U.S. patent application number 10/039733 was filed with the patent office on 2003-04-24 for process for the alkoxylation of organic compounds in the presence of novel framework materials.
Invention is credited to Baum, Eva, Bohres, Edward, Eddaoudi, Mohamed, Lobree, Lisa, Muller, Ulrich, Ruppel, Raimund, Sigl, Marcus, Stober, Michael, Yaghi, Omar M..
Application Number | 20030078311 10/039733 |
Document ID | / |
Family ID | 21907076 |
Filed Date | 2003-04-24 |
United States Patent
Application |
20030078311 |
Kind Code |
A1 |
Muller, Ulrich ; et
al. |
April 24, 2003 |
Process for the alkoxylation of organic compounds in the presence
of novel framework materials
Abstract
The present invention relates to a process for the alkoxylation
of organic compounds comprising the reaction of at least one
organic compound with at least one alkoxylating agent in the
presence of a catalyst system, wherein a polyetheralcohol is
obtained, characterized in that the catalyst system comprises a
metallo organic framework material comprising pores and at least
one metal ion and at least one at least bidentate organic compound,
which is coordinately bounded to said metal ion, and polyurethanes
or polyurethane foams, which are obtainable by using a prepared
polyether alcohol as a starting material.
Inventors: |
Muller, Ulrich; (Neustadt,
DE) ; Stober, Michael; (Neuhofen, DE) ;
Ruppel, Raimund; (Dresden, DE) ; Baum, Eva;
(Schwarzheide, DE) ; Bohres, Edward;
(Ludwigshafen, DE) ; Sigl, Marcus; (Mannheim,
DE) ; Lobree, Lisa; (Mannheim, DE) ; Yaghi,
Omar M.; (Ann Arbor, MI) ; Eddaoudi, Mohamed;
(Ann Arbor, MI) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Family ID: |
21907076 |
Appl. No.: |
10/039733 |
Filed: |
October 19, 2001 |
Current U.S.
Class: |
521/155 ; 528/76;
568/679 |
Current CPC
Class: |
C08G 65/266 20130101;
C08G 18/48 20130101 |
Class at
Publication: |
521/155 ;
568/679; 528/76 |
International
Class: |
C08G 018/30; C08G
018/38; C08G 018/48; C08G 018/52; C08G 018/00 |
Claims
1. Process for the alkoxylation of organic compounds comprising the
reaction of at least one organic compound, which is capable of
being alkoxylated, with at least one alkoxylating agent in the
presence of a catalyst system, wherein a polyether alcohol is
obtained, characterized in that the catalyst system comprises a
metallo-organic framework material comprising pores and at least
one metal ion and at least one at least bidentate organic compound,
which is coordinately bounded to said metal ion.
2. Process according to claim 1, characterized in that the metal
ion is selected among ions of elements of groups Ia, IIa, IIIa, IVa
to VIIIa and Ib to VIb of the periodic table of the elements.
3. Process according to claim 1 or 2, characterized in that the
bidentate organic compound is selected among substituted or
unsubstituted aromatic polycarboxylic acids, which may comprise one
or more nuclei; and substituted or unsubstituted aromatic
polycarboxylic acids, which comprise at least one heteroatom and
which may have one or more nuclei.
4. Process according to any of claims 1 to 3, characterized in that
the metallo-organic framework material comprising pores exhibits a
specific surface area, as determined via adsorption (BET according
to DIN 66131) of larger than 20 m.sup.2/g.
5. Process according to any of the preceding claims, characterized
in that the alkoxylation agent is selected among mono- or
multi-functional epoxides having 2 to 30 carbon atoms and mono- or
multi-functional polyetherpolyoles having a molar mass of above 600
g/mol and a mixture of two or more thereof.
6. Integrated process for the preparation of a polyurethane
comprising at least the following steps: (2) Reacting at least one
organic compound, which is capable of being alkoxylated, with at
least one alkoxylating agent via a process according to any of the
preceding claims, wherein a polyether alcohol is obtained; (3)
Reacting the polyether alcohol of step (2) with at least one
isocyanate.
7. Integrated process according to claim 6, characterized in that
the alkoxylating agent is propylene oxide, which has been obtained
in a step (1) by reacting propylene with oxygen, hydrogen and
oxygen; hydrogen peroxide; organic hydroperoxides; or halohydrins;
preferably by reacting propylene with hydrogen peroxide; further
preferred by reacting propylene with hydrogen peroxide in the
presence of a catalyst comprising a zeolitic material; particularly
by reacting propylene with hydrogen peroxide in the presence of a
catalyst comprising a titanium containing zeolitic material having
TS-1 structure.
8. Polyurethane, obtainable by an integrated process, comprising at
least the following steps: (2) Reacting at least one organic
compound, which is capable of being alkoxylated, with at least one
alkoxylating agent via a process according to any of the preceding
claims, wherein a polyether alcohol is obtained; (3) Reacting the
polyether alcohol of step (2) with at least one isocyanate.
9. Polyurethane according to claim 8, characterized in that the
polyether alcohol, which is obtainable according to step (2) and
which is used as an starting material for the preparation of the
polyurethane, comprises at least a mixed block of ethylene
oxide-propylene oxide-units or a terminal propylene oxide block or
a combination of both.
10. Process for preparing a polyurethane foam starting from a
polyurethane obtainable by an integrated process according to any
of claims 1 to 7 or starting from a polyurethane according to
claims 8 or 9, which comprises at least the following step: (4)
foaming of the said polyurethane.
11. Polyurethane foam, obtainable by an integrated process
according to any of claims 1 to 7 or starting from a polyurethane
according to claims 8 or 9, said integrated process comprising at
least the following further step: (4) foaming the polyurethane,
which has been obtained in the reaction according to step (3).
12. Shaped body comprising a polyurethane, which is obtainable by
an integrated process according to any of claims 1 to 7 or a
polyurethane according to claim 8 or 9 or a polyurethane foam
obtainable by the process according to claim 10 or a polyurethane
foam according to claim 11.
Description
[0001] The present invention relates to a process for the
alkoxylation of organic compounds in the presence of catalyst
systems comprising a metallo-organic frame-work material comprising
pores and a metal ion and an at least bidentate organic compound,
said bidentate organic compound being coordinately bound to the
metal ion. The invention further encompasses an integrated process
for preparing polyurethanes from isocyanate and polyether alcohol
or modified polyether alcohols, which have been obtained by using
the alkoxylation process according to the invention. Still further,
the present invention is directed to polyurethanes being obtainable
by the process according to the invention, as well as shaped bodies
comprising the polyurethanes as prepared according to the
invention.
[0002] The polyurethanes prepared according to the invention are
particularly useful for the preparation of polyurethane foams,
polyurethane cast skins and elastomers.
[0003] The characteristics of polyurethanes, such as mechanical
properties and smell, are particularly strongly dependent upon the
isocyanate and polyether alcohols, which are respectively used for
their preparation, and optionally upon the used driving agents.
Particularly the structure of the polyether alcohol has a strong
influence on the characteristics of the obtained polyurethane. The
properties of the polyether alcohols are in turn strongly
influenced by their method of preparation and particularly by the
characteristics and the process for preparation of the starting
materials. A detailed discussion of the phenomena may be found in
WO 01/7186 and DE 10143195.3 of the present applicant. As further
prior art for preparing polyether alcohol, WO 01/16209 and WO
00/78837 are to be mentioned.
[0004] The reduction of the impurities within the preparation of
polyether alcohols and/or polyurethanes is of high interest for
various applications. The automotive and furniture industry request
in increasing amounts polyurethanes, which possibly are free of
emissions and smelling substances. According to the guideline of
Daimler Chrysler denoted PB VWL 709 of Jan. 11, 2001 it is required
that parts to be used inside of cars exhibit a maximum of 100 ppm
for the emission of volatile substances and 250 ppm for condensable
substances, respectively.
[0005] Impurities, which are present in polyurethanes also
negatively influence the mechanical properties thereof. The
impurities and side reactions in many cases lead to mono-functional
products. The functionality of the polyetheroles and the mechanical
properties of the polyurethanes, such as elongation, tear strength
and hardness generally deteriorate.
[0006] Polyether alcohols may be prepared e.g. by way of base or
acid catalyzed polyaddition of alkaline oxides to polyfunctional
organic compounds (starters). Suitable starters are e.g. water,
alcohols, acids or amines or mixtures of two or more thereof. These
preparation methods are particularly disadvantageous in that
several elaborate purifying steps are necessary in order to
separate the catalyst residue from the reaction product.
Furthermore, with increasing chain length of polyether polyoles
prepared, the content of mono-functional products and substances
with intensive smell, which are not desired within polyurethane
production, increases.
[0007] The reduction of the functionality is particularly
disadvantageous for elastomers, since the used polyether alcohols
should generally be bi-functional. Due to the mono-functional
impurities within the polyether alcohol, the functionality
decreases below 2, resulting in a significant deterioration of the
mechanical characteristics of the polyurethanes, particularly tear
strength and elongation.
[0008] The side products generated by side reactions within the
base or acid catalyzed reaction are furthermore partly contained in
the polyurethane as smelling impurities. Particularly to be
mentioned are aldehydes, e.g. propionic aldehyde, cycloacetales,
allylic alcohol and their reaction products. The automotive and
furniture industry request in increasing amounts polyetheroles and
polyurethanes having reduced or no smell.
[0009] An object of the invention is therefore to provide a process
for the preparation of polyether alcohols and polyurethanes,
respectively, which yields polyether alcohols and polyurethanes,
respectively, having a low amount of impurities, particularly low
molecular weight substances having intensive smell, which process
does not comprise elaborate purifying steps of starting materials
and/or intermediate products.
[0010] This object is solved by a process for the alkoxylation of
organic compounds comprising the reaction of at least one organic
compound, which is capable of being alkoxylated, with at least one
alkoxylating agent in the presence of a catalyst system, wherein a
polyether alcohol is obtained, characterized in that the catalyst
system comprises a metallo-organic framework material comprising
pores and at least one metal ion and at least one at least
bidentate organic compound, which is coordinately bound to said
metal ion, and
[0011] an integrated process for the preparation of a polyurethane
comprising at least the following steps:
[0012] (2) reacting at least one organic compound, which is capable
of being alkoxylated, with at least one alkoxylating agent via a
process as described above, wherein a polyether alcohol is
obtained;
[0013] (3) reacting the polyether alcohol of step (2) with at least
one isocyanate.
[0014] As the alkoxylating agent in step (2) preferably mono- or
multifunctional expoxide having two to 30 carbon atoms or mono- or
multifunctional polyester polyoles having a molar mass of above 600
g/mol or a mixture of two or more thereof are used. Particularly,
substituted or unsubstituted alkylene oxides having two to 24
C-atoms, e.g. alkylene oxides having halogen, hydroxy, non-cyclic
ether or ammonium substituents are used.
[0015] As suitable compounds, the following are exemplarily to be
mentioned: ethylene oxide, 1,2-epoxypropane,
1,2-methyl-2-methylpropane, 1,2-epoxybutane, 2,3-epoxybutane,
1,2-methyl-3-methylbutane, 1,2-epoxypentane,
1,2-methyl-3-methylpentane, 1,2-epoxyhexane, 1,2-epoxyheptane,
1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane,
1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxycyclopentane,
1,2-epoxycyclohexane, (2,3-epoxypropyl)benzene, vinyloxirane,
3-phenoxy-1,2-epoxypropane, 2,3-epoxymethyl ether, 2,3-epoxylethyl
ether, 2,3-epoxyl isopropyl ether, 2,3-epoxyl-1-propanol,
(3,4-epoxybutyl)stearate, 4,5-epoxypentylacetate, 2,3-epoxy propane
methacrylate, 2,3-epoxy propane acrylat, glycidylbutyrate,
methylglycidate, ethyl-2,3-epoxybutanoate,
4-(trimethylsilyl)butane-1,2-e- poxide,
4-(triethylsilyl)butane-1,2-epoxide, 3-(perfluoromethyl)propane
oxide, 3-(perfluoroethyl)propane oxide, 3-(perfluorobutyl)propane
oxide, 4-(2,3-epoxypropyl)morpholine,
1-(oxirane-2-ylmethyl)pyrrolidin-2-one, and mixtures of two or more
thereof.
[0016] Particularly to be mentioned are: aliphatic 1,2-alkylene
oxide having 2 to 4 C-atoms, such as ethylene oxide, 1,2-butylene
oxide, 2,3-butylene oxide or isobutylene oxide, aliphatic
1,2-alkylene oxides having 5 to 24 C-atoms, cycloaliphatic alkylene
oxide, such as cyclopentane oxide, cyclohexane oxide or
cyclododecatriane-(1,5,9)-monoxi- de, araliphatic alkylene oxide,
e.g. styrene oxide.
[0017] Particularly preferred are within the present invention
ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane,
styrene oxide, vinyloxirane and any mixtures of two or more thereof
within each other, particularly ethylene oxide, propylene oxide and
mixtures of ethylene oxide, 1,2-epoxypropane.
[0018] As polyether alcohols, within the present invention,
particularly polyester polyoles and modified polyetheroles are
used, which are obtainable by using ethylene oxide or propylene
oxide, which may be prepared according to step (1), preferably
according to an embodiment outlined hereinunder. Subsequently, step
(1) of the present invention is exemplarily described in detail by
use of propylene oxide as an example:
[0019] Generally, propylene oxide may be obtained by reacting
propylene with oxygen; hydrogen and oxygen; hydrogen peroxide;
organic hydroperoxides; or halohydrines, preferably by reacting
propylene with hydrogen peroxide, more preferred by reacting
propylene with hydrogen peroxide in the presence of a catalyst
comprising a zeolithic material, particularly by reacting propylene
with hydrogen peroxide in the presence of a catalyst comprising a
titanium-containing zeolithic material having CS-1-structure.
[0020] As a particularly suitable hydroperoxide for the epoxidation
according to step (1), hydrogen peroxide is to be mentioned. This
can be either prepared outside the reaction according to (1) or by
starting from hydrogen and oxygen in situ within the reaction
according to (1), respectively.
[0021] Thus, the present invention also relates in a preferred
embodiment to a process for the alkoxylation of organic compounds
and an integrated process for preparing a polyurethane,
respectively, wherein the hydroperoxide as used in step (1) is
hydrogen peroxide.
[0022] The epoxidation according to step (1) is in principle known
from e.g. DE 100 55 652.3 and further patent applications of the
present applicant, such as DE 100 32 885.7, DE 100 32 884.9, DE 100
15 246.5, DE 199 36 547.4, DE 199 26 725.1, DE 198 47 629.9, DE 198
35 907.1, DE 197 23 950.1, which are fully encompassed within the
content of the present application with respect to their respective
content. By the epoxidation according to step (1), propylene oxide
is obtained in high purity. Particularly, the propylene oxide as
such obtained exhibits a content of C.sub.6-compunds of <1
ppm.
[0023] Within the present invention, as C6-compounds e.g. the
following compounds are underdstood: 2-methylpentane,
4-methylpentene-1, n-hexane, hexenes, such as 1-hexene, and
components having 6 C-atoms and in addition thereto one or more
functional groups selected among the class of aldehydes, carboxylic
acids, alcohols, ketones and ethers. Further undesired impurities
are propane derivatives, particularly chlorinated propane
derivatives, acetaldehyde, propione aldehyde, acetone, dioxolanes,
allylic alcohol, pentane, methylpentane, furane, hexane, hexene,
methoxypropane and methanol.
[0024] The propylene oxide obtained according to step (1) may
further comprise as further side components, up to 100 ppm,
particularly up to 40 ppm, methanol and up to 10 ppm, preferably up
to 4 ppm, acetaldehyde.
[0025] Compared to other known methods for preparing propylene
oxide, which are not excluded from the present application, and
which are e.g. described in Weissermel, Arpe "Industrielle
Organische Chemie", publisher VCH, Weinheim, 4.sup.th Ed., pages
288 to 318, the preferred embodiments of step (1) according to the
invention yields propylene oxide having only minor impurities of
C.sub.6-components and contain no chloro-organic impurities.
[0026] A summary of the above-referenced prior art and the
procedure when preparing polyether alcohols starting from propylene
oxide is given in DE 10143195.3.
[0027] With regard to the preparation of ethylene oxide, which may
also serve as an alkoxylating agent and which may also be prepared
prior to conducting the process for the alkoxylation of an organic
compound being capable of being alkoxylated, is e.g. broadly
disclosed in U. Onken, Anton Behr, "Chemische Prozesskunde", Vol.
3, Thieme, 1996, pages 303 to 305 and Weissermel, Arpe "Industrial
Organic Chemistry", 5.sup.th Ed., Wiley, 1998, pages 159 to
181.
[0028] Within the reaction yielding the polyether alcohols, the
alkoxylating agent obtained according to step (1), particularly
propylene oxide, may be directly used in the reaction according to
step (2). It is, however, also possible within the present
invention that the alkoxylating agent, particularly propylene
oxide, yielded according to step (1) is beforehand treated, e.g.
purified. As the purification method, mention can be made of a fine
distillation. Suitable processes are e.g. disclosed in EP-B 0 557
116.
[0029] The alkoxylating agent as obtained according to step (1),
particularly propylene oxide, may be used within the present
invention alone or together with at least one further alkoxylating
agent, particularly together with at least one further alkylene
oxide.
[0030] For preparing a polyether alcohol according to step (2), it
is possible within the present invention to use instead of or
besides propylene oxide all alkoxylating agents, particularly
alkylene oxides, which are known to the person skilled in the art,
particularly the above-mentioned compounds.
[0031] In cases where, besides the alkoxylating agent obtained
according to step (1), particularly propylene oxide, at least one
further alkoxylating agent, particularly a further alkylene oxide
is used, it is possible within the present invention that a mixture
of the alkoxylating agent as obtained according to step (1),
particularly propylene oxide, and at least one further alkoxylating
agent, particularly alkylene oxide, is employed. It is, however,
also possible within the present invention that the alkoxylating
agent as obtained according to step (1), particularly propylene
oxide, and the at least one further alkoxylating agent,
particularly an alkylene oxide, are added subsequently.
[0032] The polyether alcohols as obtained according to step (2) may
e.g. comprise also block structures. The structure of the polyether
alcohols may be controlled in wide ranges by appropriate reaction
conditions. Suitable reaction conditions for the reaction according
to step (2) are e.g. disclosed in WO 99/16775.
[0033] The polyether alcohols as obtained according to step (2) may
be modified for the reaction according to step (3). Regarding these
modified polyether alcohols, particularly to be mentioned are
grafted polyether polyoles, particularly those which are prepared
by polymerizing styrene and acrylonitril in the presence of
polyetheroles; polyurea dispersions (PHD-polyoles) which are
prepared by reacting diisocyanates and diamines in the presence of
polyetheroles; and polyisocyanate polyaddition polyoles (PIPA
polyoles), which are prepared by reacting diisocyanates and amino
alcohols in the presence of polyetheroles.
[0034] The reaction according to step (2) is carried out in the
presence of a catalyst system.
[0035] The catalyst system as used according to the invention in
step (2) comprises a metallo-organic pore containing framework
material, which in turn comprises a metal ion and an at least
bidentate organic compound, said bidentate organic compound being
coordinately bound to the metal ion. Such catalyst systems are
known as such and described in e.g. U.S. Pat. No. 5,648,508, EP-A-0
709 253, J. Sol. State Chem., 152 (2000) p. 3-20, Nature 402
(1999), p. 276 seq., Topics in Catalysis 9 (1999), p. 105-111,
Science 291 (2001), p. 1021-23. An inexpensive way for their
preparation is the subject of DE 10111230.0. The content of the
above-mentioned literature, to which reference is made herein, is
fully incorporated in the content of the present application.
[0036] The metallo-organic framework materials, as used in the
present invention, comprise pores, particularly micro- and/or
mesopores, wherein micropores are defined as being pores having a
diameter of 2 nm or below and mesopores being pores having a
diameter in the range of above 2 nm to 50 nm, respectively,
according to the definition in Pure Applied Chem. 45, p. 71 seq.,
particularly p. 79 (1976). The presence of the micro- and/or
mesopores may be monitored by sorption measurements for determining
the capacity of the metallo-organic framework materials to take up
nitrogen at 77 K according to DIN 66131, 66134. A type-I-form of
the isothermal curve indicates the presence of micropores. In a
preferred embodiment, the specific surface areas, as calculated
according to the Langmuir model (DIN 66131, 66134) are preferably
above 5 m.sup.2/g, more preferably above 50 m.sup.2/g, particularly
above 500 m.sup.2/g and may increase into the region of to above
2000 m.sup.2/g.
[0037] As the metal component within the framework material as used
according to the present invention, particularly to be mentioned
are metal ions of elements of groups Ia, IIa, IIIa, IVa to VIIIa
and Ib to VIb of the periodic system; among those particularly to
be mentioned are Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr,
Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn,
Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi, more
preferably Zn, Cu, Ni, Pd, Pt, Ru, Rh and Co. As metal ions of
these elements, particularly to be mentioned are: Mg.sup.2+,
Ca.sup.2+, Sr.sup.2+, Ba.sup.2+, Sc.sup.3+, Y.sup.3+, Ti.sup.4+,
Zr.sup.4+, Hf.sup.4+, V.sup.4+, V.sup.3+, .sup.V2+, Nb.sup.3+,
Ta.sup.3+, Cr.sup.3+, Mo.sup.3+, W.sup.3+, Mn.sup.3+, Mn.sup.3+,
Mn.sup.2+, Re.sup.3+, Re.sup.2+, Fe.sup.3+, Fe.sup.2+, Ru.sup.3+,
Ru.sup.2+, Os.sup.3+, Os.sup.2+, Co.sup.3+, Co.sup.2+, Rh.sup.2+,
Rh.sup.+, Ir.sup.2+, Ir.sup.+, Ni.sup.2+, Ni.sup.+, Pd.sup.2+,
Pd.sup.+, Pt.sup.2+, Pt.sup.+, Cu.sup.2+, Cu.sup.+, Ag.sup.+,
Au.sup.+, Zn.sup.2+, Cd.sup.2+, Hg.sup.2+, Al.sup.3+, Ga.sup.3+,
In.sup.3+, Tl.sup.3+, Si.sup.4+, Si.sup.2+, Ge.sup.4+, Ge.sup.2+,
Sn.sup.4+, Sn.sup.2+, Pb.sup.4+, Pb.sup.2+, As.sup.5+, As.sup.3+,
As.sup.+, Sb.sup.5+, Sb.sup.3+, Sb.sup.+ and Bi.sup.5+, Bi.sup.3+,
Bi.sup.+.
[0038] With regard to the preferred metal ions and further details
regarding the same, we particularly refer to: EP-A 0 790 253,
particularly p. 10, 1. 8-30, section "The Metal Ions", which
section is incorporated herein by reference.
[0039] As the at least bidentate organic compound, which is capable
to coordinate with the metal ion, in principle all compounds which
are suitable for this purpose and which fulfill the above
requirements of being at least bidentate, may be used. The organic
compound must have at least two centers, which are capable to
coordinate with the metal ions of a metal salt, particularly with
the metals of the aforementioned groups. With regard to the at
least bidentate organic compound, specific mention is to be made of
compounds having
[0040] i) an alkyl group substructure, having from 1 to 10 carbon
atoms,
[0041] ii) an aryl group substructure, having from 1 to 5 phenyl
rings,
[0042] iii) an alkyl or aryl amine substructure, consisting of
alkyl groups having from 1 to 10 carbon atoms or aryl groups having
from 1 to 5 phenyl rings,
[0043] said substructures having bound thereto at least one at
least bidentate functional group "X", which is covalently bound to
the substructure of said compound, and wherein X is selected from
the group consisting of
[0044] CO.sub.2H, CS.sub.2H, NO.sub.2, SO.sub.3H, Si(OH).sub.3,
Ge(OH).sub.3, Sn(OH).sub.3, Si(SH).sub.4, Ge(SH).sub.4,
Sn(SH).sub.3, PO.sub.3H, AsO.sub.3H, AsO.sub.4H, P(SH).sub.3,
As(SH).sub.3, CH(RSH).sub.2, C(RSH).sub.3, CH(RNH.sub.2).sub.2,
C(RNH.sub.2).sub.3, CH(ROH).sub.2, C(ROH).sub.3, CH(RCN).sub.2,
C(RCN).sub.3, wherein R is an alkyl group having from 1 to 5 carbon
atoms, or an aryl group consisting of 1 to 2 phenyl rings, and
CH(SH).sub.2, C(SH).sub.3, CH(NH.sub.2).sub.2, C(NH.sub.2).sub.2,
CH(OH).sub.2, C(OH).sub.3, CH(CN).sub.2 and C(CN).sub.3.
[0045] Particularly to be mentioned are substituted or
unsubstituted, mono- or polynuclear aromatic di-, tri- and
tetracarboxylic acids and substituted or unsubstituted, aromatic,
at least one hetero atom comprising aromatic di-, tri- and
tetracarboxylic acids, which have one or more nuclei.
[0046] A preferred ligand is 1,3,5-benzene tricarboxyllic acid
(BCT), particularly preferred metal ions are Co.sup.2+ and
Zn.sup.2+.
[0047] Besides the at least bidentate organic compound, the
framework material as used in accordance with the present invention
may also comprise one or more mono-dentate ligands, which are
preferably derived from the following mono-dentate substances:
[0048] a. alkyl amines and their corresponding alkyl ammonium
salts, containing linear, branched, or cyclic aliphatic groups,
having from 1 to 20 carbon atoms (and their corresponding ammonium
salts);
[0049] b. aryl amines and their corresponding aryl ammonium salts
having from 1 to 5 phenyl rings;
[0050] c. alkyl phosphonium salts, containing linear, branched, or
cyclic aliphatic groups, having from 1 to 20 carbon atoms;
[0051] d. aryl phosphonium salts, having from 1 to 5 phenyl
rings;
[0052] e. alkyl organic acids and the corresponding alkyl organic
anions (and salts) containing linear, branched, or cyclic aliphatic
groups, having from 1 to 20 carbon atoms;
[0053] f. aryl organic acids and their corresponding aryl organic
anions and salts, having from 1 to 5 phenyl rings;
[0054] g. aliphatic alcohols, containing linear, branched, or
cyclic aliphatic groups, having from 1 to 20 carbon atoms;
[0055] h. aryl alcohols having from 1 to 5 phenyl rings;
[0056] i. inorganic anions from the group consisting of:
[0057] sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate,
hydrogen phosphate, dihydrogen phosphate, diphosphate,
triphosphate, phosphate, phosphite, chloride, chlorate, bromide,
bromate, iodide, iodate, carbonate, bicarbonate, and the
corresponding acids and salts of the aforementioned inorganic
anions,
[0058] j. ammonia, carbon dioxide, methane, oxygen, ethylene,
hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene,
naphthalene, thiophene, pyridine, acetone, 1-2-dichloroethane,
methylenechloride, tetrahydrofuran, ehtanolamine, triethylamine and
trifluoromethylsulfonic acid.
[0059] Further details regarding the at least bidentate organic
compounds and the monodentate substances, from which the ligands of
the framework material as used in the present application are
derived, may be deduced from EP-A 0 790 253, whose respective
content is incorporated into the present application by
reference.
[0060] Particularly preferred are within the present application
framework materials of the kind described herein, which comprise
Zn.sup.2+ as a metal ion and ligands derived from teraphthalic acid
as the bidentate compound, which are known as MOF-5 in the
literature.
[0061] Further metal ions and at least bidentate organic compounds
and mono-dentate substances, which are respectively useful for the
preparation of the framework materials used in the present
invention as well as processes for their preparation are
particularly disclosed in EP-A 0 790 253, U.S. Pat. No. 5,648,508
and DE 10111230.0.
[0062] As solvents, which are particularly useful for the
preparation of MOF-5, in addition to the solvents disclosed in the
above-referenced literature dimethyl formamide, diethyl formamide
and N-methylpyrollidone, alone, in combination with each other or
in combination with other solvents may be used. Within the
preparation of the framework materials, particularly within the
preparation of MOF-5, the solvents and mother liquors are recycled
after crystallization in order to save costs and materials.
[0063] The separation of the framework materials, particularly of
MOF-5, from the mother liquor of the crystallization may be
achieved by procedures known in the art such as solid-liquid
separations, such as centrifugation, extraction, filtration,
membrane filtration, cross-flow filtration, flocculation using
flocculation adjuvants (non-ionic, cationic and anionic adjuvants)
or by the addition of pH shifting additives such as salts, acids or
bases, by flotation, spray-drying or spray granulation as well as
by evaporation of the mother liquor at elevated temperature and/or
in vacuo and concentrating of the solid.
[0064] The separated framework materials, particularly MOF-5 may be
compounded, melted, extruded, co-extruded, pressed, spinned, foamed
and granulated according to processes known within the processing
of plastics, respectively.
[0065] In step (2) according to the invention, the alkoxylating
agent, particularly propylene oxide from step (1) or a mixture of
propylene oxide of step (1) and at least one further alkylene oxide
is reacted with an organic alkoxylatable compound (organic
compound).
[0066] Within the present invention, in principle all organic
compounds, which can be alkoxylated, may be used. As particularly
suitable organic compounds, the following are to be mentioned:
[0067] water, organic mono- or dicarboxylic acids, such as acrylic
acid, methacrylic acid, succenic acid, adipinic acid, phthalic acid
and teraphthalic acid, aliphatic and aromatic, optionally N-mono-,
N,N- and N,N'-dialkyl-substituted diamine with 1 to 4 carbon atoms
in the alkyl group, such as optionally mono- or dialkyl-substituted
ethylenediamine, diethylenetriamine, triethylenetetramine,
1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,2-, 1,3-,
1,4-, 1,5- and 1,6-hexamethylenediamine, phenylenediamines, 2,3-,
2,4- and 2,6-toluylenediamine and 4,4'-, 2,4'- and
2,2'-diamino-di-phenylmethane, alkanolamines, such as ethanolamine,
N-methyl- and N-ethyl-ethanolamine, dialkanolamines, such as
diethanolamine, N-methyl- and N-ethyl-diethanolamine, and
trialkanolamines, such as triethanolamine, and ammonia and
polyvalent alcohols, such as monoethyleneglycol, propandiol-1,2
and-1,3 diethyleneglykol, dipropyleneglycol, butanediol-1,4,
hexanediol-1,6, glycerol, trimethylolpropane, pentaerythrit,
sorbite and saccharose. As the preferred polyether polyalcohols,
addition products ethylene oxide and/or propylene oxide and water,
monoethyleneglycol, diethyleneglykol, propandiol-1,2,
diproplyeneglycol, glycerol, trimethylolpropane, ethylendiamine,
triethanolamine, pentaerythrit, sorbite and/or saccharose are used
alone or in admixture with each other.
[0068] The organic compounds may also be used in the form of
alkoxylates, particularly those having a molecular weight M.sub.w
in the range of 62 to 15,000 g/mol.
[0069] Furthermore, also macromolecules having functional groups
with active hydrogen atoms, such as hydroxyl groups, particularly
those which are mentioned in WO 01/16209 may be used.
[0070] The polyether alcohols as obtained in step (2) may be
reacted with isocyanates in step (3). Step (3) may be carried out
directly after step (2). It is also possible that an additional
step, particularly a purification step, may be carried out between
step (2) and (3).
[0071] Within the present invention, one or more isocyanates may be
used. Besides the polyether alcohols as obtained according to step
(2) within the reaction according to step (3), further components
having groups which are reactive towards isocyanates, particularly
those having hydroxyl groups, may be additionally used.
[0072] As further OH-components, use can be made of e.g.
polyesters, further polyethers, polyacetales, polycarbonates,
polyesterethers, and similar compounds.
[0073] Suitable polyesterpolyoles may be prepared by reacting
organic dicarboxylic acids having 2 to 23 carbon atoms, preferably
aliphatic dicarboxylic acids having 4 to 6 carbon atoms, with
polyvalent alcohols, preferably dioles, respectively having 2 to 12
carbon atoms, preferably 2 to 6 carbon atoms. As the dicarboxylic
acids, the following may be preferably used:
[0074] succinic acid, glutaric acid, adipinic acid, suberic acid,
azelaic acid, sebacinic acid, decanedicarboxylic acid, maleic acid,
fumaric acid, phthalic acid, isophthalic acid and teraphthalic
acid. The dicarboxylic acids may be used alone or in admixture with
each other. Instead of the free dicarboxylic acid, also the
corresponding dicarboxylic acid derivatives, such as dicarboxylic
esters of alcohols having 1 to 4 carbon atoms or dicarboxylic acid
anhydrides may be used. Examples for polyvalent alcohols are:
[0075] ethanediole, diethyleneglycol, 1,2- and 1,3-propanediole,
dipropyleneglycol, 1,4-butanediole, 1,5-pentanediole,
1,6-hexanediole, 1,10-decanediole, 1,12-dodecanediole, glycerol and
trimethylolpropane. Preferably used are ethanediole,
diethyleneglycol, 1,4-butanediole, 1,5-pentanediole,
1,6-hexanediole, glycerol and/or trimethylolpropane. Furthermore,
polyesterpolyoles made of lactones, e.g. caprolactone or hydroxy
carboxylic acid, such as .alpha.-hxydroxycarpronic acid may be
used. For the preparation of the polyesterpolyoles, the organic,
e.g. aromatic or preferably aliphatic polycarboxylic acids and/or
derivatives thereof may be reacted acted with the polyvalent
alcohol in the absence of a catalyst or preferably in the presence
of an esterifying catalyst. Preferably, the reaction is carried out
in an inert atmosphere, e.g. in a nitrogen, carbon monoxide,
helium, argon, etc. atmosphere. The whole reaction is carried out
in a melt at temperatures from 150 to 250.degree. C., preferably
180 to 220.degree. C., optionally under reduced pressure, up to the
desired acid number, which preferably is lower than 10, more
preferably lower than 2. According to a preferred embodiment of
this condensation reaction, the mixture to be esterified is first
reacted up to an acid number of 80 to 30, preferably 40 to 30,
under normal pressure and at the above-mentioned temperatures, and
subsequently polycondensated at a pressure of lower than 500 mbar,
preferably 50 to 150 mbar. As esterifying catalyst, mention can be
made of e.g. Fe, Cd, Co, Pb, Zn, Sb, Mg, Ti and Sn catalysts in the
form of metals, metal oxides or metal salts. However, the
polycondensation may be also carried out in the liquid phase in the
presence of a thinning and/or entraining agent, such as benzene,
toluene, xylene or chlorobenzene, in order to azeotropically
distillate the water generated during condensation. For the
preparation of the polyesterpolyoles, the organic polycarboxylic
acids and/or acid derivatives and the polyvalent alcohols are
preferably polycondensated in molar ratios of 1:1.8, preferably
1:1.05 to 1:1.2. The obtained polyesterpolyoles exhibit preferably
a functionality of 2 to 4, particularly 2 to 3 and a hydroxyl
number of preferably 22 to 100 mg KOH/g. Furthermore, use can be
made of compounds which are reactive towards isocyanates, such as
dioles, trioles and/or polyoles having molecular weights of 60 to
<400, such as aliphatic, cycloaliphatic and/or araliphatic
dioles having 2 to 14, preferably 4 to 10 carbon atoms, such as
ethyleneglycol, propoanediole-1,3, decanediole-1,10, o-, m-,
p-dihydroxycyclohexane, diethyleneglycol, dipropylenglycol and
preferably butanediole-1,4, hexanediole-1,6 and
bis-(2-hydroxyethyl)-hydr- oquinone; triole, such as 1,2,4-,
1,3,5-trihydroxy cyclohexane, glycol and trimethylolproprane; and
low molecular weight polyalkyleneoxides having hydroxyl groups,
such as those obtained by reacting ethylene oxide and/or
1,2-propylene oxide with the above-mentioned dioles and/or trioles
as an H-functional compound.
[0076] According to the present invention, the polyether alcohol of
step (2) is reacted with at least one isocyanate. In principle, all
isocyanates which are known to the person skilled in the art, may
be used within the present invention. Particularly, the following
are to be mentioned:
[0077] aromatic, araliphatic, aliphatic and/or cycloaliphatic
organic isocyanates, preferably diisocyanates.
[0078] The following individual compounds are particularly to be
mentioned:
[0079] alkylenediisocyanates having 4 to 12 carbon atoms in the
alkylene group, such as 1,12-dodecanediisocyanate,
2-ethyl-tetramethylenediisocyan- ate-1,4,
2-methylpentamethylenediisocyanate-1,5, tetramethylenediisocyanat-
e-1,4, lysinesterdiisocyanate (LDI) and/or
hexamethylenediisocyanate-1,6 (HDI); cycloaliphatic diisocyanates,
such as cyclohexane-1,3- and 1,4-diisocyanate and arbitrary
mixtures of these isomers, 2,4- and
2,6-hexahydrotoluylenediisocyanate and the respective mixtures of
isomers, 4,4'-, 2,2'- and 2,4'-dicyclohexylmethanediisocyanate and
the respective mixtures of isomers and/or
1-isocyanato-3,3,5-trimethyl-5-isoc- yanatomethylcyclohexane
(IPDI).
[0080] Furthermore, the following isocyanates are exemplary to be
mentioned:
[0081] 2,4- and 2,6-toluyliendiisocyanate and the respective
mixtures of isomers, 4,4'-, 2,4'- and
2,2'-diphenylmethanediisocyanate and the respective mixtures of
isomers, mixtures of 4,4'- and 2,2'-diphenylmethanediisocyanates,
polyphenylpolymethylenepolyisocyanates- , mixtures of 4,4'-, 2,4'-
and 2,2'-diphenylmethanediisocyanates and
polyphenylpolymethylene-polyisocyanates (raw-MDI) and mixtures of
raw-MDl and toluylendiisocyanates. Furthermore, mixtures comprising
at least two of the above-mentioned isocyanates may also be used.
Furthermore, modified isocyanates having isocyanurate, bouret,
ester, urea, allophanate, carbodiimid, uretdione, and/or urethane
groups (in the following also denoted urethane group modified)
containing di- and/or polyisocyanates may be used.
[0082] Among those, the following indivial compounds may be
mentioned:
[0083] urethane group containing organic polyisocyanates having an
NCO-content of 50 to 10 wt.-%, preferably 35 to 15 wt.-%, relative
to the total weight, such as 4,4'-diphenylmethanediisocyanate,
4,4'- and 2,4'-diphenylmethanediisocyanate mixtures, raw-MDI or
2,4- and 2,6-toluylendiisocyanates, which are respectively
modified, e.g. with low molecular weight dioles, trioles,
dialkyleneglycoles, trialkyleneglycoles or polyoxyalkyleneglycoles
having molecular weights of up to 6000, particularly molecular
weights of up to 1500, may be used alone or in admixture with each
other. As the di- or polyoxyalkyleneglycoles, which may in turn
also be used alone or in admixture with each other, the following
are to be mentioned:
[0084] diethylene- and dipropyleneglycol, polyoxyethylene-,
polyoxypropylene- and polyoxypropylenepolyoxyetheneglycoles,
-trioles and/or tetroles. Furthermore, prepolymers comprising
NCO-groups, and respectively having NCO-contents of 25 to 3.5
wt.-%, preferably 21 to 14 wt.-%, respectively relative to the
total weight, may be also used. These compounds are prepared from
the above-described polyester- and/or preferably polyether polyoles
and 4,4'-diphenylmethanediisocyanate, mixtures of 2,4'- and
4,4'-diphenylmethanediisocyanate, 2,4- and/or
2,6-toluylenediisocyanate or raw-MDI. Furthermore, use can also be
made of liquid polyisocyanates containing carbodiimide groups,
respectively having NCO-contents of 36.6 to 15, preferably 31 to 21
wt.-%, relative to the total weight, e.g. on the basis of 4,4'-,
2,4'- and/or 2,2'-diphenylmethanediisocyanate and/or 2,4- and/or
2,6-toluylenediisocyanate. The modified polyisocyanates may be
mixed with each other or together with non-modified organic
polyisocyanates, such as e.g. 2,4'-,
4,4'-diphenylmethanediisocyanate, raw-MDI, 2,4- or
2,6-toluylenediisocyanate. As modified isocyanates, preferably use
is made of isocyanurate, biuret and/or urethane group modified
aliphatic and/or cycloaliphatic diisocyanates, e.g. those which are
already mentioned, which are provided with biuret and/or cyanurate
groups according to known processes, and which comprise at least
one, preferably at least two and more preferably at least three
free isocyanate groups, respectively. The trimerization of the
isocyanates for preparing isocyanates having isocyanurate groups
may be carried out at common temperatures in the presence of known
catalysts, such as phosphines and/or phosphorine derivatives,
amines, alkali metal salts, metal compounds and/or Mannich bases.
Furthermore, trimers of isocyanates containing isocyanurate groups
are furthermore commercially available. Isocyanates having biuret
groups may also be prepared according to generally known processes,
e.g. by reacting the above-mentioned diisocyanates with water or
diamines, wherein as an intermediate product, a urea derivative is
formed. Isocyanates containing biuret groups are also commercially
available.
[0085] The reaction according to step (3) is carried out under
conditions known to the person skilled in the art. Suitable
reaction conditions are described in e.g. Becker, Braun
"Polyurethanes", Kunststoffhandbuch, Vol. 7, Carl Hanser, Munich,
3.sup.rd Ed., 1993, p. 139 to 193.
[0086] Optionally, within the reaction according to step (3),
further, low molecular weight compounds may be added as additives.
Such compounds may be chain extenders or stopping agents.
Particularly useful for this purpose are e.g. primary amino
compounds having 2 to about 20, e.g. 2 to about 12 C-atoms. As
examples, the following are to be mentioned:
[0087] ethylamine, n-propylamine, i-propylamine, n-propylamin,
sec.-propylamine, tert.-butylamine, 1-aminoisobutane, substituted
amines having 2 to about 20 C-atoms, such as
2-(N,N-dimethylamino)-1-aminoethane- , aminomercaptanes, such as
1-amino-2-mercaptoethane, diamines, aliphatic aminoalkohols having
2 to about 20, preferably 2 to about 12 C-atoms, such as
methanolamine, 1-amino-3,3-dimethylpentane-5-ol,
2-aminohexane-2',2"-diethanolamine,
1-Amino-2,5-dimethylcyclohexane-4-ol, 2-aminopropanol,
2-aminobutanol, 3-aminopropanol, 1-amino-2-propanol,
2-amino-2-methyl-1-propanol, 5-aminopentanol,
3-aminomethyl-3,5,5-trimeth- ylcyclohexanol,
1-amino-1-cyclopentane-methanol, 2-amino-2-ethyl-1,3-propa- ndiole,
aromatic-aliphatic or aromatic or aromatic-cycloaliphatic
aminoalcohols having 6 to about 20 C-atoms, wherein as the aromatic
structures heterocyclic ring systems or preferably isocyclic ring
systems such as naphthalene or particularly benzene derivatives,
such as 2-aminobenzylalcohol, 3-(hydroxymethyl)anilin,
2-amino-3-phenyl-1-propano- l, 2-amino-1-phenylethanol,
2-phenylglycinol or 2-amino-1-phenyl-1,3-propa- ndiole and mixtures
of two or more of such compounds.
[0088] The reaction according to step (3) may optionally be carried
out in the present of a catalyst. Compounds which are suitably used
as catalysts may in principle be all compounds which strongly
accelerate the reaction of isocyanates with compounds being
reactive towards isocyanates, wherein preferably a total content of
catalyst of from 0.001 to 15 wt.-%, particularly 0.05 to 6 wt.-%,
relative to the total weight of compounds being reactive towards
isocyanates is used. In the following, possibly used catalysts are
exemplarily mentioned:
[0089] Tertiary amines, such as triethylamine, tributylamine,
dimethylbenzylamine, dicyclohexylmethylamine,
dimethylcyclohexylamine, N,N,N',N'-tetramethyldiaminodiethylether,
bis(dimethylaminopropyl)urea, N-methyl- and N-ethylmorpholine,
N-cyclohexylmorpholine, N,N,N',N'-tetramethylethylenediamine,
N,N,N',N'-tetramethylbutanediamine,
N,N,N',N'-tetramethylhexanediamine-1,6,
pentamethyldiethylenetriamine, dimethylpiperazine,
N-dimethylaminoethylpiperidine,
1,8-diazabicyclo(5.4.0)undecen-7,1,2-dimethylimidazol,
1-azabicyclo-(2.2.0)octane, 1,4-diazabicyclo(2.2.2)octan (DABCO),
alkonolamine compounds, such as triethanolamine,
triisopropanolamine, N-methyl-and N-ethyl diethanolamine,
dimethylaminoethanol, 2-(N,N-dimethylaminoethoxy)ethanol,
N,N,N',N"-tris(dialkylaminoalkyl)hexa- hydrotriazines, such as
N,N',N"-tris(dimethylaminopropyl)-s-hexahydrotriaz- ine, preferably
triethylenediamine, pentamethylenediethylentriamin and/or
bis(dimethylamino)ether; metal salts, e.g. inorganic and/or organic
compounds of Fe, Pb, Zn and/or Sn, in common oxideation stages of
the metals, respectively, such as Fe(II)-chloride, Zn-chloride,
Pb-octoate and preferably Sn-compounds, such as Sn(II)-compounds,
particularly Sn-dioctoate, Sn-diethylhexlmaleate and/or
Sn(IV)-compounds, such as dialkyl-Sn-di(isooctylmercaptoacetate),
dialkyl-Sn-di(2-ethylhexylmaleate- ),
dialkyl-Sn-di(2-ethylhexylmercaptoacetate),
dialkyl-Sn-di(isooctylmerca- ptoacetate), dialkyl-Sn-dilaurate,
dialkyl-Sn-dimaleate, dialkyl-Sn-di(mercaptoacetate). Furthermore,
amidines, such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine,
tetraalkylammonium hydroxides, such as tetramethylammonium
hydroxide, alkali metal hydroxides, such as sodium hydroxide and
alkali metal alcoholates, such as sodium methylate and potasium
isopropylate and alkali metal salts of long chain fatty acids
having 10 to 20 C-atoms and optionally OH-groups as side groups,
may respectively be used as catalysts. The exemplarily mentioned
catalysts may be used alone or in mixtures of at leas two of the
mentioned catalysts.
[0090] Optionally, as adjuvants and/or additives common substances
may be used in the process according to the invention. To be
mentioned are e.g. surfactants, internal separating agents,
fillers, colorants, pigments, flame retardants, protecting agents
against hydrolysis, substances having fungi static and/or bacterial
static effects, UV-stabilizers and anti oxygens. Pigments and/or
colorants may be used in order to obtain toned or colored shaped
particles.
[0091] In general, the use of a solvent or thinning agent is
generally not required for the reaction according to step (3).
However, within a preferred embodiment of said reaction, a solvent
or a mixture of two or more solvents is used. Suitable solvents are
e.g. carbohydrates, particularly toluene, xylene or cyclohexane,
esters, particularly ethylglycolacetate, ethylacetate or
butyacetate, amides, particularly dimethylformamide or
N-methylpyrrolidone, sulfoxides, particularly dimethylsulfoxide,
ethers, particularly diisopropylether or methyl-tert.-butyl ether
or preferably cyclic ethers, particularly THF or dioxane.
[0092] Furthermore, the present invention also relates to a
polyurethane, obtainable by an integrated process, comprising at
least the following steps:
[0093] (4) Reacting at least one organic compound with at least one
alkoxylating agent via a process according to any of the preceding
claims, wherein a polyether alcohol is obtained;
[0094] (5) Reacting the polyether alcohol of step (2) with at least
one isocyanate.
[0095] The polyether alcohol, obtainable according to step (2),
which is used for preparing the polyurethane, comprises preferably
at least one mixed block of ethylene oxide-propylene oxide-units or
a terminal propylene oxide-block or a combination of both.
[0096] Furthermore, the present invention relates to a process for
preparing a polyurethane foam, starting from a polyurethane, as
defined within the present invention, that process comprising at
least the following step:
[0097] (4) foaming the polyurethane as used as a starting
material.
[0098] The present invention also encompasses the polyurethane foam
as such, obtainable by foaming a polyurethane, as obtained by the
reaction according to step (3).
[0099] The polyurethanes according to the present invention are
predominantly characterized by their low content of impurities,
such as C6-compounds. This renders the polyurethanes according to
the invention particularly suitable for the preparation of
polyurethane foams, polyurethane cast skins and elastomers.
[0100] Among the polyurethane foams preferably polyurethane foams
are prepared, which are used in the automotive and furniture
industry, such as semi-rigid foams, hard and soft integral foams or
RIM (reaction injection moulding)-materials.
[0101] Processes for the preparation of polyurethane foams are
described in Becker, Braun, "Polyurethanes", Kunststoffhandbuch,
vol. 7, Carl Hanser, Munich, 3.sup.rd edition, 1993, p. 193 to
265.
[0102] In a preferred embodiment, the present invention relates to
a polyurethane, which is derived from a polyether alcohol,
obtainable according to step (2), which comprises at least one
mixed block of ethylene oxide-propylene oxide-units.
[0103] The present invention also relates to a polyurethane,
derived from a polyether alcohol, obtainable according to step (2),
which comprises a terminal propylene oxide block.
[0104] The polyurethane according to the present invention,
particularly the above-mentioned polyurethane, may suitably be used
for preparing shaped bodies, particularly shaped bodies made of
soft slab-stock foams on the basis of polyurethane. Particularly
advantageous in this respect is the low amount of impurities, which
results in that no disturbing smells evolve from the shaped body
made of the soft foam.
[0105] In addition thereto, the narrower molecular weight
distribution due to the lower amount of mono-functional side
compounds leads to an improved processing during foaming.
[0106] Thus, the present invention also relates to a shaped body
comprising a polyurethane or a polyurethane foam, respectively
obtainable by the integrated process of the invention.
[0107] Shaped bodies according to the invention are e.g.
mattresses, pillows, shaped bodies for the automotive industry and
upholstery furniture.
[0108] The following shaped bodies according to the invention are
to be mentioned:
[0109] soft foams, particularly mattresses, shaped bodies for the
inner section of cars, such as car seats, sound absorbent shaped
bodies, such as e.g. carpets and/or upholstery materials, sponges,
cushions, pillows, seating furniture, office furniture,
particularly seats, back-rests, orthopedic products;
[0110] thermoplastic polyurethanes, particularly for the use of
cables, hoses, animal marks, supports for rails, films, shoe soles
and accessories, ski tips and rolled bandages;
[0111] cold casted elastomers, particularly for sheathing of
lifting and carrying belts, impact protection elements, industrial
edge protectors, toothed belts, screens for abrasive bulk
materials, blades, rolls, coatings for rolls, soil protecting
sheets against heavy building machines, parts of housings,
housings, coatings for deburring drums, pump elements and pump
housings, coatings for the outer parts of tubes, coatings for the
inner walls of containers, mattresses for cars, cyclones, pulleys
for heavy loads, sheave pulleys, guide pulleys, block pulleys,
coatings for conveyer belts, coatings for channels, said coatings
being resistant against hydrolysis and abrasion, coatings for truck
loading areas, impact protectors, clutch parts, coatings for bojen
(buoys), inline-skate rolls, special rolls, high impact pump
elements;
[0112] soft integral foams, particularly steering wheels, seals for
air filters, steering knob, foaming of wires, casings for
containers, arm-rests, shoe soles made of polyurethane;
[0113] polyurethane coatings, particularly for floor coverings,
refining of materials, such as wood, leather or metal sheets;
[0114] polyurethane skins, particularly for the use as inserts for
shaped bodies, such as dashboards, coverings for car doors, truck
and car seats, floorings;
[0115] rigid polyurethane foams, particularly for the use as
damping material or construction material;
[0116] integral foams, particularly for the use as elements in the
inner and outer areas of constructions, complex furnitures,
elements for car interiors, skis and snow boards as well as
technical functioning parts;
[0117] RIM-foams, particularly for producing prefabricated units
for use in the exterior parts in automotive industry, such as
extensive facings, fenders and bumpers;
[0118] Thermoformed foams, particularly for preparing ultra-light
composite structures for the use in car manufacture, e.g. as an
element for roof covers;
[0119] semi-rigid foams, particularly for underfoaming of films,
skins or leather or fiber reinforced construction elements.
[0120] The invention is now further described by way of the
following examples, which are, however, not meant to limit the
scope of the present application.
EXAMPLES
[0121] FIG. 1 shows a X-ray powder diffractogramm of the MOF-5
catalyst as prepared according to Example 1;
[0122] FIG. 2 shows the sorptionisotherme of said catalyst.
Example 1
Preparation of MOF-5
[0123]
1 Starting Molar Material Amount Calculated Experimental
terephthalic acid 12.3 mmol 2.04 g 2.04 g zinc nitrate-tetra 36.98
mmol 9.67 g 9.68 g hydrate diethylformamide 2568.8 mmol 282.2 g
282.2 g (Merck)
[0124] The above-mentioned amounts of the starting materials were
dissolved in a beaker in the order diethylformamide, terephthalic
acid and zinc nitride. The resulting solution was introduced into
two autoclaves (250 ml), having respectively inner walls which were
covered by teflon.
[0125] The crystallization occurred at 105.degree. C. within twenty
hours. Subsequently, the orange solvent was decanted from the
yellow crystals, said crystals were again covered by 20 ml
dimethylformamide, the latter being again decanted. This procedure
was repeated three times. Subsequently, 20 ml chloroform were
poured onto the solid, which was washed and decanted by said
solvent two times.
[0126] The crystals (14.4 g), which were still moist, were
introduced into a vacuum device and first at room temperature in
vacuo (10.sup.-4 mbar), afterwards dried at 120.degree. C.
[0127] Subsequently, the resulting product was characterized by
X-ray powder diffraction and an adsorptive determination of
micropores. The resulting product shows the X-ray diffractogramm
according to FIG. 1, which coincides with MOF-5.
[0128] The determination of the sorptionsisotherme, as depicted in
FIG. 2, with argon (87K; Micromeritics ASAP 2010) shows an
isotherme of type I, being typical for microporous materials, and
having a specific surface area of 3020 m.sup.2/g, calculated
according to Langmuir, and a micropore volume of 0.97 ml/g (at a
relative pressure pp.sup.0=0,4).
Example 2
Alkoxylation of Dipropylene Glycol with Propylene Oxide
[0129] Dipropylene glycol (33.5 g corresponding to 0.25 mol) and
0.75 g of the catalyst prepared according to Example 1 were
introduced in an autoclave. Subsequently, the autoclave was filled
with 116 g propylene oxide (2 mol). The reaction was carried out at
135.degree. C. and a maximum pressure of 12.1 bar, and in total
2.44 mol propylene oxide/mol starting material were reacted to
obtain a polyol.
Example 3
Alkoxylation of Methyl Dipropylene Glycol with Ethylene Oxide
[0130] Methyl dipropylene glycol (30 g corresponding to 0.25 mol)
and 0.59 g of the catalyst as prepared according to Example 1 were
introduced in an autoclave. The autoclave was then filled with 88 g
ethylene oxide (2 mol). The reaction was carried out at 135.degree.
C. and a maximum pressure of 21.2 bar. In total, 2.45 mol ethylene
oxide/mol starting compound were reacted to obtain a polyol.
Example 4
Alkoxylation of Acrylic Acid with Ethylene Oxide
[0131] 33.2 g acrylic acid (stabilized with
2,2',6,6'-tetramethyl-4-hydrox- ypiperidine-N-oxide and
phenothiazine) and 0.5 g catalyst of Example 1 were weighed into a
300 ml steering autoclave under nitrogen atmosphere. The autoclave
was closed and pressurized with 10 bar nitrogen. Upon steering 20 g
ethylene oxide were subsequently introduced via a screw press.
After five hours at 50.degree. C. the catalyst was filtered off and
the raw product was analyzed by gas chromatography. Based on the
area percentages the following composition of the solution
(residual ethylene oxide not considered):
[0132] Acrylic acid 76%, monoethylene glycol acrylate 10%,
diethylene glycol acrylate 9%, other side products 5%.
* * * * *