Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/14—Monomers containing five or more carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/04—Reduction, e.g. hydrogenation

Definitions

• the present invention relates to a process for the preparation of poly- ⁇ -olefins by dehydrating polymerization in the presence of acidic aluminum sheet silicates and, if appropriate, subsequent hydrogenation, and poly- ⁇ -olefins which can be obtained by polymerizing primary alcohols in the presence of acidic aluminum sheet silicates and, if appropriate, then hydrogenated.
• Poly- ⁇ -olefins have been known for a long time. They are usually produced by polymerizing ⁇ -olefins in the presence of catalysts. Common catalysts are Lewis acids and transition metal compounds.
• EP 321 852 B describes the preparation of 1-olefin polymer waxes by polymerizing 1-olefins at pressures from 0.5 to 120 bar in the presence of a catalyst which consists of a metallocene as a transition metal compound and an aluminoxane as an activator.
• EP 401 776 B describes a process for the preparation of poly-1-olefins, in which 1-olefins are polymerized in the presence of a catalyst which consists of the reaction product of a magnesium alcoholate with titanium tetrachloride and an organometallic compound from group III-III of the periodic table.
• EP 607 773 B describes a process for the preparation of low molecular weight poly-1-olefins by homo- or copolymerization of a 1-olefin at temperatures in the range from 20-200 ° C. and pressures from 0.5 to 50 bar in the presence of a special catalyst, wherein the molar mass of the polymer is regulated by means of hydrogen so that low molecular weight poly-1-olefins with a viscosity number below 80 cm 3 g- 1 are formed.
• WO 01/19873 A1 describes a process for the production of polyolefins, in which a liquid raw material which contains at least one olefin is mixed with a catalyst which contains a stable BF 3 complex.
• the implementation of the reaction is characterized by further features which are directed to special apparatus parameters. Description of the invention
• poly- ⁇ -olefins are elegantly accessible, and in particular also new poly- ⁇ -olefins which have interesting properties, such as low oxidation sensitivity and low viscosity.
• a first object of the present invention is accordingly a process for the preparation of poly- ⁇ -olefins, characterized in that primary alcohols are subjected to dehydrating polymerization at temperatures in the range from 60 to 340 ° C. in the presence of acidic aluminosilicate silicates and, if appropriate, subsequently hydrogenated ,
• reaction is carried out with the water formed being removed.
• reaction is carried out under protective gas, in particular nitrogen.
• reaction temperature is set in such a way that the system comprising the desired olefin and the acidic aluminosilicate is heated until water separation is observed and this temperature is maintained until no further elimination of water takes place.
• the catalyst is then removed, for example by filtration, to give a bare, liquid product.
• an inert gas preferably nitrogen.
• Those alcohols are preferably selected which contain at least one primary OH group, preferably contain one or two primary OH groups and in particular have 6 to 72 carbon atoms per molecule.
• the alcohols can be used individually or in a mixture with one another.
• the alcohols can be linear or branched, saturated or mono- or polyunsaturated, in particular olefinically unsaturated.
• the primary alcohols used are monofunctional compounds of the formula (I)
• radical R 1 is an alkyl group having 6 to 72 carbon atoms, which can be saturated or unsaturated, straight-chain or branched.
• suitable primary monofunctional straight-chain alcohols of the formula (I) are hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosonico, tosanol , 10-Undecen-1-ol, oleyl alcohol, elaidyl alcohol, ricinol alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol, arachidone alcohol, eruca alcohol, brassidyl alcohol.
• suitable primary monofunctional branched alcohols of the formula (I) are those which have at least one methyl branch in the alkyl group, which can be anywhere in the alkyl chain, for example in the case of isononyl alcohol, isostearyl alcohol or isotridecyl alcohol.
• Other suitable primary monofunctional branched alcohols are the Guerbet alcohols known to the person skilled in the art, which are known to be accessible by dimerization of fatty alcohols and which are structurally characterized in that they have a longer alkyl radical, preferably in the ⁇ -position to the terminal CH 2 OH group, with 2 have up to 18 carbon atoms.
• Suitable Guerbet alcohols are 2-hexyldecanol, 2-butyloctanol, 2-octyldodecanol and 2-hexyldecylpalmitate / stearate, 2-ethylhexanol and 2-propylheptanol.
• Preferred primary alcohols of the formula (I) are monofunctional branched alcohols which preferably have one or more methyl or C2-C18-alkyl groups as branches, where the branches can be distributed over the entire alkyl radical of the alcohol. If the branching is methyl groups, it is also possible for several, preferably 2 to 6, methyl groups to be distributed over the alkyl radical of the alcohol. If it is a C ⁇ -Ci ⁇ -alkyl group as a branch, there are preferably no further branches in the alkyl radical of the alcohol. Guerbet alcohols, preferably 2-ethylhexyl alcohol, are particularly suitable.
• the alcohols used are primary two-functional alcohols (with 2 hydroxyl groups), which may be saturated or unsaturated, such as 1,5-pentanediol, 1,8-octanediol, 1,6-hexanediol, 1, 10-decanediol, 1, 12 dodecanediol or the dimer and / or trimer alcohols known to the person skilled in the art.
• Dimer diol / trimer triols are technical mixtures which are obtained by oligomerizing unsaturated fatty acids having 12 to 22, preferably 16 to 18 carbon atoms or their methyl esters and subsequent high-pressure hydrogenation.
• oligomerization an average of two to three fatty acids come together and form dimers or trimers, which predominantly have cycloaliphatic structures.
• the oligomerization can be carried out thermally or in the presence of noble metal catalysts. The reaction is preferably carried out in the presence of alumina.
• esters preferably methyl esters
• Dimer diol / trimer diol mixtures which are particularly preferred for the purposes of the invention, are obtained by oligomerizing technical oleic acid and subsequent high-pressure hydrogenation and have a dimer diol content of 33 to 99% by weight and a trimer triol content of 1 to 67% by weight. on.
• the dimer diols are of particular importance within the group of bifunctional alcohols, since they can be used to produce polyolefins with extremely interesting properties, such as high viscosity.
• reaction times during the polymerization are moderate per se and are usually in the range from 2 to 48 hours.
• the length of the reaction time can be determined by the fact that no further water separation takes place. In this way it can be ensured that only the minimum required reaction time is set and further thermal stress on the system is avoided.
• the reaction is induced by acidic aluminosilicate silicates.
• the acid loading of the aluminum layer silicates is preferably 3 to 300 meq / 100 g.
• the process according to the invention has the advantage that the catalyst is used only in relatively small amounts and that it can be largely reused.
• Aluminum layer silicates are minerals with a basic silicate structure, in which there are silicate layers linked to one another via dipole-dipole interactions and hydrogen bonds with partially embedded aluminum 3+ ions, and these two-dimensionally infinite anionic silicate layers are electrostatically cross-linked via cations of an intermediate layer. Structure and Compositions of such layered silicates are known to the person skilled in the art from the prior art and can be found in the relevant literature.
• aluminosilicate silicates examples include talc and clays with a leaf structure, such as kaolinite, montmorillonite, bentonite and hectorite.
• the amount of acid-loaded aluminum layer silicate is not critical in itself. Usually, however, the catalyst is used in the process according to the invention in an amount of 1-100% by weight, based on the alcohol used. The preferred amount is in the range of 1 to 10% by weight.
• the type of acid of the acid-coated aluminosilicate silicates per se is not subject to any particular restrictions. However, preference is given in particular to hydrohalic acids, in particular HCl, and sulfuric acid and phosphoric acid.
• Acid-coated montmorillonites are particularly preferred as catalysts in the context of the present invention.
• K catalysts with the acid loading described above are used. These catalysts are known to the person skilled in the art and are commercially available from Südchemie. According to the invention, in particular the commercially available type K5. The general rule is that the K catalysts can be used alone or in combination with one another.
• such aluminum layer silicates can be used as catalysts which, due to the production, already have the required critical acid loading in the above-mentioned range, as is the case, for example, with the K5 type K catalysts.
• aluminosilicate silicates it is also possible to use such aluminosilicate silicates as catalysts which, due to the production process, initially have a lower acid load, but which have subsequently been loaded with so much acid that their acid load is in the critical range mentioned above.
• the alcohol is usually made up in anhydrous form. However, it is also possible to use technical quality alcohols with a water content of up to approx. 2% by weight.
• the degree of oligomerization of the poly- ⁇ -olefins obtainable by the process according to the invention is in the range from 1 to 10.
• a specific adjustment of the degree of oligomerization can be achieved in particular by reintroducing the olefin entrained in the removal of water recycle the reaction mixture; this is particularly important if you want to set higher degrees of oligomerization.
• the dehydrating polymerization can be followed by hydrogenation of the poly- ⁇ -olefins obtained (so-called curing).
• the hydrogenation can be carried out in a manner known per se at temperatures in the range from 150 to 250 ° C., preferably 190 to 210 ° C., and pressures from 50 to 150 (low pressure process) or 150 to 350 bar (high pressure process).
• Suitable catalysts are the hydrogenation catalysts known from the prior art, such as nickel, or the noble metal catalysts, in particular based on platinum or palladium. Palladium catalysts, in particular palladium on carbon, have proven to be particularly suitable.
• the catalyst can be added in the form of a suspension or in solid form to the poly- ⁇ -olefins in customary amounts, which for the preferred palladium-on-carbon is in the range from 0.001 to 5% by weight, calculated as palladium.
• a solid support material such as activated carbon, graphite, kieselguhr, silica gel, spinels, aluminum oxide or ceramic materials in question.
• the nickel catalysts for example suspended nickel such as Nysofact 101 I a (from Engelhard), have proven suitable, which is preferably used in amounts of 0.01 to 5% by weight, drawn on nickel.
• the process according to the invention of dehydrating polymerization and, if appropriate, subsequent hydrogenation also enables access to new poly- ⁇ -olefins based on unsaturated primary monofunctional alcohols, branched primary monofunctional alcohols and / or primary diols due to its flexible use.
• Another object of the present invention therefore relates to poly- ⁇ -olefins obtainable by subjecting unsaturated primary monofunctional alcohols to dehydrating polymerization at temperatures in the range from 60 to 340 ° C. in the presence of acidic aluminosilicate silicates.
• the present invention relates to poly- ⁇ -olefins obtainable by subjecting branched primary monofunctional alcohols to dehydrating polymerization at temperatures in the range from 60 to 340 ° C. in the presence of acidic aluminosilicate silicates and, if appropriate, subsequently hydrogenating them.
• Another object of the invention relates to poly- ⁇ -olefins obtainable by subjecting primary diols to dehydrating polymerization in the presence of acidic aluminosilicate silicates at temperatures in the range from 60 to 340 ° C. and then optionally hydrogenating them.
• the suitable process conditions for the polymerization and the hydrogenation including the catalysts, quantitative ratios and the primary alcohols to be used, have already been discussed in connection with the process according to the invention.
• the new poly- ⁇ -olefins are colorless or yellowish products that can be liquid or solid.
• the percentages by weight of catalyst K5 relate to the amount of alcohol used.
• SZ acid number
• IZ iodine number
• OHZ hydroxyl number.
• the weight percent in the case of the hydrogenation catalyst relates to the quantity of palladium.

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• 2001
  • 2001-10-20 DE DE10152267A patent/DE10152267A1/de not_active Withdrawn
• 2002
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  • 2002-10-11 WO PCT/EP2002/011392 patent/WO2003035707A1/de not_active Application Discontinuation
  • 2002-10-11 JP JP2003538220A patent/JP2005506414A/ja active Pending
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