Us 2831820
6
inite - 2,831,820 F OAMED EPOXY RESIN CQMPQSKTION AND METHOD 0F MAKING Arnold S . Aase and Luther L. Boistatl, Minneapolis, Minn., assignors to Minneapolis-Honeywell Regnlator Company, Minneapoiis, Minn., a corporanon o f Beta ware No Drawing. Application April 13, N53 Serial No. 348,558 13 Claims. (Cl. zoo-4.5) This invention relates to foamed resin-con?ning com~ positions including epoxy ether condensation polymers having the following structure wherein 2: stands for a number (such as 1 , 2 , 3 , etc.) and R tands for the hydrocarbon radical of a dihydric phenol such as bis~(4-hydroxyphenyl)-2,2-propane (“bis-phenol A”). Epoxy ether resins made by condensing epichloro hydrin and bis-(4-hydroxyphenyl)-2,2-propane (herein after referred t o a s “bis-phenol”) are available commer cially. i t i s a n object of the present invention to provide a n improved heat-curable uni-cellular resin foam composi~ tion which is extremely tough, durable and resilient, hav ing good electrical and mechanical properties, and having voids which are o f a uniform size and which are uniform l y distributed throughout the foamed material. I t is a further object of the present invention t o provide an improved resin foam composition which is especiall I adapted for use a s a potting material i n either very large o r very small containers. A otting material is used generally t o ?ll interstices i n a container which may house a plurality of individual components; for example, a n electrical device enclosed in an individual container and including a plurality of small and often very delicate components. After potting, the orientation of the com ponents i s ?xed and there is consequently less danger o their becoming disorganized, and thereby possibly caus ing improper operation or destruction o f the device. A resin foam of our invention i s adaptable for use a s a “foam—in-place” resin, that is, the reaction products are introduced into the container and the foaming accom plished therein. I t i s an additional object of the present invention t o provide a foam potting material which has improved surface wetting qualities, this material being especially r adaptable for ?lling each o f the interstices in the unit 30 35 40 50 which i s to b e potted, including even the extremely small interstices which are sometimes found in small and deli cate devices. I t is still another object o f the present invention t o provide foam composition which has a controllable e x pansion and cure rate and which i s extremely stable after foaming. This foam will not “fall” after initial expan sion; “fall” is a phenomena which is sometimes designated “post expansion shrinkage.” I t is still a further object o f the invention t o provide a potting material which has good surface adhesion prop erties, and which has a uniform rate of cure, therefore, a n orientation of the constituent parts f the unit which i s t o b e potted with the material of our invention and will not b e disturbed while the resin is being foamed in place. A $31,820 Patented Apr. 22, 1958 i 2 Other and further objects and features o f the present invention will become apparent from the following de scription and appended claims. The foam compositions utilized according t o the pres ent invention comprise a n epoxy resin (made by the reac tion o f epichlorohydrin and “bis-phenol A”) and char acterized b y having the number designed in the above noted structure formula a s x being equal t o between 0.3 and 20. I t should be noted however, that epoxy resins in question are actually mixtures o f compounds falling Within the indicated structure, and that the number here i n designated x is the average o f the individual integral numbers x which characterize each o f the compounds included i n these mixtures. A s the number x increases, the resins become increas ingly viscous. For some operations, a resin o f this type i s desirable. I f desired, for additional ease i n handling especial ly viscous epoxy resins, a diluent may be added to reduce the viscosity o f the base resin. A diluent which has been found t o b e very satisfactory is phenyl glycidyl ether. When such a diluent i s desired, it is generally used in relatively small portions with respect to the amount o f epoxy resin present. A esirable feature o f the diluent i s that it b e able to form a good, non fugitive resin. Phenyl-glycidyl other has this desirable property. 1 The foam esins o f the present invention also comprise an amine hardener which s taken from the class which includes para, para’ diamino methane, and a polyethylene-polyamine having the formula wherein y i s a number ranging from 0 t o 3 . The use of these hardeners with the above described epoxy base resin i s unique i n producing a very desirable uni-cellular, foamed or frothed compound. ‘ The constituents o f the foam compound and their re spective functions are as follows: Compound Function epoxy resin ___________ ___ ______ _. base resin. argme hérrdener a s herembefore hardener for base resin. e e . primary blowing ~ _ I provides gas for expansion f resin. auxiliary blowing agent. same function a s primary blowing agent, but also acts as a heat ab sorber for exothermic “setting” reaction, and may e a solvent for base resin constituents o f the compound. assists production o f uniform cell size. stabilizes foam after initial expan sion, optional in some ompositions. surface active agent___ foam tabilizer _____ _ According t o the present invention, these various com ponents are mixed together and the resulting mixtures subjected t o an elevated temperature sufficient t o cause the primary blowing agent t o “blow,” thereby foaming 01' frothing the prepared resin mixture. The blowing o f the primary and secondary blowing agents may take place as either a vaporization or a thermal decomposition o f the agent. The gas formed b y the vaporization o r ther mal decomposition o f the blowing agent or agents causes the remainder o f the resin composition t o expand and froth. The elevated temperature necessary for the “blowing” also accelerates the reaction between the base resin and the hardener thereby causing the resin t o “set” while it i s i n the foamed o r frothed state. I n some cases, a foam stabilizer is used t o stabilize the expanded foam
description
United states patent
Transcript of Us 2831820
7/21/2019 Us 2831820
http://slidepdf.com/reader/full/us-2831820 1/5
inite
-
2 , 8 3 1 , 8 2 0
F
OAMED EPOXY
RESIN CQMPQSKTION
AND
METHOD
0F MAKING
A r n o l d
S . A a s e
a n d
L u t h e r L .
B o i s t a t l ,
M i n n e a p o l i s ,
M i n n . ,
a s s i g n o r s t o M i n n e a p o l i s - H o n e y w e l l
R e g n l a t o r
Company, M i n n e a p o i i s , M i n n . , a
c o r p o r a n o n
o f
B e t a
ware
No D r a w i n g . A p p l i c a t i o n A p r i l
1 3 , N53
S e r i a l N o .
3 4 8 , 5 5 8
1 3 C l a i m s .
( C l .
z o o - 4 . 5 )
T h i s i n v e n t i o n r e l a t e s t o
foamed
r e s i n - c o n ? n i n g com~
p o s i t i o n s i n c l u d i n g e p o x y e t h e r c o n d e n s a t i o n p o l y m e r s
h a v i n g
t h e
f o l l o w i n g
s t r u c t u r e
w h e r e i n 2 :
s t a n d s f o r
a
number
( s u c h
a s
1 ,
2 ,
3 ,
e t c . )
a n d
R t a n d s f o r t h e h y d r o c a r b o n
r a d i c a l
o f a d i h y d r i c
p h e n o l
s u c h
a s
b i s ~ ( 4 - h y d r o x y p h e n y l ) - 2 , 2 - p r o p a n e ( “ b i s - p h e n o l
A ” ) . Epoxy e t h e r r e s i n s made b y
c o n d e n s i n g
e p i c h l o r o
h y d r i n
a n d
b i s - ( 4 - h y d r o x y p h e n y l ) - 2 , 2 - p r o p a n e
( h e r e i n
a f t e r
r e f e r r e d t o
a s
“ b i s - p h e n o l ” ) a r e a v a i l a b l e c o m m e r
c i a l l y .
i t i s a n o b j e c t o f t h e
p r e s e n t
i n v e n t i o n t o p r o v i d e a n
i m p r o v e d
h e a t - c u r a b l e u n i - c e l l u l a r
r e s i n
f o a m c o m p o s i ~
t i o n
w h i c h
i s
e x t r e m e l y
t o u g h ,
d u r a b l e
a n d
r e s i l i e n t ,
h a v
i n g
g o o d
e l e c t r i c a l
a n d
m e c h a n i c a l
p r o p e r t i e s ,
a n d
h a v i n g
v o i d s which a r e
o f a uniform
s i z e
and
which a r e
uniform
l y
d i s t r i b u t e d
t h r o u g h o u t t h e f o a m e d m a t e r i a l .
I t
i s a
f u r t h e r o b j e c t
o f
t h e p r e s e n t i n v e n t i o n
t o
p r o v i d e
an impro ved
r e s i n
f o a m
c o m p o s i t i o n which i s e s p e c i a l l I
adapted
f o r
u s e a s a p o t t i n g m a t e r i a l i n e i t h e r v e r y
l a r g e o r
v e r y
s m a l l
c o n t a i n e r s .
A o t t i n g m a t e r i a l i s
u s e d g e n e r a l l y
t o
? l l i n t e r s t i c e s
i n
a
c o n t a i n e r
which m a y
h o u s e a
p l u r a l i t y o f i n d i v i d u a l
c o m p o n e n t s ;
f o r e x a m p l e ,
an
e l e c t r i c a l d e v i c e
e n c l o s e d
i n an i n d i v i d u a l c o n t a i n e r
a n d i n c l u d i n g a p l u r a l i t y o f s m a l l a n d o f t e n
v e r y
d e l i c a t e
c o m p o n e n t s . A f t e r p o t t i n g , t h e
o r i e n t a t i o n
o f t h e c o m
p o n e n t s i s ? x e d a n d t h e r e i s
c o n s e q u e n t l y
l e s s d a n g e r
o f
t h e i r b e c o m i n g d i s o r g a n i z e d ,
a n d
t h e r e b y p o s s i b l y c a u s
i n g
i m p r o p e r
o p e r a t i o n o r
d e s t r u c t i o n
o f t h e
d e v i c e .
A
r e s i n
f o a m
o f
our
i n v e n t i o n
i s
a d a p t a b l e
f o r
u s e
a s
a
“ f o a m — i n - p l a c e ”
r e s i n ,
t h a t i s , t h e r e a c t i o n p r o d u c t s a r e
i n t r o d u c e d
i n t o
t h e c o n t a i n e r a n d t h e f o a m i n g accom
p l i s h e d
t h e r e i n .
I t i s
a n a d d i t i o n a l o b j e c t o f
t h e
p r e s e n t i n v e n t i o n
t o
p r o v i d e a foam p o t t i n g
m a t e r i a l
w h i c h h a s i m p r o v e d
s u r f a c e w e t t i n g
q u a l i t i e s ,
t h i s m a t e r i a l b e i n g e s p e c i a l l y r
a d a p t a b l e f o r ? l l i n g
e a c h o f
t h e
i n t e r s t i c e s i n
t h e
u n i t
30
35
40
50
which
i s
t o b e p o t t e d , i n c l u d i n g e v e n
t h e
e x t r e m e l y s m a l l
i n t e r s t i c e s which
a r e
s o m e t i m e s found i n s m a l l and d e l i
c a t e
d e v i c e s .
I t i s s t i l l a n o t h e r o b j e c t o f t h e p r e s e n t i n v e n t i o n
t o
p r o v i d e f o a m
c o m p o s i t i o n
which h a s a c o n t r o l l a b l e e x
p a n s i o n a n d
c u r e
r a t e a n d w h i c h i s e x t r e m e l y s t a b l e a f t e r
f o a m i n g .
T h i s foam w i l l
n o t “ f a l l ” a f t e r i n i t i a l e x p a n
s i o n ; “ f a l l ”
i s
a
phenomena w h i c h i s
s o m e t i m e s
d e s i g n a t e d
“ p o s t
e x p a n s i o n
s h r i n k a g e . ”
I t
i s s t i l l a f u r t h e r
o b j e c t
o f t h e i n v e n t i o n
t o
p r o v i d e
a
p o t t i n g
m a t e r i a l w h i c h h a s good s u r f a c e a d h e s i o n p r o p
e r t i e s , a n d w h i c h h a s a u n i f o r m r a t e o f c u r e ,
t h e r e f o r e ,
a n o r i e n t a t i o n
o f
t h e c o n s t i t u e n t
p a r t s
o f t h e u n i t w h i c h
i s t o b e p o t t e d w i t h t h e
m a t e r i a l
o f our i n v e n t i o n and
w i l l n o t b e d i s t u r b e d
w h i l e
t h e
r e s i n
i s b e i n g
f o a m e d
i n
p l a c e .
A
$31,820
P a t e n t e d
A p r . 2 2 ,
1 9 5 8
i
2
O t h e r a n d f u r t h e r o b j e c t s a n d
f e a t u r e s
o f t h e p r e s e n t
i n v e n t i o n
w i l l
b e c o m e a p p a r e n t f r o m t h e f o l l o w i n g
d e
s c r i p t i o n
a n d
a p p e n d e d
c l a i m s .
The foa m c o m p o s i t i o n s u t i l i z e d a c c o r d i n g t o t h e p r e s
e n t
i n v e n t i o n
c o m p r i s e
a n
epoxy
r e s i n (made
by
t h e
r e a c
t i o n o f
e p i c h l o r o h y d r i n
a n d “ b i s - p h e n o l A ” ) a n d c h a r
a c t e r i z e d b y h a v i n g t h e n u m b e r d e s i g n e d i n
t h e a b o v e
n o t e d s t r u c t u r e
formula
a s x
b e i n g e q u a l t o between 0 . 3
a n d 2 0 . I t s h o u l d b e n o t e d
h o w e v e r ,
t h a t
e p o x y r e s i n s
i n
q u e s t i o n a r e
a c t u a l l y m i x t u r e s
o f
c o m p o u n d s f a l l i n g
W i t h i n t h e i n d i c a t e d s t r u c t u r e , a n d
t h a t t h e number
h e r e
i n
d e s i g n a t e d
x
i s t h e a v e r a g e o f t h e
i n d i v i d u a l i n t e g r a l
numbers x w h i c h c h a r a c t e r i z e e a c h
o f
t h e compounds
i n c l u d e d
i n t h e s e
m i x t u r e s .
A s t h e number x i n c r e a s e s ,
t h e
r e s i n s become
i n c r e a s
i n g l y v i s c o u s . For
some
o p e r a t i o n s ,
a
r e s i n o f
t h i s t y p e
i s d e s i r a b l e .
I f
d e s i r e d , f o r
a d d i t i o n a l
e a s e i n h a n d l i n g
e s p e c i a ll y v i s c o u s
e p o x y
r e s i n s ,
a
d i l u e n t m a y b e a d d e d
t o r e d u c e t h e v i s c o s i t y o f t h e b a s e
r e s i n .
A d i l u e n t
w h i c h
h a s b e e n
f o u n d t o
b e v e r y s a t i s f a c t o r y i s p h e n y l
g l y c i d y l
e t h e r . When s u c h a
d i l u e n t
i s
d e s i r e d ,
i t i s
g e n e r a l l y
u s e d i n
r e l a t i v e l y
s m a l l
p o r t i o n s
w i t h r e s p e c t t o
t h e
amount o f
epoxy r e s i n p r e s e n t . A e s i r a b le f e a t u r e
o f t h e
d i l u e n t
i s
t h a t
i t
b e a b l e t o form a
g o o d ,
non
f u g i t i v e
r e s i n .
P h e n y l - g l y c i d y l o t h e r
h a s t h i s d e s i r a b l e
property. 1
The foam e s i n s
o f
t h e p r e s e n t i n v e n t i o n a l s o c o m p r i s e
an am ine h a r d e n e r which
i s
t a k e n
from
t h e
c l a s s
which
i n c l u d e s p a r a , p a r a ’ d i a m i n o d i p h e n y l m e t h a n e , a n d
a
p o l y e t h y l e n e - p o l y a m i n e
h a v i n g
t h e f o r m u l a
wherein y i s a number r a n g i n g from 0 t o 3 . The u s e o f
t h e s e h a r d e n e rs w i t h t h e a b o v e d e s c r i b e d e p o x y
b a s e
r e s i n
i s
u n i q u e i n p r o d u c i n g a
v e r y d e s i r a b l e
u n i - c e l l u l a r ,
foamed
o r
frothed c o m p o u n d. ‘
The
c o n s t i t u e n t s
o f
t h e f o a m compound and t h e i r r e
s p e c t i v e f u n c t i o n s a r e a s f o l l o w s :
Compound F u n c t i o n
epoxy
resin
___________ _ _ _
______
_. base resin.
a r g m e
h é r r d e n e r
a s
h e r e m b e f o r e h a r d e n e r
f o r
b a s e
r e s i n .
e e .
p r i m a r y
b l o w i n g
a g e n t _ _
~ _ I p r o v i d e s g a s
for expansion f resin.
a u x i l i a r y
b l o w i n g
a g e n t .
same
f u n c t i o n
a s primary blowing
a g e n t , but
a l s o
a c t s a s
a heat
ab
s o r b e r
f o r e x o t h e r m i c “ s e t t i n g ”
r e a c t i o n ,
and
may
e a s o l v e n t
f o r
b a s e r e s i n
c o n s t i t u e n t s o f
t h e
c o m p o u n d .
a s s i s t s
p r o d u c t i o n o f
u n i f o r m c e l l s i z e .
s t a b i l i z e s
foam
a f t e r
i n i t i a l
expan
s i o n , o p t i o n a l i n some
o m p o s i t i o n s .
s u r f a c e a c t i v e a g e n t _ _ _
foam tabilizer
_____ _
A c c o r d i n g t o t h e p r e s e n t i n v e n t i o n , t h e s e v a r i o u s
c o m
p o n e n t s a r e
mixed
t o g e t h e r a n d t h e
r e s u l t i n g
m i x t u r e s
s u b j e c t e d t o an
e l e v a t e d
t e m p e r a t u r e s u f f i c i e n t t o c a u s e
t h e p r i m a r y b l o w i n g
a g e n t t o “ b l o w , ”
t h e r e b y
f o a m i n g
0 1 '
f r o t h i n g
t h e p r e p a r e d
r e s i n
m i x t u r e . The
b l o w i n g
o f
t h e
p r i m a r y
a n d s e c o nd a r y b l o w i n g
a g e n t s may t a k e p l a c e
a s e i t h e r a
v a p o r i z a t i o n o r
a thermal decomp osition
o f
t h e a g e n t . The g a s formed
b y
t h e v a p o r i z a t i o n
o r t h e r
mal d e c o m p o s i t i o n o f t h e b l o w i n g a g e n t o r a g e n t s c a u s e s
t h e
r e m a i n d e r
o f t h e r e s i n
c o m p o s i t i o n
t o e x p a n d a n d
f r o t h .
The e l e v a t e d t e m p e r a t u r e
n e c e s s a r y
f o r t h e
“ b l o w i n g ”
a l s o a c c e l e r a t e s t h e r e a c t i o n b e t w e e n t h e b a s e
r e s i n
a n d
t h e h a r d e n e r
t h e r e b y c a u s i n g
t h e r e s i n
t o
“ s e t ”
w h i l e i t i s i n t h e foamed
o r
f r o t h e d s t a t e .
I n
some
c a s e s ,
a foam
s t a b i l i z e r i s
u s e d
t o
s t a b i l i z e
t h e e x p a n d e d foam
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2 , 8 3 1 , 8 2 0
i m m e d i a t e l y
u p o n
e x p a n s i o n a n d
b e f o r e
t h e r e s i n
h a s
s o l i d i ? e d .
The h a r d e n e r s
which we h a v e f o u n d t o be p r e f e r r e d
a r e p a r a , p a r a ’
d i a m i n o
d i p h e n y l m e t h a n e , a n d a p o l y
ethylenepolyamine
having a
s t r u c t u r a l formula
w h e r e i n
y r e p r e s e n t s a
number r a n g i n g
from 0
t o
3 .
The
number
r e p r e s e n t e d
by
y i s a c t u a l l y an
a v e r a g
o f i n d i
v i d u a l
numbers
o f v a r i o u s
compounds i n c l u d e d i n t h e 1
p o l y a m i n e
m i x t u r e .
B o t h c o m p o u n d s a r e c o m m e r c i a l l y
a v a i l a b l e .
B o t h compounds
h a v e a c t i v e h y d r o g e n s o n
the
end
of t h e molecules.
I t
i s
t h e
f u n c t i o n o f
t h e
p r i m a r y b l o w i n g a g e n t
t o
p r o
v i d e g a s
w h i c h
p r o p e r l y f r o t h s t h e m i x t u r e . I n a c c o r d
ance w i t h t h e p r o c e s s d i s c l o s e d h e r e i n , , a t h e r m a l l y r e
s p o n s i v e p r i m a r y
b l o w i n g
a g e n t i s
u s e d .
T h i s t h e r m a l
r e s p o n s e
m a y b e e i t h e r a t h e r m a l d e c o m p o s i t i o n p e r
s e ,
o r a v a p o r i z a t i o n . A u r t h e r d e s i r a b l e
c h a r a c t e r i s t i c
o f
t h e
p r i m a r y b l o w i n g a g e n t
i s
t h a t
t h e
d e c o m p o s i t i o n b e
e x o t h e r m i c ; however
h i s
l a t t e r
c h a r a c t e r i s t i c
i s
n o t n e c e s
s a r y t o
t h e
p r o c e s s ,
a n d
e n d o t h e r m i c a l l y
d e c o m p o s a b l e
m a t e r i a l s
m a y b e u t i l i z e d s a t i s f a c t o r i l y . For t h i s p u r
p o s e , many compounds
a r e
s a t i s f a c t o r y . A m o n g t h e s e
a r e
diazo-aminobenzene, d i n i t r o s o
pentamethylene
t e t -
- -
r a m i n e ,
ammonium c a r b o n a t e , ammonium
c a r b a m a t e , h y
d r o g e n p e r o x i d e , a n d p , p ’ o x y b i s ( b e n z e n e s u l f o n y l
h y
d r a z i d e ) . The
a t t e r m a t e r i a l
i s t h e s u b j e c t
o f P a t e n t
No.
2 , 5 5 2 , 0 6 5 t o S c h o e n e , a n d
r e f e r e n c e
i s made t o t h i s
p a t
o u t
f o r
a d e s c r i p t i o n o f t h e m a t e r i a l and f o r a method
o f
p r e p a r i n g s a m e . I t i s i n t e r e s t i n g t o n o t e a t t h i s p o i n t
t h a t ,
d u e
t o t h e d i f f e r i n g d e c o m p o s i t i o n o r
b l o w i n g
tem
p e r a t u r e s o f
t h e a f o r e m e n t i o n e d
c o m p o u n d s ,
v a r i o u s
o p
e r a t i n g
t e m p e r a t u r e s
m u s t
b e e m p l o y e d .
O p e r a t i n g t e m
p e r a t u r e s
which we h a v e f o u n d s a t i s f a c t o r y f o r v a r i o u s
blowing
a g e n t s
a r e
a s
f o l l o w s :
Blowing
a g e n t :
T e m p e r a t u r e ,
°
F .
Diazo aminobenzene
___________________ _
200
Dinitroso
pentamethylene
tetra-amine
________ 200
p,p'Oxybis benzenesulfonyl hydrazide
______ __ 2 2 5
Ammonium
carbonate
___________________ _ 140
Naphtha. ____ 225
T h e s e t e m p e r a t u r e s a r e n o t i n t h e m s e l v e s
c r i t i c a l ,
and
i t
i s u n d e r s t o o d
t h a t t h e r e i s
a r a n g e o f
t e m p e r a t u r e s
w i t h i n
w h i c h t h e r e a c t i o n w i l l p r o p e r l y p r o c e e d p r o v i d e d
t h e
t e m p e r a t u r e i s i n
e x c e s s o f
t h e d e c o m p o s i t i o n
tem
p e r a t u r e
o f t h e m a t e r i a l . I t w i l l
b e
f u r t h e r
u n d e r s t o o d
t h a t v a r i o u s
o t h e r b l o w i n g
a g e n t s m a y b e
u s e d s u c c e s s
f u l l y ,
a n d
t h e r e
i s , t h e r e f o r e ,
no i n t e n t i o n
o f l i m i t i n g t h e
s c o p e
o f t h e p r e s e n t i n v e n t i o n t o t h e s p e c i ? c b l o w i n g
a g e n t s m e n t i o n e d
a b o v e .
In some c a s e s ,
i t
i s
n e c e s s a r y
t o
u s e
an a u x i l i a r y blow
i n g
a g e n t
t o d i s s i p a t e
h e a t g e n e r a t e d
i n t h e e x o t h e r m i c
d e c o m p o s i t i o n r e a c t i o n o f t h e p r i m a r y b l o w i n g a g e n t .
An
n d o t h e r m i c a l l y
v o l a t i l e m a t e r i a l i s
u s e d
f o r t h i s p u r -
p o s e .
Among
t h e
m a t e r i a l s which we
have
found
s a t
i s f a c t o r y a s a u x i l i a r y b l o w i n g a g e n t a r e t o l u e n e , naph
t h a , e t h y l e n e
c h l o r i d e ,
m e t h y l ,
e t h y l , n - p r o p y l
a n d n
b u t y l
a l c o h o l s , t r i c h l o r o
e t h y l e n e , p e r c h l o r o - e t h y l e n e , l o w
b o i l i n g k e t o n e s , b e n z e n e a n d x y l e n e . O t h e r c o m p o u n d s
h a v i n g s i m i l a r p h y s i c a l p r o p e rt i e s
may
l i k e w i s e b e
s u c
c e s s f u 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 ,
p r o v i d e d
t h e y a r e
c o m p a t i b l e
w i t h t h e
o t h e r c o n s t i t u e n t s .
A
f o a m
s t a b i l i z e r m a y b e
i n c l u d e d
i n
t h e
m i x t u r e
f o r
t h e p u r p o s e o f “ s e t t i n g ” t h e foam
a n d
p r e v e n t i n g
c o l
l a p s e o r
“ f a l l ” o f
t h e
foam a f t e r
i n i t i a l
e x p a n s i o n a n d
b e f o r e c o m p l e t e h a r d e n i n g
o f t h e r e s i n . A m o n g
t h e
c o m
pounds which we
p r e f e r
t o u s e
a r e
t h e c o n d e n s a t i o n p r o d
u c t
f o r m e d
from t h e
r e a c t i o n
b e t w e e n
p o l y v i n y l
a l c o h o l
and e i t h e r
formaldehyde
o r
acetaldehyde. Such com
p o u n d s a r e c o m m e r c i a l l y a v a i l a b l e , f o r e x a m p l e , t h e
S h a w i n i g a n C h e m i c a l Company o f New York
m a r k e t s
such a
m a t e r i a l under t h e
t r a d e name
“Formvar
1 5 / 95E.”
Compounds
w h i c h a r e
s a t i s f a c t o r y
a s
p l a s t i c i z e r s
p a r t i c u
S i )
55
6 0
65
70
7 5
4
i a r l y
when t h e s e compounds a r e u s e d i n t h i s r e g a r d a r e
t r i - o c r e s y l
p h o s p h a t e
a n d d i o c t y l p h t h a l a t e . T h e s e
com
p o u n d s
a r e
c o m m e r c i a l l y a v a i l a b l e . T h u s , i n
p r a c t i c e ,
a
b a l a n c e must b e m a i n t a i n e d b e t w e e n t h e r a t e o f b l o w i n g
a n d t h e s e t t i n g r a t e o f t h e r e s i n i n o r d e r t h a t t h e r e s i n
w i l l n o t
s e t
b e f o r e t h e b l o w i n g i s c o m p l e t e d n o r , on t h e
o t h e r h a n d , w i l l i t “ f a l l ” b e f o r e s e t t i n g . T h i s b a l a n c e
i s
a i d e d b y t h e
a d d i t i o n o f
t h e
foam
s t a b i l i z e r
s i n c e
t h e s e
s t a b i l i z e r s
t e m p o r a r i l y “ s e t ”
t h e
foam b e f o r e i t
w i l l ‘ b e
a b l e
t o h o l d i t s e l f
i n
p l a c e
a n d
w h i l e t h e b a s i c
r e a c t i o n
b e t w e e n t h e
b a s e
r e s i n
and
h a r d e n e r
i s
s t i l l i n p r o g r e s s .
A more uniform c e l l s i z e i s o b t a i n e d
by
t h e u s e o f a
s u r f a c e a c t i v e a g e n t .
I n t h i s c o n n e c t i o n , we
p r e f e r t o
u s e a n o n - i o n i c t y p e a c t i v a t o r , s u c h
a s
p o l y o x y g l y c o l
hav
i n g
t h e f o l l o w i n g s t r u c t u r e :
w h e r e i n b i s e q u a l
t o a t l e a s t 1 5 ,
a n d
w h e r e i n
t h e
e t h y l
e n e o x i d e p o r t i o n o f t h e m o l e c u l e c o m p r i s e s from
1 6
t o
8 0 p e r c e n t
o f
t h e m o l e c u l a r
w e i g h t o f
t h e
m a t e r i a l .
S u c h
compounds
a r e c o m m e r c i a l l y a v a i l a b l e . F o r e x a m p l e ,
W y a n d o t t e C h e m i c a l
C o r p o r a t i o n o f W y a n d o t t e , M i c h i
g a n , m a r k e t s s u c h a compound
u n d e r
t h e t r a d e
name
“ P l u r o n i c s . ”
I n t h e p r e f e r r e d
m o d i ? c a t i o n
o f
t h e
p r e s e n t
i n v e n t i o n ,
a s t o c k
r e s i n
i s ma de up
which
i n c l u d e s t h e b a s e r e s i n ,
p r i m a r y b l o w i n g a g e n t , s u r f a c e
a c t i v e
a g e n t ,
foam
s t a
b i l i z e r , a n d a u x i l i a r y b l o w i n g a g e n t .
T h i s
s t o c k r e s i n
h a s
a l o n g s h e l f l i f e , and m a y
b e
mixed
up a
r e a s o n a b l e
t i m e
b e f o r e
u s e .
When t h e r e s i n i s t o
b e
u s e d ,
i t
i s
mixed w i t h an
amine
h a r d e n e r s u c h a s
t h o s e p r e v i o u s l y
d e s c r i b e d
a n d
t h e m i x t u r e i s h e a t e d u n t i l i t i s f r o t h e d
and
c u r e d .
The c o n s t i t u e n t s o f t h e s t o c k r e s i n
m a y ,
f o r
e x a m p l e , b e mixed a c c o r d i n g
t o
t h e p r o p o r t i o n s s e t o u t i n
T a b l e I
b e l o w .
TABLE
P a r t s .
C o n s t i t u e n t :
g e n e r a l
r a n g e
Epoxy
r e s i n
9 5
Primary blowing
agent ____________ _
0 . 1
t o 10
Auxiliary
blowing agent______________ 0 t o 55
Surface active
agent
_______________
__ 0.01
t o 2.5
Foam stabilizer___________________
_ 0m
5
To h e above
s t o c k
r e s i n
i s added
an am ine hardener
a s
s e t f o r t h p r e v i o u s l y i n
t h e
r a t i o o f
a b o u t
2 . 0 t o Z O - p a r t s
b a s e r e s i n
t o
1 p a r t h a r d e n e r .
I n o r d e r t o
e n c a p u s l a t e a
u n i t , t h e u n i t t o b e e n c a p s u
l a t e d i s p r e f e r a b l y p r e h e a t e d
t o
a
t e m p e r a t u r e
o f a b o u t
2 5 0 °
F . , f o r
e x a m p l e .
The s t o c k r e s i n s e t f o r t h i n
T a b l e
I i s
mixed
w i t h
a
h a r d e n e r t a k e n
from t h e c l a s s
c o n s i s t
i n g o f a
p o l y e t h y l e n e - p o l y a m i n e ,
a s p r e v i o u s l y d e s c r i b e d ,
a n d p a r a ,
p a r a ’
d i a m i n o
d i p h e n y l m e t h a n e ; a n d t h e m i x
t u r e
p l a c e d
i n t h e u n i t . Foaming t a k e s p l a c e w i t h i n
5
t o
20
m i n u t e s
and t h e u n i t m a y
b e
removed from t h e oven
a t
t h a t t i m e , h o w e v e r , i t i s g e n e r a l l y more d e s i r a b l e t o
a l l o w t h e
u n i t t o
r e m a i n
i n
t h e
h e a t i n g chamber
f o r
a
l o n g e r p e r i o d o f
t i m e s i n c e a
p o s t - e x p a n s i o n c u r e s u c h
a s
t h i s w i l l
e n h a n c e
t h e h i g h t e m p e r a t u r e
r e s i s t i v i t y o f
t h e
f o a m .
T h e
f o l l o w i n g s p e c i ? c e x a m p l e s
i l l u s t r a t e
t h e
i n v e n t i o n :
E x a m p l e I
C o m p o s i t i o n : P a r t s
B a s e r e s i n
A 7 1 . 2 5
H a r d e n e r
( p a r a , p a r a ’
d i a m i n o
d i p h e n y l
methane) _________________________
_
B l o w i n g a g e n t f p , p ’ - o x y b i s
( b e n z e n e
s u l
fonyl
hydrazide)l ___________________ _
0.80
Auxiliary
blowing agent
(naphtha)
_______ __
1 0 . 9 0
S u r f a c e a c t i v e a g e n t ( p o l y o x y g l y c o l ) _____ _ 0 . 0 5
T h e
h a r d e n e r i s ’ m e l t e d a n d r a p i d l y m i x e d
w i t h t h e
b a s e r e s i n . To
h i s
r e s i n - h a r d e n e r m i x t u r e
t h e
o t h e r c o m
p o n e n t s a r e a d d e d a n d
t h o r o u g h l y m i x e d . T h i s m i x t u r e
7/21/2019 Us 2831820
http://slidepdf.com/reader/full/us-2831820 3/5
2 , 8 3 1 , 8 2 0
5
i s
t h e n f r o t h e d f o r a t i m e
a t
a
t e m p e r a t u r e
o f
from
2 2 5 ° ~
F .
t o
2 5 0 °
F . , d u r i n g
w h i c h
i t
e x p a n d s
t o a b o u t
1 0 t i m e s
i t s v o l u m e . T h i s p r o d u c e s . a foam h a v i n g a d e n s i t y o f
a p p r o x i m a t e l y 5 pounds p e r c u b i c f o o t and a c o m p r e s
s i v e
s t r e n g t h
o f o v e r 1 0 0 pounds p e r s q u a r e i n c h .
E x a m p l e
I I
The
c o m p o s i t i o n
o f E x a m p l e I e x c e p t
t h a t
t h e b l o w
i n g a g e n t u s e d
i s
d i n i t r o s o p e n t a m e t h y l e n e t e t r a - a m i n e o r
ammonium c a r b o n a t e .
E x a m p l e I I I
C o m p o s i t i o n : P a r t s
B a se resin B
__________________________
_
6 6
Hardener (polyethylene-polyamine) _______ _ 14
B l o w i n g
a g e n t l p a r a , p a r a ’ o x y b i s ( b e n z e n e
sulfonyl hydrazide)] ____________________ 0.95
A u x i l i a r y
blowing agent ( t o l u e n e ) ________ __ 1 3
Resin m o di?er (tri-o-cresylphosphate)
_____
__
6
Surface a c t i v e agent
( polyox yg lycol)
________
0.05
The
c o n s t i t u e n t s o f t h i s
c o m p o s i t i o n a r e t h o r o u g h l y
mixed and
h e a t e d
t o
a
t e m p e r a t u r e
o f
from
250° F .
t o
2 6 0 °
F .
The
r e s i n
e x p a n d s t o
6 o r 7 t i m e s i n
v o l u m e , and
p r o d u c e s a fo a m h a v i n g a d e n s i t y
o f from 8
t o 9 pounds
p e r c u b i c
f o o t , a n d
h a v i n g a c o m p r e s s i v e s t r e n g t h o f
a p p r o x i m a t e l y 3 0 0
p o u n d s
p e r s q u a r e i n c h .
E x a m p l e
IV
The
c o m p o s i t i o n o f
E x a m p l e I I I w i t h
t h e - e x c e p t i o n o f
t h e
‘ r e s i n m o d i ? e r ; i n
t h i s
e x a m p l e 6 p a r t s o f d i o c t y l
p h t h a l a t e a r e u s e d i n l i e u o f
t h e t r i - c r e s y l
p h o s p h a t e . T h i s
p r o d u c e s a r e s i n
w h i c h
i s
e x t r e m e l y
s t r o n g , e x p a n d i n g
t o a b o u t 3 t i m e s i t s o r i g i n a l v o l u m e . The c o m p r e s s i v e
s t r e n g t h
o f
t h i s
foam
i s i n e x c e s s o f 3 0 0 p o u n d s
p e r ‘
s q u a r e i n c h .
E x a m p l e
V
C o m p o s i t i o n :
P a r t s
B a s e resin C _________________________ _
57.00
Hardener
(polyethylene-polyamine)
______
_ 4.00
B l o w i n g
a g e n t E p a r a , p a r a ’ ( b e n z e n e s u l f o n y l
hydrazide)]
________________________
_ 0.95
A u x i l i a r y b l o w i n g a g e n t ( p e r c h l o r o e t h y l e n e ) - 3 1 . 0 0
Surface a c t i v e agent
(polyox yg lycol)
_____ __ 0.05
Resin
modi?er (tri-o-cresylphosphate)
____
__
7.00
T h i s
m i x t u r e i s
t h o r o u g h l y m i x e d a n d h e a t e d
t o
b e
t w e e n 3 0 0 and 3 5 0 °
F . The m a t e r i a l
expanded
t o from
3 t o
5
t i m e s
i t s
o r i g i n a l
v o l u m e ,
y i e l d i n g
a
f r o t h e d
r e s i n
h a v i n g a c o m p r e s s i v e
s t r e n g t h o f
a b o u t
3 0 0
p o u n d s p e r
s q u a r e
i n c h .
C 1
U r
1 0
0
4 5
some
o f t h e m a t e r i a l s i n t h e
m i x t u r e ,
f o r
e x a m p l e ,
t h e
e p o x y
b a s e r e s i n ,
w i l l
c h a r d u r i n g
t h e
r e a c t i o n
i f
a n op
e r a t i n g t e m p e r a t u r e
s u b s t a n t i a l l y i n
e x c e s s o f 3 5 0 ° F .
i s u s e d . I t m a y b e s e e n , h o w e v e r , t h a t
a s
t h e b l o w i n g
t e m p e r a t u r e i s
i n c r e a s e d , t h e
q u a n t i t y o f
a u x i l i a r y
b l o w
i n g a g e n t
n e e d e d i s
a l s o
i n c r e a s e d .
I n
E x a m p l e
VI
f o r
i n s t a n c e , t h e
o p e r a t i n g
t e m p e r a t u r e
i s
i n t h e
r a n g e
o f
f r om 300° F . t o 350° F .
and
t h e r e l a t i v e amount o f
aux
i l i a r y
b l o w i n g a g e n t
i s s u b s t a n t i a l l y i n c r e a s e d o v e r t h a t
o f
t h e o t h e r e x a m p l e s .
I n a d d i t i o n
t o
u s e
a s
a p o t t i n g m a t e r i a l ,
t h e
composi
t i o n o f t h e
p r e s e n t
i n v e n t i o n
m a y b e
s a t i s f a c t o r i l y u s e d
f o r o t h e r p u r p o s e s , f o r e x a m p l e e l e c t r i c a l
i n s u l a t i o n .
I n
o t h e r
u s e s , t h e
r e s i n
m a y
b e formed'in b l o c k s o r
s h e e t s
and
a t e r c u t t o p r o p e r s i z e and s h a p e .
The f r o t h e d
s e t r e s i n o f t h e
p r e s e n t i n v e n t i o n
h a s
a
d e n s i t y o f from
3
t o
9
p o u n d s p e r c u b i c
f o o t ,
‘ a n d h a s
a c o m p r e s s i v e
s t r e n g t h
o f from 1 0 0
t o
300
pounds
o r more
p e r s q u a r e i n c h . T h i s
r e s i n i s w h i t e
i n c o l o r
and
s
v e r y
t o u g h a n d d u r a b l e .
T h i s
compound s a l s o
c h a r a c t e r i z e d
b y
i t s
v e r y
e x c e l l e n t
h e a t
a n d
e l e c t r i c a l
i n s u l a t i n g
p r o p
e r t i e s . I n a d d i t i o n , t h i s
m a t e r i a l ,
b e c a u s e o f
i t s
s u r f a c e
a d h e s i o n p r o p e r t i e s , t e n d s t o
f o l l o w
a l o n g a l l s u r f a c e s
a s i t e x p a n d s a n d t h u s
c o m p l e t e l y
c o v e r s t h e p o t t e d
o b
j e c t s w i t h o u t l e a v i n g u n d e s i r e d v o i d s . F u r t h e r , b e c a u s e
i t h a s t h e s e g o o d s u r f a c e a d h e s i o n p r o p e r t i e s
w h i l e
s t i l l
? u i d , no undue f o r c e s
a r e
e x e r t e d
a g a i n s t
t h e e l e m e n t s
b e i n g
e n c a p s u l a t e d .
A l t h o u g h v a r i o u s s p e c i ? c e m b o d i m e n t s
o f
t h e i n v e n
t i o n h e r e i n
h a v e
b e e n
d i s c l o s e d ,
i t
w i l l
b e
u n d e r s t o o d
t h a t
t h e r e
i s
no i n t e n t i o n
t o
l i m i t t h e
s c o p e o f t h e p r e s
e n t
i n v e n t i o n t o
t h e s e s p e c i ? c e m b o d i m e n t s a l o n e , s i n c e
t h e y
a r e
u s e d
f o r
p u r p o s e s
o f i l l u s t r a t i o n o n l y . Many
d e t a i l s o f
c o m p o s i t i o n
and
p r o c e d u r e
m a y b e v a r i e d
w i t h
o u t d e p a r t i n g f r o m t h e ‘ p r i n c i p l e s o f t h i s i n v e n t i o n . I t
i s
t h e r e f o r e
i n t e n d e d
t h a t t h e
s c o p e o f
t h i s
i n v e n t i o n
b e
l i m i t e d
o n l y b y
t h e
a p p e n d e d
c l a i m s .
We l a i m a s our i n v e n t i o n :
1 . A o a m a b l e r e s i n c o m p o s i t i o n
c h a r a c t e r i z e d
b y s t a
‘ b i l i t y
upon foaming which
c o m p r i s e s
a
b a s e
r e s i n , a blow
i n g a g e n t
c a p a b l e
o f
c h e m i c a l l y d e c o m p o s i n g
t o f o r m a
g a s a t
e l e v a t e d
t e m p e r a t u r e t o fo am s a i d r e s i n ,
s a i d
b l o W
i n g a g e n t b e i n g t a k e n f r o m t h e
c l a s s
c o n s i s t i n g o f d i a z o
a m i n o
b e n z e n e ,
ammonium c a r b o n a t e , ammonium c a r
b a m a t e , d i n i t r o s o p e n t a m e t h y l e n e t e t r a m i n e a n d
p , p ’
o x y b i s ( b e n z e n e su l f o n y l h y d r a z i d e ) , a h a r d e n e r f o r s a i d
r e s i n , and a foam s t a b i l i z e r t o p r e v e n t
c o l l a p s e
o f
t h e
r e s i n a f t e r f o a m i n g b u t b e f o r e h a r d e n i n g , s a i d b a s e r e s i n
h a v i n g
t h e s t r u c t u r a l f o r m u l a
E x a m p l e V I
C o m p o s i t i o n : P a r t s
B a s e
resin
D
_________________________
_ 72.00
Hardener (polyethylene-polyamine)
______
__
18.00
B l o w i n g a g e n t
[ p a r a , p a r a ’
o x y b i s
( ‘ b e n z e n e
sulfonyl
hydrazide)] _________________ __
0.95
Surface
a c t i v e
agent (polyoxyglycol) _____ __ 0.05
A u x i l i a r y b l o w i n g a g e n t ( N - p r o p y l a l c o h o l ) _ 5 . 0 0
R e s i n m o d i ? e r
( c o n d e n s a t i o n
p r o d u c t
f r o m
f o r m a l d e h y d e a n d p o l y v i n y l
a l c o h o l ) _ - - -
4 . 0 0
The c o m p o s i t i o n i s
t h o r o u g h l y m i x e d
a n d
h e a t e d t o
2 2 5 ° F .
and
a l l o w e d
t o f r o t h .
A e r y good
foam
s
p r o
d u c e d , h a v i n g a d e n s i t y
o f
4
t o
5 p o u n d s
p e r c u b i c
f o o t ,
a n d
h a v i n g
a
c o m p r e s s i v e
s t r e n g t h
o f
a b o u t 1 0 0
p o u n d s
p e r
s q u a r e i n c h .
“Epoxy number” s
d e ? n e d a s
number o f e p o x y e q u i v a ~
l e n t s p e r 1 0 0 grams o f b a s e
r e s i n .
I n t h e f o r e g o i n g e x
a m p l e s ,
t h e
b a s e
r e s i n s h a v e t h e
f o l l o w i n g
e p o x y num
b e r s : v b a s e
r e s i n
A , a b o u t 0 . 4 , b a s e r e s i n
B ,
a b o u t 0 . 2 ,
b a s e
r e s i n C , a b o u t
0 . 1 ,
b a s e
r e s i n D ,
a b o u t 0 . 0 5 .
The
t o p p r a c t i c a l t e m p e r a t u r e r a n g e o f
t h e s e
s y s t e m s
i s a p p r o x i m a t e l y 3 5 0 ° F . T h i s i s d u e t o t h e f a c t t h a t
6 5
7 5
w h e r e i n
R t a n d s f o r t h e h y d r o c a r b o n r a d i c a l o f a d i
h y d r i c
p h e n o l and
x
h a s
a
v a l u e
o f
b e t w e e n 0 . 3 and 2 0 ,
a n d
b e i n g p r e p a r e d
a s t h e
c o n d e n s a t i o n
p r o d u c t
o f e p i
c h l o r o h y d r i n
a n d
b i s - ( 4 - h y d r o x y p h e n y l ) - 2 ,
2
p r o p a n e ,
s a i d h a r d e n e r b e i n g
t a k e n f r o m
t h e c l a s s
c o n s i s t i n g
o f
p a r a ,
p a r a ’
d i a m i n o d i p h e n y l m e t h a n e , a n d a compound
h a v i n g
t h e s t r u c t u r a l f o r m u l a
w h e r e i n
y
i s a number
g r e a t e r
t h a n 0
and
r a n g i n g
up
t o
3 , s a i d s t a b i l i z e r c o n s i s t i n g
e s s e n t i a l l y
o f t h e a n h y d r o u s
c o n d e n sa t i o n p r o d u c t
o f p o l y v i n y l a l c o h o l
a n d
a n a l d e
h y d e c o n t a i n i n g l e s s
t h a n
3 c a r b o n a t o m s .
2 .
The
f o a m a b l e
r e s i n
c o m p o s i t i o n
o f c l a i m
1
w h e r e i n
o n e
p a r t o f
h a r d e n e r
i s p r e s e n t f o r
two
t o t w e n t y p a r t s
o f r e s i n .
3 .
The f o a m a b l e
r e s i n
c o m p o s i t i o n
o f c l a i m 1
w h e r e i n
s a i d
s t a b i l i z e r i s p r e s e n t i n t h e amount o f one t o ? f t e e n
p a r t s f o r
e a c h
n i n e t y - ? v e p a r t s
o f b a s e
r e s i n .
4 . The f o a m a b l e r e s i n c o m p o s i t i o n o f c l a i m 3 w h e r e i n
s a i d b l o w i n g a g e n t i s t a k e n f r o m
t h e
c l a s s
c o n s i s t i n g o f
p , p ’ o x y b i s ( b e n z e n e s u l f o n y l h y d r a z i d e ) ,
d i n i t r o s o
p e n t a
7/21/2019 Us 2831820
http://slidepdf.com/reader/full/us-2831820 4/5
2 , 8 3 1 , 8 2 0
7 8
m e t h y l e n e t e t r a a m i n e , d i a z o a m i n o
b e n z e n e , a n d a m m o n i -
i u g a g e n t t a k e n
f r o m
t h e c l a s s c o n s i s t i n g o f t o l u e n e , b u t y l
um a r b o n a t e . a l c o h o l , n a p h t h a , e t h y l e n e c h l o r i d e ,
p e r c h l o r o e t h y l e n e
5 . The
f o a r n a b l e r e s i n
c o m p o s i t i o n
o f c l a i m 3 w h e r e i n a n d
t r i c h l o r o e t h y l e n e ,
s a i d
c o m p o s i t i o n
b e i n g m i x e d
i n
s a i d s t a b i l i z e r i s p o l y v i n y l f o r m a l .
t h e
f o l l o w i n g p r o p o r t i on s :
A o a m a b l e r e s n _ c o m p o s t o n c h a r a c t e r i z e d b y s t a - a C o n s t i t u e n t : P a r t s
b l l l l ' . Y
upon
foam ing which
c o m p r i s e s
a b a s e
r e s i n ,
a blow- Base
red“ 95
i n g
agent
capable
of chemically decomposing t o f o r m a
-
n
p
. . . Blowing
agent____________________ .
0.1
to
10
g a s a t e l e v a t e d t e m p e r a t u r e
t o
roam
f r o m
s a i d r e s i n , s a i d Hardener
4 5 t o 50
blowing agent being
taken
f r o m t h e
c l a s s
c o n s i s t i n g
o f
S t
b ‘ l t t 15
diazo a mi n o benzene ammonium carbonate ammonium
1 0 a HZBLT
u p
0
c a r b a m a t e d i n i t r o s o p e n t a m e t h y l e n e t e t r a m i u e a n d
p
i n ’ s u r f a c e a c t i v e a g e n t 0 0 1 t o
2 5
o x y b i s ( b e n z e n e s u l f o n y l h y d r a z i d e ) , one p a r t o f
a
h a r d — A u x i l i a r y blowing a g m t up t o 5 5
e n e r f o r
two t o
t w e n t y
p a r t s
o f s a i d b a s e r e s i n , o n e t o ? f - 8 . A n i c e l l u l a r foamed
r e s i n
c o m p o s i t i o n c o m p r i s i n g
t e e n
p a r t s o f
p o l y v i n y l f o r m a l s t a b i l i z e r
f o r
e a c h
n i n e t y -
a b a s e r e s i n h a v i n g t h e s t r u c t u r a l f o r m u l a
? v e p a r t s o f
r e s i n ‘ t o p r e v e n t
c o l l a p s e
o f
t h e r e s i n
a f t e r w h e r e i n R
t a n d s f o r t h e
h y d r o c a r b o n
r a d i c a l o f a
d i h y
foaming b u t b e f o r e h a r d e n i n g , and
a
s u r f a c e a c t i v e
a g e n t , 2 9 d r i c
p h e n o l
and x h a s
a v a l u e
o f
between
0 . 3
and
2 0 ,
and
s a i d
b a s e
r e s i n
h a v i n g t h e f o l l o w i n g
s t r u c t u r a l
f o r m u l a
b e i n g p r e p a r e d
a s
t h e c o n d e n sa t i o n p r o d u c t o f
e p i c h l o r o
w h e r e i n
R t a n d s f o r t h e h y d r o c a r b o n r a d i c a l
o f a
d i h y d r i c h y d r i n
a n d b i s - ( 4 - h y d r o x y p h e n y l ) - 2 , 2
p r o p a n e ,
a h a r d —
phenol
and
x h a s a v a l u e o f
between
0 . 3
and
2 0 ,
and
e n e r f o r
s a i d r e s i n
t a k e n
from
t h e group
c o n s i s t i n g
o f
b e i n g
p r e p a r e d
a s t h e c o n d e n s a t i o n
p r o d u c t
o f e p i c h l o r o - p a r a , p a r a ’ d i a m i n o d i p h e n y l m e t h a n e a n d a compound
h y d r i n a n d b i s - ( 4 - h y d r o x y p h e n y D - 2 , 2 p r o p a n e , s a i d
3 0
h a v i n g t h e s t r u c t u r a l
f o r m u l a
hardener
being
taken from the class consisting o f para, __ _ __
p a r a ’
a n d
d i a m i n o d i p h e n y l m e t h a n e
a n d a
c o m p o u n d
_ - H 2 I T I
( C H 2
CHzNH ) y C H z CHzNHz
h a v i n g t h e
S t r u c t u r a l formula
w h e r e i n y
1 5
a
number
r e a t e r t h a n 0 and r a n g i n g up
t o
3 ,
and a s t a b i l i z e r f o r s a i d r e s i n
c o n s i s t i n g
o f
t h e
a n h y d r o u s
H 2N'T(CH 2—CH 2NH_)yCH 2_CH 2NH 2 3 5
c o n d e n s a t i o n
p r o d u c t
o f
p o l y v i n y l a l c o h ol
a n d
a n a l d e
w h e r e i u y
i s
a number
g r e a t e r
t h a n
0 and
r a n g i n g
up
t o
3 ,
hyde h a v i n g
l e s s
t h a n
3 c a r b o n
a t o m s .
a n d s a i d s u r f a c e a c t i v e a g e n t h a v i n g t h e
f o l l o w i n g
s t r u c - 9 . The f o a m e d c o m p o s i t i o n
o f
c l a i m
8
w h e r e i n s a i d
t u r a l f o r m u l a h a r d e ne r i s p r e s e n t i n
t h e
amount
o f
one p a r t
f o r
t w o
t o
t w e n t y p a r t s o f r e s i n a n d s a i d
s t a b i l i z e r
i s p r e s e n t i n t h e
HO_(C2H4O)‘‘—(C3HGO)D_{CZH4O)°_H
4 0
amount
o f
one t o ? f t e e n p a r t s f o r n i n e t y - ? v e
p a r t s
o f
wherein
b
i s
e q u a l
t o
a t
l e a s t 1 7 and wherein t h e e t h y l e n e
r e s i n ,
o x i d e
p o r t i o n C o m p r i s e s
b e t w e e n
16%
a n d 80% o f t h e 1 0 .
The foamed c o m p o s i t i o n o f
c l a i m
9
w h e r e i n s a i d
m o le c u le.
’
stabilizer i s
p o l y v i n y l f o r m a l .
7 . A o a m a b l e
r e s i n c o m p o s i t i o n c h a r a c t e r i z e d by t a - 1 1 . The
foamed
c o m p o s i t i o n o f c l a i m 9 w h e r e i n
s a i d
b i l i t y
upon
f o a m i n g
w h i c h c o m p r i s e s a b a s e r e s i n , a
b l o w - s t a b i l i z e r i s
p o l y v i n y l
a c e t a l .
i u g a g e n t c o n s i s t i n g e s s e n t i a l l y o f p a r a , p a r a ’
o x y b i s
( b e n - 4 '
1 2 .
The method o f p r o d u c i n g a s t a b l e foam
e s i n
w h i c h
z e n e
s u l f o n y l h y d r a z i d e ) t o f o a m s a i d r e s i n , a t h a r d e n e r
compriscsprcparing
a
m i x t u r e
i n c l u d i n g a b a s e r e s i n , a
f o r s a i d r e s i n and a s t a b i l i z e r t o p r e v e n t
c o l l a p s e
o f t h e hardener f o r s a i d
b a s e
r e s i n , a s t a b i l i z e r f o r s a i d
r e s i n
and
r e s i n a f t e r f o a m i n g
b u t
b e f o r e
h a r d e n i n g
c o n s i s t i n g - e s —
h a r d e n e r h a v i n g
a
s e t t i n g
t i m e s u b s t a n t i a l l y l e s s
t h a n t h e
s e n t i a l l y
o f p o l y v i n y l f o r m a l , s a i d
b a s e r e s i n h a v i n g t h e ‘ . 9 s e t t i n g t i m e o f
s a i d
r e s i n
a n d
h a r d e n e r
t o p r e v e n t c o l
f o l l o w i n g s t r u c t u r a l
f o r m u l a
0 l a p s e o f
t h e r e s i n a f t e r f o a m i n g
b u t b e f o r e
h a r d e n i n g ,
w h e r e i n R t a n d s h i f o r t h e h y d r o c a r b o n
r a d i c a l
o f a d i h y - a n d a b l o w i n g a g e n t t a k e n f r o m t h e g r o u p c o n s i s t i n g o f
d r i ‘ c p h e n o l a n d x
h a s
a
v a l u e o f b e t w e e n
0 . 3 a n d 2 0 , a n d
d i a z o a m i n o b e n z e n e , ammonium c a r b o n a t e , ammonium
b e i n g p r e p a r e d a s t h e c o n d e n sa t i o n p r o d u c t o f e p i c h l o r o » c a r b a m a t e , d i n i t r o s o
p e n t a m e t h y l e n e
t e t r a m i n e
a n d p ,
p ’
h Y d I i H a n d
b i S - ( 4 - h Y d f 0 X Y P h e n l / 1 ) ~ 2 , 2 P r o p a n e ,
S a i d
o x y b i s ( b e n z e n e s u l f o n y l h y d r a z i d e ) , t h e n c e s u b j e c t i n g
h a r d e n e r
b e i n g
t a k e n from t h e c l a s s c o n s i s t i n g o f
p a r a ,
6 0 s a i d m i x t u r e
t o
a t e m p e r a t u r e
i n
e x c e s s
o f t h e decomposi
P?m' d i a m i n o d i p h e n l ’ l m e i h a n e a n d
a Compound h a v i n g
t i o n t e m p e r a t u r e o f t h e
b l o w i n g
a g e n t b u t n o t i n e x c e s s
t h e
S t r u c t u r a l
formula o f a b o u t 3 5 0 ° F . t o f o a m t h e r e s i n ,
s a i d b a s e
r e s i n h a v i n g
H 2N—(CH 2 -CH 2N H—)
C H z - m C f l z N H g
a
s t r u c t u r a l f o r m u l a
w h e r e i n y i s a number g r e a t e r t h a n ( i and r a n g i n g up t o
3 ,
w h e r e i n
R e p r e s e n t s a h y d r o c a r b o n
r a d i c a l
o f a d i h y
a
p o l y o x y
g l y c o l
s u r f a c e a c t i v e a g e n t h a v i n g t h e
s t r u c -
d r i c p h e n o l and x
h a s
a v a l u e o f b e t w e e n
0 . 3
and 2 0 , and
t u r a l f o r m u l a
7 0 b e i n g
p r e p a r e d a s t h e c o n d e n s a t i o n p r o d u c t o f e p i c h l o r o
\ _
hydrin
and
bis-(4-hydroxyphenyl)-2, 2
propane, s a i d
HG—(C2H‘-O)“_(C3H6O)b—(C2H4O ”_H
h a r d e n e r
b e i n g t a k e n
f r o m t h e
c l a s s
c o n s i s t i n g o f
p a r a ,
w h e r e i n
b
i s e q u a l t o a t l e a s t 1 7
and
w h e r e i n
t h e e t h y l e n e
p a r a ’
d i a m i n o
d i p h e n y l m e t h a n e a n d a compound h a v i n g
o x i d e p o r t i o n r e p r e s e n t s
from 16%
t o 8 0 % o f t h e mo- t h e S t r u c t u r a l f o r m u l a
l e c u l a r w e i g h t o f
t h e
c o m p o u n d , a n d a n a u x i l i a r y b l o w -
‘ 7 5 - IH2N—(CH2-—CH2NH—-),,CHZ-—CH2NHZ
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2 , 8 3 1 , 8 2 0
9
w h e r e i n y r e p r e s e n t s a
number
g r e a t e r t h a n 0 a n d
r a n g i n g
u p
t o 3 , s a i d
s t a b i l i z e r
c o n s i s t i n g e s s e n t i a l l y
o f
t h e
a n h y
d r o u s c o n d e n s a t i o n p r o d u c t v o f p o l y v i n y l a l c oh o l
a n d
a n
a l d e h y d e
c o n t a i n i n g
l e s s t h a n
3
c a r b o n a t o m s .
1 3 . The method o f c l a i m 1 2 w h e r e i n s a i d
m i x t u r e
i s
s u b j e c t e d
t o
s a i d
t e m p e r a t u r e f o r
a
p e r i o d
o f
a b o u t 5
m i n u t e s .
R e f e r e n c e s C i t e d i n t h e ? l e
o f t h i s
p a t e n t
UNITED STATES PATENTS
1,981,722
Ditm ar ______________ . . . Nov.
2 0 ,
1934
10
2 , 1 3 2 , 9 6 9
2 , 4 4 6 , 4 2 9
2 , 5 0 6 , 4 8 6
2 , 5 1 0 , 8 8 6
2,552,065
.
2 , 5 8 2 , 2 2 8
2 , 6 2 3 , 0 2 3
2 , 6 2 9 , 6 9 8
2 , 7 3 9 , 1 3 4
1 0
Rau _________________
__
Oct. 1 1 , 1938
Nelson e t a l .
__________
_ _
Aug.
3 , 1948
Bender
e t a l ______________
May
, 1950
Greenlee
______________
__
June
6 , 1 95 0
Sehoene ______________ _ May ,
1951
B r in k e m a ____________
__
Jan.
1 5 ,
1 95 2
Koro ly ______________ __ Dec. 2 3 , 1 95 2
S t e r l i n g
______________
_ Feb. 2 4 ,
1953
P a r r y et
a l
____ _ ~ ______
_
Mar. 2 0 ,
1956
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