Professional Documents
Culture Documents
010
407
A1
EUROPEAN PATENT A P P L I C A T I O N
Int. CI.3: C 08 G 1 8 / 2 2
(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 carboxylate 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 tertiary amines, inorganic tin compounds an organotin compounds. The use of the specified gel catalyst composition
enables the isocyanate- or isothiocyanate- polyol reaction to
be controlled over a wide range.
This
rigid
preparing
with
an
gel
invention
and
catalyst
foam
polyurethane
or
isocyanate
a blowing
composition
therefor.
catalyst
composition
the
of
combinations
Rigid
for
materials
for
insulation
of
these
place
isocyanate
that
foam
as
rapidly
and
applications,
foams
end-use
structures
the
and
such
as
formation
as
polyol
wherein
the
in
the
to
a novel
the
presence
gel
said
or
isocyanate-
be
of
controlled
possible
using
catalysts.
polyurethane
numerous
can
heretofore
art
prior
applications,
desirable
take
not
range
the
a polyol
reacting
With
of
rate
reaction
isothiocyanate-polyol
a wide
by
and
agent
for
a method
isothiocyanate
catalyst
within
to
relates
used
as
applications,
spraying,
and
insulating
including
For
containers.
possible
are
are
it
some
may b e
solidification
once
the
combined.
formulation
polyfunctional
For
must
fill
other
large
cavities
or
cavity
mould.
minimize
gel
which
alone
in
or
polyol
reaction
over
and
when
rise
the
of
minutes.
The
rise
magnitude
if
an
organotin
compound
is
the
combination
synergistic
mixture
may
with
even
compound
such
the
when
is
for
to
to
3 or
several
orders
with
dilaurate.
compound
reaction
certain
concentration
reduced
foam
organotin
the
The
slow,
combination
an
that
rapidly
the
by
in
with
result
too
foams.
the
as
dibutyltin
as
the
relatively
for
it
isocyanate-
for
long
as
used
amine
an
solidify
applications,
organotin
of
is
decreased
is
amine
the
polyurethane
be
is
either
compounds,
required
required
may
time
of
This
time
used
of
rate
amine
possible
as
Using
organotin
range
the
polyurethane
rigid
the
until
foaming
rapidly
amines
rigid
height)
occurred,
as
for
by
(the
time
reaction
a mould.
with
catalyzed
final
its
in
control
applications
the
reach
time
combination
to
reaction
occur
tertiary
feasible
various
has
to
desirable
filled
completely
this
catalysts
not
is
has
should
include
be
isocyanate-polyol
Once
residence
conventional
foams,
the
reagents
solidification
and
to
of
mixture
the
of
initiation
delay
would
it
moulds,
complex
or
of
lowest
the
the
practical
level.
It
provide
foam
that
is
an
catalyst
will
objective
of
composition
enable
the
rate
this
for
of
invention
rigid
the
to
polyurethane
isocyanate-polyol
reaction
and
reaction
to
composition
be
achieved
gel
be
can
composition
wide
zinc
notably
catalysts,
combination
any
of
the
compounds
conventionally
catalysts
for
cellular
The
preparing
all
of
rigid
the
this
or
employed
at
based
the
on
referred
addition
acids
with
oils
linoleic
of
propanoic,
to
other
carboxylic
or
acid,
animal
may
containing
acids
fats,
also
or
of
derived
including
be
employed.
be
may
10%,
can
be
more
antimony,
acids
monocarboxylic
butanoic,
acids
and
salts
pentanoic,
2-ethylhexanoic
acids
and
0.05
one
compounds
Suitable
and
atoms
These
of
of
carboxylic
between
products
basic
of
carbon
21
employed
mixtures
are
salts
polyol.
zinc.
heptanoic
Unsaturated
tall
of
reaction
acetic,
hexanoic,
zinc
as
and
potassium
include
weight
substantially
conventionally
and
2 to
from
for
polyfunctional
catalysts
a concentration
to
carboxylic
and
The
from
containing
as
useful
are
foams
isothiocyanates
potassium
and
amines
employed
catalysts
polyols
purpose.
antimony,
each
gel
with
polyurethanes.
polyurethane
known
isocyanates
for
present
This
in
organotin
rigid
carboxylate.
or
alone
used
catalyst
carboxylate,
antimony
and
This
ranges.
a gel
using
an
containing
carboxylate
potassium
other
within
this
initiate
to
required
varied
be
can
objective
time
the
up
acids
in
21
carbon
to
from
oils
such
oleic
acid
and
Aromatic
atoms.
as
acids
carboxylic
various
substituents
and
acid,
such
the
suitable.
benzoic
as
the
on
isomeric
succinic,
azelaic,
sebacic,
glutaconic,
ring,
salicylic
naphthenoic
acids
are
glutaric,
acids,
acid.
be
of
Any
separately
used
in
or
to
provide
gel
foam
polyurethane
a potassium
the
each
wherein
of
each
and
an
to
carboxylate
content
and
the
zinc
20
80%
by
weight
carboxylate
to
foam
active
by
preparing
rigid
wherein
portion
carbon
of
the
of
atoms
and
carboxylates
the
carboxylate
of
we
carboxylate,
potassium
weight
acids.
total
constitutes
total
content.
According
we p r o v i d e
by
20
employed
more
carboxylate
1 to
from
remaining
40%
dicarbox-
invention
defined
constitutes
the
the
or
antimony
and
antimony
isophthalic,
be
can
two
for
zinc
from
contains
10
fumaric,
a monocarboxylic
of
hereinafter
the
maleic,
acids
aspect
comprising
as
carboxylate
of
place
composition
carboxylate
hydrocarbyl
suberic,
1,4-cyclohexane
containing
one
catalyst
pimelic,
-hydroxymuconic,
and
in
mixtures
According
oxalic,
as
thapsic,
aforementioned
the
also
@,-diethylsuccinic,
hemimellitic
can
such
adipic,
brassylic,
a-butyl-a-ethylglutaric,
ylic
acids
a-hydroxymuconic,
terephthalic,
exhibit
may
phenyl
Polycarboxylic
malonic,
that
acid,
a method
reacting
hydrogen
to
another
for
preparing
a polyol
atoms
aspect
with
of
rigid
containing
at
the
invention
polyurethane
least
a polyfinctional
three
isocyanate
or
in
isothiocyanate
blowing
gel
known
urethane
foams,
tin
inorganic
compounds
formulae
general
of
contain
from
carbyl"
includes
20
aralkyl.
Most
preferably
contain
containing
preferably
from
carbon
including
especially
preferred.
The
zinc
of
compositions
least
in
part,
by
are
be
a solvent
compatible
polyurethane
of
lene
ethylene
glycols,
with
the
rate
oxide
desired
reaction.
for
all
the
foam.
three
polyol
Preferred
and
aryl,
R3
propylene
especially
those
are
and
for
The
and
and
alkyl
Acids
branched
acid,
be
"hydro-
atoms.
or
in
zinc
the
alkaryl
the
con-
are
antimony,
will
and
having
term
The
linear
of
amines,
hydrocarbyl
carbon
present
invention
isothiocyanate-polyol
include
amounts
that
this
in
poly-
Zn(OOCR3)2.
R3 are
2-ethylhexanoic
relative
carboxylates
12
another
potassium,
and
R2 and
R ,
4 to
atoms
figuration,
tertiary
may
rigid
acids
KOOCR2
cycloalkyl,
compounds.
atoms.
carbon
alkyl,
for
from
R2 and
R ,
There
catalyst
antimony,
Sb(OOCR1)3,
1 to
gel
and
employed
above.
monocarboxylic
wherein
respectively,
is
organotin
said
the
salts
there
a catalyst
and
compounds
are
that
chosen
preferably
Preferably
catalyst
said
the
as
se
per
a gel
defined
with
together
catalyst
gel
in
as
composition
used
be
of
presence
characterised
agent,
catalyst
also
the
potassium
catalyst
at
determined,
the
isocyanate-
composition
salts
which
employed
to
solvents
oxide.
exhibiting
and
will
prepare
include
Liquid
may
or
also
generally
the
oligomers
polypropy-
molecular
from
of
weights
icularly
and
zinc
said
be
can
in
the
of
carboxylates
desired
metric
of
of
appropriate
employ
basic
be
the
suitable.
and
zinc
the
desired
proportions.
It
such
as
The
basic
be
may
inert
aromatic
can
be
tion
it
water
to
with
be
of
completion
average
as
the
to
desirable
the
the
foams
of
stir
the
liquid
aliphatic
is
usually
the
over-heating
and
and
water
by-product
distilla-
azeotropic
liquid
hydrocarbon
Alternatively,
immiscible
is
cool
by
medium.
an
as
The
reaction
with
a water-immiscible,
reaction
localized
a portion
removed
molecular
such
Since
reaction
Polyols
polyurethane
of
also
antimony
reaction
The
presence
medium
avoid
during
the
as
can
the
are
a mixture
as
acids.
or
however,
compound,
or
to
convenient
potassium,
discolouration.
product
together
be
may
removed
employed
in
liquid
mixture
resultant
acid
basic
the
bicarbonate
or
of
with
in
basic
mixture
stoichio-
generally
the
as
combined
the
acid
zinc
individually
hydrocarbon.
exothermic,
is
compounds
carboxylic
antimony
then
reacting
and
carbonate
reacted
chemically
reactfon
oxide
the
conducted
and
carboxylic
antimony
preferably
or
by
prepared
desired
or
potassium,
Alternatively,
potassium,
a hydroxide
salts
of
individually
prepared
a part-
solvents.
carboxylates
can
constitute
5,000,
proportions.
amount
compounds
of
class
preferred
The
about
to
300
phast
the
following
reaction.
conventionally
are
liquids
weight
of
employed
which
between
to
typically
about
500
prepare
rigid
exhibit
and
6,000
an
and
include
and
polyamides
either
of
or
active
secondary
fatty
from
to
300
acid
600
"blown"
and
natural
oil,
and
glycols
of
include
polyol,
these
polypropylene
is
The
groups.
polyesters
or
hydroxyl
numbers
of
castor
hydrogenated
a preferred
polyethers,
glycols,
polyalkylene
compounds
exhibit
oils.
Hydroxyl-terminated
of
polyols
hydroxyl
having
castor
as
and
polyethers
glycerides
such
polyesters
These
glycols.
hydroxyl-containing
includes
oil
alkylene
primary
class
polyethers,
hydroxyl-containing
The
glycols.
preferably
e.g.,
polyethylene
molecular
about
between
type
weight
200
and
6,000.
A type
ferred
for
merizing
other
The
rigid
oxide
resultant
to
required
in
foams
the
reaction
of
be
obtained
or
mixtures
of
of
the
all
hydroxyl
preparing
such
acids.
as
thereof,
polyesters
acid
by
polyor
sucrose
hydroxyl
groups.
polyfunctionality
characteristic
polyesters,
of
be
second
type
of
esterification-condensation
acids
carboxylic
in
chains
contain
acids
and
aliphatic
sebacic
and
the
reacted
with
with
such
proportions
carboxylic
include
fumaric,
may
the
polymer
Dibasic
groups.
The
by
resultant
adipic,
three
crosslinking
dibasic
aliphatic
triols
of
presence
the
Hvdroxyl-terminated
can
obtained
pre-
foams.
polyurethane
polyol,
particularly
is
least
exhibits
product
achieve
the
at
containing
is
that
polyether
polyurethane
propylene
compounds
rigid
of
that
suitable
aromatic
or
most
terminal
isomeric
di-
glycols,
for
acids
phthalic
polyhydroxy-
lated
such
compound
Both
be
the
invention
the
reaction
used
the
is
greater
arylene
than
than
2,
other
contain
alkyl-NCG
of
formed
of
from
hexane
is
obtained
each
addition
hiocyanate
the
and
that
bonds
during
may
and
one
include
the
or
the
prepara-
Polymethylene
such
moles
a by-product.
of
an
arylene
e.g.,
the
products
diisocyanate
and
1 mole
polyol,
one
ecomposes
be
useful.
to
reaction
R can
3.0.
isocyanates
of
of x
substituted
a triol,
tolylene
also
triol, are
to
aryl-NCG
of
G is
value
group
reacting 3
mole
of
2.1
example
is
polyisothiocyanaytes
diisocyanate.
an
it
generic
average
obtained
by
wherein
arylene,
Suitable
paraphenyl
3 moles
In
from
more
by-products
for
diisocyanate
and
the
to
compound
any
this
hydrocarbon
or
isocyanate
Triis-ocyanates
within
alkylene,
bonds.
of
radicals
in which
one
methylene
polyphenyl
-N=C=G
divalent
references
isocyanates,
reaction
preferably
substituted
or
the
polyisocyanates
R(NCG)x
poly-functional
tion
to
While
oams.
specific
Compounds
include
polyisothiocyanates
polyfunctional
two
sulphur.
optionally
more
certain
formula
alkylene,
trimethylol
polyurethane
with
described
more
definition
of
is
applicable
containing
or
rigid
prepare
of
generically
and
polyisocyanates
to
may
oxygen
glycol,
pentaerythritol.
or
propane
ethylene
as
or
more
mixture
at
;ocyanate
polyfunctional
the
of
the
contains
present
a blowing
temperature
reaition
to
isocyanate
yield
of
agent
the
a
gaseous
the
it
as
agents
solidifies.
those
are
boiling
from
usually
contains
oxide
alkylene
from
1 to
the
Among
90C.
to about
and
copolymer,
about
5 parts
preferred
blowing
hydrocarbons
The
for
a surfactant,
surfactant
containing
-isothiocyanate
halogen-containing
30
within
entrapped
are
or
polyol-isocyanate
reacting
mixture
that
bubbles
forms
which
product
also
precursor
instance
a silicon-
preferably
a siloxane-
preferably
in
by
weight
amount
an
per
100
the
present
of
of
parts
polyol.
As
combination
of
of
of
a wide
over
of
in
used
for
zinc
are
this
type
of
of
by
the
combination
rigid
include
catalyses
triethanolamine,
triethylene
diamine
is
organic
often
tin
catalysts
dibutyltin
dilauryl
used
in
are
dilaurate,
mercaptide
gel
dimethylethanol
octoate,
dibutyltin
and
the
catalysts
conventional
with
Representative
stannous
or
as
tricyclo-
N-ethylmorpholine,
combination
compounds.
varied
composition
such
amines
tertiary
hexylamine,
amine
These
catalytic
relative
salt
conventional
foams.
be
salts
carboxylate
with
and
the
carboxylates
the
can
either
carboxylate
polyurethane
that
composition
varying
a particular
in
unique
three
with
carboxylate
antimony
range
proportions
amount
an
and
potassium
activity
disclosed,
previously
stannous
amine.
inorganic
The
and
tin-containing
oleate,
dioctoate,
dibutyltin
dibutyltin-S,S'-bis(isooctyl
be
may
by
weight
The
broad
the
rigid
with
that
demonstrate
individually
unless
otherwise
reagents
a
to
opaque,
interval
and
the
in
of
To
a base
of
Carbide
to
the
"rise
weight
of
all
of
combining
from
time".
of
the
foaming
all
the
indicated
as
mixture
"cream
as
formulation
exhibiting
the
by
clear
The
and
reagents
is
reaction
time".
"Niax"
Corporation),
from
and
parts
are
reaction
ensuing
a hydroxyl
(2)
Union
0.45
number
part
copolymer
Carbide
30.4
of
from
of
490
the
a
Union
siloxane-
available
Corporation
parts
oxide
oxide-propylene
LS-490
polyol
(1)
containing
ethylene
oxyrthylene-oxypropylene
L-5340
achieved
either
polymerization,
the
a polyhydroxy-based
as
examples
prepare
be
catalysts
All
in
and
also
cannot
between
combining
as
(available
the
of
referred
to
copolymer
examples
amine
interval
onset
between
referred
of
time
completion
The
to
using
specified.
The
is
and
compounds
range
the
alone
tin
combination.
transformation
by
broad
reported
5 parts
achieved
be
can
compositions
and
tin
in
or
percentages
the
this
conventional
using
that
foams.
polyurethane
to
demonstrate
examples
catalyst
amines
polyol.
rates
reaction
present
combination
of
parts
accompanying
of
range
of
one
100
per
catalysts
gel
from
of
concentrations
at
employed
conventional
These
mcrcaptoacetate).
and
as
(3)
9.0
parts
of
trichlorofluoromethane
of
polymethylene
polyphenyl
of
the
listed
"Niax"
as
catalysts
is
Trade
A contained
Catalyst
hexanoate
and
15
hexanoate
and
potassium
parts
of
available
employed
parts
a polypropylene
from
as
the
and
parts
zinc
each
of
antimony
bis-
solvent
(Pluracol
Corporation)
for
the
or
one
more
three
to
2-ethyl-
tris-
2-ethylhexanoate.
glycol
parts
referred
composition
20
36.7
table.
following
The
BASF-Wyandotte
a common
added
isocyanate
in
Mark.
were
2-ethylFifty
P-410
were
salts.
The
is
foam
and
The
be
achieved
seconds.
containing
of
time
a cream
146
of
the
using
amine
A and
Catalyst
wide
range
of
that
achieved
using
the
be
present
catalyst
organotin
satisfactory
cannot
a
tin
be
that
cocatalyst
foam
when
achieved
compound
considerably
higher
exhibited
these
by
to
the
activity
of
tin
compounds
used
using
with
did
an
level
exhibited
and
and
rise
This
combinations
of
by
amines.
times
of
the
a conventional
not produce
due
to
catalytic
combinations,
could
than
combination
amine
time
f o r m u l a t i o n s
alone.
of
is
dilaurate
cream
with
composition
rise
with
a rise
The
dibutyltin
the
can
and
alone.
demonstrate
not
which
shorter
are
The
amine
an
invention
seconds
times
These
did
formulation,
15
amine
quality.
using
this
fourth
the
:by
acceptable
achieved
synergism
demonstrated
of
of
not
the
A composition.
dilaurate
dibutyltin
was
that
demonstrate
Catalyst
composition
catalyst
exhibited
the
using
prepared
completely
the
than
active
more
data
foregoing
which
a
wide range
Catalyst
A or
the
activity
is
conventional
comparable
combinations
1.
A gel
rigid
polyurethane
catalyst
defined
20
wherein
carbon
by
of
weight
zinc
atoms
of
weight
1,
individually
1 to
20
A gel
wherein
4.
Claim
R11
A gel
3,
carboxylate
contains
wherein
the
each
of
the
carboxylates
from
antimony
from
remaining
10
and
20
to
40%
the
to
80%
content.
composition
Sb(OOCR1)3,
the
content
carboxylate
from
hereinbefore
constitutes
carboxylate
total
chosen
carbon
a zinc
each
catalyst
formulae
general
and
as
and
the
antimony
hydrocarbyl
constitutes
wherein
that
the
total
the
A gel
Claim
2,
the
an
carboxylate
carboxylates
carboxylate
2.
3 .
of
portion
and potassium
by
comprises
preparing
in
characterised
a potassium
carboxylate
for
composition
foam,
composition
carboxylate,
to
catalyst
to
according
have
KOOCR2
hydrocarbyl
the
and
following
Zn(OOCR3)
groups
are
containing
atoms.
catalyst
R2 and
composition
R3 are
catalyst
wherein
R1,
R2
each
composition
and
R3 a r e
according
to
alkyl.
according
each
to
Claim
5.
A gel
contains
which
claim,
preceding
composition
catalyst
for
solvent
to
according
any
the
carboxylates.
6.
A gel
Claim
is
solvent
the
wherein
5,
composition
catalyst
to
according
polypropylene
liquid
glycol.
by
atoms
a blowing
a
employed
of
gel
Claims
8.
characterised
in
that
for
the
carboxylates,
the
polyol.
A
9,
wherein
known
catalyst
method
se
per
as
there
is
according
to
any
also
Claim
solvent
the
to
used
wherein
7 or
being
8,
a solvent
miscible
of
any one
rigid
Claim
contains
another
for
a catalyst
7,
present.
composition
according
is
there
to
according
the
10.
and
catalyst
gel
Claim
surfactant is
wherein
gel
to
according
silicon-containing
A method
or
6.
1 to
A method
9.
composition
active
isocyanate
of
catalyst
three
least
a polyfunctional
the
foam
polyurethane
presence
in
agent,
at
containing
with
isothiocyanate
rigid
preparing
a polyol
reacting
hydrogen
one
for
A method
7.
gel
Claims
with
7 to
catalyst
polyurethene
foams.
11.
9,
A method
wherein
chosen
and
there
from
organctin
according
is
tertiary
also
used
amines,
compounds.
to
any one
another
inorganic
of
gel
tin
Claims
7 to
catalyst
compounds