Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02865311 2014-08-22
Rigid polyurethane foams
Description
The present invention relates to rigid polyurethane foams, to a process for
producing
them and to a polyol component comprising polyetherester polyols which is
useful in
their production.
Rigid polyurethane foams are long known and have been extensively described.
Rigid
polyurethane foams are predominantly used for thermal insulation, for example
in
district heating pipes, means of transport or buildings and also for producing
structural
elements, especially sandwich elements.
Composite elements are a significant outlet for rigid polyurethane foams.
Composite
elements, which are formed particularly of metallic outer layers and a core of
isocyanate-based foam, usually polyurethane (FUR) or polyisocyanurate (FIR)
foam,
are frequently also known as sandwich elements and are currently produced in
large
volumes on continuous double-belt plant. In addition to sandwich elements for
coolstore insulation, elements having colored outer layers are becoming more
and
more important for decorating exteriors of various buildings. The outer layers
used here
include sheets of stainless steel, copper or aluminum as well as coated steel.
It is important that the rigid polyurethane foams fill the cavities uniformly
and without
voids in order that bonding to the outer layers is as good as possible to
produce a
stable structure that ensures good thermal insulation. To prevent foam
defects, the
time within which the foamable PU reaction mixture is introduced into the
cavity to be
insulated has to be short. It is typically low-pressure or preferably high-
pressure
machines that are usually used to foam out such articles.
A comprehensive overview of the production of rigid polyurethane foams and
their use
as outer or core layer in composite elements and also their application as
insulating
layer in cooling or heating technology appears for example in "Polyurethane",
Kunststoff-Handbuch, volume 7, 3rd edition, 1993, edited by Dr. Gunter Oertel,
Carl-
Hanser-Verlag, Munich/Vienna.
Suitable rigid polyurethane foams are obtainable in known manner by reacting
organic
polyisocyanates with one or more compounds having two or more reactive
hydrogen
atoms in the presence of blowing agents, catalysts and optionally auxiliaries
and/or
additives.
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The compounds used in the production of polyurethanes as having two or more
isocyanate-reactive hydrogen atoms are preferably polyether alcohols and/or
polyester
alcohols. Polyols are selected with particular regard to costs and the desired
performance characteristics (e.g., EP-A 1
632 511, US-B 6,495,722,
WO 2006/108833).
However, the surface properties of known rigid polyurethane foams continue to
be in
need of improvement, especially with regard to the production of composite
elements,
since they have a significant influence on the adherence of outer layers to
the foam. A
good surface is also very important in the production of foams by the sprayed
foam
process.
The printed publications EP 0 728 783 Al, EP 0 826 708 Al and WO 201 0/1 06067
Al
describe processes for producing rigid PU foams where the polyol component
comprises castor oil. Castor oil can be advantageous for the surface
properties of the
=
foam. On the other hand, castor oil in the presence of water may lead to phase
separation and hence to instability on the part of the polyol component and
this may
lead to processing problems. Water is frequently used as an inexpensive and
environmentally friendly blowing agent in the polyol component. One
disadvantage of
the process described in EP 0 826 708 Al is the very poor adherence of the
rigid PU
foams formed as well as the high viscosity of the polyol component. Similarly,
the rigid
PU foams produced by the process described in EP 0 728 783 Al are still in
need of
improvement with regard to their surface properties and adherence. The rigid
PU
foams produced according to WO 2010/106067 Al do exhibit good adherence and
good surface constitution, but are still in need of improvement in respect of
the polyol
component's storage stability in the presence of comparatively large amounts
of water
(> 1.5 parts by weight).
It is an object of the present invention to provide a polyol component for
producing rigid
polyurethane foams which has a high solubility for physical blowing agents, is
phase
stable even under changes in composition and also has a low viscosity and good
processing properties, especially good curing.
We have found that this object is achieved by rigid polyurethane foams
obtainable by
reaction of
A) organic or modified organic polyisocyanates or mixtures thereof,
B) compounds having two or more isocyanate-reactive hydrogen atoms in the
presence of
C) optionally further polyester polyols,
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D) optionally polyetherol polyols,
E) optionally flame retardants,
F) one or more blowing agents,
G) catalysts, and
H) optionally further auxiliaries and/or additives,
wherein component B) comprises the reaction product of
al) 15 to 40 wt% of one or more polyols or polyamines having an average
functionality of 2.5 to 8,
a2) 2 to 30 wt% of one or more fatty acids and/or fatty acid monoesters,
a3) 35 to 70 wt% of one or more alkylene oxides of 2 to 4 carbon atoms.
The average functionality of the polyols, polyamines or mixtures of polyols
and/or
polyamines is preferably in the range from 3 to 6 and more preferably in the
range from
3.5 to 5.5.
Preferred polyols or polyamines of component al) are selected from the group
consisting of sugars (sorbitol, glucose, sucrose), pentaerythritol, sorbitol,
trimethylolpropane, glycerol, tolylenediamine, ethylenediamine, ethylene
glycols,
propylene glycol and water. Particular preference is given to sugars
(sorbitol, glucose,
sucrose), glycerol, water and ethylene glycols and also mixtures thereof,
especial
preference being given to mixtures comprising two or more compounds selected
from
sucrose, glycerol, water and diethylene glycol.
In one specific embodiment, component al) comprises a mixture of glycerol and
sucrose.
The proportion of the polyetherester polyols of the present invention which is
contributed by polyols and/or polyamines al) is generally in the range from 15
to
wt%, preferably in the range from 20 to 35 wt% and more preferably in the
range
from 25 to 30 wt%, based on the weight of polyetherester polyols.
35 In general, the fatty acid or fatty acid monoester a2) is selected from
the group
consisting of polyhydroxy fatty acids, ricinoleic acid, hydroxyl-modified
oils, hydroxyl-
modified fatty acids and fatty acid esters based on myristoleic acid,
palmitoleic acid,
oleic acid, vaccenic acid, petroselic acid, gadoleic acid, erucic acid,
nervonic acid,
linoleic acid, a- and 7-linolenic acid, stearidonic acid, arachidonic acid,
timnodonic acid,
40 clupanodonic acid and cervonic acid. Methyl esters are preferred fatty acid
monoesters.
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In one preferred embodiment of the invention, the fatty acids or fatty acid
monoesters
a2) are used in the form of fatty acid methyl esters, biodiesel or pure fatty
acids.
Particular preference is given to biodiesel and pure fatty acids and specific
preference
to pure fatty acids, preferably oleic acid and stearic acid, especially oleic
acid.
In a further preferred embodiment of the present invention, the fatty acid or
fatty acid
monoester a2) is oleic acid or stearic acid or a derivative of these fatty
acids, particular
preference being given to oleic acid, methyl oleate, stearic acid and methyl
stearate.
The fatty acid or fatty acid monoester is generally used to improve blowing
agent
solubility in the production of polyurethane foams. In a particularly
preferred
embodiment of the invention component a2) contains methyl oleate, especially
preferred component a2) consists thereof.
The fatty acid proportion of polyetherester polyols according to the present
invention is
generally in the range from 2 to 30 wt%, preferably in the range from 5 to 25
wt%, more
preferably in the range from 8 to 20 wt% and especially in the range from 12
to 17 wt%,
based on the weight of polyetherester polyols.
Useful alkylene oxides a3) have 2 to 4 carbon atoms and include for example
tetrahydrofuran, 1,3-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide,
styrene
oxide and preferably ethylene oxide and 1,2-propylene oxide. The alkylene
oxides can
be used individually, alternatingly in succession or as mixtures. Propylene
oxide and
ethylene oxide are preferred alkylene oxides, mixtures of ethylene oxide and
propylene
oxide with > 35 wt% of propylene oxide are particularly preferred, and pure
propylene
oxide is especially preferred.
One preferred embodiment utilizes an alkoxylation catalyst comprising an
amine,
preferably dimethylethanolamine or imidazole and more preferably imidazole.
The proportion of the polyetherester polyols of the present invention which is
contributed by alkylene oxides is generally in the range from 35 to 70 wt%,
preferably
in the range from 50 to 65 wt% and more preferably in the range from 55 to 60
wt%.
The OH number of the polyetherester polyols of the present invention is in the
range
from 200 to 700 mg KOH/g, preferably in the range from 300 to 600 mg KOH/g,
more
preferably in the range from 350 to 500 mg KOH/g and especially in the range
from 400
to 500 mg KOH/g.
The average functionality of the polyetherester polyols of the present
invention is
generally in the range from 2.5 to 8, preferably in the range from 3 to 6,
more
preferably in the range from 3.5 to 5.5 and especially in the range from 4 to
5.
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The viscosity of the polyetherester polyols of the present invention is
generally
< 10 000 mPas, preferably <7000 mPas, more preferably <5500 mPas and
specifically < 4000 mPas, all measured at 25 C to DIN 53018.
5 The invention further provides a process for producing rigid polyurethane
foams by
reaction of
A) organic or modified organic polyisocyanates or mixtures thereof,
B) one or more of the above-described polyetherester polyols,
C) optionally further polyester polyols,
D) optionally polyetherol polyols,
E) optionally flame retardants,
F) one or more blowing agents,
G) catalysts, and
H) optionally further auxiliaries and/or additives.
The present invention also provides a polyol mixture comprising said
components B) to
F) and H), i.e.
B) one or more of the above-described polyetherester polyols,
C) optionally further polyester polyols,
D) optionally polyether polyols,
E) optionally flame retardants,
F) one or more blowing agents,
G) optionally catalysts, and
H) optionally further auxiliaries and/or additives.
Further subjects of the present invention include rigid polyurethane foams and
rigid
polyisocyanurate foams obtainable via the process of the present invention and
also
the use of the polyetherester polyols of the present invention for producing
rigid
polyurethane foams or rigid polyisocyanurate foams.
The proportion of polyetherester polyols B) of the present invention is
generally
> 20 wt%, preferably > 40 wt%, more preferably > 60 wt% and especially
preferably
> 70 wt%, based on total components B) to H).
Production of rigid polyurethane foams by the process of the present
invention, in
addition to the specific polyetherester polyols described above, utilizes the
constructal
components known per se, which will now be detailed.
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Possible organic or modified organic polyisocyanates A) are the aliphatic,
cycloaliphatic, araliphatic and preferably aromatic polyfunctional isocyanates
known
per se.
Specific examples are: alkylene diisocyanates haying from 4 to 12 carbon atoms
in the
alkylene radical, e.g. dodecane 1,12-diisocyanate, 2-ethyltetramethylene
1,4-diisocyanate, 2-methylpentamethylene 1,5-diisocyanate,
tetramethylene
1,4-diisocyanate, and preferably hexamethylene 1,6-diisocyanate;
cycloaliphatic
diisocyanates such as cyclohexane 1,3- and 1,4-diisocyanate and also any
mixtures of
these isomers, 1-isocyanato-3,3,5-trimethy1-5-isocyanatomethylcyclohexane
(IPDI),
hexahydrotolylene 2,4- and 2,6-diisocyanate and also the corresponding isomer
mixtures, dicyclohexylmethane 4,4'-, 2,2'- and 2,4'-diisocyanate and also the
corresponding isomer mixtures, and preferably aromatic diisocyanates and
polyisocyanates such as tolylene 2,4- and 2,6-diisocyanate and the
corresponding
isomer mixtures, diphenylmethane 4,4'-, 2,4'- and 2,2'-diisocyanate and the
corresponding isomer mixtures, mixtures of diphenylmethane 4,4'- and
2,2'-diisocyanates, polyphenylpolymethylene polyisocyanates, mixtures of
diphenylmethane 4,4'-, 2,4'- and 2,2'-diisocyanates and
polyphenylpolymethylene
polyisocyanates (crude MDI) and mixtures of crude MDI and tolylene
diisocyanates.
The organic diisocyanates and polyisocyanates can be used individually or in
the form
of their mixtures.
Preferred polyisocyanates are tolylene diisocyanate (TDI), diphenylmethane
diisocyanate (MDI) and in particular mixtures of diphenylmethane diisocyanate
and
polyphenylenepolyrnethylene polyisocyanates (polymeric MDI or PMDI).
Use is frequently also made of modified polyfunctional isocyanates, i.e.
products which
are obtained by chemical reaction of organic polyisocyanates. Examples which
may be
mentioned are polyisocyanates comprising ester, urea, biuret, allophanate,
carbodiimide, isocyanurate, uretdione, carbamate and/or urethane groups.
Very particular preference is given to using polymeric MDI for producing the
rigid
polyurethane foams of the invention.
Suitable further polyester polyols C) can be prepared, for example, from
organic
dicarboxylic acids having from 2 to 12 carbon atoms, preferably aromatic or
mixtures of
aromatic and aliphatic dicarboxylic acids, and polyhydric alcohols, preferably
diols,
having from 2 to 12 carbon atoms, preferably from 2 to 6 carbon atoms.
Possible
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dicarboxylic acids are, for example: succinic acid, glutaric acid, adipic
acid, suberic
acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid,
fumaric acid,
phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids
can be used
either individually or in admixture with one another. It is also possible to
use the
corresponding dicarboxylic acid derivatives, e.g. dicarboxylic esters of
alcohols having
from 1 to 4 carbon atoms or dicarboxylic anhydrides, in place of the free
dicarboxylic
acids. As aromatic dicarboxylic acids, preference is given to using phthalic
acid,
phthalic anhydride, terephthalic acid and/or isophthalic acid as a mixture or
alone. As
aliphatic dicarboxylic acids, preference is given to using dicarboxylic acid
mixtures of
succinic, glutaric and adipic acid in weight ratios of, for example, 20-35:35-
50:20-32,
and in particular adipic acid. Examples of dihydric and polyhydric alcohols,
in particular
diols, are: ethanediol, diethylene glycol, 1,2- or 1,3-propanediol,
dipropylene glycol,
1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,
1,10-decanediol, glycerol,
trimethylolpropane and pentaerythritol. Preference is given to using
ethanediol,
diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol or mixtures
of at
least two of the diols mentioned, in particular mixtures of 1,4-butanediol,
1,5-pentane-
diol and 1,6-hexanediol. It is also possible to use polyester polyols derived
from
lactones, e.g. E-caprolactone, or hydroxycarboxylic acids, e.g. co-
hydroxycaproic acid.
To prepare the further polyester polyols C), bio-based starting materials
and/or
derivatives thereof are also suitable, for example castor oil, polyhydroxy
fatty acids,
ricinoleic acid, hydroxyl-modified oils, grapeseed oil, black cumin oil,
pumpkin kernel
oil, borage seed oil, soybean oil, wheat germ oil, rapeseed oil, sunflower
oil, peanut oil,
apricot kernel oil, pistachio oil, almond oil, olive oil, macadamia nut oil,
avocado oil, sea
buckthorn oil, sesame oil, hemp oil, hazelnut oil, primula oil, wild rose oil,
safflower oil,
walnut oil, hydroxyl-modified fatty acids and fatty acid esters based on
myristoleic acid,
palmitoleic acid, oleic acid, vaccenic acid, petroselic acid, gadoleic acid,
erucic acid,
nervonic acid, linoleic acid, a- and Thlinolenic acid, stearidonic acid,
arachidonic acid,
timnodonic acid, clupanodonic acid and cervonic acid.
The level of further polyester polyols C) is generally in the range from 0 to
20 wt%,
based on total components B) to H). One embodiment of the invention utilizes
from 1 to
10 wt% of polyester polyols C). One preferred embodiment of the invention
utilizes no
further polyester polyols C).
It is also possible to make concomitant use of polyether polyols D) which are
prepared
by known methods, for example from one or more alkylene oxides having from 2
to 4
carbon atoms in the alkylene radical by anionic polymerization using alkali
metal
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hydroxides, e.g. sodium or potassium hydroxide, or alkali metal alkoxides,
e.g. sodium
methoxide, sodium or potassium ethoxide or potassium isopropoxide, as
catalysts with
addition of at least one starter molecule comprising from 2 to 8, preferably
from 2 to 6,
reactive hydrogen atoms, or by cationic polymerization using Lewis acids, e.g.
antimony pentachloride, boron fluoride etherate, or bleaching earth, as
catalysts.
Suitable alkylene oxides are, for example, tetrahydrofuran, 1,3-propylene
oxide, 1,2- or
2,3-butylene oxide, styrene oxide and preferably ethylene oxide and 1,2-
propylene
oxide. The alkylene oxides can be used individually, alternately in succession
or as
mixtures. Preferred alkylene oxides are propylene oxide and ethylene oxide,
with
particular preference being given to propylene oxide.
Possible starter molecules are, for example: water, organic dicarboxylic
acids, such as
succinic acid, adipic acid, phthalic acid and terephthalic acid, aliphatic and
aromatic,
optionally N-nnonoalkyl-, N,N-dialkyl- and N,N'-dialkyl-substituted diamines
having from
1 to 4 carbon atoms in the alkyl radical, e.g. optionally monoalkyl- and
dialkyl-
substituted ethylenediamine, diethylenetriamine,
triethylenetetramine,
1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and
1,6-hexa-
methylenediamine, phenylenediamines, 2,3-, 2,4- and 2,6-tolylenediamine and
4,4'-,
2,4'- and 2,2'-diaminodiphenylmethane.
Further possible starter molecules are: alkanolamines such as ethanolamine,
N-methylethanolamine and N-ethylethanolamine, dialkanolamines, such as
diethanolamine, N-methyldiethanolamine and N-ethyldiethanolamine,
and
trialkanolamines, such as triethanolamine, and ammonia.
Preference is given to using dihydric or polyhydric alcohols such as
ethanediol, 1,2-
and 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol,
1,6-
hexanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and
sucrose.
Particular preference is given to the recited diprimary amines, for example
ethylenediamine.
The polyether polyols D), preferably polyoxypropylene polyols and/or
polyoxyethylene
polyols, have a functionality of preferably from 2 to 6 and in particular from
2 to 5 and
number average molecular weights of from 150 to 3000, preferably from 200 to
2000
and in particular from 250 to 1000.
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One embodiment of the invention utilizes an alkoxylated amine, preferably a
propoxylated amine, for example propoxylated ethylenediamine, as polyether
polyol D),
generally in amounts from 0 to 35 wt%, preferably in amounts from 0 to 10 wt%,
based
on total components B) to H). One embodiment utilizes a propoxylated amine in
amounts from 2 to 6 wt%. One particularly preferred embodiment utilizes no
alkoxylated amine.
One advantage of the invention is that a polyether polyol D) and especially a
propoxylated amine can also be omitted.
A further particularly preferred embodiment of the invention utilizes an
alkoxylated
polyol, preferably a propoxylated polyol, based on a mixture of glycerol and
sucrose or
diethylene glycol and sucrose as polyether polyol D), preferably in amounts
from 0 to
35 wt%, preferably from 0 to 20 wt%, more preferably from 0 to 10 wt%, based
on the
total components B) to H).
The proportion of polyether polyols D) is generally in the range from 0 to 40
wt%,
preferably in the range from 0 to 20 wt% and more preferably in the range from
0 to
10 wt%, based on total components B) to F).
As flame retardants E), it is generally possible to use the flame retardants
known from
the prior art. Suitable flame retardants are, for example, nonincorporable
brominated
substances, brominated esters, brominated ethers (Ixol) or brominated alcohols
such
as dibromoneopentyl alcohol, tribromoneopentyl alcohol and PHT-4-diol and also
chlorinated phosphates such as tris(2-chloroethyl) phosphate, tris(2-
chloropropyl)
phosphate (TCPP), tris(1,3-dichloropropyl) phosphate, tricresyl phosphate,
tris(2,3-
dibromopropyl) phosphate, tetrakis(2-chloroethyl) ethylenediphosphate,
dimethyl
methanephosphonate, diethyl diethanolaminomethylphosphonate and also
commercial
halogen-comprising flame retardant polyols. It is possible to use phosphates
or
phosphonates such as diethyl ethanephosphonate (DEEP), triethyl phosphate
(TEP),
dimethyl propylphosphonate (DMPP), diphenyl cresyl phosphate (DPK) and others
as
further liquid flame retardants.
Apart from the abovementioned flame retardants, it is possible to use
inorganic or
organic flame retardants such as red phosphorus, preparations comprising red
phosphorus, aluminum oxide hydrate, antimony trioxide, arsenic oxide, ammonium
polyphosphate and calcium sulfate, expandable graphite or cyanuric acid
derivatives
such as melamine, or mixtures of at least two flame retardants, e.g. ammonium
polyphosphates and melamine and optionally maize starch or ammonium
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polyphosphate, melamine, expandable graphite and optionally aromatic
polyesters for
making the rigid polyurethane foams flame resistant.
Preferable flame retardants are the recited phosphorus-containing flame
retardants,
5 particular preference being given to dimethyl propylphosphonate (DMPP),
diethyl
ethanephosphonate (DEEP), triethyl phosphate (TEP), diphenyl cresyl phosphate
(DPK), triphenyl phosphate (TPP) and tris-(2-chloropropyl) phosphate (TCPP),
with
special preference being given to TCPP.
10 The proportion of flame retardant E) is generally in the range from 0 to
30 wt%,
preferably in the range from 0 to 15 wt%, more preferably in the range from 0
to
10 wr/o, even more preferably in the range from 0 to 5 wt% and specifically
Owe/o,
based on components B) to H).
Blowing agents F) which are used for producing the rigid polyurethane foams
include
preferably water, formic acid and mixtures thereof. These react with
isocyanate groups
to form carbon dioxide and in the case of formic acid carbon dioxide and
carbon
monoxide. In addition, physical blowing agents such as low-boiling
hydrocarbons can
be used. Suitable physical blowing agents are liquids which are inert towards
the
organic, optionally modified polyisocyanates and have boiling points below 100
C,
preferably below 50 C, at atmospheric pressure, so that they vaporize under
the
conditions of the exothermic polyaddition reaction. Examples of such liquids
which can
preferably be used are alkanes such as heptane, hexane, n-pentane and
isopentane,
preferably industrial mixtures of n-pentane and isopentane, n-butane and
isobutane
and propane, cycloalkanes such as cyclopentane and/or cyclohexane, ethers such
as
furan, dimethyl ether and diethyl ether, ketones such as acetone and methyl
ethyl
ketone, alkyl carboxylates such as methyl formate, dimethyl oxalate and ethyl
acetate
and halogenated hydrocarbons such as methylene chloride, dichloromono-
fluoromethane, difluoromethane, trifluoromethane, difluoroethane,
tetrafluoroethane,
chlorodifluoroethanes, 1,1-dichloro-2,2,2-trifluoroethane, 2,2-dichloro-2-
fluoroethane
and heptafluoropropane. Mixtures of these low-boiling liquids with one another
and/or
with other substituted or unsubstituted hydrocarbons can also be used. Organic
carboxylic acids such as formic acid, acetic acid, oxalic acid, ricinoleic
acid and
carboxyl-containing compounds are also suitable.
It is preferable not to use any halogenated hydrocarbons as blowing agent. It
is
preferable to use water, any pentane isomer and also mixtures of water and
pentane
isomers and also formic acid.
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The blowing agents are either wholly or partly dissolved in the polyol
component (i.e.
B+C+D+E+F+G+H) or are introduced via a static mixer immediately before foaming
of
the polyol component. It is usual for water or formic acid to be fully or
partially dissolved
in the polyol component and the physical blowing agent (for example pentane)
and any
remainder of the chemical blowing agent to be introduced "on-line".
The polyol component is admixed in situ with pentane, possibly some of the
chemical
blowing agent and also with all or some of the catalysts. Auxiliaries and
additives as
well as flame retardants are - if present - already comprised in the polyol
blend.
The amount of blowing agent or blowing agent mixture used is in the range from
1 to
40 wt%, preferably in the range from 1 to 25 wt% and more preferably in the
range
from 1.5 to 17.5 wt%, all based on total components B) to H).
When water is used as blowing agent, it is preferably added to the component
B) in an
amount of 0.2 to 5 wt%, based on component B). The addition of water can take
place
in combination with the use of other blowing agents described. Preference is
given to
using water combined with pentane.
Catalysts G) used for preparing the rigid polyurethane foams are particularly
compounds which substantially speed the reaction of the component B) to F)
compounds comprising reactive hydrogen atoms, especially hydroxyl groups, with
the
organic, optionally modified polyisocyanates A).
It is advantageous to use basic polyurethane catalysts, for example tertiary
amines
such as triethylamine, tributylamine, dimethylbenzylamine,
dicyclohexylmethylamine,
dimethylcyclohexylamine, N,N,N',N'-tetramethyldiaminodiethyl ether,
bis(dimethyl-
aminopropyl)urea, N-methylmorpholine or N-ethylmorpholine, N-
cyclohexylmorpholine,
N,N,N',N'-tetramethylethylenediamine,
N,N,N,N-tetramethylbutanediamine,
N, N, N, N-tetramethylhexane-1,6-diamine, pentamethyldiethylenetriamine,
dimethylpiperazine, N-dimethylaminoethylpiperidine,
1,2-dimethylimidazole, 1-
azabicyclo-[2.2.0]octane, 1,4-diazabicyclo[2.2.2]octane (Dabco) and
alkanolamine
compounds, such as triethanolamine, triisopropanolamine, N-
methyldiethanolamine
and N-ethyldiethanolamine, dimethylaminoethanol, 2-
(N,N-
dimethylaminoethoxy)ethanol, N,N',N"-
tris(dialkylaminoalkyl)hexahydrotriazines, e.g.
N,N',N"-tris(dimethylaminopropy1)-hexahydrotriazine, and triethylenediamine.
However,
metal salts such as iron(11) chloride, zinc chloride, lead octoate and
preferably tin salts
such as tin dioctoate, tin diethylhexoate and dibutyltin dilaurate and also,
in particular,
mixtures of tertiary amines and organic tin salts are also suitable.
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Further possible catalysts are: amidines such as 2,3-dimethy1-3,4,5,6-tetra-
hydropyrimidine, tetraalkylammonium hydroxides such as tetramethylammonium
hydroxide, alkali metal hydroxides such as sodium hydroxide and alkali metal
alkoxides
such as sodium methoxide and potassium isopropoxide, and also alkali metal
salts of
long-chain fatty acids having from 10 to 20 carbon atoms and optionally
lateral OH
groups. Preference is given to using from 0.001 to 6% by weight, in particular
from 0.05
to 3% by weight, of catalyst or catalyst combination, based on the weight of
the
components B) to H). It is also possible to allow the reactions to proceed
without
catalysis. In this case, the catalytic activity of amine-initiated polyols is
exploited.
When, during foaming, a relatively large polyisocyanate excess is used,
further suitable
catalysts for the trimerization reaction of the excess NCO groups with one
another are:
catalysts which form isocyanurate groups, for example ammonium ion salts or
alkali
metal salts, either alone or in combination with tertiary amines. Isocyanurate
formation
leads to flame-resistant FIR foams which are preferably used in industrial
rigid foam,
for example in building and construction as insulation boards or sandwich
elements.
Further information regarding the abovementioned and further starting
materials may
be found in the technical literature, for example Kunststoffhandbuch, Volume
VII,
Polyurethane, Carl Hanser Verlag Munich, Vienna, 1st, 2nd and 3rd Editions
1966,
1983 and 1993.
Further auxiliaries and/or additives H) can optionally be added to the
reaction mixture
for producing the rigid polyurethane foams. Mention may be made of, for
example,
surface-active substances, foam stabilizers, cell regulators, fillers, dyes,
pigments,
flame retardants, hydrolysis inhibitors, fungistatic and bacteriostatic
substances.
Possible surface-active substances are, for example, compounds which serve to
aid
homogenization of the starting materials and may also be suitable for
regulating the cell
structure of the polymers. Mention may be made of, for example, emulsifiers
such as
the sodium salts of castor oil sulfates or of fatty acids and also salts of
fatty acids with
amines, e.g. diethylamine oleate, diethanolamine stearate, diethanolamine
ricinoleate,
salts of sulfonic acids, e.g. alkali metal or ammonium salts of
dodecylbenzenesulfonic
or dinaphthylmethanedisulfonic acid and ricinoleic acid; foam stabilizers such
as
siloxane-oxyalkylene copolymers and other organopolysiloxanes, ethoxylated
alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil esters or
ricinoleic
esters, Turkey red oil and peanut oil, and cell regulators such as paraffins,
fatty
CA 02865311 2014-08-22
13
alcohols and dimethylpolysiloxanes. The above-described oligomeric acrylates
having
polyoxyalkylene and fluoroalkane radicals as side groups are also suitable for
improving the emulsifying action, the cell structure and/or for stabilizing
the foam. The
surface-active substances are usually employed in amounts of from 0.01 to 10
wt%,
and preferably from 0.01 to 5 wt% based on the weight of components B) to H).
Fillers, in particular reinforcing fillers, are to be understood as meaning
the customary
organic and inorganic fillers, reinforcing materials, weighting agents, agents
for
improving the abrasion behavior in paints, coating compositions, etc., which
are known
per se. Specific examples are: inorganic fillers such as siliceous minerals,
for example
sheet silicates such as antigorite, serpentine, hornblendes, amphiboles,
chrisotile and
talc, metal oxides such as kaolin, aluminum oxides, titanium oxides and iron
oxides,
metal salts, such as chalk, barite and inorganic pigments such as cadmium
sulfide and
zinc sulfide and also glass, etc. Preference is given to using kaolin (china
clay),
aluminum silicate and coprecipitates of barium sulfate and aluminum silicate
and also
natural and synthetic fibrous minerals such as wollastonite, metal fibers and
in
particular glass fibers of various length, which may be coated with a size.
Possible
organic fillers are, for example: carbon, melamine, rosin, cyclopentadienyl
resins and
graft polymers and also cellulose fibers, polyamide, polyacrylonitrile,
polyurethane,
polyester fibers based on aromatic and/or aliphatic dicarboxylic esters and in
particular
carbon fibers.
The inorganic and organic fillers can be used individually or as mixtures and
are added
to the reaction mixture in amounts of from 0.5 to 50 wt%, preferably from 1 to
40 wt%,
based on the weight of the components A) to H), although the content of mats,
nonwovens and woven fabrics of natural and synthetic fibers can reach values
of up to
80 wt%.
Further information regarding the abovementioned other customary auxiliaries
and
additives may be found in the technical literature, for example the monograph
by
J.H. Saunders and K.C. Frisch "High Polymers" Volume XVI, Polyurethanes, Parts
1
and 2, Interscience Publishers 1962 and 1964, or Kunststoff-Handbuch,
Polyurethane,
Volume VII, Hanser-Verlag, Munich, Vienna, 1st and 2nd Editions, 1966 and
1983.
To produce the rigid polyurethane foams of the present invention, the
optionally
modified organic polyisocyanates A), the specific polyetherester polyols B) of
the
present invention, optionally the further polyester polyols C) and optionally
the
polyetherols and/or further compounds having two or more isocyanate-reactive
groups
CA 02865311 2014-08-22
14
D) are reacted in such amounts that the equivalence ratio of NCO groups of the
polyisocyanates A) to the sum of the reactive hydrogen atoms of the components
B),
optionally C), optionally D) and also E) and F) is in the range from 1 to 6:1,
preferably
in the range from 1.1 to 5:1 and more particularly in the range from 1.2 to
3.5:1.
In one preferred embodiment, the polyol component comprises
25 to 90 wt% of polyetherester polyols B),
0 to 20 wt% of further polyester polyols C),
0 to 35 wt% of polyether polyols D),
0 to 30 wt% of flame retardants E),
1 to 40 wt% of blowing agents F),
0.01 to 5 wt% of catalysts G),
0.01 to 10 wt% of auxiliaries and/or additives H).
It is more preferable for the polyol component to comprise
50 to 85 wt% of polyetherester polyols B),
0 to 10 wt%, especially 0 wt% of further polyester polyols C),
0 to 10 wt%, especially 0 wt% of polyether polyols D),
0 to 15 wt% of flame retardants E),
1 to 30 wt% of blowing agents F),
0.05 to 3 wt% of catalysts G),
0.01 to 5 wt% of auxiliaries and/or additives H).
The rigid polyurethane foams are advantageously produced by the one shot
process,
for example using the high pressure or low pressure technique in open or
closed
molds, for example metallic molds. It is also customary to apply the reaction
mixture in
a continuous manner to suitable belt lines to produce panels.
The starting components are, at a temperature from 15 to 90 C, preferably from
20 to
60 C and especially from 20 to 35 C, mixed and introduced into an open mold
or, if
necessary under superatmospheric pressure, into a closed mold, or applied in a
continuous workstation to a belt for receiving the reactive material. Mixing,
as already
noted, can be carried out mechanically using a stirrer or a stirring screw.
Mold
temperature is advantageously in the range from 20 to 110 C, preferably in the
range
from 30 to 70 C and especially in the range from 40 to 60 C.
The rigid polyurethane foams produced by the process of the present invention
have a
density of 15 to 300 g/I, preferably of 20 to 100 g/I and especially of 25 to
60 g/I.
CA 02865311 2014-08-22
Examples
Inventive example 1
5 Producing a polyetherester polyol with oleic acid
250.1 g of glycerol, 2.5 g of imidazole, 1139.7 g of sucrose as well as 750.6
g of oleic
acid were initially charged to a 5 L reactor at 25 C. The reactor was then
inertized with
nitrogen. The kettle was heated to 130 C and 2858.1 g of propylene oxide were
10 metered in. Following a reaction time of 4 h, the kettle was fully
evacuated at 100 C for
60 minutes and then cooled down to 25 C to obtain 4945 g of product.
The polyetherester polyol obtained had the following characteristic values:
15 OH number: 416.3 mg KOH/g
Viscosity (25 C): 7210 mPas
Acid number: 0.08 mg KOH/g
Water content: 0.016%
Inventive example 2
Producing a polyetherester polyol with methyl oleate
995.2 g of glycerol, 2.5 g of imidazole, 422.8 g of sucrose as well as 676.1 g
of methyl
oleate were initially charged to a 5 L reactor at 25 C. The reactor was then
inertized
with nitrogen. The kettle was heated to 130 C and 2903.4 g of propylene oxide
were
metered in. Following a reaction time of 3 h, the kettle was fully evacuated
at 100 C for
60 minutes and then cooled down to 25 C to obtain 4904.1 g of product.
The polyetherester polyol obtained had the following characteristic values:
OH number: 464.5 mg KOH/g
Viscosity (25 C): 783 mPas
Acid number: 0.11 mg KOH/g
Water content: 0.02%
Comparative example 1
Starting from
55.65 parts by weight of a polyether alcohol 1 having a hydroxyl number of 490
mg
KOH/g, based on propylene oxide and a mixture of sugar and glycerol as
starter,
CA 02865311 2014-08-22
16
6 parts by weight of a polyether alcohol 2 having a hydroxyl number of 750 mg
KOH/g,
based on propylene oxide and ethylenediamine as starter,
20 parts by weight of castor oil,
15 parts by weight of tris-2-chloroisopropyl phosphate (TCPP),
2 parts by weight of silicone foam stabilizer (Tegostab B 8443 from
Goldschmidt),
0.5 part by weight of a 50 wt% solution of potassium acetate in ethylene
glycol, and
0.85 part by weight of water
a polyol component was produced by mixing.
The polyol component is stable at 20 C. It was reacted with a polymeric MDI
having an
NCO content of 31.5 wt% (Lupranat M50 from BASF SE) in the presence of n-
pentane (7.5 parts by weight), dimethylcyclohexylamine and water at an
isocyanate
index of 129. The amounts of dimethylcyclohexylamine and water were chosen
such
that the fiber time was 53 seconds and the resulting foam had a density of 38
kg/m3.
Comparative example 2
Compared with the polyol component of comparative example 1 the amounts of
polyether alcohol 1 and water used were changed as follows:
54.0 parts by weight of polyether alcohol 1, and
2.5 parts by weight of water.
A polyol component was produced by mixing. The polyol component was not stable
at
T = 20 C, separating into two phases.
Comparative example 3
Compared with the polyol component of comparative example 1 the amounts of
polyether alcohol 1 and tris-2-chloroisopropyl phosphate used were changed as
follows:
60.65 parts by weight of polyether alcohol 1, and
10 parts by weight of tris-2-chloroisopropyl phosphate.
A polyol component was produced by mixing. The polyol component was not stable
at
T = 20 C, separating into two phases.
Comparative example 4
The amounts of polyether alcohol 1 and polyether alcohol 2 used in the polyol
component of comparative example 1 were changed as follows:
CA 02865311 2014-08-22
17
60.65 parts by weight of polyether alcohol 1, and
0 part by weight of polyether alcohol 2.
A polyol component was produced by mixing. The polyol component was not stable
at
T = 20 C, separating into two phases.
Comparative example 5
Starting from
56.15 parts by weight of a polyether alcohol 1,
6 parts by weight of polyether alcohol 2,
parts by weight of a polyether alcohol 3 having a hydroxyl number of 400 mg
KOH/g
based on propylene oxide and glycerol as starter,
15 parts by weight of tris-2-chloroisopropyl phosphate,
15 1.8 parts by weight of silicone foam stabilizer (Tegostab B 8443 from
Goldschmidt),
0.2 part by weight of a 50% solution of potassium acetate in ethylene glycol,
and
0.85 part by weight of water
a polyol component was produced by mixing.
20 The polyol component was stable at 20 C. It was reacted with a polymeric
MDI having
an NCO content of 31.5 wt% (Lupranat M50 from BASF SE) in the presence of n-
pentane (7.5 parts by weight), dimethylcyclohexylamine and water at an
isocyanate
index of 116. The amounts of dimethylcyclohexylamine and water were chosen
such
that the fiber time was 53 seconds and the resulting foam had a density of 38
kg/m3.
Comparative example 6
Compared with the polyol component of comparative example 5 the amounts of
polyether alcohol 1 and water used were changed as follows:
54.5 parts by weight of polyether alcohol 1, and
2.5 parts by weight of water.
A polyol component was produced by mixing. The polyol component is clear at
T = 20 C. It was reacted with a polymeric MDI having an NCO content of 31.5
wt%
(Lupranat M50 from BASF SE) in the presence of n-pentane (7.5 parts by
weight),
dimethylcyclohexylamine and water at an isocyanate index of 116. The amounts
of
dimethylcyclohexylamine and water were chosen such that the fiber time was 53
seconds and the resulting foam had a density of 38 kg/m3.
CA 02865311 2014-08-22
18
Comparative example 7
Compared with the polyol component of comparative example 5 the amounts of the
raw materials polyether alcohol 1 and tris-2-chloroisopropyl phosphate used
were
changed as follows:
61.15 parts by weight of polyether alcohol 1, and
parts by weight of tris-2-chloroisopropyl phosphate.
10 A polyol component was produced by mixing. The polyol component was
cloudy at
T = 20 C. It was reacted with a polymeric MDI having an NCO content of 31.5
wt%
(Lupranat M50 from BASF SE) in the presence of n-pentane (7.5 parts by
weight),
dimethylcyclohexylamine and water at an isocyanate index of 116. The amounts
of
dimethylcyclohexylamine and water were chosen such that the fiber time was 53
seconds and the resulting foam had a density of 38 kg/m3.
Comparative example 8
Compared with the polyol component of comparative example 1 the amounts of
polyether alcohol 1 and polyether alcohol 2 used were changed as follows:
=
60.65 parts by weight of polyether alcohol 1, and
0 part by weight of polyether alcohol 2.
A polyol component was produced by mixing. The polyol component is not stable
at
T = 20 C, separating into two phases.
Inventive example 3
Starting from
75.65 parts by weight of polyetherester polyol 1 from example 1 with a
hydroxyl
number of 416 mg KOH/g, based on propylene oxide and a mixture of sugar,
glycerol
and oleic acid as starter,
6 parts by weight of polyether alcohol 2,
15 parts by weight of tris-2-chloroisopropyl phosphate,
2.0 parts by weight of silicone foam stabilizer (Tegostab B 8443 from
Goldschmidt),
0.5 part by weight of a 50% solution of potassium acetate in ethylene glycol,
and
0.85 part by weight of water
a polyol component was produced by mixing.
The polyol component was stable at 20 C. It was reacted with a polymeric MDI
having
an NCO content of 31.5 wt% (Lupranat M50 from BASF SE) in the presence of n-
CA 02865311 2014-08-22
19
pentane (7.5 parts by weight), dimethylcyclohexylamine and water at an
isocyanate
index of 116. The amounts of dimethylcyclohexylamine and water were chosen
such
that the fiber time was 53 seconds and the resulting foam had a density of 38
kg/m3.
Inventive example 4
Compared with the polyol component of inventive example 3 the amounts of
polyetherester polyol 1 and water used were changed as follows:
74.0 parts by weight of polyetherester polyol 1, and
2.5 parts by weight of water.
A polyol component was produced by mixing. The polyol component was clear at
T = 20 C. It was reacted with a polymeric MDI having an NCO content of 31.5
wt%
(Lupranat M50 from BASF SE) in the presence of n-pentane (7.5 parts by
weight),
dimethylcyclohexylamine and water at an isocyanate index of 116. The amounts
of
dimethylcyclohexylamine and water were chosen such that the fiber time was 53
seconds and the resulting foam had a density of 38 kg/m3.
Inventive example 5
Compared with the polyol component of inventive example 3 the amounts of
polyetherester polyol 1 and tris-2-chloroisopropyl phosphate used were changed
as
follows:
80.65 parts by weight of polyetherester polyol 1, and
10 parts by weight of tris-2-chloroisopropyl phosphate.
A polyol component was produced by mixing. The polyol component was clear at
T = 20 C. It was reacted with a polymeric MDI having an NCO content of 31.5
wt%
(Lupranat M50 from BASF SE) in the presence of n-pentane (7.5 parts by
weight),
dimethylcyclohexylamine and water at an isocyanate index of 116. The amounts
of
dimethylcyclohexylamine and water were chosen such that the fiber time was 53
seconds and the resulting foam had a density of 38 kg/m3.
Inventive example 6
Compared with the polyol component of inventive example 3 the amounts of
polyetherester polyol 1 and polyether alcohol 2 used were changed as follows:
81.65 parts by weight of polyetherester polyol 1, and
CA 02865311 2014-08-22
0 part by weight of polyether alcohol 2.
A polyol component was produced by mixing. The polyol component was clear at
T = 20 C. It was reacted with a polymeric MDI having an NCO content of 31.5
wt%
5 (Lupranat M50 from BASF SE) in the presence of n-pentane (7.5 parts by
weight),
dimethylcyclohexylamine and water at an isocyanate index of 116. The amounts
of
dimethylcyclohexylamine and water were chosen such that the fiber time was 53
seconds and the resulting foam had a density of 38 kg/m3.
10 Inventive example 7
Starting from
75.65 parts by weight of polyetherester polyol 2 from example 2 with a
hydroxyl
number of 465 mg KOH/g, based on propylene oxide and a mixture of sugar,
glycerol
15 and oleic acid as starter,
6 parts by weight of polyether alcohol 2,
15 parts by weight of tris-2-chloroisopropyl phosphate,
2.0 parts by weight of silicone foam stabilizer (Tegostab B 8443 from
Goldschmidt),
0.5 part by weight of a 50% solution of potassium acetate in ethylene glycol,
and
20 0.85 part by weight of water
a polyol component was produced by mixing.
The polyol component was stable at 20 C. It was reacted with a polymeric MDI
having
an NCO content of 31.5 wt% (Lupranat M50 from BASF SE) in the presence of n-
pentane (7.5 parts by weight), dimethylcyclohexylamine and water at an
isocyanate
index of 116. The amounts of dimethylcyclohexylamine and water were chosen
such
that the fiber time was 53 seconds and the resulting foam had a density of 38
kg/m3.
Inventive example 8
Compared with the polyol component of inventive example 7 the amounts of
polyetherester polyol 2 and water used were changed as follows:
74.0 parts by weight of polyetherester polyol 2, and
2.5 parts by weight of water.
A polyol component was produced by mixing. The polyol component was clear at
T = 20 C. It was reacted with a polymeric MDI having an NCO content of 31.5
wt%
(Lupranat M50 from BASF SE) in the presence of n-pentane (7.5 parts by
weight),
dimethylcyclohexylamine and water at an isocyanate index of 116. The amounts
of
CA 02865311 2014-08-22
21
dimethylcyclohexylamine and water were chosen such that the fiber time was 53
seconds and the resulting foam had a density of 38 kg/m3.
Inventive example 9
Compared with the polyol component of inventive example 7 the amounts of
polyetherester polyol 2 and tris-2-chloroisopropyl phosphate used were changed
as
follows:
80.65 parts by weight of polyetherester polyol 2, and
10 parts by weight of tris-2-chloroisopropyl phosphate.
A polyol component was produced by mixing. The polyol component was clear at
T = 20 C. It was reacted with a polymeric MDI having an NCO content of 30.9
wt%
(Lupranat M50 from BASF SE) in the presence of n-pentane (7.5 parts by
weight),
dimethylcyclohexylamine and water at an isocyanate index of 116. The amounts
of
dimethylcyclohexylamine and water were chosen such that the fiber time was 53
seconds and the resulting foam had a density of 38 kg/m'.
Inventive example 10
Compared with the polypi component of inventive example 7 the amounts of
polyetherester polyol 2 and polyether alcohol 2 used were changed as follows:
81.65 parts by weight of polyetherester polyol 2, and
0 part by weight of polyether alcohol 2.
A polyol component was produced by mixing. The polyol component was clear at
T = 20 C. It was reacted with a polymeric MDI having an NCO content of 31.5
wt%
(Lupranat M50 from BASF SE) in the presence of n-pentane (7.5 parts by
weight),
dimethylcyclohexylamine and water at an isocyanate index of 116. The amounts
of
dimethylcyclohexylamine and water were chosen such that the fiber time was 53
seconds and the resulting foam had a density of 38 kg/m3.
Curing
Curing was determined using the bolt test. For this, at 2.5, 3, 4, 5, 6 and 7
minutes after
mixing the components in a polystyrene beaker, a steel bolt with a spherical
cap
10 mm in radius was pressed by a tensile/compressive tester 10 mm deep into
the
mushroom-shaped foam formed. The maximum force in N required here is a measure
CA 02865311 2014-08-22
22
of the curing of the foam. The mean value of the maximum forces after 3, 4 and
5
minutes is reported.
Pentane solubility
Pentane solubility was determined by incrementally adding pentane to the
component
to be measured for pentane solubility. Pentane was added to exactly 100 g of
the in-
test component according to the likely pentane solubility, and mixed
therewith. If the
mixture was neither cloudy nor biphasic, further pentane had to be added and
mixed in
again.
When the mixture was biphasic, the glass was left to stand open to the
atmosphere at
room temperature until the excess pentane had evaporated and the remaining
solution
had become clear, and then the dissolved amount of pentane was weighed back.
In the event of cloudiness, the glass was sealed and left to stand at room
temperature
until two phases had formed. This was followed by evaporating and weighing
back.
The results of the tests are summarized in tables 1 to 4.
=
CA 02865311 2014-08-22
23
Table 1: Comparative examples 1 to 4
Comparative Comparative Comparative Comparative
example 1 example 2 example 3 example 4
Polyether 1 55.65 54 60.65 61.65
Polyether 2 6 6 6
TCPP 15 15 10 15
Silicone foam 2 2 2 2
stabilizer
Castor oil 20 20 20 20
50 wt% solution 0.5 0.5 0.5 0.5
of potassium
acetate in
ethylene glycol
Water 0.85 2.5 0.85 0.85
Phase stability Clear Phase Phase Phase
separation separation separation
Fiber time [s] 53
Foam density 38
[kg/m3]
Mean curing at
81.1
3, 4, 5 min [N]
Viscosity [mPas] 3300
Pentane 7
solubility [%]
CA 02865311 2014-08-22
24
Table 2: Comparative examples 5 to 8
Comparative Comparative Comparative Comparative
example 5 example 6 example 7 example 8
Polyether 1 56.15 54.5 61.15 62.15
Polyether 2 6 6 6
TCPP 15 15 10 15
Silicone foam 1.8 1.8 1.8 1.8
stabilizer
Polyether 3 20 20 20 20
50 wt% solution of 0.2 0.2 0.2 0.2
potassium acetate
in ethylene glycol
Water 0.85 2.5 0.85 0.85
Phase stability Cloudy Clear Cloudy Phase
separation
Fiber time [s] 53 53
Foam density 38 38
[kg/m3]
Mean curing at 3, 4,
77.3 74.2
min [N]
Viscosity [mPas] 3000 2260 3850
Pentane solubility 4.5 4.5 4.2
roi
5
CA 02865311 2014-08-22
Table 3: Inventive examples 3 to 6
Inventive Inventive Inventive Inventive
example 3 example 4 example 5 example 6
Polyetherester polyol 1 75.65 74.0 80.65 81.65
Polyether 2 6 6 6
TCPP 15 15 10 15
Silicone foam stabilizer 2 2 2 2
50 wt% solution of 0.5 0.5 0.5 0.5
potassium acetate in
ethylene glycol
Water 0.85 2.5 0.85 0.85
Phase stability Clear Clear Clear Clear
Fiber time [s] 53 53 53 54
Foam density [kg/m3] 38 38 38 38.2
Mean curing at 3, 4, 5
90.9 91.4 92.9 88.3
min [N]
Viscosity [mPas] 4640 3950 4950 4200
Pentane solubility 20.1 18.5 19.1 19.0
Polyetherester polyol 1 from
5
Sugar 22.8 wt%
Glycerol 5.0 wt%
Oleic acid 15.0 wt%
PO 57.2 wt%
Hydroxyl value: 416 mgKOH/g (DIN 53240)
Viscosity (T = 25'C): 7210 nnPas (DIN 53018)
Table 4: Inventive examples 7 to 10
Inventive Inventive Inventive Inventive
example 7 example 8 example 9 example 10
Polyetherester polyol 2 75.7 74.0 80.65 81.65
Polyether 2 6 6 6
TCPP 15 15 10 15
Silicone foam stabilizer 2 2 2 2
CA 02865311 2014-08-22
26
Table 4 (continued)
Inventive Inventive Inventive Inventive
example 7 example 8 example 9 example 10
50 wt% solution of 0.5 0.5 0.5 0.5
potassium acetate in
ethylene glycol
Water 0.85 2.5 0.85 0.85
Phase stability Clear Clear Clear Clear
Fiber time [s] 53 53 53 54
Foam density [kg/nril 38 38 38 38.2
Mean curing at 3, 4,
82.5 80.7 84.1 77.3
min [N]
Viscosity [mPas] 950 640 1080 860
Pentane solubility 16.3 15.6 16.1 15
5 Polyetherester polyol 2 from
Sugar 8.46 wt%
Glycerol 19.9 wt%
Methyl oleate 13.5 wt%
PO 58.07 wt%
Hydroxyl value: 464.5 mgKOH/g (DIN 53240)
Viscosity (T = 25 C): 783 mPas (DIN 53018)
The results for the comparative examples in tables 1 and 2 show that the
standard
systems described are critical with regard to mixing gaps. Even minor changes
in the
composition lead to phase separation (comparative examples 2, 3, 4 and 8).
Inventive
examples 1 to 8 all have a phase-stable response to corresponding changes in
the
composition of the polyol components.
In addition, all inventive examples exhibit very good pentane solubilities
(all > 15%),
which are distinctly above the pentane solubilities of the comparative
examples (4.2 to
7%). High pentane solubility is relevant for many applications.
In addition, the polyetheresters used in inventive examples 3 to 6, 7 and 9
lead to
improved curing. Furthermore, use of polyetherester polyol 2 (inventive
examples 7 to
10) gives lower viscosities, which is advantageous for processing on certain
processing
machines.
