# Patent

## Title
Process for the alkoxylation of monools in the presence of metallo-organic framework materials

## Abstract

The present invention relates to a process for the alkoxylation of a monool with at least one alkoxylating agent to an alkoxylated alcohol wherein a catalyst is employed which comprises a metallo-organic framework material of metal ions and at least bidentate coordinately bound organic ligands.

## Background
The present application is a continuation application of U.S. Ser. No. 10/611,863, filed on Jul. 3, 2003, which is abandoned.


The present invention relates to a process for the alkoxylation of monools in the presence of catalyst systems comprising a porous metallo-organic framework material of metal ions and a coordinately bound organic ligand which is at least bidentate. The invention further encompasses the use of polyoxyalkylene alcohols obtained in the process according to the present invention as tensides and flotation oils.
Polyoxyalkylene alcohols can 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 thereof which are selected according to the alcohol to be prepared. The drawback of the known preparation methods is that several elaborate purifying steps are necessary in order to separate the catalyst residue from the reaction product. Furthermore, the processes known in the art result in a mixture of various alkoxylation products, ranging from mono- to polyalkoxylated alcohols.
One object of the invention is to provide a process for the preparation of polyoxyalkylene alcohols from monools which does not show the drawbacks of the processes known in the art. In particular, the thus-obtained polyoxyalkylene alcohols should have a low impurity content, without requiring elaborate purifying steps of the starting materials and/or intermediate products. The process should furthermore not require elaborate purification steps in order to separate the catalyst from the reaction product(s). In particular, the process should give defined alkoxylation products with a defined alkoxylation range.
These objects are solved by a process for the alkoxylation of a monool with at least one alkoxylating agent to a polyoxyalkylene alcohol wherein a catalyst is employed which comprises a metallo-organic framework material of metal ions and at least bidentate coordinately bound organic ligands.
The present invention is drawn towards the alkoxylation of monools which are reacted with an alkoxylating agent, in general an alkylene oxide. Examples for monools which lend themselves for an alkoxylation according to the present invention are known to the person skilled in the art. Examples include monools of linear and branched alkyl groups having 1 to 30, preferably 1 to 20, in particular 1 to 15 carbon atoms, which alkyl groups may carry one or more aryl substituents, of homo- and polynuclear aromatic groups having 4 to 30, preferably 4 to 20, in particular 1 to 10 carbon atoms, which aromatic groups may carry one or more alkyl substituents, and of linear and branched alkenyl groups having 2 to 30, preferably 2 to 20, in particular 2 to 15 carbon atoms and which alkenyl groups may carry one or more aryl substituents. The alkyl, alkenyl and aryl groups may contain one or more hetero atoms in their carbon skeleton, and all said groups may carry one or more substituents other than those named. Examples for hetero atoms include N, O and S. Examples for substituents include halides and pseudohalides. Preferred alcohols should be liquid at room temperature.
Examples for preferred alcohols include Propylheptanol, Tridecanol H und Tridecanol N.
The alkoxylating agent is in general selected from epoxides having two to 30 carbon atoms and mixtures of two or more thereof. Preferably a linear or branched, cyclic or non-cyclic alkylene oxide having two to 24 C-atoms optionally carrying one or more substituents from the group consisting of aromatic groups, halides, hydroxyl groups, silyl groups, non-cyclic ether and ammonium groups is employed.
For the preferred group of alkylene oxides, the following are cited by way of example: ethylene oxide, 1,2-epoxypropane, 1,2-epoxy-2-methylpropane, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxy-3-methylbutane, 1,2-epoxypentane, 1,2-epoxy-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-epoxide, 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, styrene oxide, vinyl oxirane, aliphatic 1,2-alkylene oxides having 5 to 24 C-atoms, cyclopentane oxide, cyclohexane oxide, cyclododecatriane-(1,5,9)-monoxide and mixtures of two or more of the compounds cited.
Particularly preferred in the context of the present invention are ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxy-2-methylpropane, styrene oxide, vinyloxirane and any mixtures of two or more of the compounds cited. The most preferred epoxides are ethylene oxide, propylene oxide and mixtures of ethylene oxide with propylene oxide.
The process of preparing an epoxide by epoxidation is hereinafter described in detail by way of example, referring to propylene oxide.
Propylene oxide can 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.
It is particularly suitable to use hydrogen peroxide for the epoxidation.
The epoxidation 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, the content of which fully encompassed in the present application.
The alkoxylating agent obtained in the epoxidation step may be directly used without further treatment. It is, however, also possible within the present invention that the alkoxylating agent is treated beforehand, 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.
According to the present invention the alkoxylation reaction is carried out in the presence of a catalyst system which comprises a so called metallo-organic framework material.
Metal-organic framwork materials are known as such. They are described in, for example, U.S. Pat. No. 5,648,508, EP-A-0 709 253, M. O'Keeffe et al., J. Sol. State Chm., 152 (2000) p. 3–20, H. Li et al., Nature 402 (1999) p. 276 seq., M. Eddaoudi et al., Topics in Catalysis 9 (1999) p. 105–111, B. Chen. Et al., Science 291 (2001) p. 1021–23. An inexpensive way for the preparation of said materials is disclosed in DE 101 11 230.0. The preparation of isoreticular MoF's is disclosed in WO 02/088148. The content of the above-mentioned publications and applications to which reference is made herein, is fully incorporated in present application.
The metal-organic framework materials, as used in the present invention, comprise pores, particularly micro- and/or mesopores. Micropores are defined as pores having a diameter of 2 nm or below and mesopores as being pores having a diameter in the range of above 2 nm to 50 nm, respectively, according to the definition given in Pure Applied Chem. 45, p. 71 seq., particularly on p. 79 (1976). The presence of the micro- and/or mesopores can be monitored by sorption measurements for determining the capacity of the metal-organic framework materials to take up nitrogen at 77 K according to DIN 66131 and/or DIN 66134. The specific surface areas cited in the context of the present invention are always determined according to DIN 66131 and/or DIN 66134.
For example, a type-1-form of the isothermal curve indicates the presence of micropores [see, for example, paragraph 4 of M. Eddaoudi et al., Topics in Catalysis 9 (1999)]. In a preferred embodiment, the specific surface area, as calculated according to the Langmuir model (DIN 66131, 66134) preferably is above 5 m2/g, further preferred above 10 m2/g, more preferably above 50 m2/g, particularly preferred above 500 m2/g and may increase to values of 3000 m2/g.
The metal ions forming the metal-organic framework material employed according to the present invention are preferably selected from the groups Ia, IIIa, IIIa, IVa to VIIIa and Ib to VIb of the periodic system of the elements. Among these metals, particular reference is made to 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. With respect to the metal ions of the aforementioned elements, particular reference is made to: Mg2+, Ca2+, Sr2+, Ba2+, Sc3+, Y3+, Ti4+, Zr4+, Hf4+, V4+, V3+, V2+, Nb3+, Ta3+, Cr3+, Mo3+, W3+, Mn3+, Mn3+, Mn2+, Re3+, Re2+, Fe3+, Fe2+, Ru3+, Ru2+, Os3+, OS2+, Co3+, Co2+, Rh2+, Rh+, Ir2+, Ir+, Ni2+, Ni+, Pd2+, Pd+, Pt2+, Pt+, Cu2+, Cu+, Ag+, Au+, Zn2+, Cd2+, Hg2+, Al3+, Ga3+, In3+, Tl3+, Si4+, Si2+, Ge4+, Ge2+, Sn4+, Sn2+, Pb4+, Pb2+, As5+, As3+, As+, Sb5+, Sb3+, Sb+, Bi5+, Bi3+ and Bi+.
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.
In addition to the metal salts disclosed in EP-A 0 790 253 and U.S. Pat. No. 5,648,508, other metallic compounds can be used, such as sulfates, phosphates and other compolex counter-ion metal salts of the main- and subgroup metals of the periodic system of the elements. Metal oxides, mixed oxides and mixutres of metal oxides and/or mixed oxides with or without a defined stoichiometry are preferred. All of the above mentioned metal compounds can be soluble or insoluble and they may be used as starting material either in form of a powder or as a shaped body or as any combination thereof.
The at least bidentate organic ligands present in the metall-organic framework material are capable of coordinating to the metal ion. Such ligands are known to the person skilled in the art. The at least bidentate organic ligand, is preferably selected from:

    i) alkyl groups having from 1 to 10 carbon atoms,
    ii) aryl groups having from 1 to 5 phenyl rings,
    iii) alkyl and aryl amines carrying one or more alkyl groups having from 1 to 10 carbon atoms and/or one or more aryl groups having from 1 to 5 phenyl rings,

which are covalently substituted by at least one functional group X which can coordinately bind to the metal ion and which is selected from the group consisting of

    CO2H, CS2H, NO2, SO3H, Si(OH)3, Ge(OH)3, Sn(OH)3, Si(SH)4, Ge(SH)4, Sn(SH)3, PO3H, AsO3H, AsO4H, P(SH)3, As(SH)3, CH(RSH)2, C(RSH)3, CH(RNH2)2, C(RNH2)3, CH(ROH)2, C(ROH)3, CH(RCN)2, C(RCN)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)2, C(SH)3, CH(NH2)2, C(NH2)2, CH(OH)2, C(OH)3, CH(CN)2 and C(CN)3. WO 02/088148 discloses bidentate organic ligand from the group of aromatic compounds which can carry one or more substituents. The content of WO 02/088148, pages 8–14 is herein fully incorporated by reference.


Particularly to be mentioned are substituted and unsubstituted aliphatic α, ω-dicarboxylic acids, substituted or unsubstituted, mono- or polynuclear aromatic di-, tri- and tetracarboxylic acids and substituted or unsubstituted, aromatic di-, tri- and tetracarboxylic acids, having one or more nuclei, and carying at least one hetero atom
Preferred ligands are selected from 1,3,5-benzene tricarboxylic acid (BCT), NDC (naphthalene dicarboxylate), BDC (benzene dicarboxylate), BTC (benzene tricarboxylate), BTB (benzene tribenzoate), and DHBC (2,5-dihydroxyterephtalic acid).
DHBC is the most preferred ligand. Besides the at least bidentate organic ligand, the framework material as used in accordance with the present invention may also comprise one or more monodentate ligands, which are preferably selected from the following monodentate substances and/or derivatives thereof:

    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);
    b. aryl amines and their corresponding aryl ammonium salts having from 1 to 5 phenyl rings;
    c. alkyl phosphonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;
    d. aryl phosphonium salts, having from 1 to 5 phenyl rings;
    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;
    f. aryl organic acids and their corresponding aryl organic anions and salts, having from 1 to 5 phenyl rings;
    g. aliphatic alcohols, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;
    h. aryl alcohols having from 1 to 5 phenyl rings;
    i. inorganic anions from the group consisting of:
    
        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,
    
    
    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.


Further details regarding the at least bidentate organic ligand and the mono-dentate 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.
Within the present application, framework materials of the kind described herein, which comprise Zn2+ as a metal ion and ligands derived from terephthalic acid as the bidentate ligand, are particularly preferred.
Further metal ions, at least bidentate and monodentats organic ligands which are 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.
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-methylpyrrolidone, 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 can be recycled after crystallization.
The pore sizes of the metal-organic framework can be adjusted by selecting suitable bidendate ligands (=linkers). Generally, the larger the linker, the larger the pore size. Any pore size that is still supported by a the metal-organic framework in the absence of a host and at temperatures of at least 200° C. is conceivable. Pore sizes ranging from 0,2 nm to 30 nm are preferred, with pore sizes ranging from 0,3 nm to 3 nm being particularly preferred.
In the following, examples of metal-organic framework materials (MOFs) are given to illustrate the general concept given above. These specific examples, however, are not intended to limit the scope of the present invention.
By way of example, a list of metal-organic framework materials already synthesized and characterized is given below. This also includes novel isoreticular metal organic framework materials (IR-MOFs), which may be used in the context of the present application. Such materials having the same framework topology while displaying different pore sizes and crystal densities are described, for example in M. Eddouadi et al., Science 295 (2002) 469, whose respective content is incorporated into the present application by reference.
The solvents used are of particular importance for the synthesis of these materials and are therefore mentioned in the table. The values for the cell parameters (angles Δ, E and θ as well as the spacings a, b and c, given in Angstrom) have been obtained by x-ray diffraction and represent the space group given in the table as well.




















Ingredients











molar ratios







Space


MOF-n
M + L
Solvents
α
β
γ
a
b
c
Group
























MOF-0
Zn(NO3)2.6H2O
Ethanol
90
90
120
16.711
16.711
14.189
P6(3)/



H3(BTC)







Mcm


MOF-2
Zn(NO3)2.6H2O
DMF
90
102.8
90
6.718
15.49
12.43
P2(1)/n



(0.246 mmol)
Toluene



H2(BDC)



0.241 mmol)


MOF-3
Zn(NO3)2.6H2O
DMF
99.72
111.11
108.4
9.726
9.911
10.45
P-1



(1.89 mmol)
MeOH



H2(BDC)



(1.93 mmol)


MOF-4
Zn(NO3)2.6H2O
Ethanol
90
90
90
14.728
14.728
14.728
P2(1)3



(1.00 mmol)



H3(BTC)



(0.5 mmol)


MOF-5
Zn(NO3)2.6H2O
DMF
90
90
90
25.669
25.669
25.669
Fm-3m



(2.22 mmol)
Chlorobenzene



H2(BDC)



(2.17 mmol)


MOF-38
Zn(NO3)2.6H2O
DMF
90
90
90
20.657
20.657
17.84
I4cm



(0.27 mmol)
Chlorobenzene



H3(BTC)



(0.15 mmol)


MOF-31
Zn(NO3)2.6H2O
Ethanol
90
90
90
10.821
10.821
10.821
Pn(−3)m


Zn(ADC)2
0.4 mmol



H2(ADC)



0.8 mmol


MOF-12
Zn(NO3)2.6H2O
Ethanol
90
90
90
15.745
16.907
18.167
Pbca


Zn2(ATC)
0.3 mmol



H4(ATC)



0.15 mmol


MOF-20
Zn(NO3)2.6H2O
DMF
90
92.13
90
8.13
16.444
12.807
P2(1)/c


ZnNDC
0.37 mmol
Chlorobenzene



H2NDC



0.36 mmol


MOF-37
Zn(NO3)2.6H2O
DEF
72.38
83.16
84.33
9.952
11.576
15.556
P-1



0.2 mmol
Chlorobenzene



H2NDC



0.2 mmol


MOF-8
Tb(NO3)3.5H2O
DMSO
90
115.7
90
19.83
9.822
19.183
C2/c


Tb2 (ADC)
0.10 mmol
MeOH



H2ADC



0.20 mmol


MOF-9
Tb(NO3)3.5H2O
DMSO
90
102.09
90
27.056
16.795
28.139
C2/c


Tb2 (ADC)
0.08 mmol



H2ADB



0.12 mmol


MOF-6
Tb(NO3)3.5H2O
DMF
90
91.28
90
17.599
19.996
10.545
P21/c



0.30 mmol
MeOH



H2 (BDC)



0.30 mmol


MOF-7
Tb(NO3)3.5H2O
H2O
102.3
91.12
101.5
6.142
10.069
10.096
P-1



0.15 mmol



H2(BDC)



0.15 mmol


MOF-69A
Zn(NO3)2.6H2O
DEF
90
111.6
90
23.12
20.92
12
C2/c



0.083 mmol
H2O2



4,4′BPDC
MeNH2



0.041 mmol


MOF-69B
Zn(NO3)2.6H2O
DEF
90
95.3
90
20.17
18.55
12.16
C2/c



0.083 mmol
H2O2



2,6-NCD
MeNH2



0.041 mmol


MOF-11
Cu(NO3)2.2.5H2O
H2O
90
93.86
90
12.987
11.22
11.336
C2/c


Cu2(ATC)
0.47 mmol



H2ATC



0.22 mmol


MOF-11


90
90
90
8.4671
8.4671
14.44
P42/


Cu2(ATC)








mmc


dehydr.


MOF-14
Cu(NO3)2.2.5H2O
H2O
90
90
90
26.946
26.946
26.946
Im-3


Cu3 (BTB)
0.28 mmol
DMF



H3BTB
EtOH



0.052 mmol


MOF-32
Cd(NO3)2.4H2O
H2O
90
90
90
13.468
13.468
13.468
P(−4)3m


Cd(ATC)
0.24 mmol
NaOH



H4ATC



0.10 mmol


MOF-33
ZnCl2
H2O
90
90
90
19.561
15.255
23.404
Imma


Zn2 (ATB)
0.15 mmol
DMF



H4ATB
EtOH



0.02 mmol


MOF-34
Ni(NO3)2.6H2O
H2O
90
90
90
10.066
11.163
19.201
P212121


Ni(ATC)
0.24 mmol
NaOH



H4ATC



0.10 mmol


MOF-36
Zn(NO3)2.4H2O
H2O
90
90
90
15.745
16.907
18.167
Pbca


Zn2 (MTB)
0.20 mmol
DMF



H4MTB



0.04 mmol


MOF-39
Zn(NO3)2 4H2O
H2O
90
90
90
17.158
21.591
25.308
Pnma


Zn3O(HBTB)
0.27 mmol
DMF



H3BTB
EtOH



0.07 mmol


NO305
FeCl2.4H2O
DMF
90
90
120
8.2692
8.2692
63.566
R-3c



5.03 mmol



formic acid



86.90 mmol


NO306A
FeCl2.4H2O
DEF
90
90
90
9.9364
18.374
18.374
Pbcn



5.03 mmol



formic acid



86.90 mmol


NO29
Mn(Ac)2.4H2O
DMF
120
90
90
14.16
33.521
33.521
P-1


MOF-0 like
0.46 mmol



H3BTC



0.69 mmol


BPR48
Zn(NO3)2 6H2O
DMSO
90
90
90
14.5
17.04
18.02
Pbca


A2
0.012 mmol
Toluene



H2BDC



0.012 mmol


BPR69
Cd(NO3)2 4H2O
DMSO
90
98.76
90
14.16
15.72
17.66
Cc


B1
0.0212 mmol



H2BDC



0.0428 mmol


BPR92
Co(NO3)2.6H2O
NMP
106.3
107.63
107.2
7.5308
10.942
11.025
P1


A2
0.018 mmol



H2BDC



0.018 mmol


BPR95
Cd(NO3)2 4H2O
NMP
90
112.8
90
14.460
11.085
15.829
P2(1)/n


C5
0.012 mmol



H2BDC



0.36 mmol


CuC6H4O6
Cu(NO3)2.2.5H2O
DMF
90
105.29
90
15.259
14.816
14.13
P2(1)/c



0.370 mmol
Chlorobenzene



H2BDC(OH)2



0.37 mmol











M(BTC)
Co(SO4) H2O
DMF
Same as MOF-0



MOF-0like
0.055 mmol



H3BTC



0.037 mmol
















Tb(C6H4O6)
Tb(NO3)3.5H2O
DMF
104.6
107.9
97.147
10.491
10.981
12.541
P-1



0.370 mmol
chlorobenzene



H2(C6H4O6)



0.56 mmol


Zn(C2O4)
ZnCl2
DMF
90
120
90
9.4168
9.4168
8.464
P(−3)1m



0.370 mmol
chlorobenzene



oxalic acid



0.37 mmol


Co(CHO)
Co(NO3)2.5H2O
DMF
90
91.32
90
11.328
10.049
14.854
P2(1)/n



0.043 mmol



formic acid



1.60 mmol


Cd(CHO)
Cd(NO3)2.4H2O
DMF
90
120
90
8.5168
8.5168
22.674
R-3c



0.185 mmol



formic acid



0.185 mmol


Cu(C3H2O4)
Cu(NO3)2.2.5H2O
DMF
90
90
90
8.366
8.366
11.919
P43



0.043 mmol



malonic acid



0.192 mmol


Zn6(NDC)5
Zn(NO3)2.6H2O
DMF
90
95.902
90
19.504
16.482
14.64
C2/m


MOF-48
0.097 mmol
chlorobenzene



14 NDC
H2O2



0.069 mmol


MOF-47
Zn(NO3)2 6H2O
DMF
90
92.55
90
11.303
16.029
17.535
P2(1)/c



0.185 mmol
Chlorobenzene



H2(BDC[CH3]4)
H2O2



0.185 mmol


MO25
Cu(NO3)2.2.5H2O
DMF
90
112.0
90
23.880
16.834
18.389
P2(1)/c



0.084 mmol



BPhDC



0.085 mmol


Cu-Thio
Cu(NO3)2.2.5H2O
DEF
90
113.6
90
15.4747
14.514
14.032
P2(1)/c



0.084 mmol



thiophene



dicarboxylic



0.085 mmol


CIBDC1
Cu(NO3)2.2.5H2O0.084 mmol
DMF
90
105.6
90
14.911
15.622
18.413
C2/c



H2(BDCCl2)



0.085 mmol


MOF-101
Cu(NO3)2.2.5H2O
DMF
90
90
90
21.607
20.607
20.073
Fm3m



0.084 mmol



BrBDC



0.085 mmol


Zn3(BTC)2
ZnCl2
DMF
90
90
90
26.572
26.572
26.572
Fm-3m



0.033 mmol
EtOH



H3BTC
Base



0.033 mmol
Added


MOF-j
Co(CH3CO2)2.4H2O
H2O
90
112.0
90
17.482
12.963
6.559
C2



(1.65 mmol)



H3(BZC)



(0.95 mmol)


MOF-n
Zn(NO3)2.6H2O
ethanol
90
90
120
16.711
16.711
14.189
P6(3)/mcm



H3(BTC)


PbBDC
Pb(NO3)2
DMF
90
102.7
90
8.3639
17.991
9.9617
P2(1)/n



(0.181 mmol)
Ethanol



H2(BDC)



(0.181 mmol)


Znhex
Zn(NO3)2.6H2O
DMF
90
90
120
37.1165
37.117
30.019
P3(1)c



(0.171 mmol)
p-xylene



H3BTB
ethanol



(0.114 mmol)


AS16
FeBr2
DMF
90
90.13
90
7.2595
8.7894
19.484
P2(1)c



0.927 mmol
anhydr.



H2(BDC)



0.927 mmol


AS27-2
FeBr2
DMF
90
90
90
26.735
26.735
26.735
Fm3m



0.927 mmol
anhydr.



H3(BDC)



0.464 mmol


AS32
FeCl3
DMF anhydr.
90
90
120
12.535
12.535
18.479
P6(2)c



1.23 mmol
Ethanol



H2(BDC)



1.23 mmol


AS54-3
FeBr2
DMF anhydr.
90
109.98
90
12.019
15.286
14.399
C2



0.927
n-propanol



BPDC



0.927 mmol


AS61-4
FeBr2
Pyridine anhydr.
90
90
120
13.017
13.017
14.896
P6(2)c



0.927 mmol



m-BDC



0.927 mmol


AS68-7
FeBr2
DMF anhydr.
90
90
90
18.3407
10.036
18.039
Pca21



0.927 mmol
Pyridine



m-BDC



1.204 mmol


Zn(ADC)
Zn(NO3)2.6H2O
DMF
90
99.85
90
16.764
9.349
9.635
C2/c



0.37 mmol
Chlorobenzene



H2(ADC)



0.36 mmol


MOF-12
Zn(NO3)2.6H2O
Ethanol
90
90
90
15.745
16.907
18.167
Pbca


Zn2(ATC)
0.30 mmol



H4(ATC)



0.15 mmol


MOF-20
Zn(NO3)2.6H2O
DMF
90
92.13
90
8.13
16.444
12.807
P2(1)/c


ZnNDC
0.37 mmol
Chlorobenzene



H2NDC



0.36 mmol


MOF-37
Zn(NO3)2.6H2O
DEF
72.38
83.16
84.33
9.952
11.576
15.556
P-1



0.20 mmol
Chlorobenzene



H2NDC



0.20 mmol


Zn(NDC)
Zn(NO3)2.6H2O
DMSO
68.08
75.33
88.31
8.631
10.207
13.114
P-1


(DMSO)
H2NDC


Zn(NDC)
Zn(NO3)2.6H2O

90
99.2
90
19.289
17.628
15.052
C2/c



H2NDC


Zn(HPDC)
Zn(NO3)2.4H2O
DMF
107.9
105.06
94.4
8.326
12.085
13.767
P-1



0.23 mmol
H2O



H2(HPDC)



0.05 mmol


Co(HPDC)
Co(NO3)2.6H2O
DMF
90
97.69
90
29.677
9.63
7.981
C2/c



0.21 mmol
H2O/ethanol



H2 (HPDC)



0.06 mmol


Zn3(PDC)2.5
Zn(NO3)2.4H2O
DMF/CIBz
79.34
80.8
85.83
8.564
14.046
26.428
P-1



0.17 mmol
H20/TEA



H2(HPDC)



0.05 mmol


Cd2 (TPDC)2
Cd(NO3)2.4H2O
Methanol/CHP
70.59
72.75
87.14
10.102
14.412
14.964
P-1



0.06 mmol
H2O



H2(HPDC)



0.06 mmol


Tb(PDC)1.5
Tb(NO3)3.5H2O
DMF
109.8
103.61
100.14
9.829
12.11
14.628
P-1



0.21 mmol
H2O/ethanol



H2(PDC)



0.034 mmol


ZnDBP
Zn(NO3)2.6H2O
MeOH
90
93.67
90
9.254
10.762
27.93
P2/n



0.05 mmol



dibenzylphosphate



0.10 mmol


Zn3(BPDC)
ZnBr2
DMF
90
102.76
90
11.49
14.79
19.18
P21/n



0.021 mmol



4,4′BPDC



0.005 mmol


CdBDC
Cd(NO3)2.4H2O
DMF
90
95.85
90
11.2
11.11
16.71
P21/n



0.100 mmol
Na2SiO3 (aq)



H2(BDC)



0.401 mmol


Cd-mBDC
Cd(NO3)2.4H2O
DMF
90
101.1
90
13.69
18.25
14.91
C2/c



0.009 mmol
MeNH2



H2(mBDC)



0.018 mmol


Zn4OBNDC
Zn(NO3)2.6H2O
DEF
90
90
90
22.35
26.05
59.56
Fmmm



0.041 mmol
MeNH2



BNDC
H2O2


Eu(TCA)
Eu(NO3)3.6H2O
DMF
90
90
90
23.325
23.325
23.325
Pm-3n



0.14 mmol
Chlorobenzene



TCA



0.026 mmol


Tb(TCA)
Tb(NO3)3.6H2O
DMF
90
90
90
23.272
23.272
23.372
Pm-3n



0.069 mmol
Chlorobenzene



TCA



0.026 mmol


Formate
Ce(NO3)3.6H2O
H2O
90
90
120
10.668
10.667
4.107
R-3m



0.138 mmol
Ethanol



Formaic acid



0.43 mmol



FeCl2.4H2O
DMF
90
90
120
8.2692
8.2692
63.566
R-3c



5.03 mmol



Formic acid



86.90 mmol



FeCl2.4H2O
DEF
90
90
90
9.9364
18.374
18.374
Pbcn



5.03 mmol



Formic acid



86.90 mmol



FeCl2.4H2O
DEF
90
90
90
8.335
8.335
13.34
P-31c



5.03 mmol



Formic acid



86.90 mmol


NO330
FeCl2.4H2O
formamide
90
90
90
8.7749
11.655
8.3297
Pnna



0.50 mmol



Formic acid



8.69 mmol


NO332
FeCl2.4H2O
DIP
90
90
90
10.0313
18.808
18.355
Pbcn



0.50 mmol



Formic acid



8.69 mmol


NO333
FeCl2.4H2O
DBF
90
90
90
45.2754
23.861
12.441
Cmcm



0.50 mmol



Formic acid



8.69 mmol


NO335
FeCl2.4H2O
CHF
90
91.372
90
11.5964
10.187
14.945
P21/n



0.50 mmol



Formic acid



8.69 mmol


NO336
FeCl2.4H2O
MFA
90
90
90
11.7945
48.843
8.4136
Pbcm



0.50 mmol



Formic acid



8.69 mmol


NO13
Mn(Ac)2.4H2O
Ethanol
90
90
90
18.66
11.762
9.418
Pbcn



0.46 mmol



Bezoic acid



0.92 mmol



Bipyridine



0.46 mmol


NO29
Mn(Ac)2.4H2O
DMF
120
90
90
14.16
33.521
33.521
P-1


MOF-0 Like
0.46 mmol



H3BTC



0.69 mmol


Mn(hfac)2
Mn(Ac)2.4H2O
Ether
90
95.32
90
9.572
17.162
14.041
C2/c


(O2CC6H5)
0.46 mmol



Hfac



0.92 mmol



Bipyridine



0.46 mmol


BPR43G2
Zn(NO3)2.6H2O
DMF
90
91.37
90
17.96
6.38
7.19
C2/c



0.0288 mmol
CH3CN



H2BDC



0.0072 mmol


BPR48A2
Zn(NO3)2 6H2O
DMSO
90
90
90
14.5
17.04
18.02
Pbca



0.012 mmol
Toluene



H2BDC



0.012 mmol


BPR49B1
Zn(NO3)2 6H2O
DMSO
90
91.172
90
33.181
9.824
17.884
C2/c



0.024 mmol
Methanol



H2BDC



0.048 mmol


BPR56E1
Zn(NO3)2 6H2O
DMSO
90
90.096
90
14.5873
14.153
17.183
P2(1)/n



0.012 mmol
n-propanol



H2BDC



0.024 mmol


BPR68D10
Zn(NO3)2 6H2O
DMSO
90
95.316
90
10.0627
10.17
16.413
P2(1)/c



0.0016 mmol
Benzene



H3BTC



0.0064 mmol


BPR69B1
Cd(NO3)2 4H2O
DMSO
90
98.76
90
14.16
15.72
17.66
Cc



0.0212 mmol



H2BDC



0.0428 mmol


BPR73E4
Cd(NO3)2 4H2O
DMSO
90
92.324
90
8.7231
7.0568
18.438
P2(1)/n



0.006 mmol
Toluene



H2BDC



0.003 mmol


BPR76D5
Zn(NO3)2 6H2O
DMSO
90
104.17
90
14.4191
6.2599
7.0611
Pc



0.0009 mmol



H2BzPDC



0.0036 mmol


BPR80B5
Cd(NO3)2.4H2O
DMF
90
115.11
90
28.049
9.184
17.837
C2/c



0.018 mmol



H2BDC



0.036 mmol


BPR80H5
Cd(NO3)2 4H2O
DMF
90
119.06
90
11.4746
6.2151
17.268
P2/c



0.027 mmol



H2BDC



0.027 mmol


BPR82C6
Cd(NO3)2 4H2O
DMF
90
90
90
9.7721
21.142
27.77
Fdd2



0.0068 mmol



H2BDC



0.202 mmol


BPR86C3
Co(NO3)2 6H2O
DMF
90
90
90
18.3449
10.031
17.983
Pca2(1)



0.0025 mmol



H2BDC



0.075 mmol


BPR86H6
Cd(NO3)2.6H2O
DMF
80.98
89.69
83.412
9.8752
10.263
15.362
P-1



0.010 mmol



H2BDC



0.010 mmol



Co(NO3)2 6H2O
NMP
106.3
107.63
107.2
7.5308
10.942
11.025
P1


BPR95A2
Zn(NO3)2 6H2O
NMP
90
102.9
90
7.4502
13.767
12.713
P2(1)/c



0.012 mmol



H2BDC



0.012 mmol


CuC6F4O4
Cu(NO3)2.2.5H2O
DMF
90
98.834
90
10.9675
24.43
22.553
P2(1)/n



0.370 mmol
Chlorobenzene



H2BDC(OH)2



0.37 mmol


Fe Formic
FeCl2.4H2O
DMF
90
91.543
90
11.495
9.963
14.48
P2(1)/n



0.370 mmol



Formic acid



0.37 mmol


Mg Formic
Mg(NO3)2.6H2O
DMF
90
91.359
90
11.383
9.932
14.656
P2(1)/n



0.370 mmol



Formic acid



0.37 mmol


MgC6H4O6
Mg(NO3)2.6H2O
DMF
90
96.624
90
17.245
9.943
9.273
C2/c



0.370 mmol



H2BDC(OH)2



0.37 mmol


Zn C2H4BDC
ZnCl2
DMF
90
94.714
90
7.3386
16.834
12.52
P2(1)/n


MOF-38
0.44 mmol



CBBDC



0.261 mmol


MOF-49
ZnCl2
DMF
90
93.459
90
13.509
11.984
27.039
P2/c



0.44 mmol
CH3CN



m-BDC



0.261 mmol


MOF-26
Cu(NO3)2.5H2O
DMF
90
95.607
90
20.8797
16.017
26.176
P2(1)/n



0.084 mmol



DCPE



0.085 mmol


MOF-112
Cu(NO3)2.2.5H2O
DMF
90
107.49
90
29.3241
21.297
18.069
C2/c



0.084 mmol
Ethanol



o-Br-m-BDC



0.085 mmol


MOF-109
Cu(NO3)2.2.5H2O
DMF
90
111.98
90
23.8801
16.834
18.389
P2(1)/c



0.084 mmol



KDB



0.085 mmol


MOF-111
Cu(NO3)2.2.5H2O
DMF
90
102.16
90
10.6767
18.781
21.052
C2/c



0.084 mmol
Ethanol



o-BrBDC



0.085 mmol


MOF-110
Cu(NO3)2.2.5H2O
DMF
90
90
120
20.0652
20.065
20.747
R-3/m



0.084 mmol



thiophene



dicarboxylic



0.085 mmol


MOF-107
Cu(NO3)2.2.5H2O
DEF
104.8
97.075
95.206
11.032
18.067
18.452
P-1



0.084 mmol



thiophene



dicarboxylic



0.085 mmol


MOF-108
Cu(NO3)2.2.5H2O
DBF/methanol
90
113.63
90
15.4747
14.514
14.032
C2/c



0.084 mmol



thiophene



dicarboxylic



0.085 mmol


MOF-102
Cu(NO3)2.2.5H2O
DMF
91.63
106.24
112.01
9.3845
10.794
10.831
P-1



0.084 mmol



H2(BDCCl2)



0.085 mmol


Clbdc1
Cu(NO3)2.2.5H2O
DEF
90
105.56
90
14.911
15.622
18.413
P-1



0.084 mmol



H2(BDCCl2)



0.085 mmol


Cu(NMOP)
Cu(NO3)2.2.5H2O
DMF
90
102.37
90
14.9238
18.727
15.529
P2(1)/m



0.084 mmol



NBDC



0.085 mmol


Tb(BTC)
Tb(NO3)3.5H2O
DMF
90
106.02
90
18.6986
11.368
19.721



0.033 mmol



H3BTC



0.033 mmol


Zn3(BTC)2
ZnCl2
DMF
90
90
90
26.572
26.572
26.572
Fm-3m


Honk
0.033 mmol
Ethanol



H3BTC



0.033 mmol


Zn4O(NDC)
Zn(NO3)2.4H2O
DMF ethanol
90
90
90
41.5594
18.818
17.574
aba2



0.066 mmol



14NDC



0.066 mmol


CdTDC
Cd(NO3)2.4H2O
DMF
90
90
90
12.173
10.485
7.33
Pmma



0.014 mmol
H2O



thiophene



0.040 mmol



DABCO



0.020 mmol


IRMOF-2
Zn(NO3)2.4H2O
DEF
90
90
90
25.772
25.772
25.772
Fm-3m



0.160 mmol



o-Br-BDC



0.60 mmol


IRMOF-3
Zn(NO3)2.4H2O
DEF
90
90
90
25.747
25.747
25.747
Fm-3m



0.20 mmol
Ethanol



H2N-BDC



0.60 mmol


IRMOF-4
Zn(NO3)2.4H2O
DEF
90
90
90
25.849
25.849
25.849
Fm-3m



0.11 mmol



[C3H7O]2-BDC



0.48 mmol


IRMOF-5
Zn(NO3)2.4H2O
DEF
90
90
90
12.882
12.882
12.882
Pm-3m



0.13 mmol



[C5H11O]2-BDC



0.50 mmol


IRMOF-6
Zn(NO3)2.4H2O
DEF
90
90
90
25.842
25.842
25.842
Fm-3m



0.20 mmol



[C2H4]-BDC



0.60 mmol


IRMOF-7
Zn(NO3)2.4H2O
DEF
90
90
90
12.914
12.914
12.914
Pm-3m



0.07 mmol



1,4NDC



0.20 mmol


IRMOF-8
Zn(NO3)2.4H2O
DEF
90
90
90
30.092
30.092
30.092
Fm-3m



0.55 mmol



2,6NDC



0.42 mmol


IRMOF-9
Zn(NO3)2.4H2O
DEF
90
90
90
17.147
23.322
25.255
Pnnm



0.05 mmol



BPDC



0.42 mmol


IRMOF-10
Zn(NO3)2.4H2O
DEF
90
90
90
34.281
34.281
34.281
Fm-3m



0.02 mmol



BPDC



0.012 mmol


IRMOF-11
Zn(NO3)2.4H2O
DEF
90
90
90
24.822
24.822
56.734
R-3m



0.05 mmol



HPDC



0.20 mmol


IRMOF-12
Zn(NO3)2.4H2O
DEF
90
90
90
34.281
34.281
34.281
Fm-3m



0.017 mmol



HPDC



0.12 mmol


IRMOF-13
Zn(NO3)2.4H2O
DEF
90
90
90
24.822
24.822
56.734
R-3m



0.048 mmol



PDC



0.31 mmol


IRMOF-14
Zn(NO3)2.4H2O
DEF
90
90
90
34.381
34.381
34.381
Fm-3m



0.17 mmol



PDC



0.12 mmol


IRMOF-15
Zn(NO3)2.4H2O
DEF
90
90
90
21.459
21.459
21.459
Im-3m



0.063 mmol



TPDC



0.025 mmol


IRMOF-16
Zn(NO3)2.4H2O
DEF
90
90
90
21.49
21.49
21.49
Pm-3m



0.0126 mmol
NMP



TPDC



0.05 mmol



FeBr2 0.927 mmol
DMF



BDC 0.927 mmol
1 Propanol



FeCl3.6H2O
DMF



BDC 1.23 mmol
Ethanol



Mg(NO3)2.6H2O
DMF



DHBC 0.185 mmol



Zn(NO3)2.4H2O
DMF
90
90
120
25.9
25.9
6.8
R-3



0.20 mmol
i-Propanol



DHBC 0.10 mmol



Mn(ClO4)2.6H2O
DMF



DHBC 0.065 mmol
i-Propanol



Tb(NO3)3.5H2O
DMF



DHBC 0.050 mmol
i-Propanol





ADC Acetylene dicarboxylic acid


NDC Naphtalene dicarboxylic acid


BDC Benzene dicarboxylic acid


ATC Adamantane tetracarboxylic acid


BTC Benzene tricarboxylic acid


BTB Benzene tribenzoate


MTB Methane tetrabenzoate


ATB Adamantane tetrabenzoate


ADB Adamantane dibenzoate


BPDC 4,4-Biphenyldicarboxylic acid


DHBC 2,5-Dihydroxyterephthalic acid






Examples for the synthesis of these materials as such can, for example, be found in: J. Am. Chem. Soc. 123 (2001) pages 8241 seq. or in Acc. Chem. Res. 31 (1998) pages 474 seq., which are fully encompassed in the present application.

The separation of the framework materials from the mother liquor of the crystallization can be achieved by procedures known in the art such as solid-liquid separations, 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, as well as by evaporation of the mother liquor at elevated temperature and/or in vacuo and concentrating of the solid. The material obtained in this step is typically a fine powder and cannot be used for most practical applications, e.g., in catalysis, where shaped bodies are required.
The separated framework materials may be compounded, melted, extruded, co-extruded, pressed, spinned, foamed and granulated according to processes known within the processing of plastics, respectively.
One advantage of the process according to the present invention is that the polyoxyalkylene alcohols obtainable have a low, preferred degree of alkoxylation. The alcohols comprise generally 1 to 5 alkoxy units, preferably 1 to 3 alkoxy units, more preferably 1 or 2 alkoxy units, in particular 1 alkoxy unit.
The polyoxyalkylene alcohols which are obtainable according to the present invention lend themselves for a number of applications. Non-limiting examples include polyurethane-foams, lubricating liquids, hydraulic fluid, carrier liquid, tenside and flotation oil.
The invention is now illustrated by way of the following examples which are not intended to limit the scope of the present invention.


EXAMPLES
Example 1
Preparation of MOF-5

















Molar





Starting Material
Amount
Calculated
Experimental









terephthalic acid
 12.3 mmol
2.04 g
2.34 g



Zinc nitrate-tetra
 36.98 mmol
9.67 g
9.66 g



hydrate



Diethylformamide
2568.8 mmol
282.2 g 
282.2 g 



(Merck)










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 transferred into two autoclaves (250 ml) with teflon covered inner walls.
The crystallization occurred at 105° C. over 68 hours. Subsequently, the orange solvent, together with the red crystals, was transferred into a beaker, and the suspension is filtered unter an N2 atmosphrere. The suspension was washed with 3 ml of chloroform before being activated in vacuo. There were obtained 2.3 g of product.
Example 2
2,5-Dihydroxyterephthalic acid (19 mg, 0,10 mmol) and Zn(NO3)2.4H2O (53 mg, 0.20 mmol) were dissolved in a mixed solution of DMF (2.0 mL), PrOH(0.10 mL) and water (0.10 mL), which was placed in a pyrex tube (10 mm×70 mm). The tube was frozen and evacuated, and flame sealed under vacuum. The tube was heated to 105° C. at 2° C./min, held for 20 hours, then cooled to room temperature at 2° C./min. Yellow needle crystals were collected and washed with DMF (3×5 mL). Yield: 26 mg, 81% based on the 2,5-dihydroxyterephthalic acid.
Example 3
Alkoxylation of i-Tridecanol N with Propylene Oxide
i-Tridecanol N (4,8 g corresponding to 0.024 mole) and 0.8 g of the catalyst prepared according to Example 1 were given into an autoclave. Subsequently, the autoclave was filled with 12 g propylene oxide (0.207 mole). The reaction was carried out at 135° C., and in total 9.4 mole propylene oxide/mole starting alcohol were reacted to obtain 18.7 g of product.
Example 4
Alkoxylation of 2-Propylheptanol with Ethylene Oxide
2-Propylheptanol (12.67 g corresponding to 0.08 mole) and 0.49 g of the catalyst prepared according to Example 2 were given into an autoclave. Subsequently, the autoclave was filled with 7.05 g ethylene oxide (0.16 mole). The reaction was carried out at 135° C. over 10 h, before the autocalve was cooled to 50° C., at which temperature the reaction mixture was stirred for another 3 h. In total 3.74 mole ethylene oxide/mole starting alcohol were reacted, to obtain 27.98 g of product.

## Claims

1. A process, which comprises:
alkoxylating a monool with at least one alkoxylating agent to obtain a polyoxyalkylene alcohol comprising 1 to 5 alkoxy units in the presence of a catalyst comprising a metallo-organic framework material of metal ions and at least bidentate coordinately bound organic ligands, wherein the bidentate coordinately bound organic ligands are selected from the group consisting of an hydroxy-substituted aromatic mononuclear polycarboxylic acid, an hydroxyl-substituted polynuclear aromatic polycarboxylic acid, an hydroxyl-substituted aromatic mononuclear polycarboxylic acid comprising at least one heteroatom, an hydroxy-substituted aromatic polynuclear polycarboxylic acid comprising at least one heteroatom, and combinations thereof.

2. The process according to claim 1, wherein the metal ion is selected from the group consisting of any one elements of Groups 1 to 18, and combinations thereof of the periodic table of the elements.

3. The process according to claim 1, wherein the bidentate organic ligand is 2,5-dihydroxyterephthalic acid.

4. The process according to claim 1, wherein the metallo-organic framework material exhibits a specific surface area, as determined via adsorption, of >20 m2/g.

5. The process according to claim 1, wherein the alkoxylation agent is selected from the group consisting of a monofunctional epoxide having 2 to 30 carbon atoms, a multifunctional epoxide having 2 to 30 carbon atoms, and mixtures thereof.

6. The process according to claim 5, wherein the epoxide is selected from the group consisting of ethylene oxide, propylene oxide, a butylene oxide, and mixtures thereof.

7. A method of using an alcohol obtained by the process as claimed in claim 1, which comprises:
preparing a tenside, a flotation oil, a lubricating liquid, a hydraulic fluid, a carrier liquid or a polyurethane foam comprising the alcohol.

8. The method of using according to claim 7 where the alcohol is selected from monools of linear and branched alkyl groups having 1 to 30 carbon atoms, which alkyl groups may carry one or more aryl substituents, of homo- and polynuclear aromatic groups having 4 to 30 carbon atoms, which aromatic groups may carry one or more alkyl substituents, and of linear and branched alkenyl groups having 2 to 30 carbon atoms and which alkenyl groups may carry one or more aryl substituents.