DE102010062374A1 - Producing homo- or copolymer, preferably highly reactive isobutene homo- or copolymer, comprises polymerizing ethylenically unsaturated monomer, in liquid phase, in presence of catalyst comprising porous organometallic framework material - Google Patents

Abstract

Producing homo- or copolymer, comprises polymerizing at least one ethylenically unsaturated monomer having at least 4 carbon atoms, in liquid phase, in presence of a catalyst system comprising a porous organometallic framework material, which comprises at least one at least bidentate organic compound that is coordinatively bonded to at least one metal ion.

Description

The present invention relates to a process for the preparation of homo- or copolymers by polymerization of one or more ethylenically unsaturated monomers having at least 4 carbon atoms, in particular for the preparation of highly reactive isobutene homo- or copolymers having a number average molecular weight M _n of 500 to 1,000,000 of isobutene or an isobutene-containing monomer mixture, in the liquid phase in the presence of a specific catalyst system.

beschrieben wird, d. h. die Doppelbindung befindet sich in der Polymerkette in α-Stellung. ”Polymer” steht für den um eine Isobuteneinheit verkürzten Polyisobutenrest. Die Vinylidengruppen zeigen die höchste Reaktivität, wohingegen eine weiter im Inneren der Makromoleküle liegende Doppelbindung keine oder auf jeden Fall geringere Reaktivität bei Funktionalisierungsreaktionen zeigt. Hochreaktive Polyisobutene werden unter anderem als Zwischenprodukte zur Herstellung von Additiven für Schmier- und Kraftstoffe verwendet, wie dies beispielsweise in DE-A 27 02 604 beschrieben wird.Highly reactive isobutene homopolymers or copolymers are understood to mean, in contrast to the so-called low-reactive polymers, those polyisobutenes which contain a high content of terminal ethylenic double bonds. In the context of the present invention, highly reactive polyisobutenes are to be understood as meaning polyisobutenes which have a proportion of vinylidene double bonds (α-double bonds) of at least 60 mol%, preferably at least 70 mol% and in particular at least 80 mol% on the polyisobutene macromolecules. For the purposes of the present application, vinylidene groups are understood to be those double bonds whose position in the polyisobutene macromolecule is represented by the general formula

is described, ie the double bond is located in the polymer chain in α-position. "Polymer" stands for the truncated to an isobutene polyisobutene. The vinylidene groups show the highest reactivity, whereas a double bond further inside the macromolecules shows no or definitely lower reactivity in functionalization reactions. Highly reactive polyisobutenes are used inter alia as intermediates for the preparation of additives for lubricants and fuels, as for example in DE-A 27 02 604 is described.

Such highly reactive polyisobutenes are, for. B. according to the method of DE-A 27 02 604 obtainable by cationic polymerization of isobutene in the liquid phase in the presence of boron trifluoride as catalyst. The disadvantage here is that the resulting polyisobutenes have a relatively high polydispersity. The polydispersity PDI is a measure of the molecular weight distribution of the polymer chains obtained and corresponds to the quotient of weight-average molecular weight M _w and number-average molecular weight M _n (PDI = M _w / M _n ).

Polyisobutenes with a similarly high proportion of terminal double bonds, but with a narrower molecular weight distribution are, for example, according to the method of EP-A 145 235 . US 5,408,018 such as WO 99/64482 wherein the polymerization is carried out in the presence of a deactivated catalyst, for example a complex of boron trifluoride, alcohols and / or ethers. The disadvantage here is that at very low temperatures, often well below 0 C, which causes a lot of energy, must be worked to actually get to highly reactive polyisobutenes.

It is also known that catalyst systems, such as those in the EP-A 145 235 . US 5,408,018 or WO 99/64482 used, lead to a certain residual fluorine content in the product in the form of organic fluorine compounds. In order to reduce or avoid such by-products, boron trifluoride-containing catalyst complexes should be dispensed with.

The object of the present invention was to provide an improved polymerization process for the preparation of homopolymers or copolymers of ethylenically unsaturated monomers, in particular for the preparation of highly reactive isobutene homo- or copolymers having a number average molecular weight M _{n of} from 500 to 1,000,000, preferably a content at least 80 mole% of terminal vinylidene double bonds using a more suitable catalyst system which serves as the polymerization catalyst. On the one hand, such a process should permit polymerization at a not too low temperature, but at the same time enable significantly shorter polymerization times.

The object was achieved by a process for the preparation of homopolymers or copolymers by polymerization of one or more ethylenically unsaturated monomers, in particular for the preparation of highly reactive isobutene homo- or copolymers having a number average molecular weight M _n of 500 to 1,000,000, in the liquid phase in Dissolved present the presence of a catalyst system, which is characterized in that the catalyst system is a porous organometallic framework material which at least one contains at least one metal ion coordinatively bound, at least bidentate organic compound.

The designated porous organometallic framework [English: "Metal Organic Framework"("MOF")] is known in the art, for example from the DE-A 101 11 230 or the EP-A 790,253 , and is recommended among other things for gas cleaning or gas storage. So will in the WO 2007/144324 describes an efficient method for the depletion or removal of methane from methane-containing gas mixtures, wherein such a method is based primarily on adsorption-desorptioris processes. Also, the porous organometallic framework is known as a solid catalyst for a wide variety of organic reaction types. So recommends the WO 2003/101975 its use as a catalyst for the epoxidation of organic compounds. As a polymerization catalyst, however, it has hitherto been described only for the Zielger-Natta polymerization of ethylene and propylene ( JM Tanski, PT Wolczanski, Inorg. Chem. 2001, 40, 2026 ).

The designated porous organometallic framework ("MOF") contains at least one at least one metal ion coordinate bound, at least bidentate organic compound. The MOF according to the present invention contains pores, especially micro and / or mesopores. Micropores are defined as those having a diameter of 2 nm or smaller and mesopores are defined by a diameter in the range of 2 to 50 nm, each according to the definition as defined in Pure Applied Chem. 45, page 71 / page 79 (1976) is specified. The presence of micro- and / or mesopores can be checked by sorption measurements, which measures the uptake capacity of the MOF for nitrogen at 77 Kelvin DIN 66131 and or DIN 66134 determine.

The specific surface is preferably calculated according to the Langmuir model ( DIN 66131 . 66134 ) for a MOF in powder form more than 5 m ² / g, more preferably more than 10 m ² / g, more preferably more than 50 m ² / g, even more preferably more than 500 m ² / g, even more preferably more than 1000 m ² / g and more preferably more than 1500 m ² / g.

MOF molded articles may have a lower active surface area; but preferably more than 10 m ² / g, more preferably more than 50 m ² / g, even more preferably more than 500 m ² / g and particularly preferably more than 1000 m ² / g.

The metal component in the framework of the MOF is preferably selected from Groups Ia, IIa, IIIa, IVa to Villa and Ib to VIb of the Periodic Table of the Elements. Particularly preferred are Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ro, 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 preferred are Zn, Cu, Ni, Pd, Pt, Ru, Rh and Co. With respect to the ions of these elements, mention is particularly made of Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ⁴⁺ , Zr ^{4 +} , Hf ⁴⁺ , V ⁴⁺ , V ³⁺ , V ²⁺ , Nb ³⁺ , Ta ³⁺ , Cr ³⁺ , Mo ³⁺ , W ³⁺ , Mn ³⁺ , Mn ²⁺ , Re ³⁺ , Re ²⁺ , Fe ³⁺ , Fe ²⁺ , Ru ³⁺ , Ru ²⁺ , Os ³⁺ , Os ²⁺ , Co ³⁺ , Co ²⁺ , Rh ²⁺ , Rh ⁺ , Ir ²⁺ , Ir ⁺ , Ni ²⁺ , Ni ⁺ , Pd ²⁺ , Pd ⁺ , Pt ²⁺ , Pt ⁺ , Cu ²⁺ , Cu ⁺ , Ag ⁺ , Au ⁺ , Zn ²⁺ , Cd ²⁺ , Hg ²⁺ , Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Si ⁴⁺ , Si ²⁺ , Ge ⁴⁺ , Ge ²⁺ , Sn ⁴⁺ , Sn ²⁺ , Pb ⁴⁺ , Pb ²⁺ , As ⁵⁺ , As ^{3 +} , As ⁺ , Sb ⁵⁺ , Sb ³⁺ , Sb ⁺ , Bi ⁵⁺ , Bi ³⁺ and Bi ⁺ .

Most preferably, a metal ion from the group consisting of Zn ²⁺ , Al ³⁺ , Co ²⁺ , Co ³⁺ , Fe ³⁺ and Cu ^{2+ is} present in the porous organometallic framework material of the MOF.

The term "at least bidentate organic compound" denotes an organic compound which contains at least one functional group capable of giving at least two, preferably two, coordinative bonds to a given metal ion and / or two or more, preferably two, Metal atoms each form a coordinative bond.

As functional groups by means of which the abovementioned coordinative bonds can be formed, the following functional groups can be mentioned in particular: -CO ₂ H, -CS ₂ H, -NO ₂ , -B (OH) ₂ , -SO ₃ H, - Si (OH) ₃ , -Ge (OH) ₃ , -Sn (OH) ₃ , -Si (SH) ₄ , -Ge (SH) ₄ , -Sn (SH) ₃ , -PO ₃ H, -AsO ₃ H , -AsO ₄ H, -P (SH) ₃ , -As (SH) ₃ , -CH (RSH) ₂ , -C (RSH) ₃ , -CH (RNH ₂ ) ₂ -C (RNH ₂ ) ₃ , - CH (ROH) ₂ , -C (ROH) ₃ , -CH (RCN) ₂ , -C (RCN) ₃ , wherein R represents a hydrocarbylene radical, for example, an alkylene group having 1, 2, 3, 4 or 5 carbon atoms such as a methylene, ethylene, n-propylene, iso-propylene, n-butylene, iso-butylene, tert-butylene or n-pentylene group, or an arylene group containing 1 or 2 aromatic nuclei such as 2C _6- Rings, which may optionally be condensed and may be independently substituted with at least one each substituent, and / or independently of each other at least one heteroatom such as For example, N, O and / or S may contain. According to likewise preferred embodiments, functional groups are to be mentioned in which the abovementioned radical R is absent. In this regard, inter alia, -CH (SH) ₂ , -C (SH) ₃ , -CH (NH ₂ ) ₂ , -C (NH ₂ ) ₃ , -CH (OH) ₂ , -C (OH) ₃ , -CH (CN) ₂ or -C (CN) ₃ to call.

The at least two functional groups can in principle be bound to any suitable organic compound as long as it is ensured that the organic compound having these functional groups is capable of forming the coordinative bond and the preparation of the framework.

Preferably, the organic compounds containing the at least two functional groups are derived from a saturated or unsaturated aliphatic compound or an aromatic compound or an aliphatic as well as an aromatic compound.

The aliphatic compound or the aliphatic portion of the both aliphatic and aromatic compound may be linear and / or branched and / or cyclic, wherein also several cycles per compound are possible. More preferably, the aliphatic compound or the aliphatic portion of the both aliphatic and aromatic compound contains 1 to 15, more preferably 1 to 14, further preferably 1 to 13, further preferably 1 to 12, further preferably 1 to 11 and particularly preferably 1 to 10 C atoms such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 C atoms. Methane, adamantane, acetylene, ethylene or butadiene are particularly preferred in this case.

The aromatic compound or the aromatic part of both aromatic and aliphatic compound may have one or more cores, such as two, three, four or five cores, wherein the cores may be separated from each other and / or at least two nuclei in condensed form. Most preferably, the aromatic compound or the aromatic moiety of the both aliphatic and aromatic compounds has one, two or three nuclei, with one or two nuclei being particularly preferred. Independently of one another, each nucleus of the compound mentioned can furthermore contain at least one heteroatom, such as, for example, N, O, S, B, P, Si, Al, preferably N, O and / or S. More preferably, the aromatic compound or the aromatic moiety of the both aromatic and aliphatic compounds contains one or two C ₆ cores, the two being either separately or in condensed form. In particular, benzene, naphthalene and / or biphenyl and / or bipyridyl and / or pyridyl may be mentioned as aromatic compounds.

Examples include trans-muconic acid or fumaric acid or phenylenebisacrylic acid.

For example, dicarboxylic acids such as oxalic acid, succinic acid, tartaric acid, 1,4-butanedicarboxylic acid, 4-oxo-pyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1, 9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, Imidazole-2,4-dicarboxylic acid, 2-methyl-quinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4 '-Diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimide dicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5- dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid acid, perylenedicarboxylic acid, Pluriol E 200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octadicarboxylic acid, pentane-3,3-dicarboxylic acid, 4,4'-diamino-1,1'- diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis (phenylamino) benzene-2,5- dicarboxylic acid, 1,1'-dinaphthyl-2,2'-dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4 bis (carboxymethyl) piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1- (4-carboxy) -phenyl-3- (4-chloro) -phenylpyrazoline-4,5 dicarboxylic acid, 1,4,5,6,7,7, hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindane dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1, 4-Cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxo-imidazolidine-4,5-cis-dicarboxylic acid, 2,2 '-Bichinolin-4,4'-dicarboxylic acid, pyrid in-3,4-dicarboxylic acid, 3,6,9-trioxaundecane-dicarboxylic acid, O-hydroxybenzophenone dicarboxylic acid, Pluriol E 300 dicarboxylic acid, Pluriol E 400 dicarboxylic acid, Pluriol E 600 dicarboxylic acid, pyrazole-3, 4-dicarboxylic acid, 2,3-pyrazine dicarboxylic acid, 5,6-dimethyl-2,3-pyrazine dicarboxylic acid, 4,4'-diaminodiphenyl ether di-imide dicarboxylic acid, 4,4'-diaminodiphenylmethane diimide dicarboxylic acid, 4,4'-diaminodiphenylsulfone diimide dicarboxylic acid, 2,6 -Naphthalenedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenedicarboxylic acid, 8-sulfo-2,3- naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2 ', 3'-diphenyl-p-terphenyl-4,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4 (1H ) Oxo-thiochromene-2,8-dicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosendicarboxylic acid, 4,4'-dihydroxydiphenylmethane 3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2, 9-di-chlorofluorubin-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2 ', 5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6- Pyridinedicarboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1-H-pyrrole-3,4-dicarboxylic acid, Anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoldicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid 1,14-tetra-decanedicarboxylic acid, 5,6 Dehydronorbornane-2,3-dicarboxylic acid or 5-ethyl-2,3-pyridinedicarboxylic acid;
Tricarboxylic acids such as
2-hydroxy-1,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono-1,2,4- butanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrolo [2,3-F] quinoline-2,7, 9-ticarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1,2,4-ticarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1,2,4-tricarboxylic acid, 1,2,3- Propane tricarboxylic acid or auric tricarboxylic acid;
or tetracarboxylic acids such as
1,1-dioxide-peroxy [1,12-BCD] thiophene-3,4,9,10-tetracarboxylic acid, perylenetetracarboxylic acids such as perylene-3,4,9,10-tetracarboxylic acid or perylene-1,12-sulfone-3, 4,9,10-tetracarboxylic acid, butanetetracarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid or meso-1,2,3,4-butanetetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7, 10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexane-tetracarboxylic acid, 1,2,7,8-octantetracarboxylic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 1,2,9,10-decantetracarboxylic acid, benzophenone tetracarboxylic acid, 3,3 ', 4,4'-benzo-phenontetracarboxylic acid, tetrahydrofurantetracarboxylic acid or cyclopentanetetracarboxylic acids, such as To call cyclopentane-1,2,3,4-tetracarboxylic acid.

Very particular preference is given to using at least mono-, di-, tri-, tetra- or higher-nuclear aromatic di-, tri- or tetracarboxylic acids, where each of the cores can contain at least one heteroatom, where two or more nuclei have identical or different heteroatoms may contain. For example, preference is given to monocarboxylic dicarboxylic acids, monocarboxylic tricarboxylic acids, monocarboxylic tetracarboxylic acids, dicercaric dicarboxylic acids, dicercaric tricarboxylic acids, dicercaric tetracarboxylic acids, tricyclic dicarboxylic acids, tricarboxylic tricarboxylic acids, tricarboxylic tetracarboxylic acids, tetracyclic dicarboxylic acids, tetracyclic tricarboxylic acids and / or tetracyclic tetracarboxylic acids. Suitable heteroatoms are, for example, N, O, S, B, P, Si, Al, preferred heteroatoms here are N, S and / or O. A suitable substituent in this regard is, inter alia, -OH, a nitro group, an amino group or an alkyl or To name alkoxy group.

Particularly preferred as the at least bidentate organic compounds are acetylenedicarboxylic acid (ADC), benzenedicarboxylic acids, naphthalenedicarboxylic acids, biphenyldicarboxylic acids such as 4,4'-biphenyldicarboxylic acid (BPDC), bipyridinedicarboxylic acids such as 2,2'-bipyridinedicarboxylic acids such as 2,2'-bipyridine-5, 5'-dicarboxylic acid, benzene tricarboxylic acids such as 1,2,3-benzenetricarboxylic acid or 1,3,5-benzenetricarboxylic acid (BTC), adamantane tetracarboxylic acid (ATC), adamantane dibenzoate (ADB) benzene tribenzoate (BTB), methanetetrabenzoate (MTB), adamantane tetrabenzoate or dihydroxyterephthalic acids such as For example, 2,5-dihydroxyterephthalic acid (DHBDC) used.

Isophthalic acid, terephthalic acid, 2,5-dihydroxyterephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 2,2'-bipyridine-5,5'-dicarboxylic acid, Naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid or 2,6-naphthalenedicarboxylic acid used.

In addition to these at least bidentate organic compounds, the MOF may also comprise one or more monodentate ligands.

Suitable solvents for the preparation of the MOF are u. a. Ethanol, dimethylformamide, toluene, methanol, chlorobenzene, diethylformamide, dimethyl sulfoxide, water, hydrogen peroxide, methylamine, caustic soda, acetonitrile, benzyl chloride, triethylamine, ethylene glycol, and mixtures thereof.

Other metal ions, at least bidentate organic compounds and solvents for the production of MOF are, inter alia, in US-A 5,648,508 or DE-A 101 11 230 described.

The pore size of the MOF can be controlled by choice of the appropriate ligand and / or the at least bidentate organic compound. Generally, the larger the organic compound, the larger the pore size. Preferably, the pore size of 0.2 nm to 30 nm, more preferably the pore size is in the range of 0.3 nm to 3 nm, each based on the crystalline material.

In a MOF shaped body, however, larger pores also occur whose size distribution can vary. Preferably, however, more than 50% of the total pore volume, in particular more than 75%, of pores having a pore diameter of up to 1000 nm is formed. Preferably, however, a majority of the pore volume is formed by pores of two diameter ranges. It is therefore further preferred if more than 25% of the total pore volume, in particular more than 50% of the total pore volume, is formed by pores which are in a diameter range of 100 nm to 800 nm and if more than 15% of the total pore volume, in particular more than 25% of the total pore volume, is formed by pores which are in a diameter range or up to 10 nm. The pore distribution can be determined by means of mercury porosimetry.

The following are examples of MOFs. In addition to the identification of the MOF, the metal and the at least bidentate ligands, the solvent and the cell parameters (angle α, β and γ and the distances A, B and C in Å) are also given. The latter were determined by X-ray diffraction. MOE-n Ingredients molar ratio M + L Solven s α β γ a b C space group MOF 0 Zn (NO _{3) 2} · 6H ₂ OH ₃ (BTC) ethanol 90 90 120 16711 16711 14189 P6 (3) / Mcm MOF-2 Zn (NO ₃ ) ₂ .6H ₂ O (0.246 mmol) H ₂ (BDC) 0.241 mmol) DMF toluene 90 102.8 90 6718 15:49 12:43 P2 (1) / n MOF-3 Zn (NO ₃ ) ₂ .6H ₂ O (1.89 mmol) H ₂ (BDC) (1.93 mmol) DMF MeOH 99.72 111.11 108.4 9726 9911 10:45 P-1 MOF-4 Zn (NO ₃ ) ₂ .6H ₂ O (1.00 mmol) H ₃ (BTC) (0.5 mmol) ethanol 90 90 90 14,728 14,728 14,728 P2 (1) 3 MOF-5 Zn (NO ₃ ) ₂ .6H ₂ O (2.22 mmol) H ₂ (BDC) (2.17 mmol) DMF chlorobenzene 90 90 90 25669 25669 25669 Fm-3m MOF-38 Zn (NO ₃ ) ₂ .6H ₂ O (0.27 mmol) H ₃ (BTC) (0.15 mmol) DMF chlorobenzene 90 90 90 20657 20657 17.84 14 cm MOF-31Zn (ADC) ₂ Zn (NO ₃ ) ₂ .6H ₂ O 0.4 mmol H ₂ (ADC) 0.8 mmol ethanol 90 90 90 10821 10821 10821 Pn (-3) m MOF-12 Zn ₂ (ATC) Zn (NO ₃ ) ₂ .6H ₂ O 0.3 mmol H ₄ (ATC) 0.15 mmol ethanol 90 90 90 15745 16907 18167 Pbca MOF-20 ZnNDC Zn (NO _{3) 2} .6H ₂ O 00:37 mmol H ₂ NDC 0:36 mmol DMF chlorobenzene 90 92.13 90 8.13 16444 12807 P2 (1) / c MOF-37 Zn (NO ₃ ) ₂ .6H ₂ O 0.2 mmol H ₂ NDC 0.2 mmol DEF chlorobenzene 72.38 83.16 84.33 9952 11576 15556 P-1 MOF-8 Tb ₂ (ADC) Tb (NO ₃ ) ₃ .5H ₂ O 0.10 mmol H ₂ ADC 0.20 mmol DMSO MeOH 90 115.7 90 19.83 9822 19183 C2 / c MOF-9 Tb ₂ (ADC) Tb (NO ₃ ) ₃ .5H ₂ O 0.08 mmol H ₂ ADB 0.12 mmol DMSO 90 102.09 90 27056 16795 28139 C2 / c MOF-6 Tb (NO ₃ ) ₃ .5H ₂ O 0.30 mmol H ₂ (BDC) 0.30 mmol DMF MeOH 90 91.28 90 17,599 19996 10545 P21 / c MOF 7 Tb (NO ₃ ) ₃ .5H ₂ O 0.15 mmol H ₂ (BDC) 0.15 mmol H ₂ O 102.3 91.12 101.5 6142 10069 10096 P-1 MOF-69A Zn (NO ₃ ) 2 .6H ₂ O 0.083 mmol 4,4'BPDC 0.041 mmol DEF H ₂ O ₂ MeNH ₂ 90 111.6 90 23:12 20.92 12 C2 / c MOF-69B Zn (NO ₃₎ 2 .6H ₂ O 0.083 mmol 2,6-NCD 0.041 mmol DEF H ₂ O ₂ MeNH ₂ 90 95.3 90 20:17 18:55 12:16 C2 / c MOF-11 Cu ₂ (ATC) Cu (NO ₃ ) ₂ .2.5H ₂ O 0.47 mmol H ₂ ATC 0.22 mmol H ₂ O 90 93.86 90 12987 11:22 11336 C2 / c MOF-11 Cu ₂ (ATC) dehydr. 90 90 90 8.4671 8.4671 14:44 P42 / mmc MOF-14 Cu ₃ (BTB) Cu (NO ₃ ) ₂ .2.5H ₂ O 0.28 mmol H ₃ BTB 0.052 mmol H ₂ O DMF EtOH 90 90 90 26946 26946 26946 In-3 MOF-32 Cd (ATC) Cd (NO ₃ ) ₂ .4H ₂ O 0.24 mol H ₄ ATC 0.10 mmol H ₂ O NaOH 90 90 90 13468 13468 13468 P (-4) 3m MOF-33 Zn ₂ (ATB) ZnCl ₂ 0.15 mmol H ₄ ATB 0.02 mmol H ₂ O DMF EtOH 90 90 90 19561 15255 23404 Imma MOF-34 Ni (ATC) Ni (NO ₃ ) ₂ .6H ₂ O 0.24 mmol H ₄ ATC 0.10 mmol H ₂ O NaOH 90 90 90 10066 11163 19201 P2 ₁ 2 ₁ 2 ₁ MOF-36 Zn ₂ (MTB) Zn (NO ₃ ) ₂ .4H ₂ O 0.20 mmol H ₄ MTB 0.04 mmol H ₂ O DMF 90 90 90 15745 16907 18167 Pbca MOF-39 Zn ₃ O (HBTB) Zn (NO ₃ ) ₂ .4H ₂ O 0.27 mmol H ₃ BTB 0.07 mmol H ₂ O DMF EtOH 90 90 90 17158 21591 25308 Pnma NO305 FeCl ₂ .4H ₂ O 5:03 mmol Ameisensre. 86.90 mmol DMF 90 90 90 8.2692 8.2692 63566 R-3c NO306A FeCl ₂ .4H ₂ O 5:03 mmol Ameisensre. 86.90 mmol DEF 90 90 90 9.9364 18374 18374 Pbcn NO29 MOF-0 similar Mn (AC) ₂ .4H ₂ O 0.46 mmol H ₃ BTC 0.69 mmol DMF 120 90 90 14:16 33521 33521 P-1 BPR48 A2 Zn (NO ₃ ) ₂ 6H ₂ O 0.012 mmol H ₂ BDC 0.012 mmol DMSO toluene 90 90 90 14.5 4.17 2.18 Pbca BPR69 B1 Cd (NO _{3) 2} 4H ₂ O 0.0212 mmol H ₂ BDC 0.0428 mmol DMSO 90 98.76 90 14:16 15.72 17.66 cc BPR92 A2 CO (NO ₃ ) ₂ .6H ₂ O 0.018 mmol H ₂ BDC 0.018 mmol NMP 106.3 107.63 107.2 7.5308 10942 11025 P1 BPR95 C5 Cd (NO ₃ ) ₂ 4H ₂ O 0.012 mmol H ₂ BDC 0.36 mmol NMP 90 112.8 90 14460 11085 15829 P2 (1) / n CuC ₆ H ₄ O ₆ Cu (NO ₃ ) ₂ .2.5H ₂ O 0.370 mmol H ₂ BDC (OH) ₂ 0.37 mmol DMF chlorobenzene 90 105.29 90 15259 14816 14:13 P2 (1) / c M (BTC) Similar to MOF-0 Co (SO ₄ ) H ₂ O 0.055 mmol H ₃ BTC 0.037 mmol DMF like MOF-0 Tb (C ₆ H ₄ O ₆ ) Tb (NO ₃ ) ₃ .5H ₂ O 0.370 mmol H ₂ (C ₆ H ₄ O ₆ ) 0.56 mmol DMF chlorobenzene 104.6 107.9 97147 10491 10981 12541 P-1 Zn (C ₂ O ₄ ) ZnCl ₂ 0.370 mmol oxalic acid 0.37 mmol DMF chlorobenzene 90 120 90 9.4168 9.4168 8464 P (-3) 1m Co (CHO) Co (NO ₃ ) ₂ .5H ₂ O 0.043 mmol formate. 1.60 mmol DMF 90 91.32 90 11,328 10049 14854 P2 (1) / n Cd (CHO) Cd (NO ₃ ) ₂ 4H ₂ O 0.185 mmol formic acid 0.185 mmol DMF 90 120 90 8.5168 8.5168 22,674 R-3c Cu (C ₃ H ₂ O ₄ ) Cu (NO ₃ ) ₂ .2.5H ₂ O 0.043 mmol Malonsre. 0.192 mmol DMF 90 90 90 8366 8366 11919 P43 Zn ₈ (NDC) ₅ MOF-48 Zn (NO ₃ ) ₂ .6H ₂ O 0.097 mmol 14 NDC 0.069 mmol DMF chlorobenzene H ₂ O ₂ 90 95902 90 19504 16482 14.64 C2 / m MOF-47 Zn (NO ₃ ) ₂ 6H ₂ O 0.185 mmol H ₂ (BDC [CH ₃ ] 4) 0.185 mmol DMF chlorobenzene H ₂ O ₂ 90 92.55 90 11303 16029 17535 P2 (1) / c MO25 Cu (NO ₃ ) ₂ .2.5H ₂ O 0.084 mmol BPhDC 0.085 mmol DMF 90 112.0 90 23880 16834 18389 P2 (1) / c Cu-Thio Cu (NO ₃ ) ₂ .2.5H ₂ O 0.084 mmol thiophene dicarboxylate. 0.085 mmol DEF 90 113.6 90 15,474 7 14514 14032 P2 (1) / c CIBDC1 Cu (NO ₃ ) ₂ 2.5H ₂ O 0.084 mmol H ₂ (BDCCl ₂ ) 0.085 mmol DMF 90 105.6 90 14911 15622 18413 C2 / c MOF-101 Cu (NO ₃ ) ₂ 2.5H ₂ O 0.084 mmol BrBDC 0.085 mmol DMF 90 90 90 21607 20607 20073 Fm3m Zn ₃ (BTC) ₂ ZnCl ₂ 0.033 mmol H ₃ BTC 0.033 mmol DMF EtOH Base Admitted 90 90 90 26572 26572 26572 Fm-3m MOF-j Co (CH ₃ CO ₂ ) ₂ .4H ₂ O (1.65 mmol) H ₃ (BZC) (0.95 mmol) H ₂ O 90 112.0 90 17482 12963 6559 C2 MOF-n Zn (NO ₃ ) ₂ .6H ₂ OH ₃ (BTC) Ethanol I 90 90 120 16711 16711 14189 P6 (3) / mc m PbBDC Pb (NO ₃ ) ₂ (0.181 mmol) H ₂ (BDC) (0.181 mmol) DMF ethanol 90 102.7 90 8.3639 17991 9.9617 P2 (1) / n Znhex Zn (NO ₃ ) ₂ .6H ₂ O (0.171 mmol) H ₃ BTB (0.114 mmol) DMF p-xylene ethanol 90 90 120 37.116 5 37117 30019 P3 (1) c AS16 FeBr ₂ 0.927 mmol H ₂ (BDC) 0.927 mmol DMF anhydr. 90 90.13 90 7.2595 8.7894 19,484 P2 (1) c AS27-2 FeBr ₂ 0.927 mmol H ₃ (BDC) 0.464 mmol DMF anhydr. 90 90 90 26735 26735 26735 Fm3m AS32 FeCl ₃ 1.23 mmol H ₂ (BDC) 1.23 mmol DMF anhydr. ethanol 90 90 120 12535 12535 18479 P6 (2) c AS54-3 FeBr ₂ 0.927 BPDC 0.927 mmol DMF anhydr. n-propanol 90 109.98 90 12019 15286 14399 C2 AS61-4 FeBr ₂ 0.927 mmol m-BDC 0.927 mmol Pyridine anhydr. 90 90 120 13017 13017 14896 P6 (2) c AS68-7 FeBr ₂ 0.927 mmol m-BDC 1.204 mmol DMF anhydr. pyridine 90 90 90 18,340 7 10036 18039 Pca2 ₁ Zn (ADC) Zn (NO ₃ ) ₂ .6H ₂ O 0.37 mmol H ₂ (ADC) 0.36 mmol DMF chlorobenzene 90 99.85 90 16764 9349 9635 C2 / c MOF-12 Zn2 (ATC) Zn (NO ₃ ) ₂ .6H ₂ O 0.30 mmol H ₄ (ATC) 0.15 mmol ethanol 90 90 90 15745 16907 18167 Pbca MOF-20 ZnNDC Zn (NO ₃ ) ₂ .6H ₂ O 0.37 mmol H ₂ NDC 0.36 mmol DMF chlorobenzene 90 92.13 90 8.13 16444 12807 P2 (1) / c MOF-37 Zn (NO ₃ ) ₂ .6H ₂ O 0.20 mmol H ₂ NDC 0.20 mmol DEF chlorobenzene 72.38 83.16 84.33 9952 11576 15556 P-1 Zn (NDC) (DMSO) Zn (NO ₃ ) ₂ .6H ₂ OH ₂ NDC DMSO 68.08 75.33 88.31 8631 10207 13114 P-1 Zn (NDC) Zn (NO ₃ ) ₂ .6H ₂ OH ₂ NDC 90 99.2 90 19289 17628 15052 C2 / c Zn (HPDC) Zn (NO ₃ ) ₂ .4H ₂ O 0.23 mmol H ₂ (HPDC) 0.05 mmol DMF H ₂ O 107.9 105.06 94.4 8326 12085 13767 P-1 Co (HPDC) Co (NO ₃ ) ₂ .6H ₂ O 0.21 mmol H ₂ (HPDC) 0.06 mmol DMF H ₂ O / ethanol 90 97.69 90 29677 9.63 7981 C2 / c Zn ₃ (PDC) 2.5 Zn (NO ₃ ) ₂ .4H ₂ O 0.17 mmol H ₂ (HPDC) 0.05 mmol DMF / ClBz H ₂ O / TEA 79.34 80.8 85.83 8564 14046 26428 P-1 Cd ₂ (TPDC) 2 Cd (NO ₃ ) ₂ .4H ₂ O 0.06 mmol H ₂ (HPDC) 0.06 mmol Methanol / CHP H ₂ O 70.59 72.75 87.14 10102 14412 14964 P-1 Tb (PDC) 1.5 Tb (NO ₃ ) ₃ .5H ₂ O 0.21 mmol H ₂ (PDC) 0.034 mmol DMF H ₂ O / ethanol 109.8 103.61 100.14 9829 12:11 14628 P-1 ZnDBP Zn (NO ₃ ) ₂ .6H ₂ O 0.05 mmol dibenzyl phosphate 0.10 mmol MeOH 90 93.67 90 9254 10762 27.93 P2 / n Zn ₃ (BPDC) ZnBr ₂ 0.021 mmol 4,4'BPDC 0.005 mmol DMF 90 102.76 90 11:49 14.79 19:18 P21 / n CDBDC Cd (NO ₃ ) ₂ .4H ₂ O 0.100 mmol H ₂ (BDC) 0.401 mmol DMF Na ₂ SiO ₃ (aq) 90 95.85 90 11.2 11:11 16.71 P21 / n Cd MBDC Cd (NO ₃ ) ₂ .4H ₂ O 0.009 mmol H ₂ (mBDC) 0.018 mmol DMF MeNH ₂ 90 101.1 90 13.69 18:25 14.91 C2 / c Zn ₄ OBND C Zn (NO ₃ ) ₂ .6H ₂ O 0.041 mmol BNDC DEF MeNH ₂ H ₂ O ₂ 90 90 90 22:35 5.26 59.56 Fmmm Eu (TCA) Eu (NO ₃ ) ₃ .6H ₂ O 0.14 mmol TCA 0.026 mmol DMF chlorobenzene 90 90 90 23325 23325 23325 Pm-3n Tb (TCA) Tb (NO ₃ ) ₃ 6H ₂ O 0.069 mmol TCA 0.026 mmol DMF chlorobenzene 90 90 90 23272 23272 23372 Pm-3n formats Ce (NO ₃ ) ₃ .6H ₂ O 0.138 mmol formate. 0.43 mmol H ₂ O ethanol 90 90 120 10668 10667 4107 R-3m FeCl ₂ .4H ₂ O 5:03 mmol Ameisensre. 86.90 mmol DMF 90 90 120 8.2692 8.2692 63566 R-3c FeCl ₂ .4H ₂ O 5:03 mmol Ameisensre. 86.90 mmol DEF 90 90 90 9.9364 18374 18374 Pbcn FeCl ₂ .4H ₂ O 5:03 mmol Ameisensre. 86.90 mmol DEF 90 90 90 8335 8335 13:34 P-31c NO330 FeCl ₂ .4H ₂ O 12:50 mmol Ameisensre. 8.69 mmol formamide 90 90 90 8.7749 11655 8.3297 Pnaa NO332 FeCl ₂ .4H ₂ O 12:50 mmol Ameisensre. 8.69 mmol DIP 90 90 90 10.031 3 18808 18355 Pbcn NO333 FeCl ₂ .4H ₂ O 12:50 mmol Ameisensre. 8.69 mmol DBF 90 90 90 45,275 4 23861 12441 Cmcm NO335 FeCl ₂ .4H ₂ O 12:50 mmol Ameisensre. 8.69 mmol CHF 90 91372 90 11,596 4 10187 14945 P21 / n NO336 FeCl ₂ .4H ₂ O 12:50 mmol Ameisensre. 8.69 mmol MFA 90 90 90 11,794 5 48843 8.4136 PBCM NO13 Mn (Ac) ₂ .4H ₂ O 0.46 mmol benzoic acid. 0.92 mmol bipyridine 0.46 mmol ethanol 90 90 90 18.66 11762 9418 Pbcn NO29 MOF-0 similar Mn (Ac) ₂ .4H ₂ O 0.46 mmol H ₃ BTC 0.69 mmol DMF 120 90 90 14:16 33521 33521 P-1 Mn (hfac) ₂ (O ₂ CC ₆ H ₆ ) Mn (AC) ₂ .4H ₂ O 0.46 mmol Hfac 0.92 mmol Bipyridine 0.46 mmol ether 90 95.32 90 9572 17162 14041 C2 / c BPR43G2 Zn (NO ₃ ) ₂ .6H ₂ O 0.0288 mmol H ₂ BDC 0.0072 mmol DMF acetonitrile 90 91.37 90 17.96 6:38 7.19 C2 / c BPR48A2 Zn (NO ₃ ) ₂ 6H ₂ O 0.012 mmol H ₂ BDC 0.012 mmol DMSO toluene 90 90 90 14.5 4.17 2.18 Pbca BPR49B1 Zn (NO ₃ ) ₂ 6H ₂ O 0.024 mmol H ₂ BDC 0.048 mmol DMSO methanol 90 91172 90 33181 9824 17884 C2 / c BPR56E1 Zn (NO ₃ ) ₂ 6H ₂ O 0.012 mmol H ₂ BDC 0.024 mmol DMSO n-propanol 90 90096 90 14,587 3 14153 17183 P2 (1) / n BPR68D10 Zn (NO ₃ ) ₂ 6H ₂ O 0.0016 mmol H ₃ BTC 0.0064 mmol DMSO benzene 90 95316 90 10,062 7 10:17 16413 P2 (1) / c BPR69B1 Cd (NO ₃ ) ₂ 4H ₂ O 0.0212 mmol H ₂ BDC 0.0428 mmol DMSO 90 98.76 90 14:16 15.72 17.66 cc BPR73E4 Cd (NO ₃ ) ₂ 4H ₂ O 0.006 mmol H ₂ BDC 0.003 mmol DMSO toluene 90 92324 90 8.7231 7.0568 18438 P2 (1) / n BPR76D5 Zn (NO ₃ ) ₂ 6H ₂ O 0.0009 mmol H ₂ BzPDC 0.0036 mmol DMSO 90 104.17 90 14,419 1 6.2599 7.0611 pc BPR80B5 Cd (NO ₃ ) ₂ .4H ₂ O 0.018 mmol H ₂ BDC 0.036 mmol DMF 90 115.11 90 28049 9184 17837 C2 / c BPR80H5 Cd (NO ₃ ) ₂ 4H ₂ O 0.027 mmol H ₂ BDC 0.027 mmol DMF 90 119.06 90 11,474 6 6.2151 17268 P2 / c BPR82C6 Cd (NO ₃ ) ₂ 4H ₂ O 0.0068 mmol H ₂ BDC 0.202 mmol DMF 90 90 90 9.7721 21142 27.77 Fdd2 BPR86C3 Co (NO ₃ ) ₂ 6H ₂ O 0.0025 mmol H ₂ BDC 0.075 mmol DMF 90 90 90 18,344 9 10031 17983 Pca2 (1) BPR86H6 Cd (NO ₃ ) ₂ .6H ₂ O 0.010 mmol H ₂ BDC 0.010 mmol DMF 80.98 89.69 83.41 2 9.8752 10263 15362 P-1 Co (NO ₃ ) ₂ 6H ₂ O NMP 106.3 107.63 107.2 7.5308 10942 11025 P1 BPR95A2 Zn (NO ₃ ) ₂ 6H ₂ O 0.012 mmol H ₂ BDC 0.012 mmol NMP 90 102.9 90 7.4502 13767 12713 P2 (1) / c CuC ₆ F ₄ O ₄ Cu (NO ₃ ) ₂ .2.5H ₂ O 0.370 mmol H ₂ BDC (OH) ₂ 0.37 mmol DMF Chlorobenzene 90 98834 90 10,967 5 24.43 22553 P2 (1) / n Fe Formic FeCl ₂ • 4H ₂ O 0.370 mmol Ameisensre. 0.37 mmol DMF 90 91543 90 11495 9963 14:48 P2 (1) / n Mg Formic Mg (NO ₃ ) ₂ .6H ₂ O 0.370 mmol formate. 0.37 mmol DMF 90 91359 90 11383 9932 14,656 P2 (1) / n MgC ₆ H ₄ O ₆ Mg (NO ₃ ) ₂ .6H ₂ O 0.370 mmol H ₂ BDC (OH) ₂ 0.37 mmol DMF 90 96624 90 17245 9943 9273 C2 / c Zn C ₂ H ₄ BDC MOF-38 ZnCl ₂ 0.44 mmol CBBDC 0.261 mmol DMF 90 94714 90 7.3386 16834 12:52 P2 (1) / n MOF-49 ZnCl ₂ 0.44 mmol m-BDC 0.261 mmol DMF CH ₃ CN 90 93459 90 13509 11984 27039 P2 / c MOF-26 Cu (NO ₃ ) ₂ .5H ₂ O 0.084 mmol DCPE 0.085 mmol DMF 90 95607 90 20,879 7 16,017 26176 P2 (1) / n MOF-112 Cu (NO ₃ ) ₂ .2.5H ₂ O 0.084 mmol o-Br-m-BDC 0.085 mmol DMF ethanol 90 107.49 90 29,324 1 21297 18069 C2 / c MOF-109 Cu (NO ₃ ) ₂ .2.5H ₂ O 0.084 mmol KDB 0.085 mmol DMF 90 111.98 90 23,880 1 16834 18389 P2 (1) / c MOF-111 Cu (NO ₃ ) ₂ .2.5H ₂ O 0.084 mmol o -BrBDC 0.085 mmol DMF ethanol 90 102.16 90 10,676 7 18781 21052 C2 / c MOF-110 Cu (NO ₃ ) ₂ .2.5H ₂ O 0.084 mmol thiophene dicarboxylate. 0.085 mmol DMF 90 90 120 20.065 2 20065 20747 R-3 / m MOF-107 Cu (NO ₃ ) ₂ .2.5H ₂ O 0.084 mmol thiophene dicarboxylate. 0.085 mmol DEF 104.8 97075 95.20 6 11032 18067 18452 P-1 MOF-108 Cu (NO ₃ ) ₂ .2.5H ₂ O 0.084 mmol thiophene dicarboxylate. 0.085 mmol DBF / methanol 90 113.63 90 15,474 7 14514 14032 C2 / c MOF-102 Cu (NO ₃ ) ₂ .2.5H ₂ O 0.084 mmol H ₂ (BDCCl ₂ ) 0.085 mmol DMF 91.63 106.24 112.0 1 9.3845 10794 10831 P-1 Clbdc1 Cu (NO ₃ ) ₂ .2.5H ₂ O 0.084 mmol H ₂ (BDCCl ₂ ) 0.085 mmol DEF 90 105.56 90 14911 15622 18413 P-1 Cu (NMOP) Cu (NO ₃ ) ₂ .2.5H ₂ O 0.084 mmol NBDC 0.085 mmol DMF 90 102.37 90 14,923 8 18727 15529 P2 (1) / m Tb (BTC) Tb (NO ₃ ) ₂ .5H ₂ O 0.033 mmol H ₃ BTC 0.033 mmol DMF 90 106.02 90 18,698 6 11368 19721 Zn ₃ (BTC) ₂ Honk ZnCl ₂ 0.033 mmol H ₃ BTC 0.033 mmol DMF ethanol 90 90 90 26572 26572 26572 Fm-3m Zn ₄ O (NDC) Zn (NO ₃ ) ₂ .4H ₂ O 0.066 mmol 14NDC 0.066 mmol DMF ethanol 90 90 90 41,559 4 18818 17,574 aba2 CdTDC Cd (NO ₃ ) ₂ .4H ₂ O 0.014 mmol thiophene 0.040 mmol DABCO 0.020 mmol DMF H ₂ O 90 90 90 12173 10485 7:33 Pmma IRMOF-2 Zn (NO ₃ ) ₂ .4H ₂ O 0.160 mmol o-Br-BDC 0.60 mmol DEF 90 90 90 25772 25772 25772 Fm-3m IRMOF-3 Zn (NO ₃ ) ₂ .4H ₂ O 0.20 mmol H ₂ N-BDC 0.60 mmol DEF ethanol 90 90 90 25747 25747 25747 Fm-3m IRMOF-4 Zn (NO ₃ ) ₂ .4H ₂ O 0.11 mmol [C ₃ H ₇ O] ₂ -BDC 0.48 mmol DEF 90 90 90 25849 25849 25849 Fm-3m IRMOF-5 Zn (NO ₃ ) ₂ .4H ₂ O 0.13 mmol [C ₅ H ₁₁ O] ₂ -BOC 0.50 mmol DEF 90 90 90 12882 12882 12882 Pm-3m IRMOF-6 Zn (NO ₃ ) ₂ .4H ₂ O 0.20 mmol [C ₂ H ₄ ] -BDC 0.60 mmol DEF 90 90 90 25842 25842 25842 Fm-3m IRMOF-7 Zn (NO ₃ ) ₂ .4H ₂ O 0.07 mmol 1.4NDC 0.20 mmol DEF 90 90 90 12914 12914 12914 Pm-3m IRMOF-8 Zn (NO ₃ ) ₂ .4H ₂ O 0.55 mmol 2.6NDC 0.42 mmol DEF 90 90 90 30092 30092 30092 Fm-3m IRMOF-9 Zn (NO ₃ ) ₂ .4H ₂ O 0.05 mmol BPDC 0.42 mmol DEF 90 90 90 17147 23322 25255 Pnnm IRMOF-10 Zn (NO ₃ ) ₂ .4H ₂ O 0.02 mmol BPDC 0.012 mmol DEF 90 90 90 34281 34281 34281 Fm-3m IRMOF-11 Zn (NO ₃ ) ₂ .4H ₂ O 0.05 mmol HPDC 0.20 mmol DEF 90 90 90 24822 24822 56734 R-3m IRMOF-12 Zn (NO ₃ ) ₂ .4H ₂ O 0.017 mmol HPDC 0.12 mmol DEF 90 90 90 34281 34281 34281 Fm-3m IRMOF-13 Zn (NO ₃ ) ₂ .4H ₂ O 0.048 mmol PDC 0.31 mmol DEF 90 90 90 24822 24822 56734 R-3m IRMOF-14 Zn (NO ₃ ) ₂ .4H ₂ O 0.17 mmol PDC 0.12 mmol DEF 90 90 90 34381 34381 34381 Fm-3m IRMOF-15 Zn (NO ₃ ) ₂ .4H ₂ O 0.063 mmol TPDC 0.025 mmol DEF 90 90 90 21459 21459 21459 In-3m IRMOF-16 Zn (NO ₃ ) ₂ .4H ₂ O 0.0126 mmol TPDC 0.05 mmol DEF NMP 90 90 90 21:49 21:49 21:49 Pm-3m ADC acetylenedicarboxylic acid
NDC naphthalene dicarboxylic acid
BDC benzene dicarboxylic acid
ATC adamantane tetracarboxylic acid
BTC benzene tricarboxylic acid
BTB benzene tribenzoic acid
MTB Methanetetrabenzoic acid
ATB adamantane tetrabenzoic acid
ADB adamantane dibenzoic acid

Other MOFs are MOF-177 and MOF-178, which are described in the literature.

A typical and commonly used MOF catalyst system is based on copper benzene-1,2,3-tricarboxylate and is commercially available under the name Basolite ^™ C300.

In addition to the conventional method of producing the MOF, such as in US 5,648,508 These can also be prepared by electrochemical means. In this regard, here on the DE-A 103 55 087 as well as the WO-A 2005/049892 to get expelled. The MOFs produced in this way have particularly good properties in connection with the adsorption and desorption of chemical substances, in particular of gases. They thus differ from those that are conventional even though they are formed of the same organic and metal ion components, and are therefore to be considered as different types of frameworks. In the context of the present invention, electrochemically produced MOFs are particularly preferred.

Accordingly, the electrochemical preparation relates to a crystalline porous organometallic framework material containing at least one at least one metal ion coordinatively bonded, at least bidentate organic compound which in a reaction medium containing the at least one bidentate organic compound and at least one metal ion by oxidation of at least one of the corresponding metal containing anode is generated.

The term "electrochemical preparation" refers to a production process in which the formation of at least one reaction product is associated with the migration of electrical charges or the occurrence of electrical potentials.

The term "at least one metal ion" as used in connection with the electrochemical preparation refers to embodiments according to which at least one ion of a metal or at least one ion of a first metal and at least one ion of at least one second metal different from the first metal by anodic Oxidation be provided.

Accordingly, the electrochemical preparation comprises embodiments in which at least one ion of at least one metal is provided by anodic oxidation and at least one ion of at least one metal via a metal salt, wherein the at least one metal in the metal salt and the at least one metal, via anodic oxidation as Metal ion can be provided, the same or different from each other. Thus, for example, with respect to electrochemically produced MOF, the present invention encompasses an embodiment in which the reaction medium contains one or more different salts of a metal and the metal ion contained in that salt or salts is additionally provided by anodic oxidation of at least one anode containing that metal , Likewise, the reaction medium may contain one or more different salts of at least one metal and at least one metal other than these metals may be provided via anodic oxidation as the metal ion in the reaction medium.

According to a preferred embodiment of the present invention, the at least one metal ion is provided by anodic oxidation of at least one of the at least one metal-containing anode, wherein no further metal is provided via a metal salt.

The term "metal" as used in the context of the present invention in connection with the electrochemical preparation of MOF includes all elements of the periodic table which can be provided via anodic oxidation by electrochemical means in a reaction medium and with at least one at least bidentate organic compounds at least one organometallic porous framework material are capable of forming.

Regardless of its preparation, the obtained MOF is obtained in powdery or crystalline form. This can be used as such as a catalyst system in the process according to the invention. This is preferably done as bulk material, in particular in a fixed bed. Furthermore, the MOF can be converted into a shaped body. Preferred methods here are the extrusion or tableting. In molded article production, additional materials such as binders, lubricants, or other additives may be added to the MOF. Likewise, it is conceivable that mixtures of MOF and other adsorbents, for example activated carbon, are produced as shaped articles or separately give shaped articles, which are then used as shaped-body mixtures.

With regard to the possible geometries of these MOF shaped bodies, there are essentially no restrictions. For example, pellets such as disc-shaped pellets, pills, spheres, granules, extrudates such as strands, honeycomb, mesh or hollow body may be mentioned.

• – Kneten des Gerüstmaterials allein oder zusammen mit mindestens einem Bindemittel und/oder mindestens einem Anteigungsmittel und/oder mindestens einer Templatverbindung unter Erhalt eines Gemisches; Verformen des erhaltenen Gemisches mittels mindestens einer geeigneten Methode wie beispielsweise Extrudieren; optional Waschen und/oder Trocknen und/oder Calcinieren des Extrudates; optional Konfektionieren;
• – Aufbringen des Gerüstmaterials auf mindestens ein gegebenenfalls poröses Trägermaterial; das erhaltene Material kann dann gemäß der vorstehend beschriebenen Methode zu einem Formkörper weiterverarbeitet werden;
• – Aufbringen des Gerüstmaterials auf mindestens ein gegebenenfalls poröses Substrat.

In principle, all suitable processes are possible for producing these shaped bodies. In particular, the following procedures are preferred:

• - Kneading the framework material alone or together with at least one binder and / or at least one pasting agent and / or at least one template compound to obtain a mixture; Shaping the resulting mixture by at least one suitable method such as extrusion; optionally washing and / or drying and / or calcining the extrudate; optional assembly;
• - Applying the framework material to at least one optionally porous support material; the material obtained can then be further processed according to the method described above to give a shaped body;
• - Applying the framework material on at least one optionally porous substrate.

Kneading and molding may be done according to any suitable method, such as in Ullmanns Enzyklopadie der Technischen Chemie, 4th Edition, Volume 2, pp. 313 ff. (1972) whose contents are incorporated by reference into the context of the present application in its entirety.

For example, kneading and / or shaping by means of a piston press, roller press in the presence or absence of at least one binder material, compounding, pelleting, tableting, extrusion, coextrusion, foaming, spinning, coating, granulation, preferably spray granulation, spraying, spray drying or a Combination of two or more of these methods.

In particular, pellets and / or tablets are produced.

Kneading and / or molding may be carried out at elevated temperatures such as, for example, in the range of room temperature to 300 ° C and / or elevated pressure such as in the range of normal pressure up to a few hundred bar and / or in a protective gas atmosphere such as in the presence of at least one Noble gas, nitrogen or a mixture of two or more thereof.

The kneading and / or shaping is carried out according to a further embodiment with the addition of at least one binder, wherein as a binder in principle any chemical compound can be used which ensures the kneading and / or deformation desired viscosity of the kneading and / or deforming mass. Accordingly, for the purposes of the present invention, binders may be both viscosity-increasing and viscosity-reducing compounds.

Preferred binders include, for example, binders containing alumina or alumina, as described, for example, in U.S. Pat WO 94/29408 are described, silica, as described for example in the EP 0 592 050 A1 is described as mixtures of silica and alumina, as described for example in the WO 94/13584 are described, clay minerals, such as those in the JP 03-037156 A For example, montmorillonite, kaolin, bentonite, halloysite, dickite, nacrit and anauxite, alkoxysilanes, as described for example in the EP 0 102 544 B1 are described, for example, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, or, for example, trialkoxysilanes such as trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane, alkoxytitanates, for example tetraalkoxy titanates such as tetramethoxy, tetraethoxy, tetrapropoxytitanate, tetrabutoxytitanate, or, for example, trialkoxytitanates such as trimethoxytitanate, triethoxytitanate , Tripropoxytitanat, Tributoxytitanat, Alkoxyzirkonate, for example Tetraalkoxyzirkonate such as tetramethoxyzirconate, tetraethoxyzirconate, tetrapropoxyzirconate, tetrabutoxyzirconate, or example Trialkoxyzirkonate such as trimethoxyzirconate, triethoxyzirconate, Tripropoxyzirkonat, Tributoxyzirkonat, silica sols, amphiphilic substances and / or graphites. Particularly preferred is graphite.

As a viscosity-increasing compound, for example, in addition to the compounds mentioned above, an organic compound and / or a hydrophilic polymer such as cellulose or a cellulose derivative such as methylcellulose and / or a polyacrylate and / or a polymethacrylate and / or a polyvinyl alcohol and / or or a polyvinylpyrrolidone and / or a polyisobutene and / or a polytetrahydrofuran.

As a pasting agent, inter alia, preferably water or at least one alcohol such as a monoalcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, iso-propanol, 1-butanol, 2-butanol, 2-methyl-1 propanol or 2-methyl-2-propanol or a mixture of water and at least one of said alcohols or a polyhydric alcohol such as a glycol a water-miscible polyhydric alcohol, alone or in admixture with water and / or at least one of said monohydric alcohols.

Other additives that can be used for kneading and / or shaping include amines or amine derivatives such as tetraalkylammonium compounds or amino alcohols, and carbonate containing compounds such as calcium carbonate. Such further additives are approximately in the EP 0 389 041 A1 , of the EP 0 200 260 A1 or the WO 95/19222 described.

The order of the additives such as template compound, binder, pasting agent, viscosity-increasing substance in the molding and kneading is basically not critical.

According to a further preferred embodiment, the molding obtained according to kneading and / or molding is subjected to at least one drying, which is generally carried out at a temperature in the range of 25 to 300 ° C, preferably in the range of 50 to 300 ° C and more preferably in the range of 100 to 300 ° C is performed. It is also possible to dry in vacuo or under a protective gas atmosphere or by spray drying.

According to a particularly preferred embodiment, as part of this drying process, at least one of the compounds added as additives is at least partially removed from the shaped body.

With the process according to the invention, it is possible in principle to prepare homo- or copolymers of all imaginable ethylenically unsaturated monomers having at least 4 carbon atoms which are also polymerizable under protic polymerization conditions, for example by means of Lewis acid catalysis. Examples of these are linear alkenes such as n-butene, n-pentene and n-hexene, alkadienes such as butadiene and isoprene, isoalkenes such as isobutene, 2-methylbutene-1, 2-methylpentene-1, 2-methylhexene-1, 2-ethylpentene -1, 2-ethylhexene-1 and 2-propylheptene-1, cycloalkenes such as cyclopentene and cyclohexene, aromatic alkenes such as styrene, α-methylstyrene, 2-, 3- and 4-methylstyrene and 4-tert-butylstyrene, and olefins having a silyl group such as 1-trimethoxysilylethene, 1- (trimethoxysllyl) propene, 1- (trimethoxysilyl) -2-methylpropene-2, 1- [tri (methoxyethoxy) silyl] ethene, 1- [tri (methoxyethoxy) silyl] propene and 1- [tri (methoxyethoxy) silyl] -2-methylpropene-2. Of course, mixtures of the stated monomers can also be used.

Preferred monomers are isobutene, isobutene-containing monomer mixtures, styrene, styrene-containing monomer mixtures, styrene derivatives such as α-methylstyrene, the abovementioned cycloalkenes, the abovementioned alkadienes and mixtures thereof.

Particularly preferred monomers are isobutene, isobutene-containing monomer mixtures, styrene, styrene-containing monomer mixtures and mixtures thereof.

The homopolymers and copolymers prepared by the process according to the invention generally have number-average molecular weights M of from 500 to 5,000,000, preferably from 1,000 to 1,000,000, in particular from 2,000 to 500,000 and in particular from 3,000 to 250,000.

The copolymers prepared by the process of the invention may be random polymers or block copolymers.

The polymerization to the above-mentioned homo- or copolymers can be carried out both continuously and discontinuously.

In a preferred embodiment, the process according to the invention for the preparation of highly reactive isobutene homopolymers or copolymers having a number average molecular weight M _n of 500 to 1,000,000 from isobutene or an isobutene-containing monomer mixture is used.

In the context of the present invention, isobutene homopolymers are understood to mean those polymers which, based on the polymer, are composed of at least 98 mol%, preferably at least 99 mol%, of isobutene. Accordingly, isobutene copolymers are understood to mean those polymers which contain more than 2 mol% of monomers in copolymerized form, which are different from isobutene.

The inventive method is thus suitable for the preparation of low, medium and high molecular weight highly reactive Isobutenhomo- or copolymers. Preferred comonomers here are styrene, Styrene derivatives such as in particular α-methylstyrene and 4-methylstyrene, styrene and styrene derivatives-containing monomer mixtures, alkadienes such as butadiene and isoprene and mixtures thereof.

For the use of isobutene or of an isobutene-containing monomer mixture as the monomer material to be polymerized, the isobutene source is both isobutene itself and also isobutene-containing C ₄ hydrocarbon streams, for example C ₄ raffinates, C ₄ cuts from isobutane dehydrogenation, C ₄ slices from steam crackers and fluid catalysed cracking (FCC) crackers, provided that they are largely free of 1,3-butadiene contained therein. Suitable C ₄ hydrocarbon streams typically contain less than 500 ppm, preferably less than 200 ppm of butadiene. The presence of 1-butene and of cis and trans-2-butene is largely uncritical. Typically, the isobutene concentration in the C ₄ hydrocarbon streams is in the range of 40 to 60 weight percent. The isobutene-containing monomer mixture may contain small amounts of contaminants such as water, carboxylic acids or mineral acids, without resulting in critical yield or selectivity losses. It is expedient to avoid an accumulation of these impurities by removing such pollutants from the isobutene-containing monomer mixture, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.

Monomer mixtures of isobutene or of the isobutene-containing hydrocarbon mixture with olefinically unsaturated monomers which are copolymerizable with isobutene can be reacted. If monomer mixtures of isobutene are to be copolymerized with suitable comonomers, the monomer mixture preferably contains at least 5% by weight, particularly preferably at least 10% by weight and in particular at least 20% by weight isobutene and preferably at most 95% by weight preferably at most 90% by weight and in particular at most 80% by weight of comonomers.

Suitable copolymerizable monomers are vinylaromatics such as styrene and α-methylstyrene, C ₁ -C ₄ -alkylstyrenes such as 2-, 3- and 4-methylstyrene and 4-tert-butylstyrene, alkadienes such as butadiene and isoprene and isoolefins having 5 to 10 C atoms such as 2-methylbutene-1, 2-methylpentene-1, 2-methylhexene-1, 2-ethylpentene-1, 2-ethylhexene-1 and 2-propylheptene-1. Comonomers also include olefins which have a silyl group, such as 1-trimethoxysilylethene, 1- (trimethoxysilyl) propene, 1- (trimethoxysilyl) -2-methylpropene-2, 1- [tri (methoxyethoxy) silyl] ethene, 1 [Tri (methoxyethoxy) silyl] propene, and 1- [tri (methoxyethoxy) silyl] -2-methylpropene-2, as well as vinyl ethers such as tert-butyl vinyl ether.

If copolymers are to be prepared by the process according to the invention, the process can be designed such that preferably random polymers or preferably block copolymers are formed. For the preparation of block copolymers, it is possible for example to feed the various monomers successively to the polymerization reaction, the addition of the second comonomer taking place in particular only when the first comonomer has already been at least partially polymerized. In this way, both diblock, triblock and higher block copolymers are accessible, which have a block of one or the other comonomer as a terminal block, depending on the order of monomer addition. In some cases, however, block copolymers also form when all comonomers are simultaneously fed to the polymerization reaction, but one of them polymerizes significantly faster than the one or the other. This is the case in particular when isobutene and a vinylaromatic compound, in particular styrene, are copolymerized in the process according to the invention. In this case, block copolymers preferably form with a terminal polyisobutene block. This is because the vinyl aromatic compound, especially styrene, polymerizes significantly faster than isobutene.

The polymerization can be carried out both continuously and discontinuously. Continuous processes can be carried out in analogy to known prior art processes for the continuous polymerization of isobutene in the presence of liquid phase Lewis acid catalysts.

The inventive method is suitable both for carrying out at low temperatures, for. B. at -78 to 0 ° C, as well as at higher temperatures, d. H. at least 0 ° C, z. B. at 0 to 100 ° C, suitable. The polymerization is mainly for economic reasons preferably at least 0 ° C, z. B. at 0 to 100 ° C, particularly preferably carried out at 20 to 60 C to keep the energy and material consumption required for cooling as low as possible. However, it can just as well at lower temperatures, eg. B. at -78 to <0 ° C, preferably at -40 to -10 ° C, performed.

If the polymerization takes place at or above the boiling point of the monomer or monomer mixture to be polymerized, it is preferably carried out in pressure vessels, for example in autoclaves or in pressure reactors.

Preferably, the polymerization is carried out in the presence of an inert diluent. The inert diluent used should be suitable for reducing the increase in the viscosity of the reaction solution which usually occurs during the polymerization reaction to such an extent that the removal of the heat of reaction formed can be ensured. Suitable diluents are those solvents or solvent mixtures which are inert to the reagents used. Suitable diluents are, for example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane and isooctane, cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and the xylenes, and halogenated hydrocarbons such as methyl chloride, dichloromethane and trichloromethane, and mixtures the aforementioned diluent. Preference is given to using at least one halogenated hydrocarbon, optionally in admixture with at least one of the abovementioned aliphatic or aromatic hydrocarbons. In particular, dichloromethane is used. Goose was particularly well proven as an inert diluent for the polymerization and a mixture of toluene and dichloromethane. Preferably, the diluents are freed before use of impurities such as water, carboxylic acids or mineral acids, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.

The polymerization is preferably carried out under largely aprotic conditions, in particular under anhydrous reaction conditions. Aprotic or anhydrous reaction conditions are understood to mean that the water content (or the content of protic impurities) in the reaction mixture is less than 50 ppm and in particular less than 5 ppm. As a rule, therefore, the feedstocks will be dried before use by physical and / or chemical means. In particular, it has proven useful to use the aliphatic or alicyclic hydrocarbons used as a solvent after conventional pre-cleaning and predrying with an organometallic compound, such as an organolithium, organomagnesium or organoaluminum compound, in an amount sufficient to remove the traces of water from the Remove solvent. The solvent thus treated is then preferably condensed directly into the reaction vessel. Similarly, one can also proceed with the monomers to be polymerized, in particular with isobutene or with the isobutene-containing mixtures. The drying with other conventional drying agents such as molecular sieves or predried oxides such as alumina, silica, calcium oxide or barium oxide is suitable. The halogenated solvents, which are not suitable for drying with metals such as sodium or potassium or with metal alkyls, are freed of water (traces) with suitable drying agents, for example with calcium chloride, phosphorus pentoxide or molecular sieve. In an analogous manner, it is also possible to dry those starting materials for which treatment with metal alkyls is likewise not suitable, for example vinylaromatic compounds.

The polymerization of the isobutene or of the isobutene-containing feedstock usually takes place spontaneously when the catalyst system is brought into contact with the monomer at the desired reaction temperature. In this case, it is possible to proceed by initially introducing the monomer in the solvent, bringing it to the reaction temperature and then adding the catalyst system, for example as a loose bed. It is also possible to introduce the catalyst system (for example as a loose bed or as a fixed bed), if appropriate in the solvent, and then to add the monomer. The beginning of polymerization is then the time at which all the reactants are contained in the reaction vessel. The catalyst system can then be present as a dispersion.

If the catalyst system is to be used in supported form, it is brought into contact with a suitable support material and thus converted into a heterogenized form. The contacting takes place, for example, by impregnation, impregnation, spraying, brushing or related techniques. The contacting also includes physisorption techniques. The contacting can be carried out at normal temperature and atmospheric pressure or at higher temperatures and / or pressures. By contacting the catalyst system with the support material physical and / or chemical interactions, usually electrostatic interactions, a.

Essential for the suitability as a carrier material in the context of the present invention are also its specific surface area and its porosity properties. In this case, mesoporous carrier materials have proven to be particularly advantageous. Mesoporous carrier materials generally have an internal surface area of from 100 to 3000 m ² / g, in particular from 200 to 2500 m ² / g, and pore diameters of from 0.5 to 50 nm, in particular from 1 to 20 nm.

Suitable carrier materials are in principle all solid inert substances with a high surface area, which can usually serve as a support or scaffold for active substance, in particular for catalysts. Typical inorganic classes of substances for such support materials are activated carbon, alumina, silica gel, kieselguhr, talc, kaolin, clays and silicates. Typical organic classes of such support materials are crosslinked polymer matrices such as crosslinked polystyrenes and crosslinked polymethacrylates, phenol-formaldehyde resins or polyalkylamine resins.

Preferably, the carrier material is selected from molecular sieves and ion exchangers.

As ion exchangers, it is possible to use both cation, anion and amphoteric ion exchangers. Preferred organic or inorganic matrices for such ion exchangers are polystyrenes wetted with divinylbenzene (crosslinked divinylbenzene-styrene copolymers), divinylbenzene crosslinked polymethacrylates, phenol-formaldehyde resins, polyalkylamine resins, hydrophilized cellulose, crosslinked dextran, crosslinked agarose, zeolites , Montmorillonites, attapulgites, bentonites, aluminum silicates and acid salts of polyvalent metal ions such as zirconium phosphate, titanium tartrate or nickel hexacyanoferrate (II). Acid ion exchangers usually carry carboxylic acid, phosphonic acid, sulfonic acid, carboxymethyl or sulfoethyl groups. Basic ion exchangers usually contain primary, secondary or tertiary amino groups, quaternary ammonium groups, aminoethyl or diethylaminoethyl groups.

Molecular sieves have a strong adsorption capacity for gases, vapors and solutes and are generally also applicable to ion exchange processes. Molecular sieves typically have uniform pore diameters, on the order of the diameter of molecules, and large internal surfaces, typically 600 to 700 m ² / g. In particular, silicates, aluminum silicates, zeolites, silicoaluminophosphates and / or carbon molecular sieves can be used as molecular sieves in the context of the present invention.

Ion exchangers and molecular sieves with an inner surface area of 100 to 3000 m ² / g, in particular 200 to 2500 m ² / g, and pore diameters of 0.5 to 50 nm, in particular from 1 to 20 nm, are particularly advantageous.

Preferably, the support material is selected from molecular sieves of the types H-AlMCM-41, H-AIMCM-48, NaAlMCM-41 and NaAlMCM-48. These types of molecular sieves are silicates or aluminum silicates, on the inner surface of which silanol groups are attached, which may be of importance for interaction with the catalyst complex. However, the interaction is believed to be mainly due to the partial exchange of protons.

Both when used as a dispersion or in supported form, the catalyst system is effective as a catalyst used in such an amount that, based on the amounts of monomers used, in a weight ratio of preferably 1:10 to 1: 1,000,0000, above all from 1: 10,000 to 1: 500,000 and in particular from 1: 5000 to 1: 100,000 is present in the polymerization medium.

The concentration ("loading") of the catalyst system in the carrier material is in the range of preferably 0.005 to 20 wt .-%, especially 0.01 to 10 wt .-% and in particular 0.1 to 5 wt .-%.

The catalyst system effective as a polymerization catalyst is present in the polymerization medium, for example, as a loose bed, as a fluidized bed, as a fluidized bed or as a fixed bed. Suitable reactor types for the polymerization process according to the invention are accordingly usually stirred tank reactors, loop reactors, tubular reactors, fluidized bed reactors, fluidized bed reactors, stirred tank reactors with and without solvent, liquid bed reactors, continuous fixed bed reactors and discontinuous fixed bed reactors (batch mode).

For the preparation of copolymers, it is possible to proceed by initially introducing the monomers, if appropriate in the solvent, and then adding the catalyst system, for example as a loose bed. The adjustment of the reaction temperature can be carried out before or after the addition of the catalyst system. It is also possible to initially introduce only one of the monomers, if appropriate in the solvent, then to add the catalyst system and to react it only after a certain time, for example when at least 60%, at least 80% or at least 90% of the monomer have reacted. the one or more monomers added. Alternatively, one can submit the catalyst system, for example as a loose bed, optionally in the solvent, then add the monomers simultaneously or sequentially and then set the desired reaction temperature. The beginning of polymerization is then that time at which the catalyst system and at least one of the monomers are contained in the reaction vessel.

In addition to the discontinuous procedure described here, the polymerization can also be designed as a continuous process. In this case, the starting materials, ie, the monomer (s) to be polymerized, optionally the solvent and, if appropriate, the catalyst system (for example as a loose bed), are added continuously to the polymerization reaction and continuously remove the reaction product, so that more or less stationary polymerization conditions occur in the reactor. The monomer or monomers to be polymerized can be supplied as such, diluted with a solvent or as a monomer-containing hydrocarbon stream.

For reaction termination, the reaction mixture is preferably deactivated, for example by adding a protic compound, in particular by adding water, alcohols, such as methanol, ethanol, n-propanol and isopropanol or mixtures thereof with water, or by adding an aqueous base, for. Example, an aqueous solution of an alkali or alkaline earth metal hydroxide such as sodium hydroxide, potassium hydroxide, magnesium hydroxide or calcium hydroxide, an alkali or alkaline earth metal carbonate such as sodium, potassium, magnesium or calcium carbonate, or an alkali or Erdalkalihydrogencarbonats such as sodium, potassium, magnesium - or calcium bicarbonate.

In a preferred embodiment of the invention, the process according to the invention is used for the preparation of highly reactive isobutene homopolymers or copolymers having a content of terminal vinylidene double bonds (α-double bonds) of at least 80 mol%, preferably of at least 85 mol%, more preferably of at least 90 mole%, and more preferably at least 95 mole%, e.g. B. of about 100 mol%. In particular, it serves to prepare highly reactive copolymers which are composed of monomers comprising isobutene and at least one vinylaromatic compound and a content of terminal vinylidene double bonds (α-double bonds) of at least 80 mol%, preferably of at least 85 mol% preferably at least 90 mole% and especially at least 95 mole%, e.g. B. from about 100 mol%, have.

In the copolymerization of isobutene or isobutene-containing hydrocarbon cuts with at least one vinyl-aromatic compound, block copolymers are preferably also formed with the simultaneous addition of the comonomers, the isobutene block generally having the terminal, d. H. represents the last block formed.

Accordingly, in a preferred embodiment, the process of the invention is used to prepare highly reactive isobutene-styrene copolymers. Preferably, the highly reactive isobutene-styrene copolymers have a content of terminal vinylidene double bonds (α-double bonds) of at least 80 mol%, more preferably at least 85 mol%, more preferably at least 90 mol%, and most preferably at least 95 Mol%, z. B. of about 100 mol%, on.

To prepare such copolymers, isobutene or an isobutene-containing hydrocarbon cut is copolymerized with at least one vinylaromatic compound, in particular styrene. Such a monomer mixture particularly preferably contains from 5 to 95% by weight, particularly preferably from 30 to 70% by weight, of styrene.

Preferably, the highly reactive isobutene homo- or copolymers prepared by the process according to the invention, especially the isobutene homopolymers, have a polydispersity (PDI = M _w / M _n ) of 1.0 to 3.0, especially of at most 2.0, preferably of 1 , 0 to 2.0, more preferably from 1.0 to 1.8, and especially from 1.0 to 1.5.

Preferably, the highly reactive isobutene homo- or copolymers prepared by the process of the invention have a number average molecular weight M _{n of} from 500 to 1,000,000, more preferably from 500 to 50,000, more preferably from 500 to 5,000, and most preferably from 800 to 2,500. Isobutene homopolymers are especially more preferably, a number average molecular weight M _{n of} from 500 to 50,000, and more preferably from 500 to 5,000, e.g. From about 1000 or from about 2300.

By means of the process according to the invention, said ethylenically unsaturated monomers having at least 4 carbon atoms, in particular isobutene and isobutene-containing monomer mixtures, are successfully polymerized with high conversions in short reaction times even at relatively high polymerization temperatures. Furthermore, highly reactive isobutene homopolymers or copolymers having a high content of terminal vinylidene double bonds and having a rather narrow molecular weight distribution are obtained. The use of fluorine-free compounds as polymerization catalysts less pollutes wastewater and the environment.

The present invention can be illustrated by suitable examples. Thus, for example, isobutene with a catalyst system based on copper benzene-1,2,3-tricarboxylate (Basolite ^™ C 300) in dichloromethane at room temperature in a glass autoclave to polymerize polyisobutene with a high content of terminal vinylidene double bonds.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 2702604 A [0002, 0003]
• EP 145235 A [0004, 0005]
• US 5408018 [0004, 0005]
• WO 99/64482 [0004, 0005]
• DE 10111230 A [0008, 0027]
• EP 790253 A [0008]
• WO 2007/144324 [0008]
• WO 2003/101975 [0008]
• US 5648508 A [0027]
• US 5648508 [0033]
• DE 10355087 A [0033]
• WO 2005/049892 A [0033]
• WO 94/29408 [0048]
• EP 0592050 A1 [0048]
• WO 94/13584 [0048]
• JP 03-037156 A [0048]
• EP 0102544 B1 [0048]
• EP 0389041 A1 [0051]
• EP 0200260 A1 [0051]
• WO 95/19222 [0051]

Cited non-patent literature

• JM Tanski, PT Wolczanski, Inorg. Chem. 2001, 40, 2026 [0008]
• Pure Applied Chem. 45, page 71 / page 79 (1976) [0009]
• DIN 66131 [0009]
• DIN 66134 [0009]
• DIN 66131 [0010]
• 66134 [0010]
• Ullmanns Enzyklopadie der Technischen Chemie, 4th Edition, Volume 2, p. 313 ff. (1972) [0043]

Claims (6)

Process for the preparation of homopolymers or copolymers by polymerization of one or more ethylenically unsaturated monomers having at least 4 carbon atoms in the liquid phase in the presence of a catalyst system, characterized in that the catalyst system is a porous organometallic framework which has at least one coordinate-coordinating to at least one metal ion, contains at least bidentate organic compound. A method according to claim 1, characterized in that in the porous organometallic framework material, an acid from the group consisting of isophthalic acid, terephthalic acid, 2,5-dihydroxyterephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 2,2 'Bipyridine-5,5'-dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid. A method according to claim 1 or 2, characterized in that in the porous organometallic framework material, a metal ion from the group consisting of Zn ²⁺ , Al ³⁺ , CO ²⁺ , Co ³⁺ , Fe ³⁺ and Cu ^{2+ is} present. Process according to claims 1 to 3 for the preparation of highly reactive Isobutenhomo- or copolymers having a number average molecular weight M _n of 500 to 1,000,000 of isobutene or an isobutene-containing monomer mixture. A process as claimed in claim 4 for the preparation of highly reactive isobutene homo- or copolymers containing at least 80 mol% of terminal vinylidene double bonds. A process according to claim 4 or 5 for the preparation of highly reactive isobutene homo- or copolymers having a polydispersity of at most 2.0.