U.S. patent application number 14/122723 was filed with the patent office on 2014-04-17 for process for the preparation of polyether polyols.
This patent application is currently assigned to Bayer Intellectual Property GmbH. The applicant listed for this patent is Jorg Hofmann, Bert Klesczewski, Michael Schneider. Invention is credited to Jorg Hofmann, Bert Klesczewski, Michael Schneider.
Application Number | 20140107245 14/122723 |
Document ID | / |
Family ID | 46331245 |
Filed Date | 2014-04-17 |
United States Patent
Application |
20140107245 |
Kind Code |
A1 |
Hofmann; Jorg ; et
al. |
April 17, 2014 |
PROCESS FOR THE PREPARATION OF POLYETHER POLYOLS
Abstract
The invention relates to a method for producing polyether
carbonate polyols, wherein (i) in a first step a polyether
carbonate polyol is produced from one or more H-functional starter
substances, one or more alkylene oxides, and carbon dioxide in the
presence of at least one DMC catalyst, and (ii) in a second step
the polyether carbonate polyol is chain-extended with a mixture of
at least two different alkylene oxides in the presence of at least
one DMC catalyst. The invention further relates to polyether
carbonate polyols that contain a terminal mixed block of at least
two alkylene oxides and to a method for producing soft polyurethane
foams, wherein a polyol component containing a polyether carbonate
polyol according to the invention is used.
Inventors: |
Hofmann; Jorg; (Krefeld,
DE) ; Klesczewski; Bert; (Koln, DE) ;
Schneider; Michael; (Odenthal, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Hofmann; Jorg
Klesczewski; Bert
Schneider; Michael |
Krefeld
Koln
Odenthal |
|
DE
DE
DE |
|
|
Assignee: |
Bayer Intellectual Property
GmbH
Monheim
DE
|
Family ID: |
46331245 |
Appl. No.: |
14/122723 |
Filed: |
May 30, 2012 |
PCT Filed: |
May 30, 2012 |
PCT NO: |
PCT/EP2012/060102 |
371 Date: |
November 27, 2013 |
Current U.S.
Class: |
521/172 ;
525/461; 558/260 |
Current CPC
Class: |
C08G 64/183 20130101;
C08G 2101/005 20130101; C08G 71/04 20130101; C08G 65/2696 20130101;
C08G 2101/0083 20130101; C08G 18/4887 20130101; C08G 64/34
20130101; C08G 18/4866 20130101; C08G 65/331 20130101; C08G 65/2663
20130101; C08G 2101/0008 20130101 |
Class at
Publication: |
521/172 ;
525/461; 558/260 |
International
Class: |
C08G 65/331 20060101
C08G065/331; C08G 71/04 20060101 C08G071/04 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 1, 2011 |
EP |
11168433.8 |
Claims
1-15. (canceled)
16. A process for the preparation of a polyethercarbonate polyol,
comprising (i) preparing, in a first step, a polyethercarbonate
polyol chain from one or more H-functional starter substances, one
or more alkylene oxides and carbon dioxide in the presence of at
least one DMC catalyst, and (ii) extending, in a second step, the
polyethercarbonate polyol chain with a mixture of at least two
different alkylene oxides in the presence of at least one DMC
catalyst, and in that the mixture of at least two different
alkylene oxides in the second step (ii) is a mixture comprising
propylene oxide (PO) and ethylene oxide (EO) in a molar ratio PO/EO
of 15/85 to 60/40.
17. The process according to claim 16, wherein, in the first step
(i), (.alpha.) the H-functional starter substance or a mixture of
at least two H-functional starter substances is taken and
optionally water and/or other highly volatile compounds are removed
by raising the temperature and/or reducing the pressure ("drying"),
the DMC catalyst being added to the H-functional starter substance
or the mixture of at least two H-functional starter substances
before or after drying, (.beta.) for activation, a fraction, based
on the total amount of alkylene oxides used in the activation and
copolymerization, of one or more alkylene oxides is added to the
mixture resulting from step (.alpha.), optionally, the alkylene
oxide fraction is added in the presence of CO.sub.2, the hotspot
that occurs due to the subsequent exothermic chemical reaction
and/or a pressure drop in the reactor then being allowed to
subside, and optionally, the activation step (.beta.) is be carried
out several times, and (.gamma.) one or more alkylene oxides and
carbon dioxide are added to the mixture resulting from step
(.beta.), wherein the alkylene oxide in step (.gamma.) is identical
or different from the alkylene oxide used in step (.beta.).
18. The process according to claim 16, wherein the mixture of at
least two different alkylene oxides used in the second step (ii) is
a mixture consisting of propylene oxide (PO) and ethylene oxide
(EO) in a molar ratio PO/EO of 15/85 to 60/40.
19. The process according to claim 16, wherein, in the second step
(ii), the molar ratio of propylene oxide (PO) to ethylene oxide
(EO) is from 15/85 to 40/60.
20. The process according to claim 16, further comprising (iii)
extending the polyethercarbonate polyol chain with terminal mixed
block, resulting from step (ii), with an alkylene oxide.
21. A polyethercarbonate polyol comprising a terminal mixed block
of at least two alkylene oxides, wherein the terminal mixed block
comprises a mixture of propylene oxide (PO) and ethylene oxide (EO)
in a molar ratio PO/EO of 15/85 to 60/40.
22. The polyethercarbonate polyol according to claim 21, wherein
the terminal mixed block consists of a mixture of propylene oxide
(PO) and ethylene oxide (EO) in a molar ratio PO/EO of 15/85 to
60/40.
23. The polyethercarbonate polyol according to claim 21, wherein
the molar ratio of propylene oxide (PO) to ethylene oxide (EO) in
the mixed block is from 15/85 to 40/60.
24. The polyethercarbonate polyol according to claim 21, wherein
the chain of the terminal mixed block is extended with an alkylene
oxide.
25. The polyethercarbonate polyol according to claim 21, wherein
the mean length of the terminal mixed block of at least two
different alkylene oxides is from 2.0 to 20.0 alkylene oxide
units.
26. A process for the production of a flexible polyurethane foam
comprising utilizing a polyol comprising the polyethercarbonate
polyol according to claim 21 as component A.
27. The process for the production of a flexible polyurethane foam
with a gross density according to DIN EN ISO 3386-1-98 in the range
from .gtoreq.10 kg/m3 to .ltoreq.150 kg/m3 and a compressive
strength according to DIN EN ISO 3386-1-98 in the range from
.gtoreq.0.5 kPa to .ltoreq.20 kPa, at 40% deformation after 4th
cycle, by reacting component A comprising A1 100 to 10 parts by
weight, based on the sum of the parts by weight of components
A.sub.1 and A2, of polyethercarbonate polyol according to claims
21, A2 0 to 90 parts by weight, based on the sum of the parts by
weight of components A1 and A2, of conventional polyether polyol,
A3 0.5 to 25 parts by weight, based on the sum of the parts by
weight of components A1 and A2, of water and/or physical blowing
agents, A4 0.05 to 10 parts by weight, based on the sum of the
parts by weight of components A1 and A2, of an auxiliary substance
and/or an additive, and A5 0 to 10 parts by weight, based on the
sum of the parts by weight of components A1 and A2, of compounds
having isocyanate-reactive hydrogen atoms with a molecular weight
of 62-399, with component B comprising a polyisocyanate, the
preparation taking place at an index of 50 to 250, and all the
parts by weight of components A1 to A5 in the present patent
application being scaled so that the sum of the parts by weight of
components A1+A2 in the composition is 100.
28. The process according to claim 27 wherein component A consists
of A1 100 parts by weight of polyethercarbonate polyol according to
claim 21, A2 0 parts by weight of conventional polyether polyol, A3
0.5 to 25 parts by weight (based on the parts by weight of
component A1) of water and/or physical blowing agents, A4 0.05 to
10 parts by weight (based on the parts by weight of component A1)
of an auxiliary substances and/or an additive, and A5 0 to 10 parts
by weight (based on the parts by weight of component A1) of
compounds having isocyanate-reactive hydrogen atoms with a
molecular weight of 62-399.
29. The process for the production of a flexible polyurethane foam
comprising utilizing a polyol component (component A) which
comprises a polyethercarbonate polyol obtained according to claim
16.
30. A flexible polyurethane foam with a gross density according to
DIN EN ISO 3386-1-98 in the range from .gtoreq.10 kg/m.sup.3 to
.ltoreq.150 kg/m.sup.3 and a compressive strength according to DIN
EN ISO 3386-1-98 in the range from .gtoreq.0.5 kPa to .ltoreq.20
kPa, at 40% deformation after 4.sup.th cycle, obtained by the
process according to claim 26.
Description
[0001] The present invention relates to a process for the
preparation of polyethercarbonate polyols from one or more
H-functional starter substances, one or more alkylene oxides and
carbon dioxide in the presence of at least one double metal cyanide
catalyst, the polyethercarbonate polyols having a mixed block of at
least two alkylene oxides at the end of the chain, and to flexible
polyurethane foams obtainable therefrom.
[0002] The preparation of polyethercarbonate polyols by the
catalytic reaction of alkylene oxides (epoxides) and carbon dioxide
in the presence or absence of H-functional starter substances
(starters) has been studied intensively for more than 40 years
(e.g. Inoue et al., Copolymerization of Carbon Dioxide and Epoxide
with Organometallic Compounds; Die Makromolekulare Chemie 130,
210-220, 1969). This reaction, e.g. using an H-functional starter
compound, is shown diagrammatically in Scheme (I), where R is an
organic radical such as alkyl, alkylaryl or aryl, each of which can
also comprise heteroatoms such as O, S, Si, etc., and e and f are
integers, and where the product shown here in Scheme (I) for the
polyethercarbonate polyol is only to be understood as meaning that
blocks with the indicated structure can in principle be found in
the polyethercarbonate polyol obtained, but that the sequence,
number and length of the blocks and the OH functionality of the
starter can vary and are not limited to the polyethercarbonate
polyol shown in Scheme (I). This reaction (cf. Scheme (I)) is
ecologically very advantageous because it represents the conversion
of a greenhouse gas like CO.sub.2 to a polymer. The cyclic
carbonate shown in Scheme (I) (e.g. propylene carbonate for
R.dbd.CH.sub.3) is formed as a further product (actually a
by-product).
##STR00001##
[0003] Activation in terms of the invention is a step in which a
fraction of the alkylene oxide compound, optionally in the presence
of CO.sub.2, is added to the DMC catalyst and the addition of the
alkylene oxide compound is then interrupted; an evolution of heat,
which can lead to a hotspot, is observed due to a subsequent
exothermic chemical reaction, and a pressure drop in the reactor is
observed due to the conversion of alkylene oxide and optionally
CO.sub.2. The process step of activation is the period of time from
the addition of the fraction of alkylene oxide compound to the DMC
catalyst, optionally in the presence of CO.sub.2, up to the start
of the evolution of heat. In general, the activation step can be
preceded by a step for drying of the DMC catalyst and optionally
the starter at elevated temperature and/or reduced pressure, this
drying step not being part of the activation step in terms of the
present invention.
[0004] The formation of copolymers from epoxides (e.g. propylene
oxide) and carbon dioxide has been known for a long time. Thus, for
example, U.S. Pat. No. 4,500,704 describes the copolymerization of
carbon dioxide and propylene oxide using DMC catalysts. In this
case, for example, with a starter substance and 12.3 g (212 mmol)
of propylene oxide in a reactor under a carbon dioxide pressure of
48 bar, 71% of the propylene oxide was converted after 48 hours at
35.degree. C. Of the 150.5 mmol of propylene oxide converted, 27
mmol (18%) reacted to give propylene carbonate, a generally
unwanted by-product.
[0005] WO-A 2008/058913 discloses a process for the preparation of
polyethercarbonate polyols having a block of pure alkylene oxide
units, especially a block of pure propylene oxide units, at the end
of the chain. However, WO-A 2008/058913 does not disclose
polyethercarbonate polyols having a mixed block of at least two
alkylene oxides at the end of the chain.
[0006] The object of the present invention was to provide
polyethercarbonate polyols that produce flexible polyurethane foams
with an increased compressive strength and an increased tensile
strength. In practice, a flexible polyurethane foam quality
improved in this way has the technical advantage that said foams
have an increased mechanical load-bearing capacity.
[0007] It has now been found, surprisingly, that flexible
polyurethane foams with an increased compressive strength and an
increased tensile strength result from polyethercarbonate polyols
having a mixed block of at least two alkylene oxides at the end of
the chain ("terminal mixed block"). The present invention thus
provides a process for the preparation of polyethercarbonate
polyols which is characterized in that [0008] (i) in a first step a
polyethercarbonate polyol is prepared from one or more H-functional
starter substances, one or more alkylene oxides and carbon dioxide
in the presence of at least one DMC catalyst, and [0009] (ii) in a
second step the polyethercarbonate polyol chain is extended with a
mixture of at least two different alkylene oxides in the presence
of at least one DMC catalyst, and in that the mixture of at least
two different alkylene oxides used in the second step (ii) is a
mixture comprising propylene oxide (PO) and ethylene oxide (EO) in
a molar ratio PO/EO of 15/85 to 60/40.
[0010] The present invention also provides a process for the
production of flexible polyurethane foams wherein the starting
material used is a polyol component (component A) comprising a
polyethercarbonate polyol obtainable by a process which is
characterized in that [0011] (i) in a first step a
polyethercarbonate polyol is prepared from one or more H-functional
starter substances, one or more alkylene oxides and carbon dioxide
in the presence of at least one DMC catalyst, and [0012] (ii) in a
second step the polyethercarbonate polyol chain is extended with a
mixture of at least two different alkylene oxides in the presence
of at least one DMC catalyst, and in that the mixture of at least
two different alkylene oxides used in the second step (ii) is a
mixture comprising propylene oxide (PO) and ethylene oxide (EO) in
a molar ratio PO/EO of 15/85 to 60/40.
[0013] The flexible polyurethane foams according to the invention
preferably have a gross density according to DIN EN ISO 3386-1-98
in the range from .gtoreq.10 kg/m.sup.3 to .ltoreq.150 kg/m.sup.3,
preferably from .gtoreq.20 kg/m.sup.3 to .ltoreq.70 kg/m.sup.3, and
a compressive strength according to DIN EN ISO 3386-1-98 in the
range from .gtoreq.0.5 kPa to .ltoreq.20 kPa (at 40% deformation
after 4.sup.th cycle).
Step (i):
[0014] The preparation of the polyethercarbonate polyol according
to step (i) is preferably carried out by adding one or more
alkylene oxides and carbon dioxide, in the presence of at least one
DMC catalyst, on to one or more H-functional starter substances
("copolymerization").
[0015] For example, the process for the preparation of
polyethercarbonate polyol according to step (i) is characterized in
that [0016] (.alpha.) the H-functional starter substance or a
mixture of at least two H-functional starter substances is taken
and optionally water and/or other highly volatile compounds are
removed by raising the temperature and/or reducing the pressure
("drying"), the DMC catalyst being added to the H-functional
starter substance or the mixture of at least two H-functional
starter substances before or after drying, [0017] (.beta.) for
activation, a fraction (based on the total amount of alkylene
oxides used in the activation and copolymerization) of one or more
alkylene oxides is added to the mixture resulting from step
(.alpha.), it optionally being possible for this addition of an
alkylene oxide fraction to take place in the presence of CO.sub.2,
the hotspot that occurs due to the subsequent exothermic chemical
reaction and/or a pressure drop in the reactor then being allowed
to subside, and it also being possible for the activation step
(.beta.) to be carried out several times, and [0018] (.gamma.) one
or more alkylene oxides and carbon dioxide are added to the mixture
resulting from step (.beta.), it being possible for the alkylene
oxides used in step (.gamma.) to be identical to or different from
the alkylene oxides used in step (.beta.).
[0019] In general, alkylene oxides (epoxides) having 2-24 carbon
atoms can be used for the process according to the invention.
Examples of alkylene oxides having 2-24 carbon atoms are one or
more compounds selected from the group comprising ethylene oxide,
propylene oxide, 1-butene oxide, 2,3-butene oxide,
2-methyl-1,2-propene oxide (isobutene oxide), 1-pentene oxide,
2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene
oxide, 1-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide,
2-methyl-1,2-pentene oxide, 4-methyl-1,2-pentene oxide,
2-ethyl-1,2-butene oxide, 1-heptene oxide, 1-octene oxide, 1-nonene
oxide, 1-decene oxide, 1-undecene oxide, 1-dodecene oxide,
butadiene monoxide, isoprene monoxide, cyclopentene oxide,
cyclohexene oxide, cycloheptene oxide, cyclooctene oxide, styrene
oxide, methylstyrene oxide, pinene oxide, mono- or polyepoxidized
fats as mono-, di- and triglycerides, epoxidized fatty acids,
C.sub.1-C.sub.24 esters of epoxidized fatty acids, epichlorohydrin,
glycidol, glycidol derivatives such as methyl glycidyl ether, ethyl
glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether
and glycidyl methacrylate, and epoxy-functional alkoxysilanes such
as 3-glycidyloxypropyltri-methoxysilane,
3-glycidyloxypropyltriethoxysilane,
3-glycidyloxypropyltripropoxy-silane,
3-glycidyloxypropylmethyldimethoxysilane,
3-glycidyloxypropylethyldi-ethoxysilane and
3-glycidyloxypropyltriisopropoxysilane. The alkylene oxides used in
step (i) are preferably ethylene oxide and/or propylene oxide,
especially propylene oxide.
[0020] Suitable H-functional starter substances which can be used
are compounds with H atoms that are active for alkoxylation.
Examples of groups with H atoms that are active for alkoxylation
are --OH, --NH.sub.2 (primary amines), --NH-- (secondary amines),
--SH and --CO.sub.2H; --OH and --NH.sub.2 are preferred and --OH is
particularly preferred. Examples of H-functional starter substances
used are one or more compounds selected from the group comprising
monohydric or polyhydric alcohols, polybasic amines, polyhydric
thiols, amino alcohols, thio alcohols, hydroxy esters, polyether
polyols, polyester polyols, polyesterether polyols,
polyethercarbonate polyols, polycarbonate polyols, polycarbonates,
polyethyleneimines, polyetheramines (e.g. so-called Jeffamine.RTM.
from Huntsman, such as D-230, D-400, D-2000, T-403, T-3000 or
T-5000, or corresponding products from BASF, such as polyetheramine
D230, D400, D200, T403 or T5000), polytetrahydrofurans (e.g.
PolyTHF.RTM. from BASF, such as PolyTHF.RTM. 250, 650S, 1000,
1000S, 1400, 1800 or 2000), polytetrahydrofuranamines (BASF product
polytetrahydrofuranamine 1700), poly-etherthiols, polyacrylate
polyols, castor oil, ricinoleic acid mono- or diglyceride, fatty
acid monoglycerides, chemically modified fatty acid mono-, di-
and/or triglycerides, and fatty acid C.sub.1-C.sub.24-alkyl esters
comprising an average of at least 2 OH groups per molecule.
Examples of fatty acid C.sub.1-C.sub.24-alkyl esters comprising an
average of at least 20H groups per molecule are commercially
available products such as Lupranol Balance.RTM. (BASF AG), various
types of Merginol.RTM. (Hobum Oleochemicals GmbH), various types of
Sovermol.RTM. (Cognis Deutschland GmbH & Co. KG) and various
types of Soyol.RTM. TM (USSC Co.).
[0021] Monofunctional starter compounds which can be used are
alcohols, amines, thiols and carboxylic acids. The following
monofunctional alcohols can be used: methanol, ethanol, 1-propanol,
2-propanol, 1-butanol, 2-butanol, tert-butanol, 3-buten-1-ol,
3-butyn-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol,
propargyl alcohol, 2-methyl-2-propanol, 1-tert-butoxy-2-propanol,
1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol,
3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol,
2-octanol, 3-octanol, 4-octanol, phenol, 2-hydroxybiphenyl,
3-hydroxybiphenyl, 4-hydroxybiphenyl, 2-hydroxypyridine,
3-hydroxypyridine, 4-hydroxypyridine. The following monofunctional
amines are suitable: butylamine, tert-butylamine, pentylamine,
hexylamine, aniline, aziridine, pyrrolidine, piperidine,
morpholine. The following monofunctional thiols can be used:
ethanethiol, 1-propanethiol, 2-propanethiol, 1-butanethiol,
3-methyl-1-butanethiol, 2-butene-1-thiol, thiophenol. The following
monofunctional carboxylic acids may be mentioned: formic acid,
acetic acid, propionic acid, butyric acid, fatty acids such as
stearic acid, palmitic acid, oleic acid, linoleic acid and
linolenic acid, benzoic acid, acrylic acid.
[0022] Examples of polyhydric alcohols suitable as H-functional
starter substances are dihydric alcohols (e.g. ethylene glycol,
diethylene glycol, propylene glycol, dipropylene glycol,
1,3-propanediol, 1,4-butanediol, 1,4-butenediol, 1,4-butynediol,
neopentyl glycol, 1,5-pentanediol, methylpentanediols (e.g.
3-methyl-1,5-pentanediol), 1,6-hexanediol, 1,8-octanediol,
1,10-decanediol, 1,12-dodecanediol, bis-(hydroxymethyl)cyclohexanes
(e.g. 1,4-bis(hydroxymethyl)cyclohexane), triethylene glycol,
tetraethylene glycol, polyethylene glycols, dipropylene glycol,
tripropylene glycol, polypropylene glycols, dibutylene glycol,
polybutylene glycols); trihydric alcohols (e.g. trimethylolpropane,
glycerol, trishydroxyethyl isocyanurate, castor oil); tetrahydric
alcohols (e.g. pentaerythritol); polyalcohols (e.g. sorbitol,
hexitol, sucrose, starch, starch hydrolysates, cellulose, cellulose
hydrolysates, hydroxy-functionalized fats and oils, especially
castor oil); and any modified products of the aforesaid alcohols
comprising different amounts of .epsilon.-caprolactone.
[0023] The H-functional starter substances can also be selected
from the class of substances comprising the polyether polyols,
especially those with a molecular weight M.sub.n ranging from 100
to 4000 g/mol. Preferred polyether polyols are those made up of
repeating ethylene oxide and propylene oxide units, preferably with
a proportion of 35 to 100% of propylene oxide units and
particularly preferably with a proportion of 50 to 100% of
propylene oxide units. They can be random copolymers, gradient
copolymers or alternating or block copolymers of ethylene oxide and
propylene oxide. Examples of suitable polyether polyols made up of
repeating propylene oxide and/or ethylene oxide units are the
Desmophen.RTM., Acclaim.RTM., Arcol.RTM., Baycoll.RTM.,
Bayfill.RTM., Bayflex.RTM., Baygal.RTM., PET.degree. and
Polyether.RTM. Polyols from Bayer MaterialScience AG (e.g.
Desmophen.RTM. 3600Z, Desmophen.RTM. 1900U, Acclaim.RTM.Polyol
2200, Acclaim.RTM. Polyol 40001, Arcol.RTM. Polyol 1004, Arcol.RTM.
Polyol 1010, Arcol.RTM. Polyol 1030, Arcol.RTM. Polyol 1070,
Baycoll.RTM. BD 1110, Bayfill.RTM. VPPU 0789, Baygal.RTM. K55,
PET.RTM. 1004, Polyether.RTM. S180). Examples of other suitable
homo-polyethylene oxides are the Pluriol.RTM. E brands from BASF
SE, examples of suitable homo-polypropylene oxides are the
Pluriol.RTM. P brands from BASF SE, and examples of suitable mixed
copolymers of ethylene oxide and propylene oxide are the
Pluronic.RTM. PE or Pluriol.RTM. RPE brands from BASF SE.
[0024] The H-functional starter substances can also be selected
from the class of substances comprising the polyester polyols,
especially those with a molecular weight M.sub.n ranging from 200
to 4500 g/mol. The polyester polyols used are at least difunctional
polyesters and preferably consist of alternating acid and alcohol
units. Examples of acid components used are succinic acid, maleic
acid, maleic anhydride, adipic acid, phthalic anhydride, phthalic
acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid,
tetrahydrophthalic anhydride, hexahydrophthalic anhydride or
mixtures of said acids and/or anhydrides. Examples of alcohol
components used are ethanediol, 1,2-propanediol, 1,3-propanediol,
1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol,
1,4-bis(hydroxymethyl)cyclohexane, diethylene glycol, dipropylene
glycol, trimethylolpropane, glycerol, pentaerythritol or mixtures
of said alcohols. If dihydric or polyhydric polyether polyols are
used as the alcohol component, polyesterether polyols are obtained
which can also be used as starter substances for preparing the
polyethercarbonate polyols. It is preferable to use polyether
polyols of M.sub.n=150 to 2000 g/mol to prepare the polyesterether
polyols.
[0025] Other H-functional starter substances which can be used are
polycarbonate polyols (e.g. polycarbonate diols), especially those
with a molecular weight M.sub.n ranging from 150 to 4500 g/mol,
preferably from 500 to 2500 g/mol, which are prepared e.g. by
reacting phosgene, dimethyl carbonate, diethyl carbonate or
diphenyl carbonate with di- and/or polyfunctional alcohols,
polyester polyols or polyether polyols. Examples of polycarbonate
polyols can be found e.g. in EP-A 1359177. Examples of
polycarbonate diols which can be used are various types of
Desmophen.RTM. C from Bayer MaterialScience AG, such as
Desmophen.RTM. C 1100 or Desmophen.RTM. C 2200.
[0026] In another embodiment of the invention, polyethercarbonate
polyols can be used as H-functional starter substances. The
polyethercarbonate polyols obtainable by the process according to
the invention described here, after step (i), step (ii) or step
(iii), are used in particular. These polyethercarbonate polyols
used as H-functional starter substances are previously prepared for
this purpose in a separate reaction step.
[0027] The H-functional starter substances generally have a
functionality (i.e. number of H atoms per molecule that are active
for polymerization) of 1 to 8, preferably of 2 or 3. The
H-functional starter substances are used either individually or as
a mixture of at least two H-functional starter substances.
[0028] Preferred H-functional starter substances are alcohols of
general formula (II):
HO--(CH.sub.2).sub.x--OH (II)
where x is a number from 1 to 20, preferably an even number from 2
to 20. Examples of alcohols of formula (II) are ethylene glycol,
1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol and
1,12-dodecanediol. Other preferred H-functional starter substances
are neopentyl glycol, trimethylolpropane, glycerol,
pentaerythritol, and reaction products of the alcohols of formula
(II) with .epsilon.-caprolactone, e.g. reaction products of
trimethylolpropane with .epsilon.-caprolactone, reaction products
of glycerol with s-caprolactone and reaction products of
pentaerythritol with .epsilon.-caprolactone. Other H-functional
starter substances which are preferably used are water, diethylene
glycol, dipropylene glycol, castor oil, sorbitol, and polyether
polyols made up of repeating polyalkylene oxide units.
[0029] Particularly preferably, the H-functional starter substances
are one or more compounds selected from the group comprising
ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol,
1,4-butanediol, 1,5-pentanediol, 2-methylpropane-1,3-diol,
neopentyl glycol, 1,6-hexanediol, diethylene glycol, dipropylene
glycol, glycerol, trimethylolpropane and di- and trifunctional
polyether polyols, the polyether polyol being made up of a di- or
tri-H-functional starter substance and propylene oxide or a di- or
tri-H-functional starter substance, propylene oxide and ethylene
oxide. The polyether polyols preferably have a molecular weight
M.sub.n ranging from 62 to 4500 g/mol and a functionality of 2 to
3, especially a molecular weight M.sub.n ranging from 62 to 3000
g/mol a functionality of 2 to 3.
[0030] The polyethercarbonate polyols are prepared by the catalytic
addition of carbon dioxide and alkylene oxides on to H-functional
starter substances. In terms of the invention, "H-functional" is
understood as meaning the number of H atoms per molecule of starter
compound that are active for alkoxylation.
[0031] DMC catalysts for use in the homopolymerization of epoxides
are known in principle from the state of the art (cf., for example,
U.S. Pat. No. 3,404,109, U.S. Pat. No. 3,829,505, U.S. Pat. No.
3,941,849 and U.S. Pat. No. 5,158,922). DMC catalysts described
e.g. in U.S. Pat. No. 5,470,813, EP-A 700 949, EP-A 743 093, EP-A
761 708, WO 97/40086, WO 98/16310 and WO 00/47649 have a very high
activity in the homopolymerization of epoxides and enable polyether
polyols to be prepared with very low catalyst concentrations (25
ppm or less), so it is generally no longer necessary to separate
the catalyst from the finished product. Typical examples are the
highly active DMC catalysts described in EP-A 700 949, which, in
addition to a double metal cyanide compound (e.g. zinc
hexacyanocobaltate(III)) and an organic complexing ligand (e.g.
tert-butanol), also comprise a polyether with a number-average
molecular weight greater than 500 g/mol.
[0032] The DMC catalysts are obtained by a process in which [0033]
(a) in the first step, an aqueous solution of a metal salt is
reacted with an aqueous solution of a metal cyanide salt in the
presence of one or more organic complexing ligands, e.g. an ether
or alcohol, [0034] (b) in the second step, the solid is separated
from the suspension obtained in (i) by known techniques (such as
centrifugation or filtration), [0035] (c) optionally, in a third
step, the isolated solid is washed with an aqueous solution of an
organic complexing ligand (e.g. by resuspension and then
re-isolation by filtration or centrifugation), and [0036] (d) the
solid obtained is then dried, optionally after pulverization, at
temperatures generally of 20-120.degree. C. and at pressures
generally of 0.1 mbar to normal pressure (1013 mbar), one or more
organic complexing ligands, preferably in excess (based on the
double metal cyanide compound), and optionally other complexing
components, being added in the first step or immediately after the
precipitation of the double metal cyanide compound (second
step).
[0037] The double metal cyanide compounds comprised in the DMC
catalysts are the reaction products of water-soluble metal salts
and water-soluble metal cyanide salts. For example, an aqueous
solution of zinc chloride (preferably in excess, based on the metal
cyanide salt, e.g. potassium hexacyanocobaltate) and potassium
hexacyanocobaltate are mixed and dimethoxyethane (glyme) or
tert-butanol (preferably in excess, based on zinc
hexacyanocobaltate) is then added to the suspension formed.
[0038] Metal salts suitable for preparing the double metal cyanide
compounds preferably have general formula (III):
M(X).sub.n (III)
where M is selected from the metal cations Zn.sup.2+, Fe.sup.2+,
Ni.sup.2+, Mn.sup.2+, Co.sup.2+, Sr.sup.2+, Sn.sup.2+, Pb.sup.2+
and Cu.sup.2+, M preferably being Zn.sup.2+, Fe.sup.2+, Co.sup.2+
or Ni.sup.2+; X are one or more (i.e. different) anions, preferably
an anion selected from the group comprising halides (i.e. fluoride,
chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate,
thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and
nitrate; n is 1 when X=sulfate, carbonate or oxalate; and n is 2
when X=halide, hydroxide, carboxylate, cyanate, thiocyanate,
isocyanate, isothiocyanate or nitrate, or suitable metal salts have
general formula (IV):
M.sub.r(X).sub.3 (IV)
where M is selected from the metal cations Fe.sup.3+, Al.sup.3+,
Co.sup.3+ and Cr.sup.3+; X are one or more (i.e. different) anions,
preferably an anion selected from the group comprising halides
(i.e. fluoride, chloride, bromide, iodide), hydroxide, sulfate,
carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate,
carboxylate, oxalate and nitrate; r is 2 when X=sulfate, carbonate
or oxalate; and r is 1 when X=halide, hydroxide, carboxylate,
cyanate, thiocyanate, isocyanate, isothiocyanate or nitrate, or
suitable metal salts have general formula (V):
M(X).sub.s (V)
where M is selected from the metal cations Mo.sup.4+, V.sup.4+ and
W.sup.4+; X are one or more (i.e. different) anions, preferably an
anion selected from the group comprising halides (i.e. fluoride,
chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate,
thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and
nitrate; s is 2 when X=sulfate, carbonate or oxalate; and s is 4
when X=halide, hydroxide, carboxylate, cyanate, thiocyanate,
isocyanate, isothiocyanate or nitrate, or suitable metal salts have
general formula (VI):
M(X).sub.t (VI)
where M is selected from the metal cations Mo.sup.6+ and W.sup.6+;
X are one or more (i.e. different) anions, preferably an anion
selected from the group comprising halides (i.e. fluoride,
chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate,
thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and
nitrate; t is 3 when X=sulfate, carbonate or oxalate; and t is 6
when X=halide, hydroxide, carboxylate, cyanate, thiocyanate,
isocyanate, isothiocyanate or nitrate.
[0039] Examples of suitable metal salts are zinc chloride, zinc
bromide, zinc iodide, zinc acetate, zinc acetylacetonate, zinc
benzoate, zinc nitrate, iron(II) sulfate, iron(II) bromide,
iron(II) chloride, iron(III) chloride, cobalt(II) chloride,
cobalt(II) thiocyanate, nickel(II) chloride and nickel(II) nitrate.
It is also possible to use mixtures of different metal salts.
[0040] Metal cyanide salts suitable for preparing the double metal
cyanide compounds preferably have general formula (VII):
(Y).sub.aM'(CN).sub.b(A).sub.c (VII)
where M' is selected from one or more metal cations from the group
comprising Fe(II), Fe(III), Co(II), Co(III), Cr(II), Mn(II),
Mn(III), Ir(III), Ni(II), Ru(II), V(IV) and V(V), M' preferably
being one or more metal cations from the group comprising Coal),
Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II); Y is
selected from one or more metal cations from the group comprising
alkali metals (i.e. Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+) and
alkaline earth metals (i.e. Be.sup.2+, Mg.sup.2+, Ca.sup.2+,
Sr.sup.2+, Ba.sup.2+); A is selected from one or more anions from
the group comprising halides (i.e. fluoride, chloride, bromide,
iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate,
isocyanate, isothiocyanate, carboxylate, azide, oxalate and
nitrate; and a, b and c are integers, the values of a, b and c
being chosen so that the metal cyanide salt is electronically
neutral; a is preferably 1, 2, 3 or 4; b is preferably 4, 5 or 6; c
preferably has the value 0.
[0041] Examples of suitable metal cyanide salts are sodium
hexacyanocobaltate(III), potassium hexacyanocobaltate(III),
potassium hexacyanoferrate(II), potassium hexacyanoferrate(III),
calcium hexacyanocobaltate(III) and lithium
hexacyano-cobaltate(III).
[0042] Preferred double metal cyanide compounds comprised in the
DMC catalysts are compounds of general formula (VIII):
M.sub.x[M'.sub.x'(CN).sub.y].sub.z (VI)
where M is as defined in formulae (III) to (VI); M' is as defined
in formula (VII); and x, x', y and z are integers and are chosen so
that the double metal cyanide compound is electronically
neutral.
[0043] Preferably:
x=3, x'=1, y=6 and z=2;
M=Zn(II), Fe(II), Co(II) or Ni(II); and
M'=Co(III), Fe(III), Cr(III) or
[0044] Examples of suitable double metal cyanide compounds a) are
zinc hexacyano-cobaltate(III), zinc hexacyanoiridate(III), zinc
hexacyanoferrate(III) and cobalt(II) hexacyanocobaltate(III). Other
examples of suitable double metal cyanide compounds can be found
e.g. in U.S. Pat. No. 5,158,922 (column 8, lines 29-66). It is
particularly preferable to use zinc hexacyanocobaltate(HI).
[0045] The organic complexing ligands added in the preparation of
the DMC catalysts are disclosed e.g. in U.S. Pat. No. 5,158,922
(cf. especially column 6, lines 9 to 65), U.S. Pat. No. 3,404,109,
U.S. Pat. No. 3,829,505, U.S. Pat. No. 3,941,849, EP-A 700 949,
EP-A 761 708, JP 4 145 123, U.S. Pat. No. 5,470,813, EP-A 743 093
and WO-A 97/40086). For example, water-soluble organic compounds
with heteroatoms, such as oxygen, nitrogen, phosphorus or sulfur,
which can form complexes with the double metal cyanide compound are
used as organic complexing ligands. Preferred organic complexing
ligands are alcohols, aldehydes, ketones, ethers, esters, amides,
ureas, nitriles, sulfides and mixtures thereof. Particularly
preferred organic complexing ligands are aliphatic ethers (such as
dimethoxyethane), water-soluble aliphatic alcohols (such as
ethanol, isopropanol, n-butanol, isobutanol, sec-butanol,
tert-butanol, 2-methyl-3-buten-2-ol and 2-methyl-3-butyn-2-ol), and
compounds comprising both aliphatic or cycloaliphatic ether groups
and aliphatic hydroxyl groups (e.g. ethylene glycol mono-tert-butyl
ether, diethylene glycol mono-tert-butyl ether, tripropylene glycol
monomethyl ether and 3-methyl-3-oxetanemethanol). Very particularly
preferred organic complexing ligands are selected from one or more
compounds from the group comprising dimethoxyethane, tert-butanol,
2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, ethylene glycol
mono-tert-butyl ether and 3-methyl-3-oxetanemethanol.
[0046] Optionally, one or more complexing components from the
following classes of compounds are used in the preparation of the
DMC catalysts: polyethers, polyesters, polycarbonates, polyalkylene
glycol sorbitan esters, polyalkylene glycol glycidyl ethers,
polyacrylamide, poly(acrylamide-co-acrylic acid), polyacrylic acid,
poly-(acrylic acid-co-maleic acid), polyacrylonitrile, polyalkyl
acrylates, polyalkyl methacrylates, polyvinyl methyl ether,
polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol,
poly-N-vinylpyrrolidone, poly(N-vinylpyrrolidone-co-acrylic acid),
polyvinyl methyl ketone, poly(4-vinylphenol), poly(acrylic
acid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic
acid and maleic anhydride copolymers, hydroxyethyl cellulose and
polyacetals, or glycidyl ethers, glycosides, carboxylic acid esters
of polyhydric alcohols, gallic acids or their salts, esters or
amides, cyclodextrins, phosphorus compounds,
.alpha.,.beta.-unsaturated carboxylic acid esters or ionic
surface-active compounds.
[0047] Preferably, in the first step of the preparation of the DMC
catalysts, the aqueous solution of the metal salt (e.g. zinc
chloride), used in stoichiometric excess (at least 50 mol %, based
on the metal cyanide salt, i.e. a molar ratio of metal salt to
metal cyanide salt of at least 2.25 to 1.00) is reacted with the
aqueous solution of the metal cyanide salt (e.g. potassium
hexacyanocobaltate) in the presence of the organic complexing
ligand (e.g. tert-butanol) to form a suspension comprising the
double metal cyanide compound (e.g. zinc hexacyanocobaltate),
water, excess metal salt and the organic complexing ligand.
[0048] The organic complexing ligand can be present in the aqueous
solution of the metal salt and/or the aqueous solution of the metal
cyanide salt, or it is added immediately to the suspension obtained
after precipitation of the double metal cyanide compound. It has
been found advantageous to mix the aqueous solutions of the metal
salt and metal cyanide salt and the organic complexing ligand with
vigorous agitation. Optionally, the suspension formed in the first
step is then treated with another complexing component, the latter
preferably being used in a mixture with water and organic
complexing ligand. A preferred procedure for carrying out the first
step (i.e. preparation of the suspension) involves the use of a
mixing nozzle, particularly preferably a jet disperser as described
in WO-A 01/39883.
[0049] In the second step, the isolation of the solid (i.e. the
precursor of the catalyst according to the invention) from the
suspension is effected by known techniques such as centrifugation
or filtration.
[0050] In one preferred embodiment, the isolated solid is then
washed, in a third process step, with an aqueous solution of the
organic complexing ligand (e.g. by resuspension and then
re-isolation by filtration or centrifugation). This makes it
possible e.g. to remove water-soluble by-products, such as
potassium chloride, from the catalyst. Preferably, the amount of
organic complexing ligand in the aqueous wash solution is between
40 and 80 wt %, based on the total solution.
[0051] Optionally, another complexing component, preferably in the
range between 0.5 and 5 wt %, based on the total solution, is added
to the aqueous wash solution in the third step.
[0052] It is moreover advantageous to wash the isolated solid more
than once. Preferably, a first washing step (c-1) is carried out
with an aqueous solution of the unsaturated alcohol (e.g. by
resuspension and then re-isolation by filtration or centrifugation)
in order e.g. to remove water-soluble by-products, such as
potassium chloride, from the catalyst according to the invention.
Particularly preferably, the amount of unsaturated alcohol in the
aqueous wash solution is between 40 and 80 wt %, based on the total
solution of the first washing step. In the other washing steps
(c-2), either the first washing step is repeated one or more times,
preferably one to three times, or, preferably, a non-aqueous
solution, e.g. a mixture or solution of unsaturated alcohol and
another complexing component (preferably in the range between 0.5
and 5 wt %, based on the total amount of wash solution of step
(c-2)), is used as the wash solution and the solid is washed
therewith one or more times, preferably one to three times.
[0053] The isolated and optionally washed solid is then dried,
optionally after pulverization, at temperatures generally of 20 to
100.degree. C. and at pressures generally of 0.1 mbar to normal
pressure (1013 mbar).
[0054] A preferred procedure for isolating the DMC catalysts
according to the invention from the suspension, by filtration,
filter cake washing and drying, is described in WO-A 01/80994.
Step (ii):
[0055] In step (ii) of a preferred embodiment of the invention, a
mixture of ethylene oxide (EO) and propylene oxide (PO) is used as
the mixture of at least two different alkylene oxides, the molar
ratio PO/EO used in step (ii) being from 15/85 to 60/40, preferably
from 15/85 to 40/60. Preferably, the polyethercarbonate polyols
resulting from step (ii), comprising a terminal mixed block of EO
and PO, have a proportion of primary OH groups of 10 to 90 mol %,
particularly preferably of 20 to 50 mol %.
[0056] The mean length of the mixed blocks of at least two
different alkylene oxides, prepared in step (ii), is preferably 2.0
to 20.0 alkylene oxide units, particularly preferably 2.5 to 10.0
alkylene oxide units, based in each case on one OH group of the
polyethercarbonate polyol.
[0057] Preferably, the polyethercarbonate polyols resulting from
step (ii), comprising a mixed block at least two alkylene oxides,
have a hydroxyl number of 20 mg KOH/g to 80 mg KOH/g, particularly
preferably of 25 mg KOH/g to 60 mg KOH/g.
Step (iii):
[0058] Optionally, the process according to the invention for the
preparation of polyethercarbonate polyols can also comprise a third
step, wherein [0059] (iii) the chain of the polyethercarbonate
polyol with terminal mixed block, resulting from step (ii), is
extended with an alkylene oxide, preferably with propylene oxide or
ethylene oxide, particularly preferably with propylene oxide.
[0060] The mean length of a pure alkylene oxide block prepared in
step (iii) is preferably 2 to 30 alkylene oxide units, particularly
preferably 5 to 18 alkylene oxide units, based in each case on one
OH group of the polyethercarbonate polyol. The reaction according
to step (iii) can be carried out e.g. in the presence of DMC
catalysts or else in the presence of acidic catalysts (such as
BF.sub.3) or basic catalysts (such as KOH or CsOH). Preferably, the
reaction according to step (iii) is carried out in the presence of
a DMC catalyst.
Polyethercarbonate Polyols
[0061] The invention thus also provides polyethercarbonate polyols
comprising a terminal mixed block of at least two alkylene oxides,
preferably a terminal mixed block of ethylene oxide (EO) and
propylene oxide (PO). Preferably, the molar ratio PO/EO is from
15/85 to 60/40, preferably from 15/85 to 40/60. In a preferred
embodiment of the invention, the polyethercarbonate polyols
comprising a terminal mixed block of EO and PO have a proportion of
primary OH groups of 10 to 90 mol %, particularly preferably of 20
to 50 mol %. Preferably, the invention provides polyethercarbonate
polyols comprising a terminal mixed block of at least two alkylene
oxides, characterized in that the mean length of the terminal mixed
block of at least two different alkylene oxides is from 2.0 to 20.0
alkylene oxide units, particularly preferably from 2.5 to 10.0
alkylene oxide units (based in each case on one OH group of the
polyethercarbonate polyol). The polyethercarbonate polyols
according to the invention comprising a mixed block of at least two
alkylene oxides have a hydroxyl number preferably of 20 mg KOH/g to
80 mg KOH/g, particularly preferably of 25 mg KOH/g to 60 mg
KOH/g.
[0062] Optionally, these polyethercarbonate polyols according to
the invention can comprise a pure alkylene oxide block at the end
of the chain, said block consisting preferably of propylene oxide
or ethylene oxide units, particularly preferably of propylene oxide
units. The mean length of such a pure alkylene oxide block at the
end of the chain is preferably 2 to 30 alkylene oxide units,
particularly preferably 5 to 18 alkylene oxide units, based in each
case on one OH group of the polyethercarbonate polyol.
Flexible Polyurethane Foams
[0063] Preferably, the invention provides a process for the
production of flexible polyurethane foams with a gross density
according to DIN EN ISO 3386-1-98 in the range from .gtoreq.10
kg/m.sup.3 to .ltoreq.150 kg/m.sup.3, preferably from .gtoreq.20
kg/m.sup.3 to .ltoreq.70 kg/m.sup.3, and a compressive strength
according to DIN EN ISO 3386-1-98 in the range from .gtoreq.0.5 kPa
to .ltoreq.20 kPa (at 40% deformation after 4.sup.th cycle) by
reacting component A (polyol formulation) comprising [0064] A1 100
to 10 parts by weight, preferably 100 to 50 parts by weight,
particularly preferably 100 parts by weight (based on the sum of
the parts by weight of components A1 and A2), of polyethercarbonate
polyol having a mixed block of at least two alkylene oxides at the
end of the chain, characterized in that the terminal mixed block
comprises a mixture of propylene oxide (PO) and ethylene oxide (EO)
in a molar ratio PO/EO of 15/85 to 60/40, [0065] A2 0 to 90 parts
by weight, preferably 0 to 50 parts by weight (based on the sum of
the parts by weight of components A1 and A2), of conventional
polyether polyol, component A particularly preferably being free of
conventional polyether polyol, [0066] A3 0.5 to 25 parts by weight,
preferably 2 to 5 parts by weight (based on the sum of the parts by
weight of components A1 and A2), of water and/or physical blowing
agents, [0067] A4 0.05 to 10 parts by weight, preferably 0.2 to 4
parts by weight (based on the sum of the parts by weight of
components A1 and A2), of auxiliary substances and additives such
as [0068] a) catalysts, [0069] b) surface-active additives and
[0070] c) pigments or flame retardants, and [0071] A5 0 to 10 parts
by weight, preferably 0 to 5 parts by weight (based on the sum of
the parts by weight of components A 1 and A2), of compounds having
isocyanate-reactive hydrogen atoms with a molecular weight of
62-399, with component B comprising polyisocyanates, the
preparation taking place at an index of 50 to 250, preferably of 70
to 130, particularly preferably of 75 to 115, and all the parts by
weight of components A1 to A5 in the present patent application
being scaled so that the sum of the parts by weight of components
A1+A2 in the composition is 100.
[0072] Preferably, the polyethercarbonate polyol of component A1 is
obtainable by the above-described preparative process according to
the invention.
Component A1
[0073] The preparation of component A1 according to steps (i) and
(ii) and according to optional step (iii) has already been
illustrated above in connection with the process for preparing the
polyethercarbonate polyols.
Component A2
[0074] The starting components of component A2 are conventional
polyether polyols. In terms of the invention, conventional
polyether polyols are understood as meaning compounds that are
alkylene oxide addition products of starter compounds with
Zerewitinoff-active hydrogen atoms, i.e. polyether polyols with a
hydroxyl number according to DIN 53240 of .gtoreq.15 mg KOH/g to
.ltoreq.80 mg KOH/g, preferably of .gtoreq.20 mg KOH/g to
.ltoreq.60 mg KOH/g.
[0075] Starter compounds with Zerewitinoff-active hydrogen atoms
that are used for the conventional polyether polyols usually have
functionalities of 2 to 6, preferably of 3, and the starter
compounds are preferably hydroxy-functional. Examples of
hydroxy-functional starter compounds are propylene glycol, ethylene
glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol,
1,3-butanediol, 1,4-butanediol, hexanediol, pentanediol,
3-methyl-1,5-pentanediol, 1,12-dodecanediol, glycerol,
trimethylolpropane, triethanolamine, pentaerythritol, sorbitol,
sucrose, hydroquinone, pyrocatechol, resorcinol, bisphenol F,
bisphenol A, 1,3,5-trihydroxybenzene, and condensation products of
formaldehyde and phenol, melamine or urea which comprise methylol
groups. It is preferable to use glycerol and/or trimethylolpropane
as the starter compound.
[0076] Examples of suitable alkylene oxides are ethylene oxide,
propylene oxide, 1,2-butylene oxide or 2,3-butylene oxide, and
styrene oxide. Preferably, propylene oxide and ethylene oxide are
added to the reaction mixture individually, as a mixture or
successively. If the alkylene oxides are metered in successively,
the products prepared comprise polyether chains with block
structures. Products with ethylene oxide blocks are characterized
e.g. by increased concentrations of primary end groups, imparting
an advantageous isocyanate reactivity to the systems.
Component A3
[0077] Water and/or physical blowing agents are used as component
A3. Examples of physical blowing agents used are carbon dioxide
and/or highly volatile organic substances.
Component A4
[0078] Substances used as component A4 are auxiliary substances and
additives such as [0079] a) catalysts (activators), [0080] b)
surface-active additives (surfactants) such as emulsifiers and foam
stabilizers, especially those with low emissions, e.g. products of
the Tegostab.RTM. LF series, and [0081] c) additives such as
reaction retarders (e.g. acid-reacting substances like hydrochloric
acid or organic acid halides), cell regulators (e.g. paraffins,
fatty alcohols or dimethylpolysiloxanes), pigments, dyestuffs,
flame retardants (e.g. tricresyl phosphate), ageing and weathering
stabilizers, plasticizers, fungistatic and bacteriostatic
substances, fillers (e.g. barium sulfate, kieselguhr, black or
white chalk) and release agents.
[0082] These auxiliary substances and additives that are optionally
to be used concomitantly are described e.g. in EP-A 0 000 389,
pages 18-21. Other examples of auxiliary substances and additives
that are optionally to be used concomitantly according to the
invention, and details of the mode of use and mode of action of
these auxiliary substances and additives, are described in
Kunststoff-Handbuch, volume VII, edited by G. Oertel,
Carl-Hanser-Verlag, Munich, 3.sup.rd edition, 1993, e.g. on pages
104-127.
[0083] Preferred catalysts are aliphatic tertiary amines (e.g.
trimethylamine, tetramethyl-butanediamine), cycloaliphatic tertiary
amines (e.g. 1,4-diaza(2,2,2)bicyclooctane), aliphatic amino ethers
(e.g. dimethylaminoethyl ether and
N,N,N-trimethyl-N-hydroxyethylbisaminoethyl ether), cycloaliphatic
amino ethers (e.g. N-ethyl-morpholine), aliphatic amidines,
cycloaliphatic amidines, urea, urea derivatives (e.g.
aminoalkylureas; cf., for example, EP-A 0 176 013, especially
(3-dimethylamino-propylamine)urea) and tin catalysts (e.g.
dibutyltin oxide, dibutyltin dilaurate, tin octanoate).
[0084] Particularly preferred catalysts are [0085] .alpha.) urea,
urea derivatives and/or [0086] (.beta.) amines and amino ethers
each comprising a functional group that reacts chemically with the
isocyanate. The functional group is preferably a hydroxyl group or
a primary or secondary amino group. These particularly preferred
catalysts have the advantage of exhibiting a greatly reduced
migration and emission behaviour.
[0087] The following may be mentioned as examples of particularly
preferred catalysts: (3-dimethylaminopropylamine)urea,
2-(2-dimethylaminoethoxy)ethanol,
N,N-bis-(3-dimethylaminopropyl)-N-isopropanolamine,
N,N,N-trimethyl-N-hydroxyethyl-bisaminoethyl ether and
3-dimethylaminopropylamine.
Component A5
[0088] Optionally, compounds used as component A5 have at least two
isocyanate-reactive hydrogen atoms and a molecular weight of 32 to
399. These are understood as meaning compounds having hydroxyl
groups and/or amino groups and/or thiol groups and/or carboxyl
groups, preferably compounds having hydroxyl groups and/or amino
groups, which serve as chain extenders or crosslinking agents.
These compounds normally have 2 to 8, preferably 2 to 4,
isocyanate-reactive hydrogen atoms. Examples of compounds which can
be used as component A5 are ethanol-amine, diethanolamine,
triethanolamine, sorbitol and/or glycerol. Other examples of
compounds of component A5 are described in EP-A 0 007 502, pages
16-17.
Component B
[0089] Suitable polyisocyanates are aliphatic, cycloaliphatic,
araliphatic, aromatic and heterocyclic polyisocyanates such as
those described e.g. by W. Siefken in Justus Liebigs Annalen der
Chemie, 562, pages 75 to 136, for example those of formula
(IX):
Q(NCO).sub.n (IX)
where n=2-4, preferably 2-3, and [0090] Q is an aliphatic
hydrocarbon radical having 2-18 C atoms, preferably 6-10 C atoms, a
cycloaliphatic hydrocarbon radical having 4-15 C atoms, preferably
6-13 C atoms, or an araliphatic hydrocarbon radical having 8-15 C
atoms, preferably 8-13 C atoms.
[0091] Examples are polyisocyanates such as those described in EP-A
0 007 502, pages 7-8. Preferred polyisocyanates are normally those
which are readily available in industry, e.g. 2,4- and
2,6-toluoylene diisocyanate and any desired mixtures of these
isomers ("TDI"); polyphenylpolymethylene polyisocyanates such as
those prepared by aniline-formaldehyde condensation followed by
phosgenation ("crude MDI"); and polyisocyanates having carbodiimide
groups, urethane groups, allophanate groups, isocyanurate groups,
urea groups or biuret groups ("modified polyisocyanates"),
especially modified polyisocyanates derived from 2,4- and/or
2,6-toluoylene diisocyanate or from 4,4'- and/or
2,4'-diphenylmethane diisocyanate. Preferably, the polyisocyanate
used is at least one compound selected from the group comprising
2,4- and 2,6-toluoylene diisocyanate, 4,4'-, 2,4'- and
2,2'-diphenylmethane diisocyanate, and polyphenylpolymethylene
polyisocyanate ("polynuclear MDI"). Particularly preferably, the
polyisocyanate used is a mixture comprising 4,4'-diphenylmethane
diisocyanate, 2,4'-diphenylmethane diisocyanate and
polyphenylpolymethylene polyisocyanate.
[0092] To produce the flexible polyurethane foams, the reactants
are reacted by the one-stage process known per se, often using
mechanical devices, e.g. those described in EP-A 355 000. Details
of processing devices which are also suitable for the invention are
described in Kunststoff-Handbuch, volume VII, edited by Vieweg and
Hochtlen, Carl-Hanser-Verlag, Munich 1993, e.g. on pages 139 to
265.
[0093] The flexible polyurethane foams can be produced as foam
mouldings or foam blocks. The invention therefore provides
processes for the production of flexible polyurethane foams, the
flexible polyurethane foams produced by these processes, the
flexible polyurethane foam blocks or flexible polyurethane foam
mouldings produced by these processes, the use of the flexible
polyurethane foams for the production of mouldings, and the
mouldings themselves. The flexible polyurethane foams obtainable
according to the invention have e.g. the following applications:
furniture upholstery, textile padding, mattresses, car seats, head
supports, arm rests, sponges and component parts.
[0094] The index indicates the percentage ratio of the amount of
isocyanate actually used to the stoichiometric amount, i.e. the
amount of isocyanate (NCO) groups calculated for conversion of the
OH equivalent.
index=[(amount of isocyanate used):(calculated amount of
isocyanate)]100 (X)
EXAMPLES
[0095] The present invention is illustrated in greater detail with
the aid of the following Examples, in which the materials and
abbreviations used have the following meanings and sources of
supply: [0096] A2-1: a trifunctional polyether polyol with an OH
number of 48 mg KOH/g, prepared by the DMC-catalysed alkoxylation
of glycerol with a mixture of propylene oxide and ethylene oxide in
proportions of 89/11, and with approx. 8 mol % of primary OH groups
[0097] A4-1: Tegostab.RTM. B 2370, a preparation of organo-modified
polysiloxanes from Evonik Goldschmidt [0098] A4-2: Addocat.RTM.
108, an amine catalyst from Rheinchemie [0099] A4-3:
Addocat.RTM.SO, a tin catalyst from Rheinchemie [0100] TDI-1: a
mixture comprising 80 wt % of 2,4-toluoylene diisocyanate and 20 wt
% of 2,6-toluoylene diisocyanate, with an NCO content of 48.3 wt %
[0101] TDI-2: a mixture comprising 65 wt % of 2,4-toluoylene
diisocyanate and 35 wt % of 2,6-toluoylene diisocyanate, with an
NCO content of 48.3 wt %
[0102] The analyses were performed as follows:
[0103] Dynamic viscosity: MCR 51 rheometer from Anton Paar,
corresponding to DIN
[0104] Hydroxyl number: according to standard DIN 53240
[0105] The gross density was determined according to DIN EN ISO
3386-1-98.
[0106] The compressive strength was determined according to DIN EN
ISO 3386-1-98 (at 40% deformation after 4.sup.th cycle).
[0107] The tensile strength and elongation at break were determined
according to DIN EN ISO 1798.
[0108] The proportion of CO.sub.2 incorporated in the resulting
polyethercarbonate polyol was determined by .sup.1H-NMR (Bruker,
DPX 400, 400 MHz, pulse program zg30, wait time d1:10 sec, 64
scans). All samples were dissolved in deuterated chloroform. The
relevant resonances in the .sup.1H-NMR (relative to TMS=0 ppm) are
as follows: cyclic carbonate (formed as a by-product) with
resonance at 4.5 ppm; carbonate (resulting from carbon dioxide
incorporated in the polyethercarbonate polyol) with resonances at
5.1 to 4.8 ppm; unreacted PO with resonance at 2.4 ppm; polyether
polyol (i.e. without incorporated carbon dioxide) with resonances
at 1.2 to 1.0 ppm; 1,8-octanediol (incorporated as starter molecule
(if present)) with resonance at 1.6 to 1.52 ppm.
[0109] The molar proportion of polymer-incorporated carbonate in
the reaction mixture is calculated as below according to formula
(XI), using the following abbreviations:
F(4.5)=area of the resonance at 4.5 ppm for cyclic carbonate
(corresponds to one H atom) F(5.1-4.8)=area of the resonance at
5.1-4.8 ppm for polyethercarbonate polyol and one H atom for cyclic
carbonate F(2.4)=area of the resonance at 2.4 ppm for free,
unreacted PO F(1.2-1.0)=area of the resonance at 1.2-1.0 ppm for
polyether polyol F(1.6-1.52)=area of the resonance at 1.6 to 1.52
ppm for 1,8-octanediol (starter), if present
[0110] Taking the relative intensities into account, the
polymer-bound carbonate ("linear carbonate" LC) in the reaction
mixture was converted to mol % according to formula (XI) below:
LC = F ( 5.1 - 4.8 ) - F ( 4.5 ) F ( 5.1 - 4.8 ) + F ( 2.4 ) + 0.33
* F ( 1.2 - 1.0 ) + 0.25 * F ( 1.6 - 1.52 ) * 100 ( XI )
##EQU00001##
[0111] The proportion by weight (in wt %) of polymer-bound
carbonate (LC') in the reaction mixture was calculated according to
formula (XII):
LC ' = [ F ( 5.1 - 4.8 ) - F ( 4.5 ) ] * 102 N * 100 % ( XII )
##EQU00002##
the value of N ("denominator" N) being calculated according to
formula (XIII):
N.dbd.[F(5.1-4.8)-F(4.5)]*102+F(4.5)*102+F(2.4)*58+0.33*F(1.2-1.0)*58+0.-
25*F(1.6-1.52)*146 (XIII)
[0112] The factor 102 results from the sum of the molecular weights
of CO.sub.2 (molecular weight 44 g/mol) and propylene oxide
(molecular weight 58 g/mol), the factor 58 results from the
molecular weight of propylene oxide and the factor 146 results from
the molecular weight of the 1,8-octanediol starter used (if
present).
[0113] The proportion by weight (in wt %) of cyclic carbonate (CC')
in the reaction mixture was calculated according to formula
(XIV):
CC ' = F ( 4.5 ) * 102 N * 100 % ( XIV ) ##EQU00003##
the value of N being calculated according to formula (XIII).
[0114] To calculate the composition based on the polymer component
(consisting of polyether polyol, synthesized from starter and
propylene oxide during the activation steps taking place under
CO.sub.2-free conditions, and polyethercarbonate polyol,
synthesized from starter, propylene oxide and carbon dioxide during
the activation steps taking place in the presence of CO.sub.2 and
during copolymerization) from the values of the composition of the
reaction mixture, the non-polymer constituents of the reaction
mixture (i.e. cyclic propylene carbonate and any unreacted
propylene oxide present) were arithmetically eliminated. The
proportion by weight of carbonate repeating units in the
polyethercarbonate polyol was converted to a proportion by weight
of carbon dioxide by means of the factor F=44/(44+58). The data for
the CO.sub.2 content of the polyethercarbonate polyol are
normalized to the proportion of the polyethercarbonate polyol
molecule formed during the copolymerization and optionally the
activation steps in the presence of CO.sub.2 (i.e. the proportion
of the polyethercarbonate polyol molecule resulting from the
starter (1,8-octanediol, if present) and from the reaction of the
starter with epoxide, added under CO.sub.2-free conditions, was not
taken into account here).
[0115] Determination of the molar proportion of primary OH groups:
by .sup.1H-NMR (Bruker DPX 400, deuterochloroform):
[0116] To determine the content of primary OH groups, the
polyethercarbonate samples were first peracetylated.
[0117] The following peracetylation mixture was prepared for this
purpose: [0118] 9.4 g of acetic anhydride p.a. [0119] 1.6 g of
acetic acid p.a. [0120] 100 ml of pyridine p.a.
[0121] For the peracetylation reaction 10 g of polyethercarbonate
polyol were weighed into a 300 ml ground-glass Erlenmeyer flask.
The volume of peracetylation mixture depended on the OH number of
the polyethercarbonate to be peracetylated, the OH number of the
polyethercarbonate polyol being rounded to the nearest tens digit
(based in each case on 10 g of polyethercarbonate polyol); 10 ml of
peracetylation mixture are then added per 10 mg KOH/g. Accordingly,
for example, 50 ml of peracetylation mixture were added to the 10 g
sample of polyethercarbonate polyol with an OH number of 45.1 mg
KOH/g.
[0122] After the addition of glass boiling beads, the ground-glass
Erlenmeyer flask was provided with a riser tube (air condenser) and
the sample was boiled for 75 min under gentle reflux. The sample
mixture was then transferred to a 500 ml round-bottom flask and
volatile constituents (essentially pyridine, acetic acid and excess
acetic anhydride) were distilled off over a period of 30 min at
80.degree. C. and 10 mbar (absolute). The distillation residue was
then treated with 3.times.100 ml of cyclohexane (toluene was used
as an alternative in cases where the distillation residue did not
dissolve in cyclohexane) and volatile constituents were removed for
15 min at 80.degree. C. and 400 mbar (absolute). Volatile
constituents were then removed from the sample for one hour at
100.degree. C. and 10 mbar (absolute).
[0123] To determine the molar proportions of primary and secondary
OH end groups in the polyethercarbonate polyol, the sample prepared
as above was dissolved in deuterated chloroform and analysed by
.sup.1H-NMR (Bruker, DPX 400, 400 MHz, pulse program zg30, wait
time dl: 10 sec, 64 scans). The relevant resonances in the
.sup.1H-NMR (relative to TMS=0 ppm) are as follows:
methyl signal of a peracetylated secondary OH end group: 2.04 ppm
methyl signal of a peracetylated primary OH end group: 2.07 ppm
[0124] The molar proportion of secondary and primary OH end groups
is then worked out as follows:
proportion of secondary OH end groups
(CH--OH).dbd.F(2.04)/(F(2.04)+F(2.07))*100% (XV)
proportion of primary OH end groups
(CH.sub.2--OH).dbd.F(2.07)/(F(2.04)+F(2.07))*100% (XVI)
[0125] In formulae (XV) and (XVI) F represents the area of the
resonance at 2.04 ppm or 2.07 ppm.
I. Preparation of Polyethercarbonate Polyol A1-1 by
Copolymerization of PO and CO.sub.2
[0126] 140 mg of DMC catalyst (prepared according to Example 6 of
WO-A 01/80994) and 160 g of an anhydrous trifunctional
poly(oxypropylene) polyol with an OH number of 235 mg KOH/g were
placed as H-functional starter substances in a 1 litre pressurized
reactor fitted with a with gas metering device. The reactor was
heated to 130.degree. C. and rendered inert by the repeated
application of nitrogen to approx. 5 bar and subsequent pressure
release to approx. 1 bar. This process was carried out 3 times. 25
g of propylene oxide (PO) were rapidly metered into the reactor at
130.degree. C. and in the absence of CO.sub.2. The start of the
reaction was signalled by a hotspot and by a pressure drop to
roughly the initial value (approx. 1 bar). After the first pressure
drop 20 g of PO and then 19 g of PO were rapidly metered in, each
time causing a further hotspot and pressure drop. After 50 bar of
CO.sub.2 had been applied to the reactor, 50 g of PO were rapidly
metered in, causing a hotspot after a further wait time. The carbon
dioxide (CO.sub.2) pressure started to drop at the same time. The
pressure was regulated in such a way that fresh CO.sub.2 was added
when the pressure dropped below the set value. Only then was the
remaining propylene oxide (387 g) pumped continuously into the
reactor at approx. 1.8 g/min; after 10 minutes the temperature was
lowered to 105.degree. C. in steps of 5.degree. C. every five
minutes. When the addition of PO was complete, stirring (1500 rpm)
was continued for a further 60 minutes at 105.degree. C. and the
pressure indicated above. Finally, highly volatile constituents
were separated from the product by film evaporation.
Analysis of the Resulting Polyethercarbonate Polyol A1-1:
[0127] Hydroxyl number: 54.9 mg KOH/g Dynamic viscosity: 4115 mPas
(25.degree. C.) Content of incorporated CO.sub.2: 12.8 wt % II.
Preparation of Polyethercarbonate Polyols with Terminal Alkylene
Oxide Block Preparation of Polyethercarbonate Polyol A1-2
(PO/EO=100/0 [mol/mol]) (Comparison)
[0128] 403 g of polyethercarbonate polyol A1-1 were placed in a 2 l
laboratory autoclave under a nitrogen atmosphere, heated to
130.degree. C. and then stripped with nitrogen at this temperature
for 30 minutes at a pressure of 0.1 bar (absolute). 68.8 g (1.184
mol) of PO were then metered into the reactor at 130.degree. C.
over a period of 5 minutes, with stirring. After a post-reaction
time of 90 minutes, highly volatile constituents were removed by
heating at 90.degree. C. for 30 minutes under vacuum and the
reaction mixture was then cooled to room temperature.
Analysis of the resulting polyethercarbonate polyol A1-2: Hydroxyl
number: 47.3 mg KOH/g Dynamic viscosity: 3130 mPas (25.degree. C.)
Content of primary OH groups: 8 mol % Preparation of
Polyethercarbonate Polyol A1-3 (PO/EO=70/30 [mol/mol])
(Comparison)
[0129] 385 g of polyethercarbonate polyol A1-1 were placed in a 2 l
laboratory autoclave under a nitrogen atmosphere, heated to
130.degree. C. and then stripped with nitrogen at this temperature
for 30 minutes at a pressure of 0.1 bar (absolute). A mixture of
46.1 g (0.793 mol) of PO and 15.0 g (0.340 mol) of EO was then
metered into the reactor at 130.degree. C. over a period of 5
minutes, with stirring. After a post-reaction time of 90 minutes,
highly volatile constituents were removed by heating at 90.degree.
C. for 30 minutes under vacuum and the reaction mixture was then
cooled to room temperature.
Analysis of the Resulting Polyethercarbonate Polyol A1-3:
[0130] Hydroxyl number: 45.1 mg KOH/g Dynamic viscosity: 3735 mPas
(25.degree. C.) Content of primary OH groups: 21 mol % Preparation
of Polyethercarbonate Polyol A1-4 (PO/EO=50/50 [mol/mol])
[0131] 310 g of polyethercarbonate polyol A1-1 were placed in a 2 l
laboratory autoclave under a nitrogen atmosphere, heated to
130.degree. C. and then stripped with nitrogen at this temperature
for 30 minutes at a pressure of 0.1 bar (absolute). A mixture of
26.4 g (0.454 mol) of PO and 20.1 g (0.456 mol) of EO was then
metered into the reactor at 130.degree. C. over a period of 5
minutes, with stirring. After a post-reaction time of 90 minutes,
highly volatile constituents were removed by heating at 90.degree.
C. for 30 minutes under vacuum and the reaction mixture was then
cooled to room temperature.
Analysis of the resulting polyethercarbonate polyol A1-4: Hydroxyl
number: 44.7 mg KOH/g Dynamic viscosity: 4380 mPas (25.degree. C.)
Content of primary OH groups: 29 mol % Preparation of
Polyethercarbonate Polyol A1-5 (PO/EO=30/70 [mol/mol]) 401 g of
polyethercarbonate polyol A1-1 were placed in a 2 l laboratory
autoclave under a nitrogen atmosphere, heated to 130.degree. C. and
then stripped with nitrogen at this temperature for 30 minutes at a
pressure of 0.1 bar (absolute). A mixture of 22.5 g (0.387 mol) of
PO and 39.8 g (0.902 mol) of EO was then metered into the reactor
at 130.degree. C. over a period of 5 minutes, with stirring. After
a post-reaction time of 90 minutes, highly volatile constituents
were removed by heating at 90.degree. C. for 30 minutes under
vacuum and the reaction mixture was then cooled to room
temperature. Analysis of the resulting polyethercarbonate polyol
A1-5: Hydroxyl number: 47.5 mg KOH/g Dynamic viscosity: not
determinable at 25.degree. C. as A1-5 is a solid Content of primary
OH groups: 37 mol % Preparation of Polyethercarbonate Polyol A1-6
(PO/EO=0/100 [mol/mol]) (comparison
[0132] 401 g of polyethercarbonate polyol A1-1 were placed in a 2 l
laboratory autoclave under a nitrogen atmosphere, heated to
130.degree. C. and then stripped with nitrogen at this temperature
for 30 minutes at a pressure of 0.1 bar (absolute). 56.8 g (1.288
mol) of EO were then metered into the reactor at 130.degree. C.
over a period of 5 minutes, with stirring. After a post-reaction
time of 90 minutes, highly volatile constituents were removed by
heating at 90.degree. C. for 30 minutes under vacuum and the
reaction mixture was then cooled to room temperature.
Analysis of the resulting polyethercarbonate polyol A1-6: Hydroxyl
number: 47.3 mg KOH/g Dynamic viscosity: not determinable at
25.degree. C. as A1-6 is a solid Content of primary OH groups: 53
mol %
III. Production of Flexible Polyurethane Foam Blocks
[0133] The starting materials listed in the Examples in Table 1
below were reacted together according to the processing method
conventionally used for the production of polyurethane foams by the
one-stage process.
[0134] Surprisingly, the flexible polyurethane foam blocks
according to the invention (Examples 4 to 6), in which
polyethercarbonate polyols with a terminal mixed block of propylene
oxide (PO) and ethylene oxide (EO) in a molar ratio PO/EO of 15/85
to 60/40 were processed, exhibited a higher compressive strength
and a higher tensile strength than flexible foam blocks based on a
polyether polyol (A2-1; cf. Table 1, Comparative Example 1) or on a
polyethercarbonate polyol with a terminal propylene oxide block
(A1-2; cf. Table 1, Comparative Example 2). Advantageous properties
in respect of compressive strength were achieved with
polyethercarbonate polyols with a terminal mixed block having a
ratio PO/EO of 50/50 or 30/70 (A1-4 or A1-5; cf. Table 1, Examples
4, 5 and 6). Particularly advantageous properties in respect of
compressive strength and tensile strength were achieved with a
polyethercarbonate polyol with a terminal mixed block having a
ratio PO/EO of 30/70 (A1-5; cf. Table 1, Examples 5 and 6).
TABLE-US-00001 TABLE 1 Production and properties of the flexible
polyurethane foam blocks 1 2 3 7 (Comp.) (Comp.) (Comp.) 4 5 6
(Comp.) Component A A2-1 [pbw] 94.95 A1-2 [pbw] 94.95 A1-3 [pbw]
94.95 A1-4 [pbw] 94.98 A1-5 [pbw] 94.97 94.97 A1-6 [pbw] 94.97
Water [pbw] 3.80 3.80 3.80 3.80 3.80 3.80 3.80 A4-1 [pbw] 0.95 0.95
0.95 0.95 0.95 0.95 0.95 A4-2 [pbw] 0.11 0.11 0.11 0.11 0.11 0.11
0.11 A4-3 [pbw] 0.19 0.19 0.19 0.15 0.17 0.17 0.17 Component B
TDI-1 [pbw] 100 100 90 100 100 80 100 TDI-2 [pbw] 10 20 WR (A:B)
100: 47.27 47.27 47.27 47.27 47.27 47.27 47.27 Index 108 108 108
108 108 108 108 Gross density [kg/m.sup.3] 27.5 28.9 31.5 30.5 27.9
27.9 24.2 Compressive [kPa] 4.8 5.7 6.4 6.8 7.6 7.3 5.5 strength
Tensile strength [kPa] 85 79 104 99 107 113 96 Elongation at [%]
123 103 114 97 96 110 104 break Abbreviations: Comp. = Comparative
Example; pbw = parts by weight; WR (A:B) = weight ratio of
component A to component B at the indicated index, based on 100
parts by weight of component A
* * * * *