ep0010407a1
DESCRIPTION
Method for preparing rigid polyurethane foams and gel catalyst composition therefor.TRANSCRIPT
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Europaisches Patentamt
European Patent Office (vj) Publication number: 0 0 1 0 4 0 7
Office europeen des brevets A1
EUROPEAN PATENT APPLICATION
@ Application number: 79302189.0 0 Int. CI.3: C 08 G 1 8 / 2 2
(22) Date of filing: 11.10.79
(So) Priority: 12.10.78 US 950816 (71) Applicant: M & T CHEMICALS, INC.
Woodbridge, New Jersey 07095(US) 43) Date of publication of application:
30.04.80 Bulletin 80/9 (g) inventor: Treadwell, Kenneth 930 Main Street
@ Designated Contracting States: Rahway, New Jersey 07065(US) AT BE CH DE FR GB IT NL SE
(74) Representative: Ellis, John Clifford Holgate et al, MEWBURN ELLIS & CO. 70-72 Chancery Lane London WC2A 1AD(GB)
(54) Method for preparing rigid polyurethane foams and gel catalyst composition therefor.
Rigid polyurethane foam is prepared by reacting a polyol containing at least three active hydrogen atoms with a polyfunctional isocyanate or isothiocyanate in the presence of a gel catalyst and a blowiegagent. As gel catalystthere is used a catalyst composition comprising an antimony carboxylate, a potassium carboxylate and a zinc carboxylate wherein the hydrocarbyl as hereinbefore defined portion of each carboxy- late contains from 1 to 2a carbon atoms and wherein each of the antimony and potassium carboxylates constitutes from 10 to 40 % by weight of the total carboxylate content and the zinc carboxylate constitutes the remaining 20 to 80% by weight of the total carboxylate content, either alone or in combination with another gel catalyst, particularly one chosen from terti- ary amines, inorganic tin compounds an organotin com- pounds. The use of the specified gel catalyst composition enables the isocyanate- or isothiocyanate- polyol reaction to be controlled over a wide range.
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This i n v e n t i o n r e l a t e s to a method f o r
p r e p a r i n g r i g i d p o l y u r e t h a n e foam by r e a c t i n g a p o l y o l
w i t h an i s o c y a n a t e or i s o t h i o c y a n a t e in t he p r e s e n c e of a
ge l c a t a l y s t and a b l o w i n g a g e n t and to a n o v e l g e l
c a t a l y s t c o m p o s i t i o n t h e r e f o r . With the s a i d
c a t a l y s t c o m p o s i t i o n the r a t e of the i s o c y a n a t e - o r
i s o t h i o c y a n a t e - p o l y o l r e a c t i o n can be c o n t r o l l e d
w i t h i n a wide r a n g e no t h e r e t o f o r e p o s s i b l e u s i n g
c o m b i n a t i o n s of p r i o r a r t c a t a l y s t s .
R i g i d p o l y u r e t h a n e foams a re used as i n s u l a t i n g
m a t e r i a l s f o r n u m e r o u s e n d - u s e a p p l i c a t i o n s , i n c l u d i n g
i n s u l a t i o n f o r s t r u c t u r e s and c o n t a i n e r s . For s o m e
of t h e s e a p p l i c a t i o n s , such as s p r a y i n g , i t may b e
d e s i r a b l e t h a t foam f o r m a t i o n and s o l i d i f i c a t i o n
t a k e p l a c e as r a p i d l y as p o s s i b l e once the p o l y f u n c t i o n a l
i s o c y a n a t e and the p o l y o l a re c o m b i n e d . For o t h e r
a p p l i c a t i o n s , w h e r e i n t he f o r m u l a t i o n must f i l l l a r g e
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c a v i t i e s or c o m p l e x m o u l d s , i t w o u l d be d e s i r a b l e t o
d e l a y i n i t i a t i o n of t h e i s o c y a n a t e - p o l y o l r e a c t i o n u n t i l
t h e m i x t u r e of r e a g e n t s has c o m p l e t e l y f i l l e d t h e
c a v i t y or m o u l d . Once t h i s has o c c u r r e d , f o a m i n g
and s o l i d i f i c a t i o n s h o u l d o c c u r as r a p i d l y as p o s s i b l e
to m i n i m i z e r e s i d e n c e t i m e in a m o u l d . U s i n g
c o n v e n t i o n a l g e l c a t a l y s t s f o r r i g i d p o l y u r e t h a n e
f o a m s , w h i c h i n c l u d e t e r t i a r y a m i n e s u s e d e i t h e r
a l o n e or in c o m b i n a t i o n w i t h o r g a n o t i n c o m p o u n d s , i t
i s n o t f e a s i b l e to c o n t r o l t h e r a t e of t h e i s o c y a n a t e -
p o l y o l r e a c t i o n o v e r t h e r a n g e r e q u i r e d f o r t h e
v a r i o u s a p p l i c a t i o n s of r i g i d p o l y u r e t h a n e f o a m s . T h e
r e a c t i o n when c a t a l y z e d by a m i n e i s r e l a t i v e l y s l o w ,
and t h e r i s e t i m e ( t h e t i m e r e q u i r e d f o r t he foam t o
r e a c h i t s f i n a l h e i g h t ) may be as l o n g as 3 or 4
m i n u t e s . The r i s e t i m e is d e c r e a s e d by s e v e r a l o r d e r s
of m a g n i t u d e i f t h e a m i n e i s u s e d in c o m b i n a t i o n w i t h
an o r g a n o t i n c o m p o u n d s u c h as d i b u t y l t i n d i l a u r a t e .
T h i s c o m b i n a t i o n of an a m i n e w i t h an o r g a n o t i n c o m p o u n d
i s s y n e r g i s t i c w i t h t h e r e s u l t t h a t t h e r e a c t i o n
m i x t u r e may s o l i d i f y too r a p i d l y f o r c e r t a i n
a p p l i c a t i o n s , even when t h e c o n c e n t r a t i o n of t h e
o r g a n o t i n c o m p o u n d is r e d u c e d to t h e l o w e s t p r a c t i c a l
l e v e l .
I t i s an o b j e c t i v e of t h i s i n v e n t i o n t o
p r o v i d e a c a t a l y s t c o m p o s i t i o n f o r r i g i d p o l y u r e t h a n e
foam t h a t w i l l e n a b l e t h e r a t e of t h e i s o c y a n a t e - p o l y o l
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r e a c t i o n and t h e t i m e r e q u i r e d to i n i t i a t e t h i s
r e a c t i o n to be v a r i e d w i t h i n w ide r a n g e s . T h i s
o b j e c t i v e can be a c h i e v e d u s i n g a ge l c a t a l y s t
c o m p o s i t i o n c o n t a i n i n g an a n t i m o n y c a r b o x y l a t e , a
p o t a s s i u m c a r b o x y l a t e and a z i n c c a r b o x y l a t e . T h i s
c o m p o s i t i o n can be u s e d a l o n e or in c o m b i n a t i o n w i t h
o t h e r ge l c a t a l y s t s , n o t a b l y any of t he a m i n e s a n d
o r g a n o t i n c o m p o u n d s c o n v e n t i o n a l l y e m p l o y e d a s
c a t a l y s t s f o r r i g i d c e l l u l a r p o l y u r e t h a n e s .
The p r e s e n t g e l c a t a l y s t s a r e u s e f u l f o r
p r e p a r i n g r i g i d p o l y u r e t h a n e foams f rom s u b s t a n t i a l l y
a l l of t h e known p o l y o l s and p o l y f u n c t i o n a l
i s o c y a n a t e s or i s o t h i o c y a n a t e s c o n v e n t i o n a l l y e m p l o y e d
f o r t h i s p u r p o s e . The c a t a l y s t s a r e m i x t u r e s o f
a n t i m o n y , p o t a s s i u m and z i n c s a l t s of c a r b o x y l i c a c i d s
each c o n t a i n i n g f rom 2 to 21 c a r b o n a toms and may b e
e m p l o y e d a t a c o n c e n t r a t i o n of b e t w e e n 0 . 0 5 and 10%,
b a s e d on t h e w e i g h t of p o l y o l . T h e s e s a l t s can b e
r e f e r r e d to as r e a c t i o n p r o d u c t s of one or m o r e
c a r b o x y l i c a c i d s w i t h b a s i c c o m p o u n d s of a n t i m o n y ,
p o t a s s i u m and z i n c . S u i t a b l e m o n o c a r b o x y l i c a c i d s
i n c l u d e a c e t i c , p r o p a n o i c , b u t a n o i c , p e n t a n o i c ,
h e x a n o i c , h e p t a n o i c and 2 - e t h y l h e x a n o i c a c i d s i n
a d d i t i o n to o t h e r a c i d s c o n t a i n i n g up to 21 c a r b o n a t o m s .
U n s a t u r a t e d c a r b o x y l i c a c i d s d e r i v e d f rom o i l s s u c h a s
t a l l o i l s or a n i m a l f a t s , i n c l u d i n g o l e i c a c i d a n d
l i n o l e i c a c i d , may a l s o be e m p l o y e d . A r o m a t i c
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c a r b o x y l i c a c i d s s u c h as b e n z o i c a c i d , t h a t may e x h i b i t
v a r i o u s s u b s t i t u e n t s on t h e p h e n y l r i n g , s a l i c y l i c
a c i d , and t h e i s o m e r i c n a p h t h e n o i c a c i d s a r e a l s o
s u i t a b l e . P o l y c a r b o x y l i c a c i d s s u c h as o x a l i c ,
m a l o n i c , s u c c i n i c , g l u t a r i c , a d i p i c , p i m e l i c , s u b e r i c ,
a z e l a i c , s e b a c i c , b r a s s y l i c , t h a p s i c , m a l e i c , f u m a r i c ,
g l u t a c o n i c , a - h y d r o x y m u c o n i c , - h y d r o x y m u c o n i c ,
a - b u t y l - a - e t h y l g l u t a r i c , @ , - d i e t h y l s u c c i n i c , i s o p h t h a l i c ,
t e r e p h t h a l i c , h e m i m e l l i t i c and 1 , 4 - c y c l o h e x a n e d i c a r b o x -
y l i c a c i d s , can be u s e d in p l a c e o f a m o n o c a r b o x y l i c
a c i d . Any of t h e a f o r e m e n t i o n e d a c i d s can be e m p l o y e d
s e p a r a t e l y or in m i x t u r e s c o n t a i n i n g two or more a c i d s .
A c c o r d i n g to one a s p e c t of t h e i n v e n t i o n we
p r o v i d e a ge l c a t a l y s t c o m p o s i t i o n f o r p r e p a r i n g r i g i d
p o l y u r e t h a n e foam c o m p r i s i n g an a n t i m o n y c a r b o x y l a t e ,
a p o t a s s i u m c a r b o x y l a t e and a z i n c c a r b o x y l a t e w h e r e i n
t h e h y d r o c a r b y l as h e r e i n a f t e r d e f i n e d p o r t i o n o f
e a c h c a r b o x y l a t e c o n t a i n s f r o m 1 to 20 c a r b o n a t o m s a n d
w h e r e i n e a c h of t h e a n t i m o n y and p o t a s s i u m c a r b o x y l a t e s
c o n s t i t u t e s f rom 10 to 40% by w e i g h t of t he t o t a l
c a r b o x y l a t e c o n t e n t and t h e z i n c c a r b o x y l a t e c o n s t i t u t e s
t h e r e m a i n i n g 20 to 80% by w e i g h t of t h e t o t a l
c a r b o x y l a t e c o n t e n t .
A c c o r d i n g to a n o t h e r a s p e c t of t he i n v e n t i o n
we p r o v i d e a m e t h o d f o r p r e p a r i n g r i g i d p o l y u r e t h a n e
foam by r e a c t i n g a p o l y o l c o n t a i n i n g a t l e a s t t h r e e
a c t i v e h y d r o g e n a t o m s w i t h a p o l y f i n c t i o n a l i s o c y a n a t e
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or i s o t h i o c y a n a t e in t h e p r e s e n c e of a ge l c a t a l y s t and a
b l o w i n g a g e n t , c h a r a c t e r i s e d in t h a t t h e r e is e m p l o y e d a
ge l c a t a l y s t c o m p o s i t i o n as d e f i n e d a b o v e . T h e r e m a y
a l s o be u s e d t o g e t h e r w i t h t h e s a i d ge l c a t a l y s t a n o t h e r
ge l c a t a l y s t known p e r se as a c a t a l y s t f o r r i g i d p o l y -
u r e t h a n e f o a m s , p r e f e r a b l y c h o s e n f rom t e r t i a r y a m i n e s ,
i n o r g a n i c t i n c o m p o u n d s and o r g a n o t i n c o m p o u n d s .
P r e f e r a b l y t h e s a i d a n t i m o n y , p o t a s s i u m , and z i n c
c o m p o u n d s a r e s a l t s of m o n o c a r b o x y l i c a c i d s h a v i n g t h e
g e n e r a l f o r m u l a e S b ( O O C R 1 ) 3 , KOOCR2 and Z n ( O O C R 3 ) 2 .
r e s p e c t i v e l y , w h e r e i n R , R 2 a n d R 3 a r e h y d r o c a r b y l a n d
c o n t a i n f rom 1 to 20 c a r b o n a t o m s . The t e r m " h y d r o -
c a r b y l " i n c l u d e s a l k y l , c y c l o a l k y l , a r y l , a l k a r y l a n d
a r a l k y l . Mos t p r e f e r a b l y R , R 2 a n d R3 a r e a l k y l a n d
p r e f e r a b l y c o n t a i n f rom 4 to 12 c a r b o n a t o m s . A c i d s
c o n t a i n i n g 8 c a r b o n a t oms in a l i n e a r or b r a n c h e d c o n -
f i g u r a t i o n , i n c l u d i n g 2 - e t h y l h e x a n o i c a c i d , a r e
e s p e c i a l l y p r e f e r r e d .
The r e l a t i v e a m o u n t s of a n t i m o n y , p o t a s s i u m a n d
z i n c c a r b o x y l a t e s t h a t a r e p r e s e n t in t h e c a t a l y s t
c o m p o s i t i o n s of t h i s i n v e n t i o n w i l l be d e t e r m i n e d , a t
l e a s t in p a r t , by t h e r a t e d e s i r e d f o r t h e i s o c y a n a t e - o r
i s o t h i o c y a n a t e - p o l y o l r e a c t i o n . The c o m p o s i t i o n may a l s o
i n c l u d e a s o l v e n t f o r a l l t h r e e s a l t s w h i c h w i l l g e n e r a l l y
be c o m p a t i b l e w i t h t h e p o l y o l e m p l o y e d to p r e p a r e t h e
p o l y u r e t h a n e f o a m . P r e f e r r e d s o l v e n t s i n c l u d e o l i g o m e r s
of e t h y l e n e o x i d e and p r o p y l e n e o x i d e . L i q u i d p o l y p r o p y -
l e n e g l y c o l s , e s p e c i a l l y t h o s e e x h i b i t i n g m o l e c u l a r
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w e i g h t s of f rom 300 to a b o u t 5 , 0 0 0 , c o n s t i t u t e a p a r t -
i c u l a r l y p r e f e r r e d c l a s s of s o l v e n t s .
The s a i d c a r b o x y l a t e s of p o t a s s i u m , a n t i m o n y
and z i n c can be p r e p a r e d i n d i v i d u a l l y and t h e n c o m b i n e d
in t h e d e s i r e d p r o p o r t i o n s . A l t e r n a t i v e l y , t h e m i x t u r e
of c a r b o x y l a t e s can be p r e p a r e d by r e a c t i n g a s t o i c h i o -
m e t r i c a m o u n t of t h e d e s i r e d c a r b o x y l i c a c i d w i t h b a s i c
c o m p o u n d s of p o t a s s i u m , a n t i m o n y and z i n c in t h e
a p p r o p r i a t e p r o p o r t i o n s . I t is g e n e r a l l y c o n v e n i e n t t o
e m p l o y a h y d r o x i d e or o x i d e as t h e b a s i c c o m p o u n d , h o w e v e r ,
b a s i c s a l t s s u c h as t he c a r b o n a t e or b i c a r b o n a t e a r e a l s o
s u i t a b l e . The b a s i c c o m p o u n d s of p o t a s s i u m , a n t i m o n y
and z i n c may be r e a c t e d i n d i v i d u a l l y or as a m i x t u r e w i t h
t h e d e s i r e d c a r b o x y l i c a c i d or a c i d s . The r e a c t i o n i s
p r e f e r a b l y c o n d u c t e d in t h e p r e s e n c e of a w a t e r - i m m i s c i b l e ,
c h e m i c a l l y i n e r t l i q u i d m e d i u m s u c h as a l i q u i d a l i p h a t i c
or a r o m a t i c h y d r o c a r b o n . S i n c e t h e r e a c t i o n is u s u a l l y
e x o t h e r m i c , i t may be d e s i r a b l e to s t i r and c o o l t h e
r e a c t f o n m i x t u r e to a v o i d l o c a l i z e d o v e r - h e a t i n g a n d
r e s u l t a n t p r o d u c t d i s c o l o u r a t i o n . The b y - p r o d u c t w a t e r
can be r e m o v e d d u r i n g t h e r e a c t i o n by a z e o t r o p i c d i s t i l l a -
t i o n t o g e t h e r w i t h a p o r t i o n o f t h e l i q u i d h y d r o c a r b o n
e m p l o y e d as t h e r e a c t i o n m e d i u m . A l t e r n a t i v e l y , t h e
w a t e r can be r e m o v e d as an i m m i s c i b l e p h a s t f o l l o w i n g
c o m p l e t i o n of t h e r e a c t i o n .
P o l y o l s c o n v e n t i o n a l l y e m p l o y e d to p r e p a r e r i g i d
p o l y u r e t h a n e foams a r e l i q u i d s w h i c h t y p i c a l l y e x h i b i t a n
a v e r a g e m o l e c u l a r w e i g h t o f b e t w e e n a b o u t 500 and 6 , 0 0 0 a n d
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i n c l u d e h y d r o x y l - c o n t a i n i n g p o l y e t h e r s , p o l y e s t e r s a n d
p o l y a m i d e s and a l k y l e n e g l y c o l s . T h e s e p o l y o l s e x h i b i t
e i t h e r p r i m a r y or s e c o n d a r y a c t i v e h y d r o x y l g r o u p s . T h e
c l a s s of h y d r o x y l - c o n t a i n i n g p o l y e t h e r s or p o l y e s t e r s
i n c l u d e s f a t t y a c i d g l y c e r i d e s h a v i n g h y d r o x y l n u m b e r s o f
f rom 300 to 600 s u c h as c a s t o r o i l , h y d r o g e n a t e d c a s t o r
o i l and " b l o w n " n a t u r a l o i l s .
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 , a p r e f e r r e d t y p e
of p o l y o l , i n c l u d e p o l y a l k y l e n e g l y c o l s , e . g . , p o l y e t h y l e n e
g l y c o l s and p o l y p r o p y l e n e g l y c o l s . The m o l e c u l a r w e i g h t
of t h e s e c o m p o u n d s is p r e f e r a b l y b e t w e e n a b o u t 200 a n d
6 , 0 0 0 .
A t y p e of p o l y e t h e r t h a t i s p a r t i c u l a r l y p r e -
f e r r e d f o r r i g i d p o l y u r e t h a n e foams is o b t a i n e d by p o l y -
m e r i z i n g p r o p y l e n e o x i d e in t h e p r e s e n c e of s u c r o s e o r
o t h e r c o m p o u n d s c o n t a i n i n g a t l e a s t t h r e e h y d r o x y l g r o u p s .
The r e s u l t a n t p r o d u c t e x h i b i t s t h e p o l y f u n c t i o n a l i t y
r e q u i r e d to a c h i e v e t h e c r o s s l i n k i n g c h a r a c t e r i s t i c o f
r i g i d p o l y u r e t h a n e f o a m s .
H v d r o x y l - t e r m i n a t e d p o l y e s t e r s , a s e c o n d t y p e o f
p o l y o l , can be o b t a i n e d by t h e e s t e r i f i c a t i o n - c o n d e n s a t i o n
r e a c t i o n of a l i p h a t i c d i b a s i c c a r b o x y l i c a c i d s w i t h g l y c o l s ,
t r i o l s or m i x t u r e s t h e r e o f , in p r o p o r t i o n s s u c h t h a t m o s t
of a l l of t h e r e s u l t a n t p o l y m e r c h a i n s c o n t a i n t e r m i n a l
h y d r o x y l g r o u p s . D i b a s i c c a r b o x y l i c a c i d s s u i t a b l e f o r
p r e p a r i n g p o l y e s t e r s i n c l u d e a l i p h a t i c and a r o m a t i c a c i d s
s u c h as a d i p i c , f u m a r i c , s e b a c i c and t h e i s o m e r i c p h t h a l i c
a c i d s . The a c i d may be r e a c t e d w i t h a d i - or p o l y h y d r o x y -
-
l a t e d compound s u c h as e t h y l e n e g l y c o l , t r i m e t h y l o l
p r o p a n e or p e n t a e r y t h r i t o l .
Bo th p o l y i s o c y a n a t e s and p o l y i s o t h i o c y a n a t e s
may be u s e d to p r e p a r e r i g i d p o l y u r e t h a n e o a m s . W h i l e
t h e i n v e n t i o n is d e s c r i b e d w i t h s p e c i f i c r e f e r e n c e s t o
t h e r e a c t i o n of c e r t a i n p o l y f u n c t i o n a l i s o c y a n a t e s , i t i s
g e n e r i c a l l y a p p l i c a b l e to t h e r e a c t i o n of any c o m p o u n d
c o n t a i n i n g more t h a n two -N=C=G r a d i c a l s w h e r e i n G i s
o x y g e n or s u l p h u r . C o m p o u n d s w i t h i n t h i s g e n e r i c
d e f i n i t i o n i n c l u d e p o l y i s o c y a n a t e s and p o l y i s o t h i o c y a n a y t e s
of t h e f o r m u l a R(NCG)x i n w h i c h t h e a v e r a g e v a l u e o f x
i s g r e a t e r t h a n 2, p r e f e r a b l y f rom 2.1 to 3 . 0 . R can b e
a l k y l e n e , s u b s t i t u t e d a l k y l e n e , a r y l e n e , s u b s t i t u t e d
a r y l e n e or o t h e r d i v a l e n t h y d r o c a r b o n g r o u p t h a t m a y
o p t i o n a l l y c o n t a i n one or more a r y l - N C G bonds and one o r
more a l k y l - N C G b o n d s . S u i t a b l e i s o c y a n a t e s i n c l u d e t h e
p o l y - f u n c t i o n a l b y - p r o d u c t s o b t a i n e d d u r i n g t h e p r e p a r a -
t i o n of m e t h y l e n e p a r a p h e n y l d i i s o c y a n a t e . P o l y m e t h y l e n e
p o l y p h e n y l i s o c y a n a t e i s an e x a m p l e of s u c h a b y - p r o d u c t .
T r i i s - o c y a n a t e s o b t a i n e d by r e a c t i n g 3 m o l e s of an a r y l e n e
d i i s o c y a n a t e f o r e a c h m o l e of a t r i o l , e . g . , t h e p r o d u c t s
f o r m e d f rom 3 m o l e s o f t o l y l e n e d i i s o c y a n a t e and 1 m o l e
of h e x a n e t r i o l , a r e a l s o u s e f u l .
In a d d i t i o n to p o l y o l , p o l y f u n c t i o n a l i s o c y a n a t e
h i o c y a n a t e and one or more of t h e p r e s e n t
the r e a c t i o n m i x t u r e c o n t a i n s a b l o w i n g a g e n t
e c o m p o s e s a t the t e m p e r a t u r e of t h e
; o c y a n a t e r e a i t i o n to y i e l d a g a s e o u s
-
p r o d u c t w h i c h f o r m s b u b b l e s t h a t a r e e n t r a p p e d w i t h i n
t h e r e a c t i n g p o l y o l - i s o c y a n a t e or - i s o t h i o c y a n a t e
m i x t u r e as i t s o l i d i f i e s . Among t he p r e f e r r e d b l o w i n g
a g e n t s a r e t h o s e h a l o g e n - c o n t a i n i n g h y d r o c a r b o n s
b o i l i n g f rom 30 t o a b o u t 90C. The p r e c u r s o r a l s o
u s u a l l y c o n t a i n s a s u r f a c t a n t , f o r i n s t a n c e a s i l i c o n -
c o n t a i n i n g s u r f a c t a n t and p r e f e r a b l y a s i l o x a n e -
a l k y l e n e o x i d e c o p o l y m e r , p r e f e r a b l y in an a m o u n t o f
f rom 1 to a b o u t 5 p a r t s by w e i g h t p e r 100 p a r t s o f
p o l y o l .
As p r e v i o u s l y d i s c l o s e d , t h e p r e s e n t
c o m b i n a t i o n of an a n t i m o n y c a r b o x y l a t e w i t h c a r b o x y l a t e s
of p o t a s s i u m and z i n c a r e u n i q u e in t h a t t h e c a t a l y t i c
a c t i v i t y of t h i s t y p e of c o m p o s i t i o n can be v a r i e d
o v e r a w ide r a n g e by v a r y i n g e i t h e r t h e r e l a t i v e
p r o p o r t i o n s of t h e t h r e e c a r b o x y l a t e s a l t s or t h e
a m o u n t of a p a r t i c u l a r c a r b o x y l a t e s a l t c o m p o s i t i o n
u s e d in c o m b i n a t i o n w i t h c o n v e n t i o n a l ge l c a t a l y s t s
f o r r i g i d p o l y u r e t h a n e f o a m s . These c o n v e n t i o n a l
c a t a l y s e s i n c l u d e t e r t i a r y a m i n e s such as t r i c y c l o -
h e x y l a m i n e , t r i e t h a n o l a m i n e , N - e t h y l m o r p h o l i n e ,
t r i e t h y l e n e d i a m i n e and d i m e t h y l e t h a n o l a m i n e . T h e
a m i n e i s o f t e n u s e d in c o m b i n a t i o n w i t h i n o r g a n i c a n d
o r g a n i c t i n c o m p o u n d s . R e p r e s e n t a t i v e t i n - c o n t a i n i n g
c a t a l y s t s a r e s t a n n o u s o c t o a t e , s t a n n o u s o l e a t e ,
d i b u t y l t i n d i l a u r a t e , d i b u t y l t i n d i o c t o a t e , d i b u t y l t i n
d i l a u r y l m e r c a p t i d e and d i b u t y l t i n - S , S ' - b i s ( i s o o c t y l
-
m c r c a p t o a c e t a t e ) . T h e s e c o n v e n t i o n a l g e l c a t a l y s t s
may be e m p l o y e d a t c o n c e n t r a t i o n s of f rom 0 to 5 p a r t s
by w e i g h t p e r 100 p a r t s of p o l y o l .
The a c c o m p a n y i n g e x a m p l e s d e m o n s t r a t e t h e
b r o a d r a n g e of r e a c t i o n r a t e s t h a t c a n be a c h i e v e d u s i n g
one of t h e p r e s e n t c a t a l y s t c o m p o s i t i o n s a l o n e and i n
c o m b i n a t i o n w i t h a m i n e s and t i n c o m p o u n d s to p r e p a r e
r i g i d p o l y u r e t h a n e f o a m s . The e x a m p l e s a l s o
d e m o n s t r a t e t h a t t h i s b r o a d r a n g e c a n n o t be a c h i e v e d
u s i n g c o n v e n t i o n a l t i n and a m i n e c a t a l y s t s e i t h e r
i n d i v i d u a l l y or i n c o m b i n a t i o n . A l l p a r t s a n d
p e r c e n t a g e s r e p o r t e d in t h e e x a m p l e s a r e by w e i g h t
u n l e s s o t h e r w i s e s p e c i f i e d .
The t i m e i n t e r v a l b e t w e e n c o m b i n i n g of a l l t h e
r e a g e n t s and t h e o n s e t of p o l y m e r i z a t i o n , as i n d i c a t e d
by a t r a n s f o r m a t i o n of t h e r e a c t i o n m i x t u r e f rom c l e a r
to o p a q u e , i s r e f e r r e d to as " c r e a m t i m e " . T h e
i n t e r v a l b e t w e e n c o m b i n i n g of a l l of t h e r e a g e n t s a n d
t h e c o m p l e t i o n of t h e e n s u i n g f o a m i n g r e a c t i o n i s
r e f e r r e d to as " r i s e t i m e " .
To a b a s e f o r m u l a t i o n c o n t a i n i n g (1) 3 0 . 4 p a r t s
of a p o l y h y d r o x y - b a s e d e t h y l e n e o x i d e - p r o p y l e n e o x i d e
c o p o l y m e r e x h i b i t i n g a h y d r o x y l n u m b e r of 4 9 0
( a v a i l a b l e as " N i a x " p o l y o l L S - 4 9 0 f r o m t h e U n i o n
C a r b i d e C o r p o r a t i o n ) , (2) 0 . 4 5 p a r t o f a s i l o x a n e -
o x y r t h y l e n e - o x y p r o p y l e n e c o p o l y m e r a v a i l a b l e a s
L - 5 3 4 0 f rom t h e U n i o n C a r b i d e C o r p o r a t i o n and (3) 9 . 0
-
p a r t s of t r i c h l o r o f l u o r o m e t h a n e we re a d d e d 3 6 . 7 p a r t s
of p o l y m e t h y l e n e p o l y p h e n y l i s o c y a n a t e and one or m o r e
of t h e c a t a l y s t s l i s t e d in t h e f o l l o w i n g t a b l e .
" N i a x " is a T r a d e Mark . The c o m p o s i t i o n r e f e r r e d t o
as C a t a l y s t A c o n t a i n e d 20 p a r t s z i n c b i s - 2 - e t h y l -
h e x a n o a t e and 15 p a r t s e a c h of a n t i m o n y t r i s - 2 - e t h y l -
h e x a n o a t e and p o t a s s i u m 2 - e t h y l h e x a n o a t e . F i f t y
p a r t s of a p o l y p r o p y l e n e g l y c o l ( P l u r a c o l P - 4 1 0
a v a i l a b l e f rom B A S F - W y a n d o t t e C o r p o r a t i o n ) w e r e
e m p l o y e d as a common s o l v e n t f o r t h e t h r e e s a l t s .
-
The f o r e g o i n g d a t a d e m o n s t r a t e t h a t t h e a m i n e
i s more a c t i v e t h a n t h e C a t a l y s t A c o m p o s i t i o n . T h e
foam p r e p a r e d u s i n g d i b u t y l t i n d i l a u r a t e d id n o t r i s e
c o m p l e t e l y and was n o t of a c c e p t a b l e q u a l i t y .
The s y n e r g i s m a c h i e v e d u s i n g an amine w i t h
t h e c a t a l y s t c o m p o s i t i o n of t h i s i n v e n t i o n i s
d e m o n s t r a t e d :by t h e f o u r t h f o r m u l a t i o n , w h i c h
e x h i b i t e d a c r eam t i m e of 15 s e c o n d s and a r i s e t i m e
of 146 s e c o n d s . T h e s e t i m e s a r e s h o r t e r t h a n c o u l d
be a c h i e v e d u s i n g t h e a m i n e a l o n e . The f o r m u l a t i o n s
c o n t a i n i n g C a t a l y s t A and d i b u t y l t i n d i l a u r a t e
d e m o n s t r a t e t he w i d e r a n g e o f c r e a m and r i s e t i m e s
t h a t can be a c h i e v e d u s i n g t h e c o m b i n a t i o n of t h e
p r e s e n t c a t a l y s t c o m p o s i t i o n w i t h a c o n v e n t i o n a l
o r g a n o t i n c o c a t a l y s t t h a t d i d n o t p r o d u c e a
s a t i s f a c t o r y foam when u s e d a l o n e . T h i s w i d e r a n g e
c a n n o t be a c h i e v e d u s i n g c o m b i n a t i o n s of C a t a l y s t A o r
a t i n c o m p o u n d w i t h an a m i n e due to t h e
c o n s i d e r a b l y h i g h e r l e v e l of c a t a l y t i c a c t i v i t y
e x h i b i t e d by t h e s e c o m b i n a t i o n s , w h i c h is c o m p a r a b l e
to t h e a c t i v i t y e x h i b i t e d by c o n v e n t i o n a l c o m b i n a t i o n s
of t i n c o m p o u n d s and a m i n e s .
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1. A ge l c a t a l y s t c o m p o s i t i o n f o r p r e p a r i n g
r i g i d p o l y u r e t h a n e foam, c h a r a c t e r i s e d in t h a t t h e
c a t a l y s t c o m p o s i t i o n c o m p r i s e s an a n t i m o n y
c a r b o x y l a t e , a p o t a s s i u m c a r b o x y l a t e and a z i n c
c a r b o x y l a t e w h e r e i n t h e h y d r o c a r b y l as h e r e i n b e f o r e
d e f i n e d p o r t i o n of e a c h c a r b o x y l a t e c o n t a i n s from 1
to 20 c a r b o n a toms and w h e r e i n each of t he a n t i m o n y
a n d p o t a s s i u m c a r b o x y l a t e s c o n s t i t u t e s f rom 10 to 40%
by w e i g h t of t h e t o t a l c a r b o x y l a t e c o n t e n t and t h e
z i n c c a r b o x y l a t e c o n s t i t u t e s t h e r e m a i n i n g 20 to 80%
by w e i g h t of t h e t o t a l c a r b o x y l a t e c o n t e n t .
2. A ge l c a t a l y s t c o m p o s i t i o n a c c o r d i n g t o
C l a i m 1, w h e r e i n t h e c a r b o x y l a t e s have t h e f o l l o w i n g
g e n e r a l f o r m u l a e S b ( O O C R 1 ) 3 , KOOCR2 and Zn(OOCR3) a r e
i n d i v i d u a l l y c h o s e n f rom h y d r o c a r b y l g r o u p s c o n t a i n i n g
1 to 20 c a r b o n a t o m s .
3 . - A ge l c a t a l y s t c o m p o s i t i o n a c c o r d i n g to C l a i m
2, w h e r e i n R11 R 2 a n d R 3 a r e each a l k y l .
4. A ge l c a t a l y s t c o m p o s i t i o n a c c o r d i n g t o
C l a i m 3, w h e r e i n R1, R2 and R3 a r e e a c h
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5. A g e l c a t a l y s t c o m p o s i t i o n a c c o r d i n g to a n y
p r e c e d i n g c l a i m , w h i c h c o n t a i n s a s o l v e n t f o r t h e
c a r b o x y l a t e s .
6. A ge l c a t a l y s t c o m p o s i t i o n a c c o r d i n g t o
C l a i m 5, w h e r e i n t h e s o l v e n t i s a l i q u i d p o l y p r o p y l e n e
g l y c o l .
7. A m e t h o d f o r p r e p a r i n g r i g i d p o l y u r e t h a n e f o a m
by r e a c t i n g a p o l y o l c o n t a i n i n g a t l e a s t t h r e e a c t i v e
h y d r o g e n a t o m s w i t h a p o l y f u n c t i o n a l i s o c y a n a t e o r
i s o t h i o c y a n a t e in t h e p r e s e n c e of a g e l c a t a l y s t a n d
a b l o w i n g a g e n t , c h a r a c t e r i s e d in t h a t t h e r e i s
e m p l o y e d a g e l c a t a l y s t c o m p o s i t i o n a c c o r d i n g to a n y
one of C l a i m s 1 to 6 .
8. A m e t h o d a c c o r d i n g to C l a i m 7, w h e r e i n a
s i l i c o n - c o n t a i n i n g s u r f a c t a n t i s p r e s e n t .
9. A m e t h o d a c c o r d i n g to C l a i m 7 or C l a i m 8 ,
w h e r e i n t h e ge l c a t a l y s t c o m p o s i t i o n c o n t a i n s a s o l v e n t
f o r t h e c a r b o x y l a t e s , t h e s o l v e n t b e i n g m i s c i b l e w i t h
t h e p o l y o l .
10. A m e t h o d a c c o r d i n g to a n y o n e of C l a i m s 7 t o
9, w h e r e i n t h e r e is a l s o u s e d a n o t h e r ge l c a t a l y s t
known p e r se as a c a t a l y s t f o r r i g i d p o l y u r e t h e n e
f o a m s .
11. A m e t h o d a c c o r d i n g to a n y o n e of C l a i m s 7 t o
9, w h e r e i n t h e r e is a l s o u s e d a n o t h e r g e l c a t a l y s t
c h o s e n f rom t e r t i a r y a m i n e s , i n o r g a n i c t i n c o m p o u n d s
and o r g a n c t i n c o m p o u n d s .
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