Note: Descriptions are shown in the official language in which they were submitted.
0~~J0/50643 CA 02382613 2002-02-22
Polyether alcohols
The present invention relates to polyetherols, their preparation
and their use for producing polyurethanes.
Polyether alcohols are used in large quantities for producing
polyurethanes. They are usually prepared by catalytic addition of
lower alkylene oxides, in particular ethylene oxide and propylene
oxide, onto H-functional initiator molecules. The catalysts used
are usually basic metal hydroxides or salts, with potassium
hydroxide having the greatest industrial importance.
In the synthesis of polyether alcohols having long chains and
hydroxyl numbers of from about 26 to about 60 mg KOH/g, as are
used especially for the production of flexible polyurethane
foams, secondary reactions occur as chain growth progresses and
these lead to malfunctions in the buildup of the chains. The
by-products are referred to as unsaturated constituents and have
an adverse effect on the properties of the resulting polyurethane
materials. In particular these unsaturated constituents, which
have an OH functionality of 1, have the following consequences:
Owing to their sometimes very low molecular weight, they are
volatile and thus increase the total content of volatile
constituents in the polyether polyol and in the polyurethanes
produced therefrom, in particular flexible polyurethane
foams.
_ They act as chain terminators in the production of the
polyurethane because they delay.or reduce the crosslinking of
the polyurethane or the buildup of the molecular weight of
the polyurethane.
It is therefore very desirable in industry to avoid the
unsaturated constituents as far as possible.
One way of preparing polyether alcohols having a low content of
unsaturated constituents is the use of multimetal cyanide
catalysts, usually zinc hexacyanometalates, as alkoxylation
catalysts. There is a large number of documents in which the
preparation of polyether alcohols by means of such catalysts is
described. Thus, DD-A-203 735 and DD-A-203 734 describe the
preparation of polyether alcohols using zinc hexacyanocobaltate.
The use of multimetal cyanide catalysts can reduce the content of
unsaturated constituents in the polyether polyol to about
0.003-0.009 meq/g - in the case of conventional catalysis using
005/50643 CA 02382613 2002-02-22
2
potassium hydroxide, about 10 times these amounts are found
(about 0.03-0.08 meq/g).
The preparation of the multimetal cyanide catalysts is also
known. These catalysts are usually prepared by reacting solutions
of metal salts such as zinc chloride with solutions of alkali
metal or alkaline earth metal cyanometalates, e.g. potassium
hexacyanocobaltate. A water-miscible, heteroatom-containing
component is generally added to the resulting suspension
immediately after the precipitation process. This component can
also be present beforehand in one or both starting solutions.
This water-miscible, heteroatom-containing component can be, for
example, an ether, polyether, alcohol, ketone or a mixture
thereof. Such processes are described, for example, in US
3,278,457., US 3,278,458, US 3,278,459, US 3,427,256, US 3,427,334
and US 3,404,109.
A problem when using polyether alcohols which have been prepared
by means of multimetal.cyanide catalysts is that these polyols
behave differently in the production of polyurethanes than do
polyether alcohols which have been prepared from the same
starting materials but using alkali metal hydroxides as
catalysts. These effects show up particularly in polyether
alcohols whose chains are made up of two or more alkylene oxides.
Thus, it has been found that polyether alcohols having a random
end block of propylene oxide and ethylene oxide which have been
prepared by means of multimetal cyanides as catalysts have a
significantly higher reactivity than polyether alcohols of the
same composition which have been prepared by means of potassium
hydroxide as catalyst. This increased reactivity, which is
attributable to a higher primary hydroxyl group content, causes
considerable problems in most applications of such polyether
alcohols.
Thus, WO 97/27,236 (EP 876,416) describes a polyether alcohol for
use in high-elasticity flexible foams, which polyether alcohol
comprises an inner propylene oxide block which makes up not more
than 35% by weight of the total amount of alkylene oxide and one
or more external blocks of ethylene oxide and propylene oxide
containing at least 2% by weight of ethylene oxide, and the inner
block is catalyzed at least partly and the external blocks
completely by means of multimetal cyanide catalysts. However,
such polyether alcohols are, as mentioned above, significantly
more reactive than commercial base-catalyzed polyether alcohols
0050/50643 CA 02382613 2002-02-22
3
and can thus not be readily incorporated into polyurethane
systems.
The problems indicated show up particularly in polyurethane
foams, in particular flexible foams, and most clearly in the case
of flexible slabstock foams. In particular, crack formation
occurs in the foam and the mechanical properties of the foams are
impaired.
A possible way of alleviating this deficiency is to change the
proportions of the alkylene oxides used in the preparation of the
polyether alcohols. However, the variations possible here are
only small, since such a change would cause problems in setting
the foam properties, which is usually undesirable. Changes in the
I5 formulation of the polyurethanes which would be able to
compensate for the altered reactivity of the polyether alcohols
are usually associated with adverse effects on the foam
properties.'
A further possible way of alleviating this deficiency is proposed
in EP-A-654 056, in which alkali metal oxides and hydroxides
and/or alkaline earth metal oxides and hydroxides are added in an
amount of from 0.5 to 10 ppm to the polyether alcohols prepared
by means of multimetal cyanide catalysts after removal of the
catalyst.
However, it has been found that polyether alcohols which have
been prepared by means of multimetal cyanide catalysts and to
which the compounds described in EP-A-654 056 have been added
cannot be used for producing flexible polyurethane foams. In
particular, foams produced in this way displayed poor curing
behavior with pronounced crack formation. In addition, such
flexible foams have an insufficient open cell content.
It has now surprisingly been found that polyether alcohols
prepared by means of multimetal cyanide catalysts have the same
reactivity as polyether alcohols which have the same proportions
of ethylene oxide and propylene oxide in the polymer chain but
have been catalyzed using potassium hydroxide if a propylene
oxide block is incorporated at the end of the polyether chain of
the polyether alcohols prepared by means of multimetal cyanide
catalysts.
The present invention accordingly provides polyether alcohols
which can be prepared by catalytic molecular addition of ethylene
oxide and propylene oxide, wherein at least one multimetal
0050/50643 CA 02382613 2002-02-22
4
cyanide compound is used as catalyst and a block of propylene
oxide units is added on at the end of the chain.
The present invention further provides a process for preparing
polyether alcohols by catalytic molecular addition of ethylene
oxide and propylene oxide, wherein at least one multimetal
cyanide compound is used as catalyst and a block of an alkylene
oxide having at least three carbon atoms, in particular propylene
oxide, is added on at the end of the chain.
The invention further provides a process for producing
polyurethanes, preferably flexible polyurethane foams, in
particular flexible slabstock foam, by reacting polyisocyanates
with the polyether alcohols of the present invention, and also
provides the polyurethanes produced by this process.
In a preferred embodiment of the present invention, the end block
of an alkylene oxide having at least three carbon atoms, in
particular propylene oxide, makes up from 2 to 50% by weight,
preferably from 2 to 20% by weight and particularly preferably
from 5 to 15% by weight, of the total mass of the polyether
alcohol.
In the polyether alcohols of the present invention, preferably at
least 80%, particularly preferably at least 90% and in particular
at least 95%, of the total number of hydroxyl groups are
secondary hydroxyl groups. The content of unsaturated
constituents is preferably less than 0.015 meq/g. The value was
determined.tritrimetrically by means of the iodine number
measured in accordance with the BASF Schwarzheide GmbH standard
test method PPU 00/03-12.
The molecular addition of the end block of alkylene oxides having
at least three carbon atoms, in particular propylene oxide, can
be carried out in various possible ways. Thus, it is possible to
prepare polyether alcohols having a purely blockwise arrangement
of the alkylene oxides. In this process variant, only one
alkylene oxide is metered in at a time, followed by the next, and
so forth. According to the present invention, a pure propylene
oxide block is added on as last block.
In a further preferred variant, a pure alkylene oxide block,
preferably propylene oxide, is, if desired, first added onto the
initiator substance, followed by metered addition of a mixture of
ethylene oxide and propylene oxide, with the ratio of ethylene
oxide to propylene oxide being able to vary over the time of
metered addition or preferably remaining constant, and, at the
005/50643 CA 02382613 2002-02-22
end of the metered addition of alkylene oxide, a pure propylene
oxide block is added on as specified according to the present
invention.
5 In a further preferred variant, firstly, if desired, a pure
alkylene oxide block, preferably propylene oxide, 'is likewise
preferably added on and then a mixture of ethylene oxide and
propylene oxide is likewise added on, with the proportion of
ethylene oxide in the mixture being reduced during the course of
the metered addition until only propylene oxide is being metered
in at the end of the metered addition.
It is also possible to add small amounts of ethylene oxide to the
end block of at least one alkylene oxide having at least three
carbon atoms provided that this does not adversely affect the
properties of the polyether alcohols of the present invention.
Here, small amounts means a proportion of not more than 5% by
weight, preferably not more than 2% by weight, in each case based
on the weight of the end block.
As al.kylene oxide having at most 3 carbon atoms, particular
preference is given to using propylene oxide. Further preferred
compounds are butylene oxide, styrene oxide or epoxidized fatty
oils such as epoxidized soybean oil. The compounds mentioned can
be used individually or in the form of any mixtures with one
another.
The polyether alcohols of the present invention usually have a
functionality of from 2 to 8, preferably from 2 to 4 and in
particular from 2 to 3, and an equivalent weight of greater than
500 g/mol. Initiator substances used may be relatively high
functionality initiator substances, in particular sugar alcohols
such as sorbitol, hexitol and sucrose, but are usually
bifunctional and/or trifunctional alcohols or water, either as
the individual substance or as a mixture of at least two of the
initiator substances mentioned. Examples of bifunctional
initiator substances are ethylene glycol, diethylene glycol,
propylene glycol, dipropylene glycol, 1,4-butanediol and
1,5-pentanediol. Examples of trifunctional initiator substances
are trimethylolpropane, pentaerythritol and, in particular,
glycerol. The initiator substances can also be used in the form
of alkoxylates, in particular those having a molecular weight MW
in the range from 62 to 15,000 g/mol. These alkoxylates can be
prepared in a separate process step, and it is also possible to
use catalysts other than multimetal cyanide compounds, for
example alkali metal hydroxides, for preparing them. When using
alkali metal hydroxides for preparing the alkoxylates, it is
~~~JD/50643 CA 02382613 2002-02-22
6
necessary to remove virtually all of the catalyst since alkali
metal hydroxides can deactivate the multimetal cyanide catalysts.
The advantage of using alkoxylates as initiator substances is
faster starting of the reaction, but disadvantages are the
introduction of an additional process step and; as mentioned
above, possibly the complicated purification of the alkoxylate.
At the beginning of the reaction, the initiator substance is
placed in a reaction vessel and, if necessary, water and other
volatile compounds are removed. This is usually~carried out by
means of distillation, preferably under reduced pressure. The
catalyst may already be present in the initiator substance, but
it is also possible to add the catalyst only after the treatment
of the initiator substance. In the latter variant, the catalyst
is subject to less thermal stress. Prior to metering in the
alkylene oxides, it is customary to make the reactor inert in
order to avoid undesirable reactions of the alkylene oxides with
oxygen. The alkylene oxides are then metered in and the molecular
addition is carried out in the manner described above. The
molecular addition of the alkylene oxides is usually carried out
at from 50 to 200°C, preferably from 90 to 150°C, and pressures
in
the range from 0.01 bar to 10 bar. It has been found that the
rate at which the alkylene oxides are metered in likewise has an
influence on the reactivity of the polyether alcohols formed. The
faster the alkylene oxides are metered in, the higher the
reactivity of the resulting polyether alcohols.
The multimetal cyanide catalysts used in the process of the
present invention usually have the formula (I)
Mla[M2(CN)b(A)c]d ~ fMlgXn ~ h(H20) ~-eL (I)
where
M1 is a metal ion selected from the group consisting of Zn2+,
Fe2+, Co3+, Ni2+, Mn2+, Co2+, Sn2+, Pb2+, Mo4+, Mo6+, A13+,
V4+, V5+, Sr2+, W4+, W6+, Cr2+, Cr3+, Cd2+,
MZ is a metal ion selected from the group consisting of Fe2+,
Fe3+, Co2+, Co3+, Mn2+, Mn3+, V4+, V5+, Cr2+, Cr3+, Rh3+,
Ru2+, Ir3+
and M1 and MZ are identical or different,
0050/50643 CA 02382613 2002-02-22
7
A is an anion selected from the group consisting of halide,
hydroxide, sulfate, carbonate, cyanide, thiocyanate,
isocyanate, cyanate, carboxylate, oxalate and nitrate,
X is an anion selected from the group consisting of halide,
hydroxide, sulfate, carbonate, cyanide, thiocyanate,
isocyanate, cyanate, carboxylate, oxalate and nitrate,
L is a water-miscible ligand selected from the group consisting
of alcohols, aldehydes, ketones, ethers, polyethers, esters;
ureas, amides, nitriles and sulfides,
and
a, b, c, d, g and n are chosen so that the compound is
electrically neutral, and
a is the coordination number of the ligand,
f is a fraction or an integer greater than or equal to 0 and
h is a fraction or an integer greater than or equal to 0.
These compounds are prepared by generally known methods by
combining the aqueous solution of a water-soluble metal salt with
the aqueous solution of a hexacyanometalate compound, in
particular a salt or an acid, and adding a water-soluble ligand
thereto either during or after the mixing of the two solutions.
The catalyst is usually used in an amount of less than 1% by
weight, preferably in an amount of less than 0.5% by weight,
particularly preferably in an amount of less than 1000 ppm and in
particular in an amount of less than 500 ppm, in each case based
on the weight of the polyether alcohol.
The process of the present invention is preferably carried out
using multimetal cyanide catalysts prepared by combining a metal
salt and a cyanometallic acid as described in EP-A-862,947.
Preference is also given to multimetal cyanide catalysts which
contain acetate, formate or propionate and display an X-ray
diffraction pattern as described in DE 97,42,978 or crystallize
in a monoclinic system.
These multimetal cyanide catalysts are crystalline and have, if
they can be prepared as a single phase, a strict stoichiometry in
respect of the metal salt and the cyanometallic component. Thus,
a multimetal cyanide catalyst which is prepared as described in
~05~/50643 CA 02382613 2002-02-22
8
DE 197,42,978 and contains acetate and crystallizes in a
monoclinic system always has a zinc: cobalt ratio of 2:1.
Among these crystalline multimetal cyanide catalysts, preference
is given to those which have a platelet-like morphology. In this
context, the term platelet-like refers to a particle whose width
and length are more than five times the thickness of the
particle.
Compared to the use of amorphous and nonstoichiometric multimetal
cyanide catalysts, the use of crystalline and stoichiometric
multimetal cyanide catalysts has the advantage that tailoring of
the solid state structure and surface structure makes it possible
to avoid undesirable polymerization-active centers which can
lead, for example, to the.formation of high molecular weight
polyols.
The reaction can be carried out continuously or batchwise. After
the reaction is complete, the unreacted monomers and volatile
compounds are removed from the reaction mixture, usually by means
of distillation. The catalyst may remain in the polyether
alcohol, but it is usually removed, for example by means of
filtration.
As mentioned above, the polyether alcohols of the present
invention are preferably reacted with polyisocyanates to give
polyurethanes, preferably polyurethane foams and thermoplastic
polyurethanes, in particular flexible polyurethane foams. Here,
the polyether alcohols of the present invention can be used
individually, as a mixture of at least two polyether alcohols
according to the present invention or in admixture with other
compounds containing at least two active hydrogen atoms.
Polyisocyanates which can be used here are all isocyanates having
two or more isocyanate groups in the molecule. It is possible to
use either aliphatic isocyanates such as hexamethylene
diisocyanate (HDI) or isophorone diisocyanate (IPDI), or
preferably aromatic isocyanates such as tolylene diisocyanate
(TDI), diphenylmethane diisocyanate (MDI) or mixtures of
diphenylmethane diisocyanate and polyphenylpolymethylene
polyisocyanates (crude MDI). It is also possible to use
isocyanates which have been modified by incorporation of
urethane, uretdione, isocyanurate, allophanate, uretonimine and
other groups, referred to as modified isocyanates.
005/50643 CA 02382613 2002-02-22
9
As compounds.which contain at least two isocyanate-reactive
groups and can be used in admixture with the polyether alcohols
of the present invention, it is possible to use amines,
mercaptans and preferably polyols. Among the polyols, polyether
polyols and polyester polyols have the greatest industrial
importance. The polyether polyols used for producing
polyurethanes are usually prepared by base-catalyzed addition of
alkylene oxides, in particular ethylene oxide and/or propylene
oxide, onto H-functional initiator substances. Polyester polyols
are usually prepared by esterification of polyfunctional
carboxylic acids with polyfunctional alcohols.
The compounds containing at least two groups which are reactive
toward isocyanate groups also include chain extenders and/or
crosslinkers which may be employed if desired. These are at least
bifunctional amines and/or alcohols having molecular weights in
the range from 60 to 400.
As blowing agents, use is usually made of water and/or compounds
which are gaseous at the reaction temperature of the urethane
reaction and are inert toward the starting materials for the
polyurethanes, known as physically acting blowing agents, and
also mixtures thereof. Physically acting blowing agents used are
hydrocarbons having from 2 to 6 carbon atoms, halogenated
hydrocarbons having from 2 to 6 carbon atoms, ketones, acetals,
ethers, inert gases such as carbon dioxide and/or noble gases.
Catalysts used are, in particular, amine compounds and/or metal
compounds, in particular heavy metal salts and/or organic metal
compounds. In particular, known tertiary amines and/or organic
metal compounds are used as catalysts. Suitable organic metal
compounds are, for example, tin compounds such s tin(II) salts of
organic carboxylic acids, e.g. tin(II) acetate, tin(II) octoate,
tin(II) ethylhexanoate and tin(II) laurate, and the
dialkyltin(IV) salts of organic carboxylic acids, e.g. dibutyltin
diacetate, dibutyltin dilaurate, dibutyltin maleate and
dioctyltin diacetate. Examples of organic amines customary for
this purpose are: triethylamine, 1,4-diazabicyclo(2.2.2]octane,
tributylamine, dimethylbenzylamine,
N,N,N',N'-tetramethylethylenediamine,
N,N,N',N'-tetramethyl-butanediamine,
N,N,N',N'-tetramethylhexane-1,6-diamine, dimethylcyclohexylamine,
pentamethyldipropylenetriamine, pentamethyldiethylenetriamine,
3-methyl-6-dimethylamino-3-azapentol, dimethylaminopropylamine,
1,3-bis(dimethylamino)butane, bis(2-dimethylaminoethyl) ether,
N-ethylmorpholine, N-methylmorpholine, N-cyclohexylmorpholine,
2-dimethylaminoethoxyethanol, dimethylethanolamine,
' 0050/50643 CA 02382613 2002-02-22
tetramethylhexamethylenediamine,
dimethylamino-N-methylethanolamine, N-methylimidazole,
N-formyl-N, N'-dimethylbutylenediamine,
N-dimethylaminoethylmorpholine,
5 3,3'-bis(dimethylamino)di-n-propylamine and/or
bis(2-piperazinoisopropyl) ether, diazabicyclo[2.2.2]octane,
dimethylpiperazine, N,N'-bis(3-aminopropyl)ethylenediamine and/or
tris(N,N-dimethylaminopropyl)-s-hexahydrotriazine,
4-chloro-2,5-dimethyl-1-(N-methylaminoethyl)imidazole,
10 2-aminopropyl-4,5-dimethoxy-1-methylimidazole,
1-aminopropyl-2,4,5-tributylimidazole,
1-aminoethyl-4-hexylimidazole,
1-aminobutyl-2,5-dimethylimidazole,
1-(3-aminopropyl)-2-ethyl-4-methylimidazole,
1-(3-aminopropyl)imidazole and/or
1-(3-aminopropyl)=2-methylimidazole, preferably
1,4-diazabicyclo[2.2.2]octane and/or imidazoles, particularly
preferably 1-(3-aminopropyl)imidazole,
1-(3-aminopropyl)-2-methylimidazvle and/or
1,4-diazabicyclo[2.2.2]octane. The catalysts described can be
used individually or in the form of mixtures.
Auxiliaries and/or additives used are, for example, mold release
agents, flame retardants, colorants, fillers and/or reinforcing
materials.
It is customary in industry to mix all starting materials with
the exception of the polyisocyanates to form a polyol component
and to react this with the polyisocyanates to give the
polyurethane.
The polyurethanes can be produced by the one-shot method or by
the prepolymer method. The flexible polyurethane foams may be
either slabstock foams or molded foams.
An overview of the starting materials for producing polyurethanes
and the processes employed for this purpose may be found, for
example, in the Kunststoffhandbuch, Volume 7, "Polyurethane",
Carl-Hanser-Verlag, Munich, Vienna, 1St edition 1966, 2nd edition
1983 and 3rd edition 1993.
It has surprisingly been found that, in the polyurethane systems,
the polyether alcohols of the present invention behave like
conventional polyether alcohols catalyzed by means of alkali
metal hydroxides.
0050/50643 CA 02382613 2002-02-22
11
The processability of polyols which have been prepared by means
of multimetal cyanide catalysts and have no propylene oxide end
block is, particularly when these polyols are used for producing
flexible polyurethane foams, especially in the production of
flexible slabstock foams, very restricted. The high reactivity of
these polyols does not allow crack-free and 100% open-celled
foams, in particular flexible slabstock foams, to be obtained.
Increasing the catalysis, in particular tin catalysis, in foam
production leads to a reduction in crack formation but the open
cell content of the foams decreases greatly at the same time, so
that the foams shrink. These polyols are therefore unsuitable for
the production of flexible slabstock foams. These disadvantages
are completely overcome when using the polyether alcohols of the
present invention.
The invention is illustrated by the following examples.
Example 1 (comparison)
The synthesis was carried out in a cleaned and dried 10 1
stirring autoclave. At 50°C, 211.6 g of a propoxylate of glycerol
and propylene oxide having a molecular weight MW of 400 g/mol were
placed in the stirring autoclave and admixed with 0.8 g of a
multimetal cyanide catalyst. The contents of the autoclave were
made inert using nitrogen and treated at 110°C under reduced
pressure for a total of 1.5 hours. At 125°C, 3.5 bar of nitrogen
were introduced and a mixture of 2018.1 g of propylene oxide and
297.4 g of ethylene oxide were subsequently metered in over a
period of 5 hours 15 minutes. The mixture was stirred for a
further 30 minutes and degassed at 105°C and 9 mbar. The polyether
alcohol was worked up by filtration. The resulting polyether
alcohol had the following properties:
Hydroxyl number: 35.2 mg KOH/g;
Viscosity at 25°C: 934 mPas;
Zn/Co content: 3/6 ppm;
Primary hydroxyl group content: 10~ (determined in accordance
with BASF Schwarzheide test method PFO/A 00/22-28)
Example 2
The synthesis was carried out in a cleaned and dried 10 1
stirring autoclave. At 50°C, 437.9 g of propoxylated glycerol
having a molecular weight MW of 400 g/mol were placed in the
stirring autoclave and admixed with 1.5 g of a multimetal cyanide
catalyst. The contents of the autoclave were made inert using
nitrogen and treated at 110°C under reduced pressure for a total
of 1.5 hours. At 125°C, 3.5 bar of nitrogen were introduced and a
050/50643 CA 02382613 2002-02-22
12
mixture of 3462.2 g of propylene oxide and 585.4 g of ethylene
oxide were subsequently metered in over a period of 2 hours 44
minutes. After a 10 minute pause, 487.8 g of propylene oxide were
metered in. The mixture was stirred for a further 30 minutes and
.5 degassed at 105°C and 9 mbar. The polyether alcohol was worked up
by filtration. The resulting polyether alcohol had the following
properties:
Hydroxyl number: 34.2 mg KOH/g;
Viscosity at 25°C: 880 mPas;
Zn/Co content: 4/9 ppm;
Primary hydroxyl group content: 5% (determined in accordance with
BASF Schwarzheide test method PFO/A 00/22-28)
Example 3 (comparison)
The synthesis was carried out in a cleaned and dried 20 1
stirring autoclave. 2.0 kg of propoxylated glycerol having a
molecular weight Mw of 400 g/mol (L3300) and 0.196 g of
propoxylated ethylene glycol having a molar mass of 250 g/mol
were placed in the stirring autoclave and admixed with 19.2 g of
multimetal cyanide catalyst. The contents of the autoclave were
made inert using nitrogen and treated at 110°C under reduced
pressure for a total of 1.5 hours. At 115°C, 3.5 bar of nitrogen
were introduced and subsequently, over a period of 3.5 hours,
firstly 3.45 kg of propylene oxide then 12.37 kg of a mixture of
10.5 kg of propylene oxide and 1.87 kg of ethylene oxide were
metered in. The mixture was stirred for a further 0.6 hour and
degassed at 115°C and 9 mbar. The polyether alcohol was worked up
by filtration. The resulting polyether alcohol had the following
properties:
Hydroxyl number: 47.4 mg KOH/g;
Viscosity at 25°C: 536 mPas;
Zn/Co content: 4/9 ppm;
Primary hydroxyl group content: 10 % (determined in accordance
with BASF Schwarzheide test method PFO/A 00/22-28)
Example 4
The synthesis was carried out in a cleaned and dried 20 1
stirring autoclave. 2.0 kg of propoxylated glycerol having a
molecular weight MW of 400 and 0.196 g of propoxylated ethylene
glycol having a molar mass of 250 g/mol were placed in the
stirring autoclave and admixed with 19 g of multimetal cyanide
catalyst. The contents of the autoclave were made inert using
nitrogen and treated at 110°C under reduced pressure for a total
of 1.5 hours. At 115°C, 3.5 bar of nitrogen were introduced and
subsequently, over a period of 3.5 hours, firstly 3.45 kg of
0050/50643 CA 02382613 2002-02-22
13
propylene oxide then 12.1 kg of a mixture of 10.2 kg of propylene
oxide and 1.9 kg of ethylene oxide were metered in. 2.0 kg of
propylene oxide were subsequently added on. The mixture was
stirred for a further 0.6 hour and degassed at 115°C and 9 mbar.
The product was worked up by filtration. The resulting polyether
alcohol had the following properties:
Hydroxyl number: 47.4 mg KOH/g;
Viscosity at 25°C: 578 mPas;
Zn/Co content: 22/55 ppm;
Primary hydroxyl group content: 5~ (determined in accordance with
BASF Schwarzheide test method PFO/A 00/22-28)
To determine the primary hydroxyl group content, the hydroxyl
groups of the polyether alcohol are reacted with trichloroacetyl
isocyanate and this reaction product is examined by NMR
spectroscopy. The measurement was carried out using a Bruchner
DPX 250 NMR spectrometer. In the spectrum, primary and secondary
hydroxyl groups appear as different peaks.
25
35
45
0050/50643
CA 02382613 2002-02-22
14
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16
Examples 5 to 7
Production of the polyisocyanate polyaddition products
5.
The starting materials indicated in Table 1 apart from the
isocyanate Lupranat~ T80 A (BASF Aktiengesellschaft) were
intensively mixed. The Lupranat~ T80 A was then added while
stirring and the reaction mixture was poured into an open mold
(400 x 400 x 400 mm) in which it foamed to give the polyurethane
foam. The foaming data and the properties of the resulting
polyurethane foams are likewise shown in Table 1.
Polyol A: Polyetherol prepared as described in Example 3
Polyol B: Polyetherol prepared as described in Example 4
Lupragen~ N201: 1,4-Diazabicyclo[2.2.2]octane (33%) in
dipropylene glycol (67%) (BASF
Aktiengesellschaft)
Lupragen~ N206: Bis(2-dimethylaminoethyl) ether (70%) in
dipropylene glycol (30%) (BASF
Aktiengesellschaft)
Kosmus~ 29: Tin(II) salt of ethylhexanoic acid
(Goldschmidt AG)
Tegostab~ BF 2370: Silicone stabilizer
(Goldschmidt AG)
Lupranat~ T80: 2,4-/2,6-tolylene diisocyanate mixture
(BASF Aktiengesellschaft)
Test Standard
Foam density DIN 53420
Tensile test
-tensile strength DIN 53571
-elongation
Compressive set DIN 53572
Rebound resilience DIN 53573
Indentation hardnessDIN 53576
Compressive strengthDIN 53577
~
