d a b ov e .
Th e h i g h t e mpe ra t u re ( a rou n d 2 9 3 F . ) re s u l t s
i n a re s i n a f t e r on e h ou r wh i c h c a n f u rt h e r b e
c u re d a s i n t h e ?rs t i n s t a n c e t o a f i n a l s t a g e of
pol y me ri z a t i on . b u t a l e s s e r pe ri od of h e a t i n g i s
re qu i re d , t o c ompl e t e t h e c on d e n s a t i on a c t i on .
As c ompa re d wi t h a c i d i c f u rf u ry l ' a l c oh ol re s i n s ,
t h e re s u l t i n g prod u c t ma y b e a d mi xe d wi t h s ol
v e n t s s u c h a s a c e t on e a n d e t h y l a l c oh ol , t o pro
d u c e v a rn i s h e s f or i mpre g n a t i n g pa pe r, l i n e n or
c a n v a s f or ma k i n g t h e m i n t o a c i d re s i s t a n t l a mi
n a t e d ma t e ri a l s f or e xa mpl e , wi t h ou t t h e h y d ro
l y z i n g e f f e c t on t h e ?b e rs wh i c h t a k e s pl a c e wh e n
t h e a c i d i c re s i n s a re u s e d . Th e c on t rol 0 1 ' t h e
d e g re e of pol y me ri z a t i on i n t h e c on c l u d i n g h e a t
i n g c y c l e , pe rmi t s 0 1 ' pre pa ra t i on of a c i d prot e c
t i v e s u b s t a n c e s f or u s e i n c ompou n d s wi t h ru b b e r
a n d b i t u me n . Mol d i n g powd e rs c a n b e f orme d of
t h i s re s i n wh i c h re s u l t i n a c i d re s i s t a n t mol d e d
a rt i c l e s .
Ha v i n g t h u s d e s c ri b e d ou r i n v e n t i on , wh a t we
c l a i m a s n e w a n d . i n h e re n t i n t h e e xa mpl e s g i v e n
1 s :
1 . Th a t proc e s s f or pol y me ri z a t i on of f u rf u ry l
a l c oh ol u n d e r h e a t wh i c h e mpl oy s s u l f u r a s t h e
c a t a l y t i c a g e n t u n d e r n e u t ra l c on d i t i on s a n d i n
t h e pre s e n c e of wa t e r.
2 . Th a t proc e s s f or pol y me ri z a t i on of f u rf u ry l
a l c oh ol u n d e r h e a t wh i c h e mpl oy s s u l f u r a s t h e
c a t a l y t i c a g e n t u n d e r n e u t ra l c on d i t i on s i n t h e
pre s e n c e of wa t e r f ol l owe d b y h e a t i n g t h e re s u l t
i n g re s i n ou s prod u c t a f t e r s e pa ra t i on f rom t h e
wa t e r.
3 . Th a t proc e s s f or pol y me ri z a t i on of f u rf u ry l 3 5
a l c oh ol u n d e r h e a t wh i c h e mpl oy s s u l f u r a s t h e
c a t a l y t i c a g e n t u n d e r n e u t ra l c on d i t i on s i n t h e
2 5 v
3 0
4
pre s e n c e of d i s t i l l e d wa t e r, f ol l owe d b y h e a t i n :
t h e re s i n ou s prod u c t wh e n s e pa ra t e d f rom t h e
a qu e ou s c on s t i t u e n t .
. 4 . Th e proc e s s of c l a i m 1 i n wh i c h s u b s t a n t i a l l y
e qu a l we i g h t s of f u rf u ry l a l c oh ol a n d wa t e r a re
e mpl oy e d , a n d a rou n d on e pe rc e n t of e l e me n t a l
s u l f u r wi t h re l a t i on t o t h e a mou n t b y we i g h t of
t h e a l c oh ol .
5 . Th e proc e s s s e t f ort h i n c l a i m 1 , i n wh i c h
t h e re a c t i on t a k e s pl a c e u n d e r pre s s u re a t a t e m
pe ra t u re e qu i v a l e n t t o a rou n d s i xt y pou n d s of
s t e a m.
6 . A re s i n ou s ma t e ri a l wh i c h i s t h e re s u l t of
t h e pol y me ri z a t i on of f u rf u ry l a l c oh ol u n d e r h e a t
wi t h s u l ph u r a s t h e c a t a l y t i c a g e n t , a n d u n d e r
n e u t ra l c on d i t i on s i n t h e pre s e n c e of wa t e r.
7. A re s i n ou s ma t e ri a l wh i c h i s t h e re s u l t of
t h e pol y me ri z a t i on of f u rf u ry l a l c oh ol u n d e r h e a t
wi t h s u l ph u r a s t h e c a t a l y t i c a g e n t , a n d u n d e r
n e u t ra l c on d i t i on s i n t h e pre s e n c e of wa t e r, f ol - .
l owe d b y h e a t i n g t h e pa rt i a l l y pol y me ri z e d ma t e
ri a l a f t e r s e pa ra t i on f rom t h e wa t e r.
EDWARD R. DILLEHAY.
RO BERT D. SC HUETZ.
REF ERENC ES C ITED
Th e f ol l owi n g re f e re n c e s a re of re c ord i n t h e
?l e of t h i s pa t e n t :
UNITED STATES P ATENTS
Nu mb e r Na me Da t e
2 , 3 3 4 , 5 2 6 Al l i s on __________ . . Nov . 1 6 , 1 9 4 3
2 , 3 6 8 , 4 2 6 Root _____________ __ Ja n . 3 0 , 1 9 4 5
2 , 3 77, 9 9 5 C oe s . . . ' . __________ __ Ju n e 1 2 , 1 9 4 5
O THER REF ERENC ES .
P e n n Bri t i s h P l a s t i c s Ju l y , 1 9 4 4 , pa g e s 2 8 6 - 2 9 2 .