17 An Overview of Sugars in Urethanes
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K. C. FRISCH and J. E. KRESTA Polymer Institute, University of Detroit, 4001 W. McNichols Rd., Detroit, Mich. 48221
Polyurethanes, or urethanes as they are generally r e f e r r e d t o i n i n d u s t r y , a r e among t h e f a s t e s t g r o w i n g polymers i n t h ew o r l d . H i s t o r i c a l l y , u r e t h a n e s were f i r s t d e v e l o p e d i n t h e l a b o r a t o r i e s o f t h e I.G. F a r b e n i n d u s t r i e i n Germany i n t h e n i n e t e e n t h i r t i e s u n d e r t h e l e a d e r s h i p o f P r o f e s s o r O t t o B a y e r , a n d i t was n o t u n t i l the l a t e f i f t i e s that urethanes gained s i g n i f i c a n t i n d u s t r i a l importance i n t h e United States. I ti s the more r e m a r k a b l e t h a t u r e t h a n e s g r e w i n t h i s c o u n t r y f r o m 8 m i l l i o n p o u n d s i n 1 9 5 6 t o a b o u t 1.4 - 1.5 b i l l i o n pounds i n 1975 ( 1 - 3 ) . I n order t o understand the continued r a p i d growth and commercial acceptance of urethanes i n t h e v a r i o u s markets, one hast o r e a l i z e t h a t u r e t h a n e s a r e p r o b a b l y t h e most v e r s a t i l e c l a s s o f polymers. The p r i n c i p a l method o f m a n u f a c t u r e h a s been t h e r e a c t i o n o f h y d r o x y l - t e r m i n a t e d p o l y e t h e r s o r p o l y e s t e r s (commonly r e f e r r e d t o a s p o l y o l s ) w i t h d i or p o l y i s o c y a n a t e swhich c a n be r e p r e s e n t e d s c h e m a t i c a l l y as f o l l o w s :
HO-R-OH polyether or polyester
+
OCN-R -NCO
-~> 4-O-R-0-C-NH-R -NH-Of—
diisocyanate
Polyurethane
n
If the functionality of the hydroxyl o r isocyanate component i s i n c r e a s e d t o t h r e e o r more, b r a n c h e d o r c r o s s l i n k e d polymers a r e formed. The p r o p e r t i e s o f u r e t h a n e p o l y m e r s a r e dependent p r i m a r i l y upon molecul a r weight, degree o f c r o s s l i n k i n g , e f f e c t i v e i n t e r m o l e c u l a r f o r c e s , s t i f f n e s s o f c h a i n segments, and 238
In Sucrochemistry; Hickson, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
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17.
FRISCH
A N D KRESTA
Sugars in Urethanes
239
crystallinity. Due t o t h e many s t r u c t u r a l v a r i a t i o n s t h a t a r e p o s s i b l e , urethanes c a n be f o r m u l a t e d and p r o c e s s e d i n t o many d i v e r s i f i e d f o r m s . They i n c l u d e f l e x i b l e , s e m i r i g i d and r i g i d foams; s o f t and h a r d elastomers, c o a t i n g s , and adhesives; t h e r m o p l a s t i c and t h e r m o s e t t i n g p l a s t i c s , f i b e r s (Spandex), f i l m s ; poromerics; etc. A breakdown o f t h e p r i n c i p a l areas o f u r e t h a n e p o l y m e r s i n m i l l i o n p o u n d s i s shown i n T a b l e I (1). The p r i n c i p a l s u p p l i e r s o f u r e t h a n e raw materi a l s ( i s o c y a n a t e s and p o l y o l s ) and an e s t i m a t e o f t h e i r r e s p e c t i v e p r o d u c t i o n c a p a c i t y f o r 1976 a r e l i s t e d i n T a b l e I I (3). Sugars and sugar d e r i v a t i v e s p l a y v e r y important r o l e s i n t h e manufacture o f urethane foams, e s p e c i a l l y of r i g i d urethane foams, W h i l e p o l y o l s used f o r t h e manufacture o f f l e x i b l e foams, c o a t i n g s , a d h e s i v e s , a n d e l a s t o m e r s g e n e r a l l y have a f u n c t i o n a l i t y ( f ) o f 2 t o 3 ( 2 - 3 OH g r o u p s ) , p o l y o l s u s e d f o r t h e m a n u f a c t u r e o f r i g i d foams have u s u a l l y a f u n c t i o n a l i t y o f 4 o r g r e a t er. The most commonly u s e d p o l y o l s f o r r i g i d foams are based on sucrose (f=8), s o r b i t o l (f=6), p e n t a e r y t h r i t o l (f=4) a n d o n a l i p h a t i c o r a r o m a t i c p o l y a m i n e s (4-5), such as e t h y l e n e d i a m i n e , d i e t h y l e n e t r i a m i n e , tolylenediamine andcondensation products of aniline and f o r m a l d e h y d e . Due t o t h e i r s u p e r i o r h y d r o l y s i s r e s i s t a n c e and l o w e r c o s t s , p o l y e t h e r p o l y o l s have been employed i n p r e f e r e n c e t o p o l y e s t e r p o l y o l s a l t h o u g h many f l a m e r e t a r d a n t p o l y o l s c o n t a i n i n g p h o s p h o r u s a n d halogens possess e s t e r l i n k a g e s . The p o l y e t h e r p o l y o l s a r e p r o d u c e d b y t h e a d d i t i o n of a l k y l e n e o x i d e s , p r i m a r i l y p r o p y l e n e o x i d e , t o t h e above p o l y o l s u s i n g m o s t l y base c a t a l y s i s . The r e a c t i o n mechanism o f t h e base c a t a l y z e d a d d i t i o n o f propylene oxide t o a p o l y o l (schematically represented as ( R - C H 2 O H ) c a n b e r e p r e s e n t e d a s shown i n F i g u r e 1 ( 4 - 6 ) . The b a s i c c a t a l y s t f o r m s a n i o n s b y t h e a c t i o n o f the c a t a l y s t upon t h e p o l y o l i n i t i a t o r l e a d i n g t o t h e o p e n i n g o f o x i r a n e r i n g a n d t h e f o r m a t i o n o f a new a n ion. Propagation occurs by successive attacks o f t h e s e a n i o n s u p o n p r o p y l e n e o x i d e monomer. Chain t e r m i n a t i o n r e s u l t s by combination o f the polymer anion with a proton. T h i s r e p r e s e n t a t i o n may b e a n o v e r s i m p l i f i c a t i o n s i n c e G e e , e t a l {1) h a v e shown t h a t i o n p a i r s may b e i n v o l v e d . W h i l e t h e above mechanism shows o n l y t h e f o r m a t i o n o f t e r m i n a l s e c o n d a r y a l c o h o l g r o u p s , a c e r t a i n amount (5-10%) o f p r i m a r y a l c o h o l groups i s a l s o formed i n t h e o x i r a n e r i n g opening. The r i n g o p e n i n g p o l y m e r i z a t i o n o f 1 , 2 - e p o x i d e s h a s b e e n r e v i e w e d b y I s h i i a n d S a k a i (£) a n d P r i c e (9) and more r e c e n t l y b y L u n d s t e d a n d S c h m o l k a ( 1 0 ) .
In Sucrochemistry; Hickson, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
SUCROCHEMISTRY
240 Table I.
Overall
Urethane Demand - 1975, and Outlook - 1976 Demand * M i l l i o n s o f Pounds 1975
1976
Foams Rigid
293
353
Flexible
915
1043
1208
1396
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SUB-TOTAL Elastomers
84
94
Surface Coatings
77
82
Adhesives and S e a l a n t s
37
42!
TOTAL
1406
* On a urethane r e s i n
ILL
1614
basis
URETHANE RAW MATERIAL SUPPLIERS AND CAPACITIES 1976 Estimate ( M i l l i o n s o f Pounds)
TD I Allied BASF Wyandotte Dow Dupont Mobay Olin Rubicon Union Carbide Total
80 90 90 105 225 130 40 55 815
MDI Jefferson Mobay Rubicon Upjohn Total
35 160 60 240 495
Polyols BASF Wyandotte E. R. Carpenter Dow Jefferson Mobay Olin Union Carbide Other Total
330 120 400 100 180 210 400 250 1,990
In Sucrochemistry; Hickson, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
17.
FRISCH
Sugars in Urethanes
A N D KRESTA
R-CH OH + 1^
? R - C H c ß + BH
2
(1)
2
CH-
CH-
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R-CH-CT + CH
- C%-
CKU R-CH
241
2
2
CH,
l ,0 C H C H 0
(2)
-> R-CH 0 CH CHO^-
CH
I
e w
+ nCH
2
CH,
0
- CI^
I >R-CH 0(CH CHO) CHjCHnK 2
I
©
(3)
2
0
CH
CH
3
R-CH 0(CH CHO) CH i:H0 2
2
n
2
CH
3
9
+ BH
CH
3
3
> R-CH 0(CHjCHO) CH CHOH 2
n
+ B
(4)
2
e
Figure 1. Mechanism of base-catalyzed addition of propylene oxide to polyols
When t e r m i n a l p r i m a r y h y d r o x y l g r o u p s a r e d e s i r e d e t h y l e n e o x i d e may b e u s e d e i t h e r a s t h e s o l e a l k y l e n e o x i d e w i t h t h e p o l y o l i n i t i a t o r , o r i t may b e e m p l o y e d to "cap" o r " t i p " t h eoxypropylated p o l y o l with ethyl e n e o x i d e a s shown i n t h e f o l l o w i n g s c h e m e : CH.
CH.
CH—
CH
0
CH.
R-(CH.-CH-O) CH.CHOH > R- (CH.-CH-O) _ C H C H 0 H 2 n 2 2 n+l 2 2 However, s i n c e o x y e t h y l e n e groups a r e h y d r o p h i l i c i n n a t u r e and most a p p l i c a t i o n s r e q u i r e good w a t e r r e s i s t a n c e , p o l y e t h e r p o l y o l s f o r r i g i d u r e t h a n e foams c o n s i s t u s u a l l y o f oxypropylene adducts o f p o l y o l o r polyamine i n i t i a t o r s . The o x y p r o p y l e n e adducts e x h i b i t also better fluorocarbon (blowing agent) s o l u b i l i t y a n d i m p r o v e d i s o c y a n a t e c o m p a t i b i l i t y a s compared t o t h e corresponding p o l y o l s containing oxyethylene adducts. o
In Sucrochemistry; Hickson, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
o
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242
SUCROCHEMISTRY
Base c a t a l y s i s u s u a l l y i s p r e f e r r e d i n t h e epoxide condensation o f " n e u t r a l " p o l y o l s w i t h potassium hydroxide being the favored c a t a l y s t although other a l k a l i h y d r o x i d e s , a l k a l i a l k o x i d e s , and v a r i o u s t e r t i a r y a m i n e s may b e u s e d . T e r t i a r y amine c a t a l y s t s a r e s u g g e s t e d f o r t h e a d d i t i o n o f a l k y l e n e oxides under anhydrous c o n d i t i o n s to a l k a l i s e n s i t i v e , s o l i d p o l y o l i n i t i a t o r s such as sucrose (11, 1 2 ) . I t has been claimed t h a t t h e use of a t r i a l k y l a m i n e c a t a l y s t c o n t a i n i n g two o r t h r e e c a r b o n atoms i n t h e a l k y l g r o u p l i m i t s t h e a d d i t i o n t o o n l y one h y d r o x y p r o p y l group on each o f t h e h y d r o x y l groups o f t h e i n i t i a t o r ( 1 2 ) . When h a l o g e n a t o m s a r e p r e s e n t i n t h e e p o x i d e such as i n e p i c h l o r o h y d r i n , 3 , 3 , 3 - t r i c h l o r o p r o p y l e n e o x i d e (TCPO) o r 4 , 4 , 4 - t r i c h l o r o - l , 2 - b u t y l e n e o x i d e ( T C B O ) , o r i n . t h e i n i t i a t o r , a c i d c a t a l y s t s , e.g. boron t r i f l u o r i d e e t h e r a t e , may b e u s e d ( 1 3 - 1 8 ) . Vogt and D a v i s (16) f o u n d t h a t , i f t h e c o n c e n t r a t i o n o f c a t a l y s t / i n i t i a t o r ( p o l y o l ) complex i s decreased w i t h r e s p e c t t o TCPO i n o r d e r t o o b t a i n h i g h e r m o l e c u l a r w e i g h t p r o d u c t s , s i d e r e a c t i o n s such as c y c l i z a t i o n r e a c t i o n s become i n c r e a s i n g l y i m p o r t a n t . Boron t r i f l u o r i d e a l s o promotes d i m e r i z a t i o n o f a l k y l e n e oxides t o dioxane o r a l k y l d e r i v a t i v e s o f dioxane as d e s c r i b e d by F i f e a n d R o b e r t s (19_) . The u s e o f a c i d c a t a l y s t s , e . g . L e w i s a c i d s , p r o m o t e s f o r m a t i o n o f a g r e a t e r amount o f t e r m i n a l p r i m a r y a l c o h o l g r o u p s when c o m p a r e d t o b a s e c a t a l y s i s o f epoxides. When u n c a t a l y z e d , p r i m a r y a l c o h o l g r o u p s r e a c t w i t h i s o c y a n a t e s two o r t h r e e t i m e s a s f a s t a s secondary a l c o h o l groups, whereas t h e presence o f c a t a l y s t s , p a r t i c u l a r l y m e t a l c a t a l y s t s , cause an even g r e a t e r spread i n r e a c t i v i t y between primary and secondary a l c o h o l groups (20-22). R e c e n t l y K n o d e l (23) r e p o r t e d the use o f m i x t u r e s o f e t h y l e n e o x i d e and propylene oxide i n t h e p r e p a r a t i o n o f p o l y e t h e r p o l y o l s from s o l i d p o l y o l i n i t i a t o r s such as sucrose i n t h e presence of t r i m e t h y l - o r t r i e t h y l a m i n e as c a t a l y s t s . This p r o c e s s was s a i d t o r e d u c e t h e p r e p a r a t i o n t i m e f o r t h e p o l y e t h e r p o l y o l s b y a s much a s 67 p e r c e n t , a n d t h e v i s c o s i t y o f t h e r e s u l t i n g p o l y e t h e r p o l y o l was l o w e r than i n c o n v e n t i o n a l processes u s i n g propylene oxide as the s o l e a l k y l e n e oxide. The i s o c y a n a t e s u s e d i n r i g i d u r e t h a n e f o a m s c o n s i s t primarily of polymeric isocyanates, i . e . isocyan a t e s h a v i n g a n NCO f u n c t i o n a l i t y o f g r e a t e r t h a n 2 (most o f them = 2 . 6 - 2 . 8 ) . These a r e produced by phosgenation o f a n i l i n e - formaldehyde condensation prod u c t s a n d a r e a l s o r e f e r r e d t o a s " c r u d e " MDI. The
In Sucrochemistry; Hickson, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
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17.
FRISCH
AND
KRESTA
Sugars in Urethanes
243
commercial p r o d u c t s from the v a r i o u s i s o c y a n a t e supp l i e r s d i f f e r somewhat i n t h e i r r e a c t i v i t y w h i c h i s d u e m a i n l y t o t h e r a t i o o f t h e o- a n d p-NCO s u b s t i t u t i o n i n the molecule, the molecular weight d i s t r i b u t i o n o f t h e p o l y m e r i c f r a c t i o n s o f t h e " c r u d e " MDI a n d a l s o p a r t i a l l y due t o the d i f f e r e n t a c i d i t y i n the i s o c y a nates (24). I n a d d i t i o n t o " c r u d e " MDI, "crude" ( u n d i s t i l l e d grades) TDI ( t o l y l e n e d i i s o c y a n a t e ) , a l s o a r e employed i n the manufacture o f r i g i d foams, e s p e c i a l l y f o r u s e i n a p p l i a n c e s such as r e f r i g e r a t o r s and f r e e z ers. The m o s t i m p o r t a n t s u g a r s o r s u g a r d e r i v a t i v e s used i n the p r e p a r a t i o n o f p o l y o l s are sucrose, s o r b i t o l , a-methyl g l u c o s i d e and dextrose although other d i - and monosaccharides a n d d e r i v a t i v e s t h e r e o f have been employed i n s m a l l e r q u a n t i t i e s . Due t o t h e i r r e l a t i v e l y high f u n c t i o n a l i t y (4-8), polyols derived from these i n i t i a t o r s f i n d a p p l i c a t i o n s p r i m a r i l y i n the manufacture o f r i g i d foams. P o l y o l s based on a-methyl g l u c o s i d e were phased out o f the market a l m o s t t h r e e y e a r s a g o when CPC I n t e r n a t i o n a l , t h e m a j o r s u p p l i e r o f these p o l y o l s , d i s c o n t i n u e d t h e i r manufacture. I t i s e s t i m a t e d t h a t about one t h i r d o f t h e r i g i d u r e t h a n e foam p o l y o l s a r e b a s e d on s u c r o s e a n d s o r b i t o l {25) . Many p r o c e d u r e s h a v e b e e n d e v e l o p e d f o r t h e manuf a c t u r e o f p o l y e t h e r p o l y o l s b a s e d o n t h e a b o v e monoa n d d i s a c c h a r i d e s a s w e l l a s some o f t h e i r d e r i v a t i v e s such as the c o r r e s p o n d i n g p o l y h y d r i c a l c o h o l s (26-44). S i n c e the o x y p r o p y l a t i o n o f s o l i d i n i t i a t o r s , such as sucrose and other s o l i d p o l y h y d r i c a l c o h o l s p a r t i c u l a r l y f o r low adducts o f p r o p y l e n e o x i d e ( h i g h hydroxy1 number), leads t o the f o r m a t i o n o f p o l y e t h e r p o l y o l s h a v i n q v e r y h i g h v i s c o s i t i e s ( a s h i g h a s >1,000,000 c p s a t 2 5 C ) , a number o f c o i n i t i a t o r s a r e b e i n g u s e d t o reduce the v i s c o s i t y and t o impart other d e s i r a b l e prop e r t i e s , e.g. r e d u c e d f r i a b i l i t y , l o w e r combustion, etc. These i n c l u d e the u s e o f w a t e r (26-29), p o l y o l s such as g l y c e r o l (30-32), s o r b i t o l (33), alkanolamines s u c h a s t r i e t h a n o l a m i n e (3_i'3_5) a n d 3Tamines s u c h a s ethylenediamine (36). The p r e s e n c e o f w a t e r i n a n y s i g n i f i c a n t a m o u n t l o w e r s t h e f u n c t i o n a l i t y , i . e . , t h e number o f h y d r o x y l groups i n the r e s u l t i n g product, because the p o l y e t h e r d e r i v e d from the r e a c t i o n o f water w i t h propylene oxide h a s a f u n c t i o n a l i t y o f 2, t h u s r e d u c i n g t h e a v e r a g e f u n c t i o n a l i t y o f the oxypropylated p o l y e t h e r p o l y o l . H i g h f u n c t i o n a l i t y i s d e s i r a b l e f o r good d i m e n s i o n a l s t a b i l i t y s i n c e i t h a s b e e n shown t h a t d i m e n s i o n a l s t a b i l i t y increases with increased functionality of the Ö
In Sucrochemistry; Hickson, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
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244
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polyether. Therefore, polyols with a functionality of 3 o r g r e a t e r and amine-based p o l y o l s a r e used w i d e l y i n t h e p r e p a r a t i o n o f l o w v i s c o s i t y p o l y o l s i m p a r t i n g good d i m e n s i o n a l s t a b i l i t y t o t h e r e s u l t i n g foams. Phenol formaldehyde condensation products (hydroxy1-containing p h e n o l i c r e s i n i n t e r m e d i a t e s ) a l s o may s e r v e a s c o i n i t i a t o r s w i t h sucrose i n the manufacture o f polyether p o l y o l s f o r r i g i d u r e t h a n e f o a m s (39) . As has p r e v i o u s l y been p o i n t e d o u t , w h i l e propylene adducts o f p o l y o l i n i t i a t o r s generally are preferred, combinations o f o x y e t h y l e n e a n d o x y p r o p y l e n e a d d u c t s h a v e b e e n emp l o y e d , e s p e c i a l l y w i t h sucrose as i n i t i a t o r (23, 37, 38) . I n a d d i t i o n t o p o l y o l s d e r i v e d f r o m mono- o r d i saccharides or t h e i r d e r i v a t i v e s , polyether polyols a l s o have been p r e p a r e d from s t a r c h - d e r i v e d g l u c o s i d e s . They g e n e r a l l y a r e p r e p a r e d by t h e t r a n s g l y c o s y l a t i o n of s t a r c h w i t h p o l y o l s such as g l y c e r o l o r ethylene g l y c o l i n t h e p r e s e n c e o f an a c i d (45-49) t o y i e l d a m i x t u r e o f g l u c o s i d e s a s shown i n F i g u r e 2. The r e s u l t i n g glucoside mixture then reacts f u r t h e r with propylene oxide t o y i e l d the corresponding polyethers. D i f f e r e n t t y p e s o f p o l y o l s may b e u s e d i n t h e t r a n s g l y c o s y l a t i o n r e a c t i o n as w e l l as g l y c o l e t h e r s o f t h e g e n e r a l f o r m u l a ROCH CH OH ( 4 7 ) . In a d d i t i o n t o c o i n i t i a t i o n o f p o l y o l s , blends o f p o l y o l s a r e b e i n g employed t o i m p r o v e c e r t a i n foam 2
2
In Sucrochemistry; Hickson, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
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p r o p e r t i e s such as f r i a b i l i t y and flame r e s i s t a n c e . For instance, sucrose and sorbitol-based p o l y e t h e r p o l y o l s f r e q u e n t l y a r e b l e n d e d w i t h t e r t i a r y aminec o n t a i n i n g p o l y o l s (e.g. oxypropylene adducts o f ethylenediamine o r d i e t h y l e n e t r i a m i n e ) t o reduce t h e f r i a b i l i t y o f t h e r e s u l t i n g foams. A t t h e same t i m e , t h e p r e s e n c e o f t h e t e r t i a r y n i t r o g e n atom i n t h e amine-containing polyols hasa c a t a l y t i c effect i n promoting f a s t e r r e a c t i o n r a t e s , hence reduces t h e amount o f e x t r a n e o u s c a t a l y s t ( s ) r e q u i r e d . In addit i o n , l o w e r amounts o f f l a m e r e t a r d a n t p o l y o l s o r a d d i t i v e s a r e r e q u i r e d t o a t t a i n a c e r t a i n degree o f l o w c o m b u s t i o n i n t h e f o a m d u e t o t h e w e l l known s y n e r g i s m between n i t r o g e n a n d p h o s p h o r u s o r (and) h a l o g e n s . Blending o f sugar-based p o l y o l s w i t h flame r e t a r d a n t p o l y o l s o r a d d i t i v e s a l s o i s q u i t e common. Cert a i n flame r e t a r d a n t a d d i t i v e s such as t r i s - ( c h l o r o ethyl) phosphate a l s o serve as a v i s c o s i t y r e d u c i n g agent a l t h o u g h t h e a d d i t i o n o f g r e a t e r amounts o f t h i s p h o s p h a t e may a f f e c t a d v e r s e l y c e r t a i n f o a m p r o p e r t i e s , e.g. humid a g i n g c h a r a c t e r i s t i c s . Many f l a m e - r e t a r d a n t p o l y o l s b a s e d o n s u g a r s a n d s u g a r d e r i v a t i v e s have b e e n p r e p a r e d , most o f them c o n t a i n i n g phosphorus, halogens, o r a combination o f these elements (17, 50-59). An example o f a f l a m e retardant sugar-based p o l y o l c o n t a i n i n g o n l y halogens a r e a d d u c t s o f t r i c h l o r o b u t y l e n e o x i d e (TCBO) t o o x y e t h y l a t e d s u c r o s e (r7). T h e p r e p a r a t i o n o f t h i s TCBOc o n t a i n i n g p o l y o l i s shown s c h e m a t i c a l l y b e l o w :
R-OH + n C l C-CH -CH-CH 9
Initiator
TCBO
Catalyst
TCBO-Polyol
Other h a l o g e n - c o n t a i n i n g sugar based p o l y o l s i n c l u d e chlorinated o r brominated a l l y l glucoside polyethers w h i c h have been r e p o r t e d t o y i e l d foams o f l o w combusti b i l i t y and good r e s i s t a n c e t o d r y and humid a g i n g ( 5 0 51). Hydroxyl-containingtetrabromophthalic esters Tby r e a c t i o n o f t e t r a b r o m o p h t h a l i c a n h y d r i d e w i t h a n excess o f a g l y c o l o r another p o l y h y d r i c a l c o h o l , e.g. s o r b i t o l ) which a r e t h e n p r o p o x y l a t e d , have been used i n t h e p r e p a r a t i o n o f f l a m e r e t a r d a n t u r e t h a n e foams (60). However, more e f f e c t i v e f l a m e - r e t a r d a n t p o l y o l s were o b t a i n e d b y t h e c o m b i n a t i o n o f t e t r a b r o m o p h t h a l i c anhydride, oxypropylated sucrose, phosphoric a c i d and propylene oxide(61).
In Sucrochemistry; Hickson, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
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A number o f s u g a r - b a s e d p o l y o l s ( e . g . d e r i v e d f r o m sucrose, a-methyl g l u c o s i d e , d e x t r o s e , s o r b i t o l , e t c . ) c o n t a i n i n g phosphorus i n t h e form o f phosphate, phosp h i t e o r phosphonate l i n k a g e s have been r e p o r t e d f o r use i n f l a m e - r e t a r d a n t , r i g i d u r e t h a n e foams ( 5 2 - 5 9 ) . Recent r e v i e w s on f l a m e - r e t a r d a n t u r e t h a n e s i n c l u d e t h o s e o f P a p a (62) a n d F r i s c h a n d R e e g e n (6_3) . The e f f e c t s o f c h e m i c a l s t r u c t u r e o f p o l y e t h e r p o l y o l s f o r r i g i d foams and o f d i - and p o l y i s o c y a n a t e s on t h e p h y s i c a l p r o p e r t i e s o f t h e r e s u l t i n g u r e t h a n e p o l y m e r s have b e e n d e s c r i b e d b y a number o f a u t h o r s (64-67) . D a r r , e t a l (100,000 22,500 200,000 30,000 30,000-40,000
0 0 0 0 0 16.4 U2
14.8 123 50.0
* Not otherwise identified by manufacturer.
In Sucrochemistry; Hickson, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
TYPE aliphatic aliphatic aliphatic aliphatic aliphatic heterocyclic heterocyclic heterocyclic heterocyclic aromatic
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T a b l e I V . VICAT SOFTENING POINTS OF HIGHLY CROSSLINKED URETHANE SOLID POLYMERS (SOFTENING POINTS, °C.) RESINS ALI PH ATIC Isocyanate
3(150)* 4(125)
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HDI TDI MDI-2 MDI-2S MDI-3
22 79 95 105 110
35 94 103 120 130
4(150)
6(125)
6(150)
4(125)
60 136 155 160 170
45 96 116 124 122
80 160 178 150 154
23 75 99 100 108
AROMATIC
HETEROCYCLIC 4(150) 63 126 140 150 160
8(125)
8(150)
3(150)
63 130 154 165 150
52 112 127 133 150
90 168 >200
—
170
(a) Numbers in parentheses indicate equivalent weights.
T a b l e V. 1975 U. S. RIGID FOAM MARKET ( M i l l i o n s o f Pounds)
Construction Tanks and P i p e Appliances Transportation Furniture Marine F l o t a t i o n Packaging Miscellaneous
Pounds 133 44 70 36 20 10 12 15 340
% 39.1 12.9 20.6 10.6 5.9 2.9 3.5 4.4 100.0
mensional s t a b i l i t y (assuming t h a t t h e e q u i v a l e n t w e i g h t i s t h e same) (65) . The c o m p r e s s i v e s t r e n g t h o f the foams u s u a l l y t e n d s t o i n c r e a s e w i t h i n c r e a s e d f u n c t i o n a l i t y w h i l e t h e t e n s i l e s t r e n g t h and e l o n g a t i o n tend t o decrease. A breakdown o f t h e r i g i d u r e t h a n e foam m a r k e t s f o r 1975 i s g i v e n i n T a b l e V (3)• I t c a n be seen r e a d i l y t h a t t h e c o n s t r u c t i o n market r e p r e s e n t s by f a r t h e l a r g e s t segment o f t h e r i g i d foam m a r k e t , A more r e c e n t u p d a t e o f t h e s i z e o f t h e r i g i d foam m a r k e t s i n c o n s t r u c t i o n r a n g e d f r o m 1 4 5 m i l l i o n p o u n d s (1) t o 176 m i l l i o n pounds (£8). Mobay C h e m i c a l C o r p o r a t i o n m a r k e t i n g r e p r e s e n t a t i v e s e s t i m a t e d t h a t 975 m i l l i o n b o a r d f e e t (209 m i l l i o n pounds) o f u r e t h a n e foam i n s u l a t i o n w i l l be u s e d by t h e c o n s t r u c t i o n i n d u s t r y i n 1976, w h i c h r e p r e s e n t s a 19 p e r c e n t i n c r e a s e o v e r 1 9 7 5 ' s 818 m i l l i o n b o a r d f e e t ( 1 7 6 m i l l i o n p o u n d s ) (6_8) . A summary o f Mobay
American Chemical Society Library
1155 16th St. N.Hickson, W. J.; In Sucrochemistry; ACS SymposiumWashington, Series; AmericanD.Chemical Society: Washington, DC, 1977. C. 20031
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Table V I . Summary o f Mobay E s t i m a t e s o f U r e t h a n e Foam C o n s u m p t i o n i n C o n s t r u c t i o n Market ( a l l f i g u r e s a r e i n m i l l i o n s ) 1975
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Board
Feet
1976 Pounds
Board
Feet
Pounds
% Change
Pour
144
30
192
40
+33
Spray
159
37
184
43
+16
Board
339
65
407
78
+20
Pipe
60
15
40
10
-33
Tank
116
29
152
38
+31
Total:
818
176
975
209
+19
e s t i m a t e s o f t h e r i g i d u r e t h a n e foam m a r k e t i n c o n s t r u c t i o n , a c c o r d i n g t o t h e f i v e forms i n which uret h a n e i n s u l a t i o n i s m o s t f r e q u e n t l y p r o d u c e d , i s shown i n T a b l e V I (£8). The l a r g e s t c a t e g o r y o f u r e t h a n e i n s u l a t i o n i n 1976 w i l l b e b o a r d s t o c k , u s e d m a i n l y f o r r o o f and p e r i m e t e r i n s u l a t i o n . Poured-in-place foam i s employed most f r e q u e n t l y i n f a c t o r y f a b r i c a t e d p a n e l s and f o r o n - s i t e i n s u l a t i o n o f c a v i t y w a l l s and i s e x p e c t e d t o i n c r e a s e 33 p e r c e n t o v e r 1 9 7 5 p r o v i d e d that the industry can develop metal o r other s u i t a b l e m a t e r i a l - f a c e d u r e t h a n e foam p a n e l s w i t h a c c e p t a b l e f l a m e s p r e a d a n d smoke e v o l u t i o n ( 6 8 ) . Sprayed-on u r e t h a n e foam i s b e i n g used f o r r o o f i n s u l a t i o n and f o r the i n s u l a t i o n of perimeters, precast concrete w a l l s and o t h e r i r r e g u l a r s u r f a c e s . L a r g e g a i n s i n 1976 a r e p r e d i c t e d f o r t a n k i n s u l a t i o n — 3 1 p e r c e n t (60), w h i c h i s p r i m a r i l y a p p l i e d b y means o f s p r a y i n g - o n a t the j o b s i t e . Pipe i n s u l a t i o n i s the only category t h a t has been f o r e c a s t t o d e c l i n e i n 1976, a drop o f 33 p e r c e n t (68) , d u e m a i n l y t o t h e n e a r c o m p l e t i o n o f the A l a s k a p i p e l i n e . The p r i n c i p a l r e a s o n f o r t h e g r o w i n g a c c e p t a n c e and p o p u l a r i t y o f r i g i d u r e t h a n e foams i s t h e t h e r m a l c o n d u c t i v i t y , w h i c h i s l o w e s t among c o m m e r c i a l l y u s e d i n s u l a t i n g m a t e r i a l s , r e p r e s e n t i n g s i g n i f i c a n t energy savings. A c o m p a r i s o n o f t h e e f f i c i e n c y o f common tank i n s u l a t i n g m a t e r i a l s i s given i n Table V I I ( 6 9 ) .
In Sucrochemistry; Hickson, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
In Sucrochemistry; Hickson, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
*
Table V I I .
—
0.14 0.22 0.28 0.28 0.30 0.30 0.35 0.35 10.0
K Factor* or Thermal C o n d u c t i v i t y
7.1 4.5 3.6 3.6 3.3 3.3 2.9 2.9 0.1 Negligible
R Factor*, 1-in. Thicknesses
—
1.0 1.6 2.0 2.0 2.1 2.1 2.5 2.5 71.0
T h i c k n e s s i n Inches Required f o r E q u i v a l e n t I n s u l a t i n g Value
EFFICIENCY OF COMMON TANK INSULATING MATERIALS
The l o w e r t h e K f a c t o r and t h e h i g h e r t h e R, t h e g r e a t e r e f f e c t i v e n e s s as an i n s u l a t i n g material. The R f a c t o r , which i s t h e r e c i p r o c a l o f t h e K f a c t o r , i s a measure o f t h e r e s i s t a n c e o f a " m a t e r i a l t o t r a n s m i s s i o n o f h e a t and c o l d .
Urethane Foam Glass F i b e r S t y r e n e Foam S t y r e n e Board M i n e r a l Wool R e g r a n u l a t e d Cork Calcium S i l i c a t e Foam G l a s s Asphaltic Paint Rust I n h i b i t i n g Paint
Material
COMPARATIVE
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SUCROCHEMISTRY
250 Table
VIII,
Densitv lb per cu ft
Material
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BUOYANCY
Approx. pounds o f s u p p o r t i n water f o r each c u b i c f o o t
RIGID URETHANE FOAM
2
60
Polystyrene
1.5
60
B a l s a Wood
6
56
Cork
7
55
P i n e Wood
28
34
Oak
48
14
O t h e r i m p o r t a n t r i g i d foam a p p l i c a t i o n s a r e i n appliances, t r a n s p o r t a t i o n , f u r n i t u r e , packaging and marine and f l o t a t i o n . M a j o r u s a g e s f o r r i g i d foam i n a p p l i a n c e s i n c l u d e i n s u l a t i o n o f f r e e z e r s and r e f r i g e r a t o r s , and i n t r a n s p o r t a t i o n , i n s u l a t i o n o f r e f r i g e r a t e d r a i l r o a d c a r s and t r a i l e r t r u c k s . R i g i d u r e t h a n e foam i s u s e d f o r m a r i n e s a l v a g e a n d f o r i n s u l a t i o n o f ships and o l d barges i n order t o extend their lives. A comparison o f the buoyancy o f r i g i d u r e t h a n e f o a m w i t h o t h e r m a t e r i a l s i s shown i n T a b l e V I I I (69) . O t h e r g r o w t h a r e a s among r i g i d f o a m s a r e i n the f u r n i t u r e i n d u s t r y ( h i g h d e n s i t y foams) a n d i n p a c k a g i n g where i n most c a s e s v e r y low d e n s i t y foams (0.5 - 1.0 l b / c u f t ) a r e b e i n g u s e d . More r e c e n t l y , r i g i d u r e t h a n e foams have been u t i l i z e d i n t h e manufact u r e o f s t r u c t u r a l f o a m s {3), a n d t h i s m a r k e t p r o m i s e s to be a major f a c t o r i n the f u t u r e . Dr. I r a n i , E x e c u t i v e V i c e P r e s i d e n t f o r the Chemic a l s Group o f O l i n C o r p o r a t i o n , p r e d i c t e d t h a t t h e p r o d u c t i o n o f r i g i d u r e t h a n e foam i n t h e n e x t t e n y e a r s w o u l d i n c r e a s e t o 1.3 b i l l i o n p o u n d s (7£)with c o n s t r u c t i o n b e i n g t h e most i m p o r t a n t f a c t o r i n t h i s growth. A composite f o r the t o t a l urethane i n d u s t r y p r o j e c t i o n b y Mobay m a r k e t r e s e a r c h e r s t h r o u g h 1980 i s d e p i c t e d i n F i g u r e 3 (3). Sugar o r sugar d e r i v a t i v e - b a s e d p o l y o l s have found the w i d e s t a p p l i c a t i o n s i n r i g i d u r e t h a n e foams f o r various industries. However, h i g h e r e q u i v a l e n t w e i g h t p o l y o l s (low h y d r o x y l numbers) o f t h e s e s u g a r o r s u g a r
In Sucrochemistry; Hickson, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
17.
FRISCH A N D KRESTA
251
Sugars in Urethanes POLYURETHANE PROJECTION 1976 - 1980 (Billions of Pounds) 2.369 2.170 1.983
2.0 —
1.325
SS
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1.67b
1.5
H
î.o H
0.5
1976
1977
1978
1979
1980
RIGID URETHANE FOAM
MICROCELLULAR
FLEXIBLE URETHANE FOAM NON-CELLULAR Figure 3.
d e r i v a t i v e s may b e e m p l o y e d i n f l e x i b l e o r s e m i r i g i d f o a m s , p a r t i c u l a r l y when b l e n d e d w i t h conventional f l e x i b l e foam p o l y o l s (e.g. based on g l y c e r o l o r t r i me t h y l o l p r o p a n e ) . I n a d d i t i o n , urethane resins based on d e x t r o s e and m a l t o s e p o l y e t h e r p o l y o l s have been found u s e f u l as r e s i n b i n d e r s f o r f o u n d r y u s e (71) . Other uses include s o l i d urethane p l a s t i c s (72) a n d f o a m c o a t i n g s (730 . I n a d d i t i o n , RIM ( r e a c t i o n i n j e c t i o n molding) technology could u t i l i z e sugar polyols f o r the molding o f s o l i d p l a s t i c s , elastoplast i c s a n d r i g i d a n d s e m i r i g i d foam p r o d u c t s . P o l y e t h e r p o l y o l s f o r r i g i d u r e t h a n e foams c u r r e n t l y a r e ( A u g u s t , 1 9 7 6 ) p r i c e d a t 37 - 45 c e n t s / p o u n d w h i l e s p e c i a l , f l a m e - r e t a r d a n t p o l y o l s command p r e m i u m p r i c e s
In Sucrochemistry; Hickson, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
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o f 70 c e n t s / p o u n d o r m o r e . P o l y e t h e r s based ons u c r o s e and s o r b i t o l a r e i n t h e lower p r i c e range o f t h e r i g i d foam p o l y o l s ( 3 7 - 4 0 c e n t s / p o u n d ) .
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Conclusions Sugar o r sugar d e r i v a t i v e s a r e p l a y i n g i m p o r t a n t r o l e s i n t h e manufacture o f p o l y o l s f o r urethane polymers, i n p a r t i c u l a r f o r u s e i n r i g i d u r e t h a n e foams. In view o f t h e a n t i c i p a t e d growth o f t h i s market ( a v e r a g e g r o w t h o f 12 p e r c e n t p e r y e a r ) a n d t h e c o m b i n a t i o n o f t h e r e l a t i v e l y low costs o f sugar-based polyo l s and e x c e l l e n t p h y s i c a l p r o p e r t i e s o f t h e r e s u l t i n g urethane polymers, sugar and sugar d e r i v a t i v e s a r e expected t o enjoy c o n t i n u e d f u t u r e growth.
Abstract Urethanes have grown at an astounding pace in the last twenty years in the United States and worldwide. The total urethane production in the U.S.A. in 1956 amounted only to 8 million lb and reached 1.3 billion lb in 1975. The principal components of urethanes are hydroxyl-terminated polyethers and polyesters referred to briefly as polyols- and d i - and polyisocyanates. Flexible and rigid foams make up the bulk of the urethane market, 1.4 billion lb (1975) and it is in the foam area that sugars and sugar derivatives have found their widest acceptance, particularly in the rigid foam field. The most commonly used sugar derivatives are propylene oxide adducts of sucrose, sorbitol, starch-derived glucosides, dextrose, etc. Frequently these polyols are modified either by blending with other polyols or employing water, polyhydric alcohols, amines or aminoalcohols as coinitiators prior to propoxylation. This is being done in order to reduce the viscosity of the polyol or to impart certain desirable properties, such as reduced friability, to the resulting foams. A comparison is made of sugar or sugar derivative-based polyols with other competitive products as far as price structure and performance characteristics are concerned. Some present uses and future potential of sugars in the urethane foam market are discussed. Literature Cited 1. 2.
Upjohn Polymer Chemicals Division "Urethane '76, Market Review and Outlook". Chemical Week, (1976), 118, (15), 32.
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17. FRISCH AND KRESTA
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