Europaisches P a t e n t a m t

European Patent Office

(vj) Publication number:

010

407

A1

Office europeen des brevets

EUROPEAN PATENT A P P L I C A T I O N

@ Application number: 79302189.0

Int. CI.3: C 08 G 1 8 / 2 2

(22) Date of filing: 11.10.79

(So) Priority: 12.10.78 US 950816

43) Date of publication of application:
30.04.80 Bulletin 80/9
@ Designated Contracting States:
AT BE CH DE FR GB IT NL SE

(71) Applicant: M & T CHEMICALS, INC.

Woodbridge, New Jersey 07095(US)
(g) inventor: Treadwell, Kenneth
930 Main Street
Rahway, New Jersey 07065(US)
(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 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