Alkoxycarbonylation of trivinylcyclohexane

Abstract

The present invention relates to a process for the alkoxycarbonylation of trivinylcyclohexane. The present invention relates to a process comprising the following process steps: a) placing one of the compounds (i), (ii), (iii) or a mixture of at least two of these compounds in advance; b) adding a ligand (L) and a compound containing Pd, or adding a complex containing Pd and a ligand (L); c) adding an alcohol having 1 to 12 carbon atoms; d) feeding CO; e) heating the reaction mixture from a) to d), thereby converting the compound / mixture obtained from a) into a triester.

Description

Field of the Invention

[0001] The present invention relates to a process for the alkoxycarbonylation of trivinylcyclohexane. Background Art

[0002] The alkoxycarbonylation of olefinically unsaturated compounds is an increasingly important process. Alkoxycarbonylation is understood to mean the reaction of olefinically unsaturated compounds, such as olefins, with carbon monoxide and alcohols in the presence of metals or metal complexes and ligands to give the corresponding esters:

[0003] . Summary of the invention

[0004] The object of the present invention is to provide a method for the alkoxycarbonylation of trivinylcyclohexane, wherein all three vinyl groups are converted into esters.

[0005] A further object was to provide a fast-gelling plasticizer for plastics, in particular for PVC, which enables the processing temperature to be reduced.

[0006] This object is achieved by a method according to claim 1 .

[0007] A method comprising the following steps:

[0008] a) one of the compounds (i), (ii), (iii) or a mixture of at least two of these compounds is pre-added:

[0009]

[0010] b) adding a ligand (L) and a compound containing Pd,

[0011] Or add a complex containing Pd and a ligand (L):

[0012]

[0013] c) adding an alcohol having 1 to 12 carbon atoms;

[0014] d) Supplying CO;

[0015] e) Heating the reaction mixture from a) to d), thereby converting the compound / mixture obtained from a) into a triester.

[0016] In one variant of the process, compound (i) is initially charged in process step a).

[0017] In one variant of the process, compound (ii) is initially charged in process step a).

[0018] In one variant of the process, the alcohol in process step c) contains no further heteroatoms besides oxygen and no multiple bonds.

[0019] In one variant of the process, the alcohol in process step c) is selected from:

[0020] Methanol, ethanol, n-butanol, methyl propanol, n-pentanol, isopentanol, 2-methylbutanol, 3-methylbutanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, n-octanol, isooctyl alcohol, 2-ethylhexanol, n-nonanol, isononanol, n-decanol, isodecanol, 2-propylheptanol.

[0021] In one variant of the process, the alcohol in process step c) is methanol.

[0022] In one variant of the process, CO is fed in process step d) up to a pressure of 20 to 60 bar.

[0023] In one variant of the process, CO is fed in process step d) up to a pressure of 30 to 50 bar.

[0024] In one variant of the process, the heating in step e) is to a temperature of 90° C. to 130° C.

[0025] In one variant of the process, heating in step e) is to a temperature of 100° C. to 120° C.

[0026] In one variant of the method, it comprises the additional method step f):

[0027] f) purifying the triester.

[0028] In one variant of the method, it comprises the additional method step g):

[0029] g) Converting the purified triester to triol using NaOMe and H2.

[0030] In one variant of the process, the conversion in process step g) is catalyzed by Ru-MACHO-BH.

[0031] In one variant of the process, the conversion in process step g) is carried out with an H 2 pressure of 30 bar to 70 bar.

[0032] In one variant of the process, the conversion in process step g) is carried out with an H 2 pressure of 40 to 60 bar.

[0033] In one variant of the process, the conversion in process step g) is carried out at a temperature of 80 to 120°C.

[0034] In one variant of the process, the conversion in process step g) is carried out at a temperature of 90 to 110°C.

[0035] In addition to the process, a compound is claimed.

[0036] Compound of formula (1):

[0037] .

[0038] Preferably, the compounds are prepared according to the methods described herein.

[0039] The compounds were prepared according to the methods described above. DETAILED DESCRIPTION

[0040] The invention will be explained in more detail below with the aid of examples.

[0041] Synthesis of trimethyl 3,3',3''-(cyclohexane-1,2,4-triyl)triproinate (1) ("triester")

[0042]

[0043]

[0044] Under argon atmosphere, [Pd(acac)2] (15.2 mg, 0.1 mol%), L (103 mg, 0.4 mol%) and p-toluenesulfonic acid (PTSA) (143 mg, 1.5 mol%) were provided in a 100-ml steel autoclave. MeOH (30 ml) and trivinylcyclohexane (i) (8.1 g, 50 mmol) were then injected by means of a syringe. The autoclave was purged with CO 3 times and then loaded with a CO pressure of 40 bar. The reaction was carried out at 110°C for 10 h. The autoclave was then cooled to room temperature and decompressed. The reaction mixture was purified by distillation (165°C, 10 -3 bar) to purify the desired product and use 1 H-, 13 The product was characterized by C-NMR and HR-MS (15.6 g, 91% yield).

[0045] 1 H-NMR (300 MHz, C6D6) δ = 3.39-3.37 (m,9H), 2.24-1.86 (m, 7H), 1.48-0.27 (m, 14H).

[0046] 13C-NMR (75 MHz, C6D6) δ = 173.68-173.54 (m), 51.04, 40.60-40.47 (m), 38.24, 38.14, 37.51, 37.07, 36.54, 36.10, 35.52, 35.14, 33.87, 32.70, 32.55,32.51, 32.38, 32.29, 32.23, 32.08, 31.97, 31.86, 31.76, 31.68, 31.63, 31.43,30.98, 30.79, 30.75, 29.31, 28.52, 28.47, 28.34, 28.13, 28.11, 27.13, 26.58,25.12, 20.79, 19.74.

[0047] MS (EI): 311 (13.40), 293 (3.65), 269 (75.76), 237 (60.40), 219(25.13), 205 (100), 191 (17.62), 177 (14.83), 145 (24.59).

[0048] HR-MS (ESI): Calculation of C 18 H 30 O6 [M + H] + : 343.21152, found: 343.21113.

[0049] Synthesis of 3,3',3''-(cyclohexane-1,2,4-triyl)tri(propan-1-ol) (2) ("triol")

[0050]

[0051] Under argon atmosphere, Ru-MACHO-BH (59 mg, 2 mol%) and NaOMe (27 mg, 10 mol%) were provided in a 25 ml steel autoclave. Then, MeOH (8 ml) and triester (1) (1.93 g, 5.67 mmol) were injected by syringe. The autoclave was purged with H2 3 times and then loaded with 50 bar H2-pressure. The reaction was carried out at 100 ° C for 10 h. The autoclave was then cooled to room temperature and decompressed. The desired product was purified by filtration on silica gel and purified by 1 H-, 13 The product was characterized by C-NMR and HR-MS (1.4 g, 96% yield).

[0052] 1H-NMR (400 MHz, CD3OD) δ = 3.32-3.30 (m,6H), 1.85-1.77 (m, 2H), 1.63-0.62 (m, 19H). 13 C-NMR (100 MHz, CD3OD) δ = 63.53-63.29 (m), 42.69, 42.53,42.39, 42.31, 40.34, 40.24, 39.28, 38.89, 38.12, 38.02, 37.58, 37.27, 35.89,34.78, 34.72, 34.53, 34.37, 33.17, 31.52, 31.50, 31.40, 31.38, 31.05, 30.60,30.48, 30.41, 30.32, 30.24, 30.17, 28.77, 28.22, 26.61, 22.53, 21.45. MS(EI): 222 (1.06), 194 (1.14), 181 (2.96), 163 (11.54), 135 (9.81), 121(17.04), 107 (15.25), 93 (32.69).

[0053] HR-MS (ESI): Calculation of C 15 H 30 O3 [M + H] + : 259.22677, found: 259.2269.

[0054] Preparation of plastisol

[0055] PVC plastisols were prepared, which were used, for example, to produce topcoat films for floor coverings. The data in the plastisol formulations are each in parts by mass. The formulation of the polymer composition is listed in Table 1.

[0056] Table 1: Plastisol formulations

[0057] phr PVC (Vestolit B 7021 – Ultra; Vestolit) 100 Plasticizers 50 Epoxidized soybean oil as co-stabilizer (Drapex 39, Galata) 3 Ca / Zn based heat stabilizer (Reagens CLX / 759 / 6PF) 2

[0058] The data unit is phr (phr = parts per 100 parts of resin ( p arts per h Unwrapped parts r esin) ).

[0059] First the liquid and then the powdered components are weighed into the PE cup. The mixture is stirred manually with a spatula so that no unwetted powder remains. The mixing cup is then fixed in the clamping device of the dissolving stirrer. After switching on the stirrer, the speed is slowly increased to about 2000 rpm. At the same time, the plastisol is carefully vented; the pressure must be below 20 mbar.

[0060] As soon as the plastisol has reached a temperature of approximately 30°C, the speed is reduced to approximately 350 rpm. From this point on, the plastisol is vented for 9 minutes at this speed and a pressure of less than 20 mbar. This ensures that the plastisol is homogenized at a given energy input. The plastisol is then immediately tempered to 25.0°C in a climate cabinet for further investigations.

[0061] Gelling properties of plastisols

[0062] The investigation of the gelling properties of the paste was carried out with a Physica MCR 101 in oscillating mode with a plate-plate measuring system (PP25) operating under shear stress control. An additional temperature-controlled hood was connected to the apparatus to achieve uniform heat distribution and homogeneous sample temperature.

[0063] Set the following parameters:

[0064] Mode: Temperature Gradient

[0065] Starting temperature: 25℃

[0066] Final temperature: 180℃

[0067] Heating / cooling rate: 5℃ / min

[0068] Oscillation frequency: 4-0.1 Hz logarithmic ramp (Rampe logarithmisch)

[0069] Angular frequency ω: 101 / s

[0070] Number of measurement points: 63

[0071] Measuring point duration: 0.5 min

[0072] Automatic gap adjustment (Spaltnachführung) F: 0 N

[0073] Constant measuring point duration

[0074] Gap width 0.5 mm.

[0075] Implementation of measurement

[0076] A few grams of the paste to be measured are applied to the lower measuring system plate with a spatula without air bubbles. It should be noted that after the measuring system is moved together, some paste can seep out of the measuring system evenly (no more than 6 mm on all sides). The temperature control hood is then placed over the sample and the measurement is started. After 24 hours, the complex viscosity of the paste is determined (the paste is stored at 25°C in a temperature control cabinet from Memmert) as a function of temperature.

[0077] A clear increase in the complex viscosity is considered a measure of gelation. Therefore, the temperature at which the paste viscosity reaches 1000 Pa·s is used as a comparison value.

[0078] The experiment was repeated with three comparative plastisols, each using a different plasticizer.

[0079] Table 2: Gelation of plastisols after 24 hours, when the paste viscosity reaches 10 3 Temperature in °C at Pa·s

[0080] experiment Plasticizers Gelation temperature [℃] 1* 3,3',3''-(Cyclohexane-1,2,4-triyl)tripropionate trimethyl ester (1) 65 2 Diisononyl phthalate (DINP), VESTINOL 9, Evonik Performance Materials GmbH 83 3 Diisononyl-1,2-cyclohexanedicarboxylate (DINCH), ELATUR CH from Evonik Performance Materials GmbH 101 4 Diisopentyl terephthalate (DPT), ELATUR DPT from Evonik Performance Materials GmbH 70

[0081] *Experiments performed with compounds according to the invention.

[0082] With the compounds (1) according to the invention, it is already possible to achieve desired values ​​of 1000 Pa*s at 65° C. Such low gelling temperatures are advantageous for processing. They allow plastisol processing at relatively low temperatures.

Claims

1. A method for alkoxycarbonylating trivinylcyclohexane, comprising the following steps: a) Add compound (i) in advance: b) adding a ligand (L) and a compound comprising Pd, Or add a complex containing Pd and a ligand (L): c) adding an alcohol having 1 to 12 carbon atoms; d) supplying CO; e) heating the reaction mixture of a) to d), thereby converting the compound obtained from a) into a triester of formula (1), f) purifying the triester, g) converting the purified triester into a triol of formula (2) using NaOMe and H2: wherein in step e) the heating is to a temperature of 90° C. to 120° C., The alcohol in process step c) is methanol.

2. The method according to claim 1, In process step d), CO is fed in up to a pressure of 20 to 60 bar.

3. The method according to claim 1 or 2, The conversion in process step g) is catalyzed by Ru-MACHO-BH.

4. The method according to claim 3, The conversion in process step g) is carried out at an H 2 pressure of 30 to 70 bar.

5. The method according to claim 3, The conversion in process step g) is carried out at a temperature of 80°C to 120°C.

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