U.S. patent application number 10/831135 was filed with the patent office on 2004-10-07 for polyurethane foams.
This patent application is currently assigned to BASF Aktiengesellschaft. Invention is credited to Arlt, Andreas, Becker, Armin, Bertleff, Werner, Bruchmann, Bernd, Decker, Juergen, Kreyenschmidt, Martin, Rahm, Rainer, Riegel, Willi, Steuerle, Ulrich, Treuling, Ulrich.
Application Number | 20040198851 10/831135 |
Document ID | / |
Family ID | 26004021 |
Filed Date | 2004-10-07 |
United States Patent
Application |
20040198851 |
Kind Code |
A1 |
Becker, Armin ; et
al. |
October 7, 2004 |
Polyurethane foams
Abstract
The invention relates to polyurethane foams comprising (i)
ethylenimine, polyethylenimine, polyvinylamine, polyvinylamine
copolymers, carboxymethylated polyethylenimines,
phosphonomethylated polyethylenimines, quaternized
polyethylenimines and/or dithiocarbamatized polyethylenimines or
(ii) alkali metal hydroxides and/or alkaline earth metal hydroxides
or a mixture of (i) and (ii).
Inventors: |
Becker, Armin;
(Grossniedesheim, DE) ; Bruchmann, Bernd;
(Freinsheim, DE) ; Arlt, Andreas; (Drebber,
DE) ; Treuling, Ulrich; (Bensheim, DE) ; Rahm,
Rainer; (Ludwigshafen, DE) ; Decker, Juergen;
(Speyer, DE) ; Steuerle, Ulrich; (Heidelberg,
DE) ; Kreyenschmidt, Martin; (Lohne, DE) ;
Riegel, Willi; (Waghaeusel, DE) ; Bertleff,
Werner; (Viernheim, DE) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
BASF Aktiengesellschaft
Ludwigshafen
DE
|
Family ID: |
26004021 |
Appl. No.: |
10/831135 |
Filed: |
April 26, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10831135 |
Apr 26, 2004 |
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10168864 |
Oct 28, 2002 |
|
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10168864 |
Oct 28, 2002 |
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PCT/EP01/00791 |
Jan 25, 2001 |
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Current U.S.
Class: |
521/53 ;
521/155 |
Current CPC
Class: |
C08G 18/6423 20130101;
C08G 2110/0008 20210101; C08G 18/4804 20130101; C08G 18/482
20130101; C08J 2375/04 20130101; C08J 9/0061 20130101; C08G 2101/00
20130101; C08G 18/6715 20130101; C08J 2205/05 20130101; B01J 20/26
20130101; C08J 9/42 20130101; C08G 2110/0083 20210101; C08J 2479/00
20130101; C08G 18/833 20130101 |
Class at
Publication: |
521/053 ;
521/155 |
International
Class: |
C08G 018/00; C08J
009/36 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 26, 2000 |
DE |
100 03 156.0 |
Oct 12, 2000 |
DE |
100 50 418.3 |
Claims
1. A composition, comprising: a polyurethane foam and a component
which is: (i) ethylenimine, polyethylenimine, polyvinylamine,
polyvinylamine copolymers, carboxymethylated polyethylenimines,
phosphonomethylated polyethylenimines, quaternized
polyethylenimines dithiocarbamatized polyethylenimines or a mixture
thereof, (ii) alkali metal hydroxides, alkaline earth metal
hydroxides, or a mixture thereof, or (iii) a mixture of (i) and
(ii).
2. The polyurethane foam as claimed in claim 1, comprising
component (i), wherein (i) is covalently bound to the polymer of
the foam.
3. The polyurethane foam as claimed in claim 1, in which component
(ii) is sodium hydroxide, potassium hydroxide, or a mixture
thereof.
4. The polyurethane foam as claimed in claim 1, which contains from
0.1 to 80% by weight of (i), (ii), or a mixture thereof, based on
the weight of the foam.
5-9. (canceled)
10. A shaped body, comprising the composition of claim 1.
Description
[0001] The present invention relates to polyurethane foams, for
example flexible, semirigid or rigid foams, preferably open-celled
foams, comprising (i) ethylenimine, polyethylenimine,
polyvinylamine, polyvinylamine copolymers, carboxymethylated
polyethylenimines, phosphonomethylated polyethylenimines,
quaternized polyethylenimines and/or dithiocarbamatized
polyethyleneimines or (ii) alkali metal hydroxides or alkaline
earth metal hydroxides, to their use and to a process for producing
them.
[0002] The production of polyurethane foams, hereinafter also
referred to as PUR foams, by reacting polyisocyanates with
compounds having at least two reactive hydrogen atoms has been
known for a long time and has been described many times.
[0003] Owing to the advantageous properties of PUR foams, for
example in respect of their low abrasion and their resistance to
chemicals, these foams are in principle very useful as support
materials for active compounds. The immobilization of active
compounds on polymers offers the advantages of heterogeneous
reactions in both physical and chemical processes. These advantages
include, for example, the ready removal and recovery of compounds,
e.g. by simple filtration or regeneration, recycling and the
opportunity of using the active compounds in continuous flow
processes and also the high activity due to the large surface area
of the support material.
[0004] Thus, WO 95/18159 describes the preparation of an
ion-exchange material based on a polyurethane foam, in which the
ion-exchange material is either added to the starting materials for
the production of the foam or is subsequently polymerized on the
foam. As ion-exchange material, mention is made of many polymers
including polystyrene-polyethylenimine. The use of a
polystyrene-polyethylenimine is disadvantageous for two reasons.
Firstly, the polyethylenimine has to be bound to the polystyrene in
an additional process step. Secondly, the effective amount of
active compound introduced is reduced by the inactive polystyrene,
compared to direct use of pglyethylenimine.
[0005] Odorous substances are usually mixtures of organic
substances which even in extraordinarily low concentrations lead to
appreciable odor pollution. Many sorbents are available for
separating off these odorous substances; for example, it is
possible to use activated carbon, silica gels, aluminas or
molecular sieves. In general, these sorbents are supported on
polymeric framework substances, for example foams.
[0006] JP 03009950 describes a deodorized polyurethane foam which
binds a large number of odorous substances. Components which are
deodorized are, for example, compounds based on phosphoric acid,
phosphorous acid, hypophosphorous acid, hydrochloric acid and their
salts (alkaline earth metal and alkaline metal salts). In addition,
the active compounds are preferably applied to a support (silica or
alumina).
[0007] U.S. Pat. No. 4,877,816 describes a foam cloth comprising
fine particles of a deodorant and a disinfectant. Deodorants
mentioned are zinc carbonate and iron sulfate, while phthalimide is
mentioned as disinfectant. Preference is given to using a
polyurethane foam.
[0008] JP 49131986 discloses polyurethane foams which are
impregnated with a solution or suspension of metallic compounds.
These compounds are subsequently treated with alkaline, oxidizing
or reducing compounds to produce metals, metal oxides or metal
complexes on the foam. The foams can be used for odor
adsorption.
[0009] JP 09057050 describes a deodorizing filter comprising a
polyurethane foam which comprises an active compound, e.g.
activated carbon, an ion-exchange resin, or a catalyst.
[0010] It is an object of the present invention, to develop
polymers having excellent adsorption capabilities for various
compounds, in particular heavy metal ions and dyes. In addition,
the foams produced should also be suitable for the adsorption of
anionic heavy metal complexes, anions of organic molecules (e.g.
aldehydes or acids) and for the purification of wastewater from
paper manufacture. A further object of the present invention is to
develop a foam which reliably and quickly reduces the concentration
of odorous substances, preferably without the gas comprising
odorous substances flowing through it.
[0011] We have found that this object is achieved by polyurethane
foams comprising compounds (i) and/or (ii).
[0012] The present invention accordingly provides polyurethane
foams comprising
[0013] (i) ethylenimine, polyethylenimine, polyvinylamine,
polyvinylamine copolymers, carboxymethylated polyethylenimines,
phosphonomethylated polyethylenimines, quaternized
polyethylenimines and/or dithiocarbamatized polyethylenimines
or
[0014] (ii) alkali metal hydroxides and/or alkaline earth metal
hydroxides or
[0015] a mixture of (i) and (ii).
[0016] The invention also provides a process for producing the
polyurethane foams of the present invention and provides for their
use for the adsorption of odorous substances and for producing
shaped bodies.
[0017] According to the present invention, ethylenimine,
polyethyleninime, polyvinylimine, polyvinylamine copolymers,
carboxymethylated polyethylenimines, phosphonomethylated
polyethylenimines, quaternized polyethyleneimines and/or
dithiocarbamatized polyethylenimines are used as compounds (i).
[0018] Possible compounds (i) are, for example: ethylenimine,
polyethylenimines having a mean molecular weight of from 500 to
800,000 g/mol, carboxymethylated polyethylenimines having a mean
molecular weight of from 1000 to 100,000 g/mol, phosphonomethylated
polyethylenimines having a mean molecular weight of from 1000 to
100,000 g/mol, quaternized polyethylenimines having a mean
molecular weight of from 1000 to 250,000 g/mol, dithiocarbamatized
polyethylenimines having a mean molecular weight of from 1000 to
250,000 g/mol, polyvinylamines having a mean molecular weight of
from 1000 to 150,000 g/mol, polyvinylamine copolymers having a mean
molecular weight of from. 1000 to 250,000 g/mol. In all these
cases, the figures quoted are based on the number average molecular
weight.
[0019] Preference is given to polyethylenimine and/or
polyvinylamine as (i).
[0020] As alkali metal hydroxides or alkaline earth metal
hydroxides (ii) to be used according to the present invention,
preference is given to sodium hydroxide and potassium
hydroxide.
[0021] Apart from the adsorption of heavy metal ions and odorous
substances, the foams produced are also suitable for the adsorption
of dyes, anionic heavy metal complexes or anions. In addition, the
foams can be used for the adsorption of organic molecules (e.g.
aldehydes), for the purification of wastewater from paper
manufacture or for fixing acidic gases.
[0022] The polyurethane foams of the present invention are produced
by reacting polyisocyanates with compounds having at least two
hydrogen atoms which are reactive toward isocyanates, with the
compounds (i) or (ii) being applied to the surface of the foam. The
compounds (i) and (ii) can be applied to the polyurethane foam by
two preferred methods.
[0023] In the first method, the polyurethane foam is produced by
reacting polyisocyanates with compounds having at least two
hydrogen atoms which are reactive toward isocyanates in the
presence of (i) or (ii). However, prepolymers can also be prepared
from the compounds (i) by reaction with isocyanate. For the present
purposes, prepolymers are reaction products of compounds (i) and
polyisocyanates, which preferably have free isocyanate groups at
the end of the chain. The prepolymers and pseudoprepolymers and
their preparation are generally known.
[0024] In the second method, the polyurethane foam is dipped into
solutions of the compounds (i) or (ii). Dipping the foam into the
liquid compound (i) or a solution of the solid or liquid compound
(i) or (ii) in a suitable solvent results in the foam being
impregnated with (i) or (ii). Suitable solvents are protic
solvents, for example water, acetone, ethanol, i-propanol, methyl
ethyl ketone or haloalkanes such as 1,2-dichloromethane. The
solvent can subsequently be removed from the foams which have been
impregnated with compound (i) or (ii). This can be achieved by
applying a vacuum or by drying at up to 50.degree. C. Thermal
treatment at from 50 to 150.degree. C. for a period of from 4 to 72
hours can enable the compounds (i) to react with the foam and thus
be covalently bound thereto.
[0025] Furthermore, application of the compounds (i) or (ii) can be
carried out, for example, by spraying on. In this case, the solvent
also has to be removed. This can be carried out, for example, by
application of a vacuum and/or heating.
[0026] In a subsequent impregnation of the foams with a solution of
the compounds (i) or (ii), the uptake capacity of the foam is
dependent, inter alia, on the type and polarity of the solvent in
which the active compound has been dissolved. The use of acetone in
particular as preferred solvent for the compounds (i) increases the
capacity of the foam for (i). In the case of the compounds (ii),
preference is given to using alcohol, e.g. ethanol.
[0027] The compounds (i) or (ii) applied to the foam by
impregnation can, if desired, be crosslinked on the foam in a
further step. Suitable crosslinkers are generally known; examples
are nonvolatile PEG bisglycidyl ethers or polycarboxylic acids such
as tetracarboxylic acids. The temperatures required for
crosslinking are 80.degree. C. for the ethers and from 120 to
130.degree. C. for the polycarboxylic acids.
[0028] To achieve improved immobilization of the compound (i), the
foam can be produced using an excess of isocyanate: in this case,
the compound (i) can be fixed to the foam framework via remaining
isocyanate groups.
[0029] The polyurethane foams of the present invention preferably
have a content of (i) or (ii) or mixtures of (i) and (ii) of from
0.1 to 80% by weight, preferably from 20 to 70% by weight,
particularly preferably from 25 to 60% by weight, based on the
weight of the foam.
[0030] The polyurethane foams of the present invention are
preferably employed in the adsorption of odorous substances and of
heavy metal ions and dyes from liquids. However, the foams can also
be used for the adsorption of anionic heavy metal complexes,
anions, acidic compounds and organic substances such as
formaldehyde. The foams can likewise be used for the purification
of wastewater from paper manufacture. The foams can likewise be
used for gas scrubbing, for example as ozone filter in passenger
cars.
[0031] The pollutants, in particular heavy metal ions and dyes,
which can advantageously be adsorbed by the polyurethane foams of
the present invention are determined by the choice of the supported
complexing agent. Some heavy metals (particularly mercury and lead)
are also adsorbed by the polyurethane foam, which effects an
additional increase in the degree of removal. Heavy metals which
are adsorbed by the supported active compounds are, in particular,
copper, nickel, cobalt, cadmium, mercury, lead, chromium,
manganese, iron, rhenium, silver and zinc.
[0032] Liquids from which the pollutants can be adsorbed are in
principle all liquids in which the latter are soluble and which do
not destroy the polyurethane foam matrix. Particularly useful
liquids are water, polar, water-miscible or organic solvents and
any mixtures of these compounds. In the case of aqueous solutions,
the proportion of organic solvents is preferably not more than 30%
by weight, based on the weight of the solution, since otherwise
partial demixing can occur during adsorption and lead to problems
in the adsorption process.
[0033] The pollutant-containing liquid is preferably brought into
contact with the novel polyurethane foam comprising (i). The
polyurethane foam can be introduced as geometric shaped bodies,
e.g. as cubes or spheres, or in comminuted form into the liquid,
stirred in this and removed again after adsorption has occurred,
for example by means of filtration. In a further embodiment of the
invention, the polyurethane foam can, for example, be fixed in a
tube or a cartridge and the liquid can be passed through this fixed
foam. The foam can be fixed, for example, as a fixed bed in an
exchange column. It has been found to be useful to employ the
comminuted foam as a filter bed and to pass the solution to be
purified through this filter.
[0034] Comminuted foams are particularly suitable for the process
of the present invention, since the available surface area is
particularly high here.
[0035] The adsorption preferably takes place at a pH in the range
from 2 to 12, preferably from 4 to 10. The pH can be set by means
of buffer solutions. If metal hydroxides precipitate, these can
likewise be physisorbed on the foam and be separated off in this
way. As buffers, it is possible to choose known buffer solutions
for this pH range, e.g. a citrate buffer or a phosphate buffer.
[0036] After the exchange capacity of the polyurethane foams used
according to the present invention has been exhausted, it may be
possible to carry out an extraction by means of acids or complexing
agents. The functionalized foam can be reused after this
regeneration.
[0037] If regeneration of the foam is not possible or possible only
with difficulty, it can be thermally utilized in a financially
advantageous manner. The relevant metals may be present as alloy
constituents in blast furnace metals.
[0038] The adsorption of radioactive compounds, atoms or ions
enables radiation-emitting constituents to be collected. The
increase in the volume concentration achieved in this way
constitutes a great economic advantage. The resulting contaminated
PUR foams can then, if appropriate, be encased in concrete or
permanently sealed. Final storage is then possible.
[0039] The polyurethane foams of the present invention can also be
used in the form of foam pads, particularly for the adsorption of
odorous substances. Furthermore, they can be used for producing
shaped articles and consumer goods. Examples include shoe soles,
coathangers and padding for clothing. The production of these
shaped articles also encompasses the backfoaming of articles, for
example coathangers, cupboard or wardrobe doors or dashboards in
vehicles.
[0040] The adsorbent foams used according to the present invention
are preferably usable in a temperature range from >0.degree. C.
to 110.degree. C., although only a limited operation life is to be
expected at temperatures of >90.degree. C.
[0041] The polyurethane foams of the present invention are
preferably open-celled so as to provide a very large surface area
for contact between the compounds (i) and/or (ii) and the
substances to be adsorbed.
[0042] Furthermore, it is advantageous to make the polyurethane
foams hydrophilic, especially those containing the compounds (i),
which makes optimum wetting of the foam with a liquid containing
pollutants to be adsorbed possible. The hydrophilicity of the
polyurethane foams can be increased, for example, by the use of
polyetherols having a high content of ethylene oxide in the
chain.
[0043] The polyurethane foams produced by the process of the
present invention preferably have a density of from 10 to 800
kg/m.sup.3, particularly preferably from 20 to 700 kg/m.sup.3 and
in particular from 40 to 60 kg/m.sup.3.
[0044] To produce the polyurethanes of the present invention, the
isocyanates are reacted in a customary manner with the compounds
having at least two active hydrogen atoms in the presence of
blowing agents and, if desired, catalysts and/or auxiliaries and/or
additives. In such a production process, the compounds having at
least two hydrogen atoms which are reactive toward isocyanate
groups and the blowing agents, catalysts and auxiliaries and/or
additives described below are frequently combined to form a polyol
component prior to the reaction and this is then reacted with the
isocyanate component.
[0045] As regards the possible starting materials for carrying out
the process of the present invention, i.e. the isocyanates, the
compounds having at least two active hydrogen atoms, the blowing
agents and, if desired, the catalysts and/or the auxiliaries and/or
additives, the following details may be provided:
[0046] as isocyanates, preferably polyisocyanates, particularly
preferably diisocyanates, more preferably organic diisocyanates, it
is possible to use the customary and known (cyclo)aliphatic and
aromatic polyisocyanates. Examples of aromatic polyisocyanates are
tolylene 2,4- and 2,6-diisocyanate (TDI), diphenylmethane 4,4'-,
2,4'- and 2,2'-diisocyanate (MDI), polyphenylene-polymethylene
polyisocyanate (crude MDI), naphthylene 1,5-diisocyanate.
[0047] Examples of (cyclo)aliphatic diisocyanates or triisocyanates
are tetramethylene 1,4-diisocyanate, hexamethylene
1,6-diisocyanate, isophorone diisocyanate, 2-methylpentamethylene
diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene
1,6-diisocyanate, 2-butyl-2-ethylpentamethyl- ene diisocyanate,
1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-1-methyl-
-1-isocyanatocyclohexane, isocyanatopropylcyclohexyl isocyahate,
xylylene diisocyanate, tetramethylxylylene diisocyanate,
bis(4-isocyanatocyclohexy- l)methane, lysine ester isocyanate, 1,3-
or 1,4-bis(isocyanatomethyl)cyclo- hexane,
4-isocyanatomethyloctamethylene 1,8-diisocyanate and also their
mixtures or the oligoisocyanates or polyisocyanates prepared
therefrom.
[0048] The oligoisocyanates or polyisocyanates can be prepared from
the abovementioned diisocyanates or triisocyanates or their
mixtures by linkage via urethane, allophanate, urea, biuret,
uretdione, amide, isocyanurate, carbodiimide, uretonimine,
oxadiazinetrione or iminooxadiazinedione structures.
[0049] The abovementioned isocyanates can also be modified, for
example by incorporation of carbodiimide groups. The
polyisocyanates are also frequently used in the form of
prepolymers. These are reaction products of the abovementioned
polyisocyanates with polyol components. Use is usually made of
isocyanate prepolymers, i.e. reaction products of polyols and
polyisocyanates which have free isocyanate groups at the end of the
chain. The prepolymers and pseudoprepolymers and their preparation
are generally known and have been described many times. In the
process of the present invention, particular preference is given to
using prepolymers having an NCO content in the range from 25 to
3.5% by weight.
[0050] In a preferred embodiment of the process of the present
invention, MDI and/or crude MDI and biurets, isocyanurates and
allophanates based on aliphatic isocyanates are used as isocyanate
components.
[0051] As compounds having at least two active hydrogen atoms,
preference is given to using polyester alcohols and particular
preference is given to using polyetherols having a functionality of
from 2 to 8, in particular from 2 to 4, preferably from 2 to 3, and
a mean molecular weight in the range from 1000 to 8500 g/mol,
preferably from 1000 to 6000. Compounds having at least two active
hydrogen atoms also include the chain extenders and crosslinkers
which may also be used. Preferred chain extenders and crosslinkers
are 2- and 3-functional alcohols having molecular weights of less
than 1000 g/mol, in particular in the range from 60 to 150.
Examples are ethylene glycol, propylene glycol, diethylene glycol,
dipropylene glycol, polyethylene glycol having a molecular weight
of less than 1000, polypropylene glycol having a molecular weight
of less than 1000 and/or 1,4-butanediol. Diamines can also be used
as crosslinkers. If chain extenders and crosslinkers are used,
their amount is preferably up to 5% by weight, based on the weight
of the isocyanates.
[0052] As catalysts for the production of the polyurethane foams of
the present invention, it is possible to use the customary and
known polyurethane formation catalysts, for example organic tin
compounds such as tin diacetate, tin dioctoate, dialkyltin
dilaurate and/or strongly basic amines such as triethylamine,
pentamethyldiethylenetriamine, bis(dimethylaminoethyl) ether,
1,2-dimethylimidazole, dimethylcyclohexylamine, dimethylbenzylamine
or preferably triethylenediamine. The catalysts are preferably used
in an amount of from 0.01 to 5% by weight, preferably from 0.05 to
2% by weight, based on the weight of the isocyanates.
[0053] As blowing agent for producing the polyurethane foams,
preference is given to using water which reacts with the isocyanate
groups to liberate carbon dioxide. It is also possible to use
physically acting blowing agents, for example hydrocarbons such as
n-pentane, isopentane or cyclopentane or halogenated hydrocarbons
such as tetrafluoroethane, pentafluoropropane, heptafluoropropane,
pentafluorobutane, hexafluorobutane or dichloromonofluoroethane or
acetals such as methylal in combination with or in place of water.
The amount of the physically acting blowing agent is preferably in
the range from 1 to 15% by weight, in particular from 1 to 10% by
weight, and the. amount of water is preferably in the range from
0.5 to 10% by weight, in particular from 1 to 5% by weight, based
on the weight of the compounds having at least two active hydrogen
atoms.
[0054] As auxiliaries and/or additives, it is possible to use, for
example, surface-active substances, foam stabilizers, cell
regulators, external and internal mold release agents, fillers,
pigments, hydrolysis inhibitors and also fungistatic and
bacteriostatic substances.
[0055] In the production of the polyurethane foams of the present
invention, the polyisocyanates and the compounds having at least
two hydrogen atoms which are reactive toward isocyanate groups are
preferably reacted in such an amount that the equivalence ratio of
isocyanate groups to the sum of active hydrogen atoms is 0.7-1.8:1,
preferably 0.7-1.2:1.
[0056] The polyurethane foams are preferably produced by the
one-shot process, for example with the aid of the high-pressure or
low-pressure technique. The foams can be produced in open or closed
metallic molds or by continuous application of the reaction mixture
to belts for producing slabstock foams.
[0057] It is particularly advantageous to employ the two-component
process in which, as indicated above, a polyol component and an
isocyanate component are prepared and then foamed together. The
components are preferably mixed at from 15 to 90.degree. C.,
preferably from 20 to 60.degree. C. and particularly preferably
from 20 to 35.degree. C., and introduced into the mold or applied
to the belt. The temperature in the mold is usually in the range
from 20 to 110.degree. C., preferably from 30 to 60.degree. C. and
particularly preferably from 35 to 55.degree. C.
[0058] In the case of the direct addition of the compounds (i) or
(ii) in the production of the polyurethane foams, they can be added
either to the polyol component or the isocyanate component
reference is given to adding (i) or (ii) to the polyol
component.
[0059] The invention is illustrated by the following examples.
EXAMPLES
Example 1
Production of a Polyurethane Foam
[0060] The polyurethane foam was produced using the foam
formulation indicated in Table 1. Isocyanate component and polyol
component were foamed at an index of 100.
1TABLE 1 Formulation of the polyurethane foam produced in Example 1
Constituent % by weight Lupranol 2040 5.0 Lupranol 2047 87.0
Lupranol 3402 8.0 Lupragen N 201 0.15 Lupragen N 206 0.1 Tegostab B
8418 3.2 Water 3.2 B 620/1 75.0 Lupranat M20W 25.0 Lupranol .RTM.
2040, (BASF Aktiengesellschaft), polyetherol based on glycerol, OHZ
= 28.0 Lupranol .RTM. 2047, (BASF Aktiengesellschaft), polyetherol
based on glycerol, OHZ = 42.0 Lupranol .RTM. 3402, (BASF
Aktiengesellschaft), polyetherol based on ethylenediamine, OHZ =
470 Lupragen .RTM. N 201, (BASF Aktiengesellschaft), (33% strength
solution of DABCO in dipropylene glycol) Lupragen .RTM. N 206,
(BASF Aktiengesellschaft), bis(dimethylaminoethyl)ether, 70% in
dipropylene glycol Tegostab B 8418 B 620/1 .RTM., (Goldschmidt),
silicone stabilizer Elastogran, prepolymer derived from Lupranat
MI, Lupranat M20W and Lupranol 2030 Lupranat .RTM. M20W,(BASF
Aktiengesellschaft), oligomeric MDI
[0061] After they had been produced, the foams were processed in a
mill to give foam particles.
Example 2
Immobilization of Polyethylenimine
[0062] The foam particles produced in Example 1 were shaken with 5%
strength aqueous Lupasol solutions for 15 minutes, using 25 ml of
the Lupasol solutions per gram of foam. The foam particles were
subsequently filtered off, heated at 100.degree. C. for 16 hours
and then washed with distilled water.
[0063] a) Lupasol.RTM. FG (BASF Aktiengesellschaft,
polyethylenimine having an MG of 800 g/mol)
[0064] b) Lupasol PR (BASF Aktiengesellschaft, polyethylenimine
having an MG of 2000 g/mol)
[0065] c) Lupasol.RTM. WF (BASF Aktiengesellschaft,
polyethylenimine having an MG of 25000 g/mol)
Example 3
Immobilization of Polyethylenimine
[0066] The foam particles produced in Example 1 were shaken with a
20% strength aqueous Lupasol.RTM. WF solution for 15 minutes, using
25 ml of the solution per gram of foam. The foam particles were
subsequently filtered off, heated at 100.degree. C. for 16 hours
and then washed with distilled water.
Example 4
Immobilization of Polyethylenimine
[0067] The foam particles produced in Example 1 were shaken with a
20% strength Lupasol.RTM. WF solution in acetone for 15 minutes,
using 25 ml of the solution per gram of foam. The foam particles
were subsequently filtered off, heated at 100.degree. C. for 16
hours and then washed with distilled water.
Example 5
Immobilization of Polyethylenimine
[0068] The foam particles produced in Example 1 were shaken with a
20% strength aqueous Lupasol.RTM. P solution for 15 minutes, using
25 ml of the solution per gram of foam. The foam particles were
subsequently filtered off, heated at 100.degree. C. for 16 hours
and then washed with distilled water.
[0069] Lupasol.RTM. P (BASF Aktiengesellschaft, polyethylenimine
having an MG of 750000 g/mol)
Example 6
Immobilization of Polyethylenimine
[0070] The foam particles produced in Example 1 were shaken with a
10% strength Lupasol.RTM. WF solution in acetone for 15 minutes,
using 25 ml of the solution per gram of foam. The foam particles
were subsequently filtered off, heated at 100.degree. C. for 16
hours and then washed with distilled water.
Example 7
Immobilization of Polyethylenimine
[0071] The foam particles produced in Example 1 were shaken with a
27% strength Lupasol.RTM. WF solution in acetone for 15 minutes,
using 25 ml of the solution per gram of foam. The foam particles
were subsequently filtered off, heated at 100.degree. C. for 16
hours and then washed with distilled water.
Example 8
Immobilization of Polyvinylamine
[0072] The foam particles produced in Example 1 were shaken with an
aqueous polyvinylamine solution (k=88.9) for 15 minutes, using 25
ml of the polyvinylamine solution per gram of foam. The foam
particles were subsequently filtered off, heated at 100.degree. C.
for 16 hours and then washed with distilled water
[0073] a) Concentration of the polyvinylamine solution: 6.5%
[0074] b) Concentration of the polyvinylamine solution: 13%
Example 9
Immobilization of Polyvinylamine
[0075] The foam particles produced in Example 1 were shaken with an
aqueous polyvinylamine solution (k=162) for 15 minutes, using 25 ml
of the polyvinylamine solution per gram of foam. The foam particles
were subsequently filtered off, heated at 100.degree. C. for 16
hours and then washed with distilled water
[0076] a) Concentration of the polyvinylamine solution: 2.1%
[0077] b) Concentration of the polyvinylamine solution: 4.2%
Example 10
Use of the Foams for Reducing the Concentration of Heavy Metals
[0078] The suitability of the foams produced in Example 2 for
reducing the concentration of heavy metals was qualified by way of
example for the case of the copper binding capacity. For this
purpose, 2 g of each foam were shaken with 100 ml of copper
solution for 2 hours. The copper concentrations of the starting
solution and of the solutions after contact with the foam particles
were determined photometrically using a cuvette tester from the
company Dr. Lange. The following copper removals were obtained.
[0079] Foam from Example 2a) 43.7 mg of Cu
[0080] Foam from Example 2b) 47.0 mg of Cu
[0081] Foam from Example 2c) 60.8 mg of Cu
Example 11
Use of the Foams for Decreasing the Concentration of Heavy
Metals
[0082] The suitability of the foams produced in Examples 3 and 4
for reducing the concentration of heavy metals was qualified by way
of example for the case of the copper binding capacity. For this
purpose, 1 g of each foam was shaken with 100 ml of copper solution
for 2 hours. The copper concentrations of the starting solution and
of the solutions after contact with the foam particles were
determined photometrically using a cuvette tester from the company
Dr. Lange. The results are summarized in Table 2.
2TABLE 2 Comparison of the copper removals achieved by the foams
produced in Examples 3 and 4 Foam from Example 3 Foam from Example
4 Available copper: bound copper: bound copper: 49 mg/g of foam
45.5 mg/g of foam 43.8 mg/g of foam 101 mg/g of foam 73.7 mg/g of
foam 70.1 mg/g of foam 201 mg/g of foam 84.3 mg/g of foam 146.2
mg/g of foam 299 mg/g of foam 94.6 mg/g of foam 178.4 mg/g of
foam
Example 12
Use of the Foams for Reducing the Concentration of Heavy Metals
[0083] The suitability of the foams produced in Examples 3 and 5
for reducing the concentration of heavy metals was qualified by way
of example for the case of the copper binding capacity. For this
purpose, 1 g of each foam was shaken with 100 ml of copper solution
for 2 hours. The copper concentrations of the starting solution and
of the solutions after contact with the foam particles were
determined photometrically using a cuvette tester from the company
Dr. Lange. The results are summarized in Table 3.
3TABLE 3 Comparison of the copper removals achieved by the foams
produced in Examples 3 and 5 Foam from Example 3 From from Example
5 Available copper: Bound copper: Bound copper: 49 mg/g of foam
45.5 mg/g of foam 44.0 mg/g of foam 101 mg/g of foam 73.7 mg/g of
foam 82.0 mg/g of foam 201 mg/g of foam 84.3 mg/g of foam 129.4
mg/g of foam 299 mg/g of foam 94.6 mg/g of foam 132.8 mg/g of foam
399 mg/g of foam 94.6 mg/g of foam 136.4 mg/g of foam
Example 13
Use of the Foams for Reducing the Concentration of Heavy Metals
[0084] The suitability of the foams produced in Examples 4, 6 and 7
for reducing the concentration of heavy metals was qualified by way
of example for the case of the copper binding capacity. For this
purpose, 1 g of each foam was shaken with 100 ml of copper solution
for 2 hours. The copper concentrations of the starting solution and
of the solutions after contact with the foam particles were
determined photometrically using a cuvette tester from the company
Dr. Lange. The results are summarized in Table 4.
4TABLE 4 Comparison of the copper removals achieved by the foams
produced in Examples 3 and 5 Concentration of the Foam Foam Foam
solution from Example 6 from Example 4 from Example 7 Available
copper: bound copper: bound copper: bound copper: 49 mg/g of foam
33.5 mg/g of foam 43.8 mg/g of foam 44.0 mg/g of foam 101 mg/g of
foam 55.6 mg/g of foam 70.1 mg/g of foam 71.5 mg/g of foam 201 mg/g
of foam 76.4 mg/g of foam 146.2 mg/g of foam 142.3 mg/g of foam 299
mg/g of foam 178.4 mg/g of foam 211.4 mg/g of foam 399 mg/g of foam
239.0 mg/g of foam 499 mg/g of foam 258.0 mg/g of foam
Example 14
Use of the Foams for Reducing the Concentration of Heavy Metals
[0085] To determine the kinetics of heavy metal removal, which was
qualified by way of example for the case of copper removal, 0.1 g
of the foam produced in Example 4 was shaken with 100 ml of a 250
ppm copper solution for various times. The copper concentrations of
the starting solution and of the solutions after contact with the
foam particles were determined photometrically using a cuvette
tester from the company Dr. Lange. The results are summarized in
Table 5.
5TABLE 5 Kinetics of copper removal by means of the foam produced
in Example 4 Copper concentration Contact time of the solution
Starting concentration 245 ppm t = 5 min. 203 ppm t = 15 min. 195
ppm t = 30 min. 184 ppm t = 60 min. 172 ppm t = 240 min. 138 ppm t
= 1440 min. 137 ppm
Example 15
Use of the Foams for Reducing the Concentration of Heavy Metals
[0086] Foam particles produced in Example 7 were used for reducing
the concentration of various heavy metals. For this purpose, 1 g of
the foam particles were in each case shaken with 100 ml of a
solution containing 3000 ppm of heavy metal for 2 hours. The heavy
metal concentrations of the starting solution and of the solutions
after contact with the foam particles were determined by means of
atomic absorption spectrometry. The results are summarized in Table
6.
6TABLE 6 Removal of various heavy metals by means of the foam
produced in Example 7 Starting remaining in the heavy metal
concentration solution removed mg/g of foam Nickel(II) 3300 mg/l
2500 mg/l 80.0 mg/g of foam Iron(III) 2800 mg/l 2500 mg/l 30.0 mg/g
of foam Lead(II) 2900 mg/l 185 mg/l 271.5 mg/g of foam Copper(II)
2990 mg/l 876 mg/l 211.4 mg/g of foam Zinc(II) 2800 mg/l 1600 mg/l
120.0 mg/g of foam Mercury(II) 3000 mg/l 34 mg/l 296.6 mg/g of
foam
Example 16
Regeneration of the Foams
[0087] 15 g of the foam particles produced as described in Example
5 were shaken with 375 ml of a 2000 ppm copper chloride solution
for 30 minutes. The supernatant copper solution was subsequently
filtered off, and the foam particles were regenerated using 0.5 N
hydrochloric acid. The foam particles were loaded again by shaking
them once more with 375 ml of a 2000 ppm copper chloride solution
(30 minutes). The results are summarized in Table 7.
7TABLE 7 Removal of copper ions Copper ions removed Pass mg/g of
foam 1 32.3 2 22.8 3 23.4 4 22.7 5 22.9 6 22.2 7 22.4 8 23.2 9 23.6
10 24.7 11 22.8 12 23.2 13 23.4 14 23.7 15 24.3 16 23.7 17 22.5 18
22.8 19 23.4
Example 17
Use of the Foams for Purification of Wastewater from Paper
Manufacture
[0088] Foam particles produced as described in Examples 7 and 9b
were used for purifying an original wastewater from a paper
factory. For this purpose,. varying amounts of the foam were shaken
with 50 ml of the wastewater for 30 minutes. The quality of the
purification was determined photometrically via the reduction in
the absorbance at a wavelength of 297 nm. The results are
summarized in Table 8.
8TABLE 8 Reduction in the absorbance of a wastewater from paper
manufacture Absorbance (l = 297 nm), Absorbance (l = 297 nm), % of
foam from % of foam from Foam, g/50 ml Example 7 Example 9b
Starting 100 100 solution 0.05 g 85.4 95.3 0.1 g 55.5 92.0 0.2 g
26.3 79.9 0.3 g 23.9 63.3 0.5 g 27.2 15.0
Example 18
Use of the Foams for Reducing the Concentration of Dyes
[0089] The wastewater of a dyeing works comprises mainly hydrolyzed
dyes, and for this reason the reactive dye Remazol.RTM. Rot 198
(Dystar) was dissolved beforehand in 0.01N sodium hydroxide
solution and subsequently hydrolyzed on a waterbath at
60-70.degree. C. for about 3 hours.
[0090] To decrease the concentration of the dye, 1 g of foam
particles from Example 7 were subsequently shaken with 50 ml of dye
solution for 5 hours, and the dye concentration in the solution was
determined photometrically at the absorption maximum. Calibration
was carried out using hydrolyzed dyes with identical sample
treatment. The results of the removal of Remazol Rot 198 at various
pH values are summarized in Table 9.
9TABLE 9 Reduction in the concentration of the reactive dye Remazol
Rot 198 Dye removed Available dye mg/g mg/g of foam of foam pH = 10
pH = 7 pH = 5 25 22 22 23 50 47 47 48 125 115 115 119 200 170 171
185
Example 19
Use of the Foams for Reducing the Concentration of Dyes
[0091] The wastewater of a dyeing works comprises mainly hydrolyzed
dyes, and for this reason the reactive dye Procion Blue MX-R
(Fluka, CAS: 13324-20-4) was dissolved beforehand in 0.01N sodium
hydroxide solution and subsequently hydrolyzed on a waterbath at
60-70.degree. C. for about 3 hours.
[0092] To decrease the concentration of the dye, 1 g of foam
particles from Example 7 was subsequently shaken with 50 ml of dye
solution for 6 hours, and the dye concentration in the solution was
determined photometrically at the absorption maximum. Calibration
was carried out using hydrolyzed dyes with identical sample
treatment. The results are summarized in Table 10.
10TABLE 10 Reduction in the concentration of the reactive dye
Procion Blue MX-R Available dye mg/g Dye removed of foam mg/g of
foam 25 25 50 50 120 99 200 198
Example 20
Use of the Foams for Reducing the Concentration of Heavy Metals
[0093] The suitability of the foams produced in Examples 8 and 9
for reducing the concentration of heavy metals was qualified by way
of example for the case of the copper binding capacity. For this
purpose, 1 g of each foam was shaken with 100 ml of copper solution
for 2 hours. The copper concentrations of the starting solution and
of the solutions after contact with the foam particles were
determined photometrically using a cuvette tester from the company
Dr. Lange. The results are summarized in Table 11.
11TABLE 11 Comparison of the copper removals achieved by the foams
produced in Examples 8 and 9 Available bound copper copper Example
8a Example 8b Example 9a Example 9b 50 mg/g of foam 27.9 mg/g of
foam 28.5 mg/g of foam 99 mg/g of foam 35.2 mg/g of foam 62.1 mg/g
of 27.5 mg/g of 59.6 mg/g of foam foam foam 199 mg/g of foam 46.1
mg/g of foam 102.3 mg/g of 36.0 mg/g of 74.3 mg/g of foam foam foam
299 mg/g of foam 48.7 mg/g of foam 113.4 mg/g of 47.0 mg/g of 85.4
mg/g of foam foam foam 401 mg/g of foam 138.0 mg/g of 52.0 mg/g of
100.1 mg/g of foam foam foam 499 mg/g of foam 144.1 mg/g of 53.0
mg/g of 101.0 mg/g of foam foam foam
[0094] Examples 21 to 31 relate to the use of the foams of the
present invention for the adsorption of odorous substances.,
[0095] To assess the adsorption of odorous substances according to
the present invention, various modified or unmodified polyurethane
foams were produced and tested. The odorous substances were
simulated by acidic odorous substances such as acetic acid. The
adsorption of the model compounds was carried out at 25.degree. C.
in a controlled-temperature cabinet having a capacity of 560 l.
Concentrations of about 140-160 ppm v/v (v/v=volume-based
concentrations) of model substance were set within the
temperature-controlled cabinet. After the foam had been added, the
decrease in concentration was determined by means of gas
chromatography. The Lupranols are various polyetherols which had
been prepared using various starters and differ in the amount of
ethylene oxide/propylene oxide; the Lupranats are various products
based on MDI.
Example 21
[0096] An aromatic flexible polyurethane foam, hereinafter referred
to as comparative system 1, was produced by intensive mixing of
105.2 g of the A component with 100 g of the B component (Index
100) with the aid of a stirrer at a rotational speed of 1250 rpm
and transfer of the foaming mixture to a plastic container having a
capacity of 5 l, with the components being made up as follows:
12 Polyol component: 97.0 parts of Lupranol 2040 .RTM. (BASF
Aktiengesellschaft) 3.0 parts of Lupranol 2047 .RTM. (BASF
Aktiengesellschaft) 3.3 parts of water 0.6 part of Lupragen N 107
.RTM. (BASF Aktiengesellschaft) 0.8 part of aminopropylimidazol 0.5
part of Tegostab B 8631 .RTM. (Goldschmidt) B Component: 42 parts
of Lupranat M 20 W .RTM. 11 parts of Lupranat MES .RTM. 47 parts of
Lupranat MI .RTM.
Example 22
[0097] An aromatic flexible polyurethane foam, hereinafter referred
to as comparative system 2, was produced by intensive mixing of
115.24 g of the A component with 100 g of the B component (Index
100) with the aid of a stirrer at a rotational speed of 1250 rpm
and transfer of the foaming mixture to a plastic container having a
capacity of 5 l, with the components being made up as follows:
13 Polyol component: 95 parts of Lupranol 2045 .RTM. (BASF
Aktiengesellschaft) 5 parts of Lupranol 2047 .RTM. (BASF
Aktiengesellschaft) 10.71 parts of Lupranol 2030 .RTM. (BASF
Aktiengesellschaft) 3.45 parts of water 0.48 part of Lupragen N 201
.RTM. (BASF Aktiengesellschaft) 0.13 part of Lupragen N 206 .RTM.
(BASF Aktiengesellschaft) 0.37 part of
tetramethylhexamethylenediamine (BASF Aktiengesellschaft) 0.1 part
of Tegostab B 8680 .RTM. (Goldschmidt) B Component: 75 parts of
Lupranat M 20 W .RTM. 25 parts of Lupranat MP 111 .RTM.
Example 23
[0098] An aliphatic flexible polyurethane foam, hereinafter
referred to as comparative system 3, was produced by intensive
mixing of 110 g of the A component with 100 g of the B component
(Index 110) with the aid of a stirrer at a rotational speed of 1250
rpm and transfer of the foaming mixture to a plastic container
having a capacity of 5 l, with the components being made up as
follows:
14 Polyol component: 56 parts of Lupranol 2042 .RTM. (BASF
Aktiengesellschaft) 35 parts of Lupranol 2045 .RTM. (BASF
Aktiengesellschaft) 2 parts of water 3 parts of Lupragen N 209
.RTM. (BASF Aktiengesellschaft) 2 parts of Lupragen N 201 .RTM.
(BASF Aktiengesellschaft) 1 part of Lupragen N 206 .RTM. (BASF
Aktiengesellschaft) 1 part of Kosmos 29 .RTM. (Goldschmidt) 1 part
of Tegostab B 8680 .RTM. (BASF Aktiengesellschaft)
[0099] B Component:
[0100] 100 parts of Basonat HI 100.RTM. (BASF
Aktiengesellschaft)
Example 24
[0101] To modify the polyurethane foams of Examples 1 to 3, the
foams were impregnated with an ethanolic KOH solution (KOH
content=5% and subsequently heated at 100.degree. C.
Example 25
[0102] To modify the polyurethane foams of Examples 1 to 3, the
foams were impregnated with a 5% strength solution of
polyethylenimine in acetone and subsequently heated at 100.degree.
C.
Example 26
[0103] A plate having dimensions of 20.times.30.times.1 cm.sup.3
was cut from the foam produced in Example 2). This was subsequently
introduced into a temperature-controlled cabinet having a capacity
of 560 l in which an acetic acid concentration of about 140-160 ppm
v/v (v/v=volume-based concentration) had previously been set. The
decrease in the acetic acid concentration was measured every five
minutes by means of a gas chromatograph and is shown graphically in
FIG. 1. The acetic acid concentrations obtained using Basotect.RTM.
(melamine-formaldehyde foam from BASF Aktiengesellschaft) and an
open-celled polystyrene foam are shown as a function of time for
comparison.
Example 27
[0104] Plates having dimensions of 20.times.30.times.1 cm.sup.3
were in each case cut from the foams produced in Examples 1), 2)
and 3). These were subsequently introduced into a
temperature-controlled cabinet having a capacity of 560 l in which
an acetic acid concentration of about 140-160 ppm v/v
(v/v=volume-based concentration) had previously been set. The
decrease in the acetic acid concentration was measured every five
minutes using a gas chromatograph and is shown graphically in FIG.
2.
Example 28
[0105] Two plates having dimensions of 20.times.30.times.1 cm.sup.3
were cut from the aromatic polyurethane foam produced in Example
1). One of these plates was additionally treated as described in
Example 4). The results in FIG. 3 show, for comparison, the
decrease in the acetic acid concentration as monitored by gas
chromatography for the modified foam and the unmodified foam. The
acetic acid concentration was arbitrarily set as 100% at time
t=0
Example 29
[0106] Two plates having dimensions of 20.times.30.times.1 cm.sup.3
were cut from the aliphatic polyurethane foam produced in Example
3). One of these plates was additionally treated as described in
Example 4). The results in FIG. 4 show, for comparison, the
decrease in the acetic acid concentration as monitored by gas
chromatography for the modified foam and the unmodified foam.
Example 30
[0107] Two plates having dimensions of 20.times.30.times.1 cm.sup.3
were cut from the aromatic polyurethane foam produced in Example
1). One of these plates was additionally treated as described in
Example 5). The results in FIG. 5 show, for comparison, the
decrease in the acetic acid concentration as monitored by gas
chromatography for the modified foam and the unmodified foam.
Example 31
[0108] Plates of various dimensions were cut from the aromatic
polyurethane foam produced in Example 1), and the plates were
treated as described in Example 5). The results in FIG. 6 show, for
comparison, the decrease in the acetic acid concentration monitored
by gas chromatography for the modified foam pads of differing
dimensions.
* * * * *