PROCESS FOR PREPARATION OF POLYISOBUTENE DERIVATIVES

Abstract

A process for the preparation of polyisobutene derivatives involves bringing an oxygen-containing gas in contact with polyisobutene, in the presence of a photosensitizer, and irradiating the reaction mixture. The polyisobutene derivatives are useful, for example, in hydrocarbon mixtures or hydrocarbon-containing oils.

Claims

1. A derivative of polyisobutene, selected from the group consisting of 1a to 6a: ##STR00008## wherein n is a positive integer of at least 1.

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

3. A mixture of the derivatives of polyisobutene selected from the group consisting of 1a to 6a as defined in claim 1, containing: at least 5 wt % of the derivatives of polyisobutene, polyisobutene, and optionally, at least one solvent.

4. A process for preparation of the derivative of polyisobutene of the general structure 1a to 6a as defined in claim 1, the process comprising bringing an oxygen-containing gas in contact with polyisobutene of the general structure 7 and/or 8 and/or 9 and/or 10 and/or 11 or their E-/Z-isomers or a solution of polyisobutene in a suitable solvent ##STR00009## wherein n is a positive integer of at least 1, in the presence of a photosensitizer, and irradiating the reaction mixture by an electroluminescent lighting device emitting monochromatic light, at least 90% of power of said monochromatic light and at most 100% of said power being emitted in the range from 350 nm to 680 nm.

5. The process according to claim 4, wherein the oxygen-containing gas is oxygen, air, or an oxygen/inert gas mixture containing oxygen in a range of 1-99 vol %.

6. The process according to claim 4, wherein the photosensitizer is one or more selected from the group consisting of fluorescein, eosin, rose bengal, erythrosine, tetraphenylporphyrin, cobalt-tetraphenyl-porphyrin, zinc-tetraphenylporphyrin, hematoporphyrin, rhodamine B, basacryl brilliant red, methyl violet, methylene blue, fullerene C60, fullerene C70, graphene, carbon nanotubes, Ru(bpy).sub.3.sup.2+, Ru(phen).sub.3.sup.2+, cercosporin, and hypocrellin-A.

7. The process according to claim 4, wherein the process is performed without solvent.

8. The process according to claim 4, wherein a solvent, selected from one or more of the group consisting of benzene, C.sub.1-C.sub.4-alkylbenzene, 1,2-xylene, 1,3-xylene, 1,4-xylene, C.sub.4-C.sub.10-alkanes, C.sub.3-C.sub.6-alkanones, C.sub.1-C.sub.10-alkanols, dichloromethane, trichloromethane, tetrachloromethane, 1,1-dichloroethane, 1,2-dichloro-ethane, trichloroethane, 1-chlorobutane, tetrachloroethylene, carbondisulfide, C.sub.5-C.sub.12-cycloalkanes, C.sub.5-C.sub.12-cycloalkanones, acetonitrile, C.sub.6D.sub.6, D.sub.2O, Freon 11, C.sub.6F.sub.6, tert, butyl methylether (MTBE), and tert, butyl ethylether (ETBE), is present in the reaction mixture.

9. The process according to claim 4, wherein the electroluminescent lighting device consists of at least one light emitting diode (LED).

10. The process according to claim 4, wherein only a distinct portion of the reaction mixture is irradiated.

11. The process according to claim 4, 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 ranging from 20 C. to +150 C.

12. The process according to claim 4, 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 ranging from atmospheric pressure to 100 bar.

13. The process according to claim 4, wherein the reaction is performed in a side-loop photoreactor, in a continuous flow-photoreactor; or in a submersible photoreactor.

14. The process according to claim 4, wherein at least 50% of the power of the monochromatic light emitted by the electroluminescent lighting device is in the wavelength range of an absorption maximum of the photosensitizer+/100 nm.

15. A method for improving the lubricity of a hydrocarbon mixture or a hydrocarbon-containing oil, the method comprising: adding the derivative of polyisobutene according to claim 1, to the hydrocarbon mixture or the hydrocarbon-containing oil.

16. The derivative of polyisobutene according to claim 2, wherein n is a positive integer of at least 13.

17. A mixture, comprising at least 5 wt. % of at least two of the derivatives of polyisobutene according to claim 1.

Description

EXAMPLES

Example 1

[0094] A photochemical batch reactor, equipped with eighty-eight 405 nm LEDs is charged with 50 g highly reactive polyisobutene (Glissopal 1000 of BASF, Ludwigshafen, molecular weight approx. 1000 g/mol (a-double bonds in PIB: -double bonds in PIB are in a ratio of ca. 9:1), 307 mg tetraphenylporphyrin and 492 g dichloromethane. Oxygen (5 I/h) is bubbled through the reaction mixture while it is irradiated at 20 C. After 12 h the reaction is terminated. After evaporation of the solvent the residue is analysed by NMR spectroscopy. The structure (1a) was assigned to the main product:

##STR00004##

[0095] .sup.1H-NMR (CDCl3): =5.04, 5.25 (C-1); 4.47 (C-2); 2.08 (C-3) ppm.

[0096] .sup.13C-NMR (CDCl3): =118.21 (C-1), 81.38 (C-2), 141.94 (C-4) ppm.

Example 2

[0097] A photochemical batch reactor, equipped with eighty-eight 420 nm LEDs is charged with 201 g Glissopal 1000 (-double bonds: -double bonds=ca. 9: 1), 123 mg tetraphenylporphyrin and 266 g dichloromethane. Oxygen (5 I/h) is bubbled through the reaction mixture while it is irradiated at 30 C. After 21 h the reaction is terminated. After evaporation of the solvent the residue is analysed by NMR spectroscopy. The structures of 1a (70.6 mol-%), 2a (6.3 mol-%), and 6a (15.6 mol-%) were assigned to the reaction products.

##STR00005##

[0098] .sup.1H-NMR (CDCl3) (1a): 5=5.04, 5.25 (C-1); 4.47 (C-2); 2.08 (C-3) ppm.

[0099] .sup.1H-NMR (CDCl3) (2a): =5.01, 5.14 (C-1); 1.83 (C-2); 4.13 (C-3) ppm.

[0100] .sup.1H-NMR (CDCl3) (6a): =5.47, 5.59 (C-1); 4.38 (C-2); 4.31 (C-3) ppm.

[0101] .sup.13C-NMR (CDCl3) (1a): 8=113.8 (C-1), 80.7 (C-2), 47.9 (C-3), 139.4 (C-4) ppm.

[0102] .sup.13C-NMR (CDCl3) (2a): 6=113.5 (C-1), 19.8 (C-2), 92.7 (C-3), 143.8 (C-4) ppm.

[0103] .sup.13C-NMR (CDCl3) (6a): 8=115.4 (C-1), 78.0 (C-2), 89.4 (C-3), 139.5 (C-4) ppm.

Example 3

[0104] A 5 ml vial is charged with 1 millilitre of a solution of 0,89 g Indopol H100 17107 (a-double bonds: -double bonds: tetra-substituted double bonds=ca. 10: 61: 25), 1 mg tetraphenylporphyrin, 40.8 mg dimethylterephthalate and 11,5 g trichloromethane. The vial is flushed with oxygen, capped an irradiated with a single 405 nm LED for 1.5 min at 15 C. After evaporation of the solvent the residue is analysed by NMR spectroscopy. Aside of starting material, the structures of (3a) and (4a) were assigned to the reaction products.

##STR00006##

[0105] .sup.1H-NMR (CDCl3) (3a): =5.00, 5.28 (C-1); 4.51 (C-2) ppm.

[0106] .sup.1H-NMR (CDCl3) (4a): =5.03, 5.16 (C-1) ppm.

[0107] .sup.13C-NMR (CDCl3) (3a): =113.9 (C-1), 84.2 (C-2), 48.9 (C-3), 147.2.4 (C-4), 18.4 (C-5) ppm.

[0108] .sup.13C-NMR (CDCl3) (4a): =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.

Example 4

[0109] A 5 ml vial is charged with 1 millilitre of a solution of 0.82 g polyisobutene (a-double bonds: -double bonds: tetra-substituted double bonds=ca. 8: 43: 43), 1 mg tetraphenylporphyrin, 39.2 mg dimethylterephthalate and 10.6 g trichloromethane. The vial is flushed with oxygen, capped an irradiated with a single 405 nm LED for 1.5 min at 15 C. After evaporation of the solvent the residue is analysed by NMR spectroscopy. Aside of starting material and compound (4a) the structure of (5a) was assigned to one of the reaction products.

##STR00007##

[0110] The quantity of 4a and 5a amounts to about 40% of polyisobutene subjected to the reaction.

[0111] .sup.1H-NMR (CDCl3) (5a): =5.15 (C-2), 1.58 (C-5) ppm.

[0112] .sup.13C-NMR (CDCl3) (5a): =135.5 (C-2), 89.3 (C-3), 161.1 (C-4), 13.2 (C-5) ppm.

Example 5

[0113] A photochemical batch reactor, equipped with one-hundred-eighty 525 nm LEDs is charged with 77.9 g Glissopal 1000 (a-double bonds: 58.6 mmol, -double bonds=8.1 mmol), 20 mg tetraphenylporphyrin, 763 mg dimethylterephthalate (NMR standard) and 298 g trichloromethane. Oxygen (3 I/h) is bubbled through the reaction mixture while it is irradiated at 7 C. After 504 min the reaction is terminated. After evaporation of the solvent the residue is analysed by quantitative NMR spectroscopy. 43.4 mmol (1a), 4.6 mmol (2a) and 6.4 mmol (6a) were found in the reaction mixture.

Example 6

[0114] A photochemical batch reactor, equipped with one twenty-four 405 nm LEDs is charged with 5.11 g Glissopal 1000 (a-double bonds: 3.9 mmol, -double bonds: 0.6 mmol), 7 mg tetraphenylporphyrin, 112 mg dimethylterephthalate (NMR standard) and 52 g trichloromethane. Air (0.5 I/h) is bubbled through the reaction mixture while it is irradiated at 15 C. After 252 min the reaction is terminated. After evaporation of the solvent the residue is analysed by quantitative NMR spectroscopy. 2.7 mmol (1a), 0.3 mmol (2a) and 0.5 mmol (6a) were found in the reaction mixture.

Example 7

[0115] A solution of 104.4 g Glissopal 1000 (a-double bonds: 79.2 mmol, -double bonds: 10.3 mmol), 61 mg tetraphenylporphyrin, 2.5 g dimethylterephthalate (NMR standard) and 1350 g trichloromethane is reacted in the presence of 8 bar oxygen at 15 C. in a continuous photo flow reactor (G1 Photo Corning reactor: 10 LED panels: in total two hundred 405 nm LEDs, 5 G1 heart plates, volume: 8.2 ml/plate, flow rate: 4.1 ml/min, residence time: 10 min, single pass). After evaporation of the solvent the residue is analysed by quantitative NMR spectroscopy. 59.4 mmol a-PIB, 0.6 mmol p-PIB, 13.3 mmol (1a), 8.3 mmol (2a) and 0.3 mmol (6a) were found in the reaction mixture.

Example 8

[0116] A solution of 80.6 g Glissopal 1000 (a-double bonds: 62.5 mmol, -double bonds: 7.5 mmol), 13 mg tetraphenylporphyrin, 1.0 g dimethylterephthalate (NMR standard) and 106 g dichloromethane is reacted in the presence of 5 bar oxygen at 15 C. in a side-loop continuous photo flow reactor (G1 Photo Corning reactor: 10 LED panels: in total two hundred 405 nm LEDs, 5 G1 heart plates, volume: 8.2 ml/plate, flow rate: 6.3 kg/h). The reaction was terminated after 935 min. After evaporation of the solvent the residue is analysed by quantitative NMR spectroscopy. 10.7 mmol a-PIB, 0 mmol p-PIB, 35.3 mmol (1a), 4.7 mmol (2a) and 2.6 mmol (6a) were found in the reaction mixture.

Example 9

[0117] A solution of 30.5 g polyisobutene (a-double bonds: 3.7 mmol, -double bonds: 14.9 mmol), 15 mg tetraphenylporphyrin, 0.6 g dimethylterephthalate (NMR standard) and 266 g dichloromethane is reacted in the presence of 2 bar oxygen at 17 C. in a side-loop continuous photo flow reactor (G1 Photo Corning reactor: 10 LED panels: in total two hundred 405 nm LEDs, 5 G1 heart plates, volume: 8.2 ml/plate, flow rate: 5.6 kg/h). The reaction was terminated after 141 min. After evaporation of the solvent the residue is analysed by quantitative NMR spectroscopy. 3.1 mmol (1a), 9.9 mmol (2a) and 0 mmol (6a) were found in the reaction mixture.

Example 10

[0118] A photochemical batch reactor, equipped with one-hundred-eighty 525 nm LEDs is charged with 50.0 g Glissopal 1000 (a-double bonds: 40 mmol, p-double bonds: 7 mmol), 20 mg tetraphenylporphyrin, and 357.6 g trichloromethane. Oxygen (3 I/h) is bubbled through the reaction mixture while it is irradiated at 5 C. After 520 min the reaction is terminated. After evaporation of the solvent the residue is analysed by quantitative NMR spectroscopy. 30 mmol (1a) was found in the reaction mixture.

Example 11: Lubrification in Fuel

[0119] Description of the HFRR Test for Measurement of Wear and Friction

[0120] The High Frequency Reciprocating Rig (HFRR) procedure used according to ISO 12156 is the standard diesel fuel lubricity procedure.

[0121] In the Example, the HFRR Tests were Carried Out Under the Following Conditions:

[0122] Time: 75 min, Temperature: 60 C., Stroke Length: 1 mm, Frequency: 50 Hz, Mass: 200 g, Volume 2 ml, Surface 600 mm.sup.2

[0123] Additionally, the same operator and machine were used for all tests.

[0124] Examples of the action regarding the samples over base fuel Given in the table are the mean results which were statistically fitted in order to overcome a drift in time.

[0125] Base fuel was a standard Diesel fuel without additives.

[0126] As an additive polyisobutene (Mw 1000 g/mol, Glissopal(R) 1000 by BASF SE, Ludwigshafen) and the reaction mixture of photooxygenation thereof according to Example 10 was used in the treat rate specified in Table 1.

TABLE-US-00001 Mean HFRR Mean HFRR Amount wear scar coefficient Additive [wt %] [m] of friction Hydroperoxide 0.05% 609 m 0.341 Hydroperoxide 0.50% 453 m 0.217 polyisobutene 0.05% 635 m 0.341 polyisobutene 0.50% 588 m 0.333