19 Sucrose-Based Rigid Urethanes in Furniture Applications
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STEPHEN FUZESI Olin Corp., 275 Winchester Ave., New Haven, Conn. 06504
The f u r n i t u r e i n d u s t r y i s m o v i n g f r o m c o n v e n t i o n a l m a t e r i a l s , m a i n l y wood, t o p l a s t i c foams t o e f f e c t c o s t savings i nl a b o r and m a t e r i a l s . By 1 9 8 5 , i n d u s t r y e s t i m a t e s s u g g e s t , t h a t p l a s t i c s w i l l a c c o u n t f o r 35 p e r c e n t o f f u r n i t u r e c o s t s a n d may a m o u n t t o $3 b i l l i o n ( 1 ) i n s a l e s volume. (Figure 1 ) .
Figure 1. Value of plastics used in furniture manufacture (Source: U.S. Department of
Agriculture, Industrial Outlook,
1974; SRI and industry estimates)
1973 1975
1980
1985
The m a r k e t f o r m o l d a b l e , h i g h d e n s i t y , u r e t h a n e foam a l s o i s w e l l e s t a b l i s h e d , andi s growing r a p i d l y . M o r e t h a n 1.0 b i l l i o n p o u n d s o f p l a s t i c s w e r e u s e d i n t h e f u r n i t u r e i n d u s t r y i n 1974. F i f t y m i l l i o n pounds, 5 p e r c e n t o f t h e t o t a l , was a c c o u n t e d f o r b y r i g i d u r e t h a n e foams ( T a b l e I ) . This f i g u r e i s expected t o grow t o 150 m i l l i o n pounds p e r y e a r b y 1980.
264 Hickson; Sucrochemistry ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
19. FUZEsi
R i a i d U r e t h a n e Foam M a r k e t s (-0 ( m i l l i o n s o f pounds) 1974 1975 1972 1970 1973 90 96 Appliances 60 75 42 160 160 Construction 75 155 130 12 20 8 Marine 10 13 55 60 Vehicles 37 50 40 70 50 Furniture 23 29 40 5 10 Miscellaneous 6 6 8 372 Total 416 341 191 275
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Table
Furniture Applications
265
I.
1980 120 290 30 80 150 15 685
The s t r u c t u r e a n d t h e p r o p e r t i e s o f h i g h d e n s i t y , r i g i d u r e t h a n e foams c a n b e c o n t r o l l e d (a) b y c h e m i c a l f o r m u l a t i o n s a n d (b) b y v a r i a t i o n o f t h e p r o c e s s i n g parameters. The t e c h n o l o g y o f m o l d i n g r i g i d urethanes has a d v a n c e d r a p i d l y d u r i n g r e c e n t y e a r s . Newly dev e l o p e d m o l d i n g t e c h n i q u e s now make p o s s i b l e ; a . The p r o d u c t i o n o f f i n i s h e d p a r t s w i t h s o l i d s k i n s and m i c r o - c e l l u l a r i n t e r i o r s i n a s i n g l e o p e r a t i o n f r o m t h e same r a w m a t e r i a l s . T h i s t y p e o f u r e t h a n e foam i s c a l l e d s e l f s k i n n e d o r i n t e g r a l s k i n n e d s t r u c t u r a l foam. b . T h e p r o d u c t i o n o f f i n i s h e d p a r t s w i t h homogeneously uniform c e l l s t r u c t u r e s , possess i n g v e r y t h i n s k i n o r w i t h p r a c t i c a l l y no skin at a l l . T h i s t y p e o f u r e t h a n e foam i s c a l l e d c o n v e n t i o n a l , high d e n s i t y , molded, r i g i d u r e t h a n e wood f o a m s . The c h e m i c a l c o m p o n e n t s ( T a b l e I I ) i n i n t e g r a l s k i n , r i g i d u r e t h a n e foams a r e s i m i l a r t o t h o s e used i n c o n v e n t i o n a l , h i g h d e n s i t y , r i g i d u r e t h a n e wood foams, and i n c l u d e : p o l y m e r i c i s o c y a n a t e s ; c a t a l y s t s ; blowing agents; s u r f a c t a n t s ; and p o l y o l s . P o l y m e r i c i s o c y a n a t e s l i k e PAPI-135 (Upjohn C o . ) , M o n d u r MR (Mobay C h e m i c a l ) a n d R u b i n a t e - M ( R u b i c o n C h e m i c a l ) a r e t h e most w i d e l y u s e d . C a t a l y s t s used a r e both amines and metal s a l t s , m a i n l y t i n b a s e d , and sometimes i n c o m b i n a t i o n s . The a m i n e - t y p e c a t a l y s t s i n i t i a t e t h e p o l y m e r f o r m a t i o n and p r o m o t e m o l d f i l l . The t i n - t y p e c a t a l y s t s promote the f i n a l g e l l i n g , complete t h e cure and c o n t r o l t h e demolding time. The s u r f a c t a n t s r e g u l a t e t h e i n t e r f a c i a l t e n s i o n i n t h e foaming system and c o n t r o l u n i f o r m c e l l formation. H i g h d e n s i t y , r i g i d foams do n o t r e q u i r e s o p h i s t i c a t e d s u r f a c t a n t s , most c o m m e r c i a l p r o d u c t s p e r f o r m well (2). Both water and f l u o r o c a r b o n s a r e used as blowing agents, sometimes i n c o m b i n a t i o n . Water i s used mainly i npreparation of theconventional, high density,
Hickson; Sucrochemistry ACS Symposium Series; American Chemical Society: Washington, DC, 1977.
266
SUCROCHEMISTRY
Table I I M a j o r Components 1.
i n High
Density Rigid
Isocyanate-Polymeric PAPI-135 Rubinate-M Mondur MR 1
2
2.
U r e t h a n e Wood Foams
Polymer Formation Polyurethane Polyurea Isocyanurate
Catalyst (A) Amine C a t a l y s t Dabco c Polycat-8 TMBDA (B) O r g a n o t i n C a t a l y s t DBTDL 7~ Stannous Octoate UL-6(blocked) , UL-24(blocked)
Initiate Blow and
the polymer f o r m a t i o n . promote mold f i l l .
6
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7
Promote the f i n a l g e l l i n g , Complete cure. C o n t r o l the demolding time.
9
n
the
1
Surfactant 11 Dow DC-193 U.C.-5420 U.C.-5430
Regulate the i n t e r f a c i a l t e n s i o n i n the foaming system. Control the u n i f o r m c e l l s f o r m a t i o n .
1 2
1 3
4.
Water Used
5.
6.
(H 0) 2
i n low
level
only
Fluorocarbon-blowing R-11B"
P o l y u r e a and CO^(Î)-Improve t h e r i g i d i t y o f t h e foam. Reduce t h e skin density.
agent Blow t h e foam. C o n t r o l the s k i n t h i c k n e s s and t h e foam d e n s i t y .
Polyols
1. U p j o h n 2. R u b i c o n 3. Mobay
Polyurethane formation. M o s t d i v e r s i f i e d and m o s t
4. A i r P r o d u c t 5. A b b o t t 6. W i t c o
7. M & T 8. M & T 9. A r g u s
10. 11. 12.
critical.
Argus 13. Dow C o r n i n g 14. Union Carbide
Union Carbide DuPont
Table I I I Selection
of
the
Polyols
f o r Wood Foam
Applications
Optimum H y d r o x y l numbers Functionalities C y c l i c backbones
Viscosity Reactivity
Other
330 - 430 4 - 5 Carbohydrate-based
Crosslink Strength Structure Hardness,
