Method for preparing polyisobutene derivatives

Abstract

The present application describes a novel process for preparing polyisobutene derivatives, such polyisobutene derivatives, and their uses.

Description

[Technical Field]

[0001] This application describes a novel method for preparing polyisobutene derivatives, such polyisobutene derivatives, and their uses. [Background technology]

[0002] Polyisobutene is known to improve the combustion efficiency of fuel combustion devices, as seen, for example, in U.S. Patent No. 8425630B2. The same is true for its derivatives, such as polyisobuteneamine (PIBA), a common fuel additive used as a valve cleaner in gasoline fuels. The mechanism of improved combustion efficiency is unknown, but it may be hypothesized that polyisobutene depolymerizes under combustion conditions, releasing isobutene or low-molecular-weight isobutene oligomers that act favorably on the combustion process; see, for example, RS. Lehrle, Journal of Analytical and Applied Pyrolysis, 64(2002) 207-227.

[0003] The object of the present invention was to provide a polyisobutene derivative that exhibits further effects in fuel, in addition to polyisobutene itself.

[0004] It has been found that the hydroperoxide of polyisobutene according to the present invention exhibits different lubricity than that of polyisobutene.

[0005] Furthermore, a method for preparing such polyisobutene derivatives in which polyisobutene is photo-oxygenated is disclosed.

[0006] Photooxygenation of olefins is known from prior art.

[0007] Korean Patent No. 101748827B1 (machine translation) discloses the synthesis of epoxides from olefins, including photooxygenation in the presence of a sensitizer under irradiation in the presence of oxygen, and epoxidation of an intermediate hydroperoxide with the help of a titanium catalyst.

[0008] Clear examples using 2,3-dimethyl-2-butene are disclosed, and the scope of the disclosure is limited to olefins substituted with up to C12 alkyl groups.

[0009] W. Pritzkow et al. (Journal f.prakt.Chemie, vol.324, no.1, 1982, pages 123-141) describe the auto-oxidation of certain branched olefins, particularly the dimer isobutenes (2,4,4-trimethylpenta-1-ene and 2,4,4-trimethylpenta-2-ene).

[0010] The products of auto-oxidation are mainly epoxides, with only small amounts of hydroperoxides being formed.

[0011] The mechanism of epoxide formation has been further elucidated by W. Adam et al., J. Am. Chem. Soc. 1989, 11, 203-212.

[0012] However, it is well known that in the polymerization of isobutene dimers, isobutene acts not as a monomer but as a chain transfer agent (see, for example, U.S. Patent No. 9,598,655B2 or H. Mayr et al., Macromolecules 1997, 30, 3965-3970), and therefore, those skilled in the art could not apply the results obtained with dimeric isobutene to polyisobutene.

[0013] R. Pazur et al., J. Polym. Sci. Polym. Chem. Ed., 35, 9, 1689-1701, 1997, disclose the oxidative degradation of high-molecular-weight polyisobutene. Their observations reveal non-selective oxidation along with polymer depolymerization.

[0014] U.S. Patent No. 3,484,353 discloses the photosensitized oxidation reaction of polymers having internal double bonds, particularly copolymers prepared from diolefins. A reaction mechanism for hydroperoxide formation from internal double bonds in polymerized isoprene units is presented.

[0015] However, the monomer mixture contains little or no isoprene, and this reaction mechanism, if any, only plays a secondary role in polyisobutene, so polyisobutene contains little or no internal double bonds.

Summary of the Invention

Problems to be Solved by the Invention

[0016] A further object of the present invention is to provide a method for producing derivatives of such polyisobutenes having high selectivity and defined functionality without significantly decomposing the starting materials.

Means for Solving the Problems

[0017] The object is achieved by polyisobutene derivatives selected from the group consisting of 1a - 6a

Chemical Formula

Embodiments for Carrying Out the Invention

[0018] In a preferred embodiment, the polyisobutene derivative according to the present invention is a high polymer in which n is a positive integer of at least 8, preferably at least 9, more preferably at least 11, and most preferably at least 13.

[0019] The upper limit of the integer n is usually 100, preferably 85, more preferably 45, and most preferably 25.

[0020] Polyisobutene derivatives are hydroperoxides of polyisobutene, and these terms are used synonymously throughout this text.

[0021] Another object of the present invention is a mixture of such polyisobutene derivatives containing at least 5% by weight, preferably at least 7% by weight, more preferably at least 10% by weight, even more preferably at least 15% by weight, and particularly at least 20% by weight, of such polyisobutene derivatives selected from one or more compounds of general structure 1a to 6a.

[0022] In preferred embodiments of the present invention, such a mixture comprises polyisobutene in addition to a polyisobutene derivative selected from one or more compounds of general structure 1a to 6a.

[0023] The polyisobutene content in such a mixture according to the present invention, comprising polyisobutene and at least one polyisobutene derivative selected from compounds of general structure 1a to 6a, may be 10 to 95% by weight, preferably 15 to 90%, more preferably 20 to 85%, and even more preferably 25 to 80% by weight, provided that the sum of all components is always 100% by weight.

[0024] Furthermore, such mixtures may contain one or more solvents (see below) in amounts typically used to adjust the mixture to 100% by weight.

[0025] Another object of the present invention is a method for preparing polyisobutene hydroperoxide, -Oxygen-containing gas, General formula 7 and / or 8 and / or 9 and / or 10 and / or 11 [ka] [In the formula, n is as defined above] polyisobutene or its E- / Z-isomers or a suitable solution of such polyisobutene in a suitable solvent - A step of contacting in the presence of a photosensitizer, - A step of irradiating a reaction mixture with an electroluminescent illumination device that emits monochromatic light, wherein at least 90% of the power of the monochromatic light and up to 100% of the power are emitted in the range of 350 nm to 680 nm. This method includes [something].

[0026] Compounds 7-11 also include, if any, their E- / Z-isomers having different stereochemistrys of the double bond as clearly shown in the above chemical structures.

[0027] Polyisobutene The polyisobutene used in the method according to the present invention contains, as a main component, one or more compounds of general formula 7 and / or 8 and / or 9 and / or 10 and / or 11, preferably at least 50% by weight, more preferably at least 60% by weight, even more preferably at least 75% by weight, and particularly at least 85% by weight, based on the total amount of compounds of formulas 7, 8, 9, 10, and 11.

[0028] The polyisobutene used in the method according to the present invention can be prepared by any method known to those skilled in the art, provided that it contains a sufficient amount of the compound of general formula 7 and / or 8 and / or 9 and / or 10 and / or 11 for photooxygenation. Preferred methods for preparing polyisobutene are disclosed, for example, in German Patent Application Publication A2702604, European Patent Application Publication A145235, U.S. Patent No. 5408018, International Publication Brochure 99 / 64482, and International Publication Brochure 11 / 101281.

[0029] Polyisobutene is a homopolymer or copolymer of isobutene. In the context of the present invention, isobutene homopolymer is understood to mean a polymer formed from isobutene to a degree of at least 98 mol%, preferably at least 99 mol%, based on the polymer. Therefore, isobutene copolymer is understood to mean such polymers containing more than 0.5 mol%, preferably more than 1 mol%, more preferably more than 2 mol%, preferably with a maximum content of 10 mol%, more preferably up to 5 mol%, copolymer monomers other than isobutene, preferably isoprene or linear butene, preferably 1-butene, cis-2-butene, and trans-2-butene.

[0030] In preferred embodiments, isobutene copolymer is understood to mean a polymer comprising 0.5 mol% or less of isoprene, preferably 0.45 mol% or less, more preferably 0.4 mol% or less, particularly 0.35 mol% or less of isoprene, and up to 10 mol%, more preferably up to 5 mol%, of linear butene, preferably 1-butene, cis-2-butene, and trans-2-butene as copolymer monomers.

[0031] In preferred embodiments, the polyisobutene is a highly reactive polyisobutene, and the content of highly reactive double bonds per polyisobutene chain end is at least 70 mol%, preferably at least 75%, very preferably at least 80 mol%, and particularly at least 90 mol%, based on the individual chain ends of the polyisobutene macromolecule. The highly reactive double bonds are those carbon-carbon double bonds located at the α position (in general structure 7) or β position (in general structure 8) of the chain ends.

[0032] In the context of the reaction according to the present invention, the double bond at the α-position of the chain terminal is less reactive with respect to singlet oxygen than the double bond at the β-position, and the double bond at the β-position is less reactive than the tetrasubstituted double bond.

[0033] The molecular weight of the polyisobutene used is determined by the parameter n. As a polymer, polyisobutenes follow a statistical distribution of chain length, and typically they exhibit a polydispersity (PDI = Mw / Mn) of 1.05 to less than 3.5, preferably 1.05 to less than 3.0, preferably 1.05 to less than 2.5, preferably 1.05 to 2.3, more preferably 1.05 to 2.0, and particularly 1.1 to 1.85. A typical PDI value is 1.2 to 1.7. To calculate the polydispersity, the number-average molecular weight Mn and weight-average molecular weight Mw are determined by gel permeation chromatography.

[0034] In addition to compounds of general formula 7 and / or 8 and / or 9 and / or 10 and / or 11, polyisobutenes used may also be of other formulas, for example, [ka] The polyisobutene may also be included, where the degree of polymerization of such compound, i.e., the number of isobutene monomers incorporated into the polymer, corresponds to that of the polyisobutene used.

[0035] solvent The reaction may be carried out in the absence, or preferably in the presence, of at least one solvent in order to reduce the viscosity of the reaction medium.

[0036] The reaction solvents include benzene, C1-C4 alkylbenzene, 1,2-xylene, 1,3-xylene, 1,4-xylene, and C4-C 10 - Alkanes, C3-C6 alkanones, 2-ethylhexanol, etc. C1-C 10 - Alkanols, dichloromethane, trichloromethane, tetrachloromethane, 1,1-dichloroethane, 1,2-dichloroethane, trichloroethane, 1-chlorobutane, tetrachloroethylene, carbon disulfide, C5~C 12 -Cycloalkanes, C5~C 12-Cycloalkanones, acetonitrile, C6D6, D2O, Freon 11, C6F6, tert. butyl methyl ether (MTBE), tert. butyl ethyl ether (ETBE), or mixtures thereof may be used.

[0037] It is also possible to use a mixture of hydrocarbons such as Solvesso(R).

[0038] In a preferred embodiment, a solvent with a long singlet oxygen half-life is used.

[0039] It is preferable to add an amount of solvent to the polyisobutene such that the reaction mixture can be easily transported through the reactor under storage and reaction conditions.

[0040] A preferred solvent is one that can be easily separated from the reaction mixture after photooxygenation by, for example, evaporation, stripping with an inert gas, or distillation. The preferred solvent has a boiling point of 200°C or lower, preferably 150°C or lower.

[0041] In one embodiment of the present invention, the solvent may remain in the reaction mixture after the reaction.

[0042] In another preferred embodiment, after the reaction, the solvent is removed, for example, by evaporation, stripping with an inert gas, distillation, rectification, membrane filtration, or reverse osmosis.

[0043] In this case, the solvent content in the mixture is, for example, 10% by weight or less, preferably 5% by weight or less, more preferably 2% by weight or less, even more preferably 1% by weight or less, and particularly 0.5% by weight or less.

[0044] Photosensitizer To carry out the reaction, one or more photosensitizers are required in the reaction mixture to convert triplet oxygen into singlet oxygen, which is necessary for photooxygenation.

[0045] Suitable photosensitizers are known to those skilled in the art, and preferably, the photosensitizer is fluorescein, eosin, rose bengal, erythrocin, tetraphenyl Porphyrin , cobalt-tetraphenyl Porphyrin , zinc-tetraphenyl Porphyrin Hematoporphyrin, Rhodamine B, Basacryl Brilliant Red, Methyl Violet, Methylene Blue, Fullerene C60, Fullerene C70, Graphene, Carbon Nanotube, Ru(bpy)3 2+ Ru(phen)3 2+ It is one or more selected from the group consisting of cercosporine and hypocrelin-A.

[0046] Preferred photosensitizers include rose bengal and tetraphenyl Porphyrin , methylene blue, and Ru(bpy)3 2+ That is the case.

[0047] Typically, the photosensitizer is used in the reaction mixture in an amount of 1 to 1000 ppm by weight, preferably 2 to 750, and more preferably 5 to 500 ppm by weight.

[0048] After the reaction, the photosensitizer may remain in the reaction mixture, or it may be removed by adsorption to silica gel, aluminum oxide, zeolite, diatomaceous earth, mixed aluminum silicon oxide, carbon black, or charcoal, or by extraction with a solvent, preferably a polar solvent that is immiscible with the reaction mixture, such as water, methanol, ethanol, isopropanol, or diethyl ether.

[0049] Oxygen-containing gas The oxygen-containing gas is used to provide oxygen that is converted from a triplet state to a singlet state under irradiation in the presence of at least one photosensitizer.

[0050] The oxygen-containing gas may be oxygen, air, or an oxygen / inert gas mixture containing oxygen in the range of 1-99% by volume, preferably 2-90%, more preferably 3-80%, even more preferably 5-60%, and most preferably 10-50% by volume.

[0051] Suitable inert gases may be nitrogen, noble gases such as helium, neon, argon, or krypton, carbon dioxide, or exhaust gas, preferably nitrogen, argon, or carbon dioxide, more preferably nitrogen.

[0052] Lighting devices The electroluminescent illumination device for the reaction according to the present invention emits monochromatic light.

[0053] Monochromatic light as understood in this disclosure is all radiation, at least 90% and up to 100% of its power, emitted into the reaction mixture in the range of 350 nm to 680 nm. For clarity, these figures represent the radiant energy accumulated in the reaction mixture. The power of the radiation source is not necessarily meaningful, as the power includes radiant energy in a desired range as well as wavelengths in an undesirable range, such as infrared radiation. Furthermore, the emission spectrum of the radiation source may be altered and attenuated by passing through glass, for example, a photoreactor. The power of trace components of monochromatic light outside a given wavelength range can be up to 10%, depending on the properties and amounts of the unfiltered electroluminescent lighting device, photosensitizer, and organic solvent used. However, the vast majority of embodiments of monochromatic light contain only a small amount of light portion from over 350 nm to 680 nm. In one embodiment, monochromatic light is understood to be an entity in which at least 95% and up to 100% of the power of the monochromatic light is emitted in the range of 350 nm to 680 nm. In yet another embodiment, monochromatic light means that at least 98%, more preferably at least 99%, and up to 100%, of the power of the monochromatic light is emitted in the range of 350 nm to 680 nm. The amount of monochromatic light is expressed in power because it eliminates the need to define the allowable amount of light in lumens (lm) or candela (cd) in a different way above and below the required wavelength range. If the amount is not expressed in power, it will vary as a function of the wavelength considered. In yet another specific embodiment, monochromatic light is all radiation, as understood in this disclosure, with at least 90%, and up to 100%, of its power emitted in the range of 350 nm to 680 nm, and its unimodal emission spectrum exhibits a full width at half maximum (FWHM) of + / -10 to + / -30 nm with respect to the wavelength of emission maximum. The FWHM defined above provides a highly structured illumination signal, which results in an improved yield of photooxygenation according to the present invention.

[0054] The wavelength of the monochromatic light must match the absorption of the sensitizer used to obtain the optimal quantum yield. In a preferred embodiment, the wavelength of the monochromatic light corresponds to the absorption maximum of the sensitizer used, at least within the full width at half maximum of the spectrum.

[0055] In a preferred embodiment, at least 50%, preferably at least 60%, more preferably at least 70%, and even more preferably at least 80% of the radiant power emitted by the radiation source is within a wavelength range of ±100 nm, preferably ±90 nm, more preferably ±80 nm, and especially ±70 nm, of the absorption maximum of the sensitizer used.

[0056] The filterless electroluminescent lighting devices in this disclosure are any light-emitting electroluminescent devices that can operate simply by switching them on and off for intentionally selected periods and do not have filtering means. The filtering means may be a layer, compound, or product applied to the lighting device. The filtering means may be a compound adapted to absorb different ranges of light, circulated, pumped, or suspended in a solvent around the lighting device. The electroluminescent lighting devices are required not to operate by chemically induced illumination or heating, such as ionization of any kind of gas. The filterless electroluminescent lighting devices are understood to provide light (photons) emerging from electrons filling pores or gaps in electron-deficient material, preferably with the emission of electromagnetic radiation in the form of visible light. Electroluminescent lighting devices without the above-mentioned filters are selected from the group consisting of light-emitting electrochemical cells, electroluminescent wires, magnetic field-induced electroluminescent polymers, light-emitting diodes, organic light-emitting diodes, polymer light-emitting diodes, active-matrix organic light-emitting diodes (AMOLEDs), in particular electroluminescent films based on inorganic light-emitting materials, semiconductor lasers, diode lasers, chemical lasers, dye lasers, free-electron lasers, gas dynamic lasers, gas lasers, ion lasers, laser flashlights, metal vapor lasers, single-line optical quantum well lasers, ruby ​​lasers, and solid-state lasers. Preferably, electroluminescent lighting devices without the above-mentioned filters are selected from the group consisting of light-emitting electrochemical cells, electroluminescent wires, magnetic field-induced electroluminescent polymers, light-emitting diodes, organic light-emitting diodes, polymer light-emitting diodes, active-matrix organic light-emitting diodes (AMOLEDs), in particular electroluminescent films based on inorganic light-emitting materials.

[0057] In a preferred embodiment, the electroluminescent lighting device comprises at least one light-emitting diode (LED).

[0058] reactor The method of the present invention is preferably implemented in a side-loop photoreactor, a continuous flow photoreactor, or an underwater photoreactor, more preferably a continuous flow photoreactor.

[0059] A side-loop photoreactor is a reactor that is introduced into or attached to a part of a reaction circuit. A reaction circuit is a device or equipment through which a reaction mixture circulates. A side-loop photoreactor can be easily attached to or incorporated into an existing reaction vessel or reaction plant. From this reaction vessel or reaction plant, the reaction mixture circulates through the side-loop photoreactor during operation. In this way, only a portion of the reaction mixture is in contact with radiation from an unfiltered electroluminescent lighting device (placed in the side-loop photoreactor) for a certain period of time. The portion then enters the reaction plant or reaction vessel and travels through the side-loop photoreactor again. The intermittent contact between the reaction mixture and the radiation from the lighting device accelerates the reaction process.

[0060] In a continuous flow reactor, the reaction mixture passes through the electroluminescent illumination device only once.

[0061] Underwater photoreactors are particularly useful when you want to work under a vacuum, which is easier to achieve when the photoreactor is completely immersed in the reaction mixture.

[0062] Reaction conditions A reaction mixture containing polyisobutene, a photosensitizer, and optionally a solvent is placed in or circulated in a reactor, preferably under stirring or forced convection, and exposed to irradiation with an electroluminescent lighting device.

[0063] At the same time, the reaction mixture is brought into contact with an oxygen-containing gas.

[0064] Preferably, an oxygen-containing gas is passed through the reaction mixture and bubbled, and the bubbles are dissipated using, for example, a nozzle, frit, stirring, electrostatic dissipator, or static mixer to increase their surface area and exchange oxygen with the reaction mixture.

[0065] In a preferred embodiment, sufficient mixing is achieved by circulating the reaction mixture and bubbling an oxygen-containing gas through the reaction mixture, so further stirring is unnecessary.

[0066] Therefore, it is preferable to bubble the reaction mixture through the reaction mixture at a volume that is a multiple of the reaction mixture per hour, preferably 1 to 100 times the volume of the reaction mixture per hour, preferably 2 to 50 times, and more preferably 5 to 20 times.

[0067] The reaction is carried out at temperatures ranging from -20°C to +150°C, preferably -10°C to 100°C, more preferably 0°C to 80°C, very preferably 5 to 50°C, and especially 10 to 40°C.

[0068] In preferred embodiments, the reaction according to the present invention is carried out at a temperature of 100°C or lower, preferably 80°C or lower, more preferably 60°C or lower, and particularly 50°C or lower. At these low temperatures, the reaction can usually be stopped at the stage of single oxidation products such as compounds 1a to 5a. The reaction rate for forming more highly oxidized products decreases, allowing for control of the products formed in the reaction. Higher reaction temperatures may lead to an increase in the formation of single oxidation products and beyond depolymerization.

[0069] Furthermore, the formation of the hydroperoxyl group primarily occurs at the α-position relative to the reactive double bond (i.e., the allyl hydrogen atom). Methyl and methylene groups, which are not at the α-position relative to the double bond, do not react significantly under these reaction conditions.

[0070] The reaction can be carried out at atmospheric pressure, a maximum reduction or increase of 100 bar, preferably at atmospheric pressure up to 20 bar.

[0071] The reaction time for a batch reaction or the residence time for a continuous reaction may range from a few minutes to several hours, preferably from 1 minute to 10 hours, more preferably from 5 minutes to 5 hours, and even more preferably from 10 minutes to 1 hour.

[0072] Post-processing As noted above, the reaction mixture may be left as is after the reaction is complete; that is, the solvent and photosensitizer may remain in the reaction mixture after the reaction.

[0073] In another preferred embodiment, after the reaction, the solvent is removed, for example, by evaporation, stripping with an inert gas, distillation, rectification, membrane filtration, or reverse osmosis.

[0074] The photosensitizer may be removed, for example, by adsorption to silica gel, aluminum oxide, zeolite, diatomaceous earth, mixed aluminum silicon oxide, carbon black, or charcoal, or by extraction with a solvent, preferably a polar solvent that is immiscible with the reaction mixture, such as water, methanol, ethanol, isopropanol, or diethyl ether.

[0075] Purpose The hydroperoxides according to the present invention, preferably mixtures thereof, have been found to exhibit improved lubrication activity compared to the polyisobutenes from which they are obtained. They exhibit this lubrication activity as solutions in the above-mentioned solvents, preferably hydrocarbon-containing solvents, more preferably fuels, particularly gasoline or diesel fuels. Therefore, a further object of the present invention is to use the hydroperoxides according to the present invention to improve the lubricity of hydrocarbon mixtures or hydrocarbon-containing oils, more preferably fuels or lubricating oils, particularly gasoline or diesel fuels.

[0076] The hydroperoxide according to the present invention typically exhibits a lubricating effect in an amount of at least 750 ppm by weight, preferably at least 1000 ppm, more preferably at least 1500 ppm, even more preferably at least 2000 ppm, and especially at least 3000 ppm by weight, based on the total amount of fuel.

[0077] The upper limit is determined by the viscosity of the solution obtained for the intended purpose of the fuel, and is usually not greater than 50,000 ppm by weight, preferably 30,000 or less, more preferably 20,000 or less, even more preferably 15,000 or less, and particularly less than 10,000 ppm by weight.

[0078] The hydroperoxides according to the present invention exhibit their lubricating effects in addition to their effects on combustion.

[0079] The following examples are intended to explain in detail without limiting the present invention.

Example

[0080] Example 1: A photochemical batch reactor equipped with 88 405 nm LEDs is filled with 50 g of highly reactive polyisobutene (Glissopal 1000 from BASF, Ludwigshafen, molecular weight approximately 1000 g / mol (the ratio of α-double bonds in PIB:β-double bonds in PIB is about 9:1)), 307 mg of tetraphenyl Porphyrin , and 492 g of dichloromethane. Irradiation is carried out at 20 °C while bubbling oxygen (5 l / h) through the reaction mixture. After 12 hours, the reaction is stopped. After evaporation of the solvent, the residue is analyzed by NMR spectroscopy. Structure (1a) was assigned to the main product;

Chemical formula

[0081] Example 2: A photochemical batch reactor equipped with 88 420 nm LEDs is filled with 201 g of Glissopal 1000 (α-double bond:β-double bond = about 9:1), 123 mg of tetraphenyl PorphyrinThe mixture was then packed with 266 g of dichloromethane. Oxygen (5 l / h) was passed through the reaction mixture while bubbling, and the mixture was irradiated at 30°C. After 21 hours, the reaction was stopped. After evaporation of the solvent, the residue was analyzed by NMR spectroscopy. Structures 1a (70.6 mol-%), 2a (6.3 mol-%), and 6a (15.6 mol-%) were assigned to the reaction products. [ka] 1 H-NMR (CDCl3) (1a): δ = 5.04, 5.25 (C-1); 4.47 (C-2); 2.08 (C-3) ppm. 1 H-NMR (CDCl3) (2a): δ = 5.01, 5.14 (C-1); 1.83 (C-2); 4.13 (C-3) ppm. 1 H-NMR (CDCl3) (6a): δ = 5.47, 5.59 (C-1); 4.38 (C-2); 4.31 (C-3) ppm. 13 C-NMR (CDCl3) (1a): δ = 113.8 (C-1), 80.7 (C-2), 47.9 (C-3), 139.4 (C-4) ppm. 13 C-NMR (CDCl3) (2a): δ = 113.5 (C-1), 19.8 (C-2), 92.7 (C-3), 143.8 (C-4) ppm. 13 C-NMR (CDCl3) (6a): δ = 115.4 (C-1), 78.0 (C-2), 89.4 (C-3), 139.5 (C-4) ppm.

[0082] Example 3: 0.89 g of Indopol H100 17107 (α-double bond:β-double bond:tetrasubstituted double bond = approximately 10:61:25) and 1 mg of tetraphenyl in a 5 mL vial. PorphyrinA 1 ml solution of 40.8 mg of dimethyl terephthalate and 11.5 g of trichloromethane was filled into the vial. The vial was flushed with oxygen, capped, and irradiated with a single 405 nm LED at 15°C for 1.5 minutes. After evaporation of the solvent, the residue was analyzed by NMR spectroscopy. Apart from the starting materials, structures (3a) and (4a) were assigned to the reaction products. [ka] 1 H-NMR (CDCl3) (3a): δ = 5.00, 5.28 (C-1); 4.51 (C-2) ppm. 1 H-NMR (CDCl3) (4a): δ = 5.03, 5.16 (C-1) ppm. 13 C-NMR (CDCl3) (3a): δ = 113.9 (C-1), 84.2 (C-2), 48.9 (C-3), 147.2.4 (C-4), 18.4 (C-5) ppm. 13 C-NMR (CDCl3) (4a): δ = 117.9 (C-1), 85.2 (C-2), 33.6 (C-3), 161.1 (C-4), 28.3 (C-5), 21.2 (C-6), 21.4 (C-7) ppm.

[0083] Example 4: A 5 mL vial contains 0.82 g of polyisobutene (α-double bond:β-double bond:tetrasubstituted double bond = approximately 8:43:43) and 1 mg of tetraphenyl Porphyrin A 1 ml solution of 39.2 mg of dimethyl terephthalate and 10.6 g of trichloromethane was filled into the vial. The vial was flushed with oxygen, capped, and irradiated with a single 405 nm LED at 15°C for 1.5 minutes. After evaporation of the solvent, the residue was analyzed by NMR spectroscopy. Apart from the starting materials and compound (4a), the structure of (5a) was assigned as one of the reaction products. [ka] The amounts of 4a and 5a constitute approximately 40% of the polyisobutene used in the reaction. 1 H-NMR (CDCl3) (5a): δ = 5.15 (C-2), 1.58 (C-5) ppm. 13 C-NMR (CDCl3) (5a): δ = 135.5 (C-2), 89.3 (C-3), 161.1 (C-4), 13.2 (C-5) ppm.

[0084] Example 5: In a photochemical batch reactor equipped with 108 525nm LEDs, 77.9g of Glissopal 1000 (α-double bond: 58.6 mmol, β-double bond: 8.1 mmol) and 20mg of tetraphenyl Porphyrin The reaction mixture was packed with 763 mg of dimethyl terephthalate (NMR standard) and 298 g of trichloromethane. Oxygen (3 l / h) was passed through the reaction mixture while bubbling, and the mixture was irradiated at -7°C. After 504 minutes, the reaction was stopped. After evaporation of the solvent, the residue was analyzed by quantitative NMR spectroscopy. 43.4 mmol (1a), 4.6 mmol (2a), and 6.4 mmol (6a) were found in the reaction mixture.

[0085] Example 6: In a photochemical batch reactor equipped with 124 405nm LEDs, 5.11g Glissopal 1000 (α-double bond: 3.9 mmol, β-double bond: 0.6 mmol) and 7mg tetraphenyl Porphyrin The reaction mixture was packed with 112 mg of dimethyl terephthalate (NMR standard) and 52 g of trichloromethane. Air (0.5 l / h) was passed through the reaction mixture while bubbling, and the mixture was irradiated at 15°C. After 252 minutes, the reaction was stopped. After evaporation of the solvent, the residue was analyzed by quantitative NMR spectroscopy. 2.7 mmol (1a), 0.3 mmol (2a), and 0.5 mmol (6a) were found in the reaction mixture.

[0086] Example 7: 104.4 g of Glissopal 1000 (α-double bond: 79.2 mmol, β-double bond: 10.3 mmol), 61 mg of tetraphenyl Porphyrin A solution of 2.5 g of dimethyl terephthalate (NMR standard) and 1350 g of trichloromethane was reacted in the presence of 8 bar of oxygen at 15°C in a continuous flow photoreactor (G1 Photo Corning reactor: 10 LED panels: 200 405 nm LEDs in total, 5 G1 heart plates, volume: 8.2 mL / plate, flow rate: 4.1 mL / min, residence time: 10 minutes, single pass). After evaporation of the solvent, the residue was analyzed by quantitative NMR spectroscopy. 59.4 mmol of α-PIB, 0.6 mmol of β-PIB, 13.3 mmol (1a), 8.3 mmol (2a), and 0.3 mmol (6a) were found in the reaction mixture.

[0087] Example 8: 80.6 g of Glissopal 1000 (α-double bond: 62.5 mmol, β-double bond: 7.5 mmol), 13 mg of tetraphenyl Porphyrin A solution of 1.0 g of dimethyl terephthalate (NMR standard) and 106 g of dichloromethane was reacted at 15°C in the presence of 5 bar of oxygen in a side-loop continuous flow reactor (G1 Photo Corning reactor: 10 LED panels: 200 405 nm LEDs in total, 5 G1 heart plates, volume: 8.2 mL / plate, flow rate: 6.3 kg / h). The reaction was stopped after 935 minutes. After evaporation of the solvent, the residue was analyzed by quantitative NMR spectroscopy. 10.7 mmol of α-PIB, 0 mmol of β-PIB, 35.3 mmol (1a), 4.7 mmol (2a), and 2.6 mmol (6a) were found in the reaction mixture.

[0088] Example 9: 30.5 g of polyisobutene (α-double bond: 3.7 mmol, β-double bond: 14.9 mmol), 15 mg of tetraphenyl Porphyrin A solution of 0.6 g of dimethyl terephthalate (NMR standard) and 266 g of dichloromethane was reacted at 17°C in the presence of 2 bar of oxygen in a side-loop continuous flow reactor (G1 Photo Corning reactor: 10 LED panels: 200 405 nm LEDs in total, 5 G1 heart plates, volume: 8.2 mL / plate, flow rate: 5.6 kg / h). The reaction was stopped after 141 minutes. After evaporation of the solvent, the residue was analyzed by quantitative NMR spectroscopy. 3.1 mmol (1a), 9.9 mmol (2a), and 0 mmol (6a) were found in the reaction mixture.

[0089] Example 10: A photochemical batch reactor equipped with 180 525nm LEDs was packed with 50.0 g of Glissopal 1000 (α-double bond: 40 mmol, β-double bond: 7 mmol), 20 mg of tetraphenylporphyrin, and 357.6 g of trichloromethane. The reaction mixture was irradiated at -5°C while bubbling oxygen (3 l / h) through it. After 520 minutes, the reaction was stopped. After evaporation of the solvent, the residue was analyzed by quantitative NMR spectroscopy. 30 mmol (1a) was found in the reaction mixture.

[0090] Example 11: Lubricity of fuel Description of the HFRR test for measuring wear and friction The high-frequency reciprocating rig test (HFRR) procedure used in accordance with ISO 12156 is a standard diesel fuel lubrication procedure.

[0091] In the examples, the HFRR test was performed under the following conditions: Time: 75 minutes, Temperature: 60℃, Stroke length: 1 mm, Frequency: 50 Hz, Mass: 200 g, Volume: 2 mL, Surface area: 600 mm 2 Furthermore, the same operator and machine were used in all tests.

[0092] Examples of actions regarding samples of base fuels The table shows the average results, statistically fitted to compensate for time lags.

[0093] The base fuel was standard diesel fuel without additives. Polyisobutene (Mw 1000 g / mol, Glissopal® 1000 (BASF SE, Ludwigshafen)) and the photooxygenation reaction mixture according to Example 10 were used as additives at the treatment rates specified in Table 1.

[0094] [Table 1] The present invention includes, for example, the following embodiments. [Section 1] 1a~6a [ka] [In the formula, n is a positive integer of at least 1, preferably at least 2, more preferably at least 3, even more preferably at least 5, and especially at least 8. A mixture of such polyisobutene derivatives containing at least 5% by weight of a polyisobutene derivative selected from the group consisting of and a polyisobutene derivative selected from those having the general structures 1a to 6a. [Section 2] The polyisobutene derivative according to claim 1, wherein n is a positive integer of at least 8, preferably at least 9, more preferably at least 11, and most preferably at least 13. [Section 3] A mixture of polyisobutene derivatives selected from the group consisting of 1a to 6a as defined in item 1 or 2, containing at least 5% by weight of polyisobutene hydroperoxide together with polyisobutene and optionally at least one solvent. [Section 4] A method for preparing a hydroperoxide of polyisobutene of the general structure 1a to 6a as defined in item 1 or 2 and a mixture described in item 3, -Oxygen-containing gas, General Structure 7 and / or 8 and / or 9 and / or 10 and / or 11 [ka] Polyisobutene [wherein n is as defined in item 1 or 2] or its E- / Z-isomers or a solution of polyisobutene in a suitable solvent - A step of contacting in the presence of a photosensitizer, - A step of irradiating a reaction mixture with an electroluminescent illumination device that emits monochromatic light, wherein at least 90% of the power of the monochromatic light, and up to 100% of the power, is emitted in the range of 350 nm to 680 nm. A method that includes this. [Section 5] The method according to claim 4, wherein the oxygen-containing gas is oxygen, air, or an oxygen / inert gas mixture containing oxygen in the range of 1 to 99 volume percent. [Section 6] The aforementioned photosensitizers include fluorescein, eosin, rose bengal, erythrocin, and tetraphenyl Porphyrin , cobalt-tetraphenyl Porphyrin , zinc-tetraphenyl Porphyrin Hematoporphyrin, Rhodamine B, Basacryl Brilliant Red, Methyl Violet, Methylene Blue, Fullerene C60, Fullerene C70, Graphene, Carbon Nanotube, Ru(bpy)3 2+ Ru(phen)3 2+ The method according to item 4 or 5, wherein one or more of the following are selected from the group consisting of cercosporine and hypocrelin-A. [Section 7] The method according to any one of claims 4 to 6, wherein the method is carried out without a solvent. [Section 8] Benzene, C1-C4-alkylbenzene, 1,2-xylene, 1,3-xylene, 1,4-xylene, C4-C 10-Alkane, C3~C6-Alkanon, C1~C 10 - Alkanols, dichloromethane, trichloromethane, tetrachloromethane, 1,1-dichloroethane, 1,2-dichloroethane, trichloroethane, 1-chlorobutane, tetrachloroethylene, carbon disulfide, C5~C 12 -Cycloalkanes, C5~C 12 - The method according to any one of claims 4 to 6, wherein a solvent selected from one or more of the group consisting of cycloalkanone, acetonitrile, C6D6, D2O, Freon 11, C6F6, tert. butyl methyl ether (MTBE), and tert. butyl ethyl ether (ETBE) is present in the reaction mixture. [Section 9] The method according to any one of claims 4 to 8, wherein the electroluminescent lighting device comprises at least one light-emitting diode (LED). [Section 10] The method according to any one of claims 4 to 9, wherein only a distinct portion of the reaction mixture is irradiated. [Section 11] The method according to any one of claims 4 to 10, wherein at least one of the polyisobutene compounds 7 to 11 supplemented with a photosensitizer is reacted with an oxygen-containing gas by irradiation at a temperature in the range of -20°C to +150°C. [Section 12] The method according to any one of claims 4 to 11, wherein at least one of the polyisobutene compounds 7 to 11 supplemented with a photosensitizer is reacted with an oxygen-containing gas by irradiation at a pressure in the range of atmospheric pressure to 100 bar. [Section 13] The method according to any one of claims 4 to 12, wherein the reaction is carried out in a side-loop photoreactor, a continuous flow photoreactor, or an underwater photoreactor. [Section 14] The method according to any one of claims 4 to 13, wherein at least 50% of the power of the radiation emitted by the radiation source is within the wavelength range of + / - 100 nm of the absorption maximum of the sensitizer used. [Section 15] To improve the lubricity of hydrocarbon mixtures or hydrocarbon-containing oils, more preferably fuels or lubricating oils, especially gasoline or diesel fuels. of or use of polyisobutene derivatives available according to any one of items 1 to 3, or according to the methods described in any one of items 4 to 14.

Claims

1. 1a-6a 【Chemistry 1】 [In the formula, n is a positive integer of at least 1. A mixture of such polyisobutene derivatives containing at least 5% by weight of a polyisobutene derivative selected from the group consisting of, or selected from those with the general structures 1a to 6a.

2. The polyisobutene derivative according to claim 1, wherein n is at least a positive integer of 8.

3. A mixture of polyisobutene derivatives containing at least 5% by weight of a polyisobutene derivative selected from the group consisting of 1a to 6a as defined in claim 1 or 2, together with polyisobutene and optionally at least one solvent.

4. A method for preparing a polyisobutene derivative of the general structure 1a to 6a as defined in claim 1 or 2, or a mixture according to claim 3, - Oxygen-containing gas, General structure 7 and / or 8 and / or 9 and / or 10 and / or 11 【Chemistry 2】 A solution in a solvent of polyisobutene of the formula [wherein n is as defined in claim 1 or 2] or an E- / Z-isomer thereof, or polyisobutene of general structure 7 and / or 8 and / or 9 and / or 10 and / or 11 or an E- / Z-isomer thereof - A process of contacting in the presence of a photosensitizer, - A step of irradiating a reaction mixture with an electroluminescent illumination device that emits monochromatic light, wherein at least 90% and up to 100% of the power of the monochromatic light is in the range of 350 nm to 680 nm. A method that includes this.

5. The method according to claim 4, wherein the oxygen-containing gas is oxygen, air, or an oxygen / inert gas mixture containing oxygen in the range of 1 to 99 volume percent.

6. The aforementioned photosensitizers include fluorescein, eosin, rose bengal, erythrosine, tetraphenylporphyrin, cobalt-tetraphenylporphyrin, zinc-tetraphenylporphyrin, hematoporphyrin, rhodamine B, basacryl brilliant red, methyl violet, methylene blue, fullerene C60, fullerene C70, graphene, carbon nanotube, and Ru(bpy). ３ ２＋ Ru(phen) ３ ２＋ The method according to claim 4 or 5, wherein one or more are selected from the group consisting of cercosporine and hypocrelin-A.

7. The method according to any one of claims 4 to 6, wherein the method is carried out without a solvent.

8. Benzene, C １ to C ４ -alkylbenzene, 1,2-xylene, 1,3-xylene, 1,4-xylene, C ４ to C １０ -alkane, C ３ to C ６ -alkanone, C １ to C １０ -alkanol, dichloromethane, trichloromethane, tetrachloromethane, 1,1-dichloroethane, 1,2-dichloroethane, trichloroethane, 1-chlorobutane, tetrachloroethylene, carbon disulfide, C ５ to C １２ -cycloalkane, C ５ to C[[ID=​​​​​​​​​​​

9. The method according to any one of claims 4 to 8, wherein the electroluminescent lighting device comprises at least one light-emitting diode (LED).

10. The method according to any one of claims 4 to 9, wherein at least one of the polyisobutene compounds 7 to 11 supplemented with a photosensitizer is reacted with an oxygen-containing gas by irradiation at a temperature in the range of -20°C to +150°C.

11. The method according to any one of claims 4 to 10, wherein at least one of the polyisobutene compounds 7 to 11 supplemented with a photosensitizer is reacted with an oxygen-containing gas by irradiation at a pressure in the range of atmospheric pressure to 100 bar.

12. The method according to any one of claims 4 to 11, wherein the reaction is carried out in a side-loop photoreactor, a continuous flow photoreactor, or an underwater photoreactor.

13. The method according to any one of claims 4 to 12, wherein at least 50% of the power of the radiation emitted by the radiation source is within the wavelength range of + / - 100 nm of the absorption maximum of the sensitizer used.

14. Use of a polyisobutene derivative available according to any one of claims 1 to 3 or according to the method described in any one of claims 4 to 13, for improving the lubricity of a hydrocarbon mixture or hydrocarbon-containing oil as measured by a high-frequency reciprocating rig test (HFRR) in accordance with ISO 12156.

15. Use of a polyisobutene derivative available according to any one of claims 1 to 3, or according to the method described in any one of claims 4 to 13, for improving the lubricity of a fuel or lubricating oil as measured by a high-frequency reciprocating rig test (HFRR) in accordance with ISO 12156.

16. Use of a polyisobutene derivative available according to any one of claims 1 to 3, or according to the method described in any one of claims 4 to 13, to improve the lubricity of gasoline or diesel fuel as measured by high-frequency reciprocating rig testing (HFRR) in accordance with ISO 12156.

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