Preparation method and application of tricyclodecane monomethanol

Abstract

The invention relates to the technical field of chemical synthesis, in particular to the field of IPC C07C61, and more particularly relates to a preparation method and application of tricyclodecane monomethanol. Comprising the following steps: S1, catalyzing hydroformylation reaction of dicyclopentadiene through a ruthenium catalyst and a phosphine ligand to obtain an intermediate tricyclodecane formaldehyde; and S2, carrying out catalytic hydrogenation on the intermediate tricyclodecane formaldehyde, and distilling to obtain tricyclodecane monomethanol. The hydroformylation catalyst adopts the combination of trivalent phosphorus and trivalent phosphine oxide, so that the reaction selectivity and the product yield can be improved.

Description

Technical Field

[0001] The invention relates to the technical field of chemical synthesis, in particular to the field of IPC C07C61, and more specifically to a preparation method and application of tricyclodecane monomethanol. Background Art

[0002] As raw materials for highly heat-resistant alicyclic polyesters, tricyclodecane monomethanol monocarboxylic acid and its derivatives have excellent heat resistance, transparency and water resistance. These characteristics make them have broad application prospects in the fields of optical materials, electronic parts, etc. In addition, this type of compound can also be processed into films, sheets, special-shaped materials, fibers, tubes and containers through various forming methods, further broadening its application field. Dicyclopentadiene is a common basic chemical in petrochemical industry, but there are few literature reports on the preparation of tricyclodecane monomethanol TCDM using dicyclopentadiene as raw material, and its application performance has not been disclosed.

[0003] Chinese invention patent CN103261278B discloses a method for preparing tricyclodecane monomethanol monocarboxylic acid derivatives which can be used as raw materials for highly heat-resistant alicyclic polyesters, etc. In the presence of a catalyst system containing a ruthenium compound, a cobalt compound and a halide salt, the following dicyclopentadiene and a formic acid compound are reacted to obtain the following tricyclodecene monocarboxylic acid derivatives, and then the tricyclodecene monocarboxylic acid derivatives are hydroformylated. The selectivity and product yield of the invention need to be improved. Summary of the invention

[0004] The first aspect of the present invention provides a method for preparing tricyclodecane monomethanol, comprising the following steps:

[0005] S1, dicyclopentadiene is subjected to hydroformylation reaction catalyzed by a ruthenium catalyst and a phosphine ligand to obtain an intermediate tricyclodecane carboxaldehyde;

[0006] S2. The intermediate tricyclodecane carboxaldehyde is subjected to catalytic hydrogenation and then distilled to obtain tricyclodecane monomethanol.

[0007] The ruthenium catalyst is selected from triruthenium dodecacarbonyl (Ru 3 (CO) 12 ), at least one of ruthenium acetylacetonate, tetrakis(dimethyl sulfoxide)dichlororuthenium, ruthenium trichloride, ruthenium acetate, and cyclooctadiene dichlororuthenium.

[0008] Preferably, the ruthenium catalyst is selected from triruthenium dodecacarbonyl.

[0009] The molar ratio of dicyclopentadiene to the ruthenium catalyst is 1:(0.0001-0.05).

[0010] Preferably, the molar ratio of dicyclopentadiene to ruthenium catalyst is 1:(0.0001-0.001).

[0011] Further preferably, the molar ratio of dicyclopentadiene to ruthenium catalyst is 1:(0.0003-0.0009).

[0012] The phosphine ligands are trivalent phosphine and trivalent phosphine oxide.

[0013] Preferably, the structure of the trivalent phosphine comprises Formula L1 or Formula L2:

[0014]

[0015] The trivalent phosphine oxide is selected from at least one of triphenylphosphine oxide, tri(alkyl substituted)phenylphosphine oxide such as tri(p-tolyl)phosphine oxide, tri(p-methoxyphenyl)phosphine oxide, tri(m-tolyl)phosphine oxide, etc., tricyclohexylphosphine oxide, and 2-diphenylphosphine oxide-biphenyl.

[0016] Preferably, the trivalent phosphine oxide is selected from at least one of triphenylphosphine oxide, tri(p-tolyl)phosphine oxide, tri(p-methoxyphenyl)phosphine oxide, and 2-diphenylphosphine oxide-biphenyl.

[0017] The molar ratio of the trivalent phosphine to the ruthenium catalyst is (0.1-5):1.

[0018] Preferably, the molar ratio of the trivalent phosphine to the ruthenium catalyst is (0.3-3):1.

[0019] Further preferably, the molar ratio of the trivalent phosphine to the ruthenium catalyst is (13-36):15.

[0020] The molar ratio of the trivalent phosphine to the trivalent phosphine oxide is 1:(0.5-4).

[0021] Preferably, the molar ratio of the trivalent phosphine to the trivalent phosphine oxide is 1:(0.8-3).

[0022] More preferably, the molar ratio of the trivalent phosphine to the trivalent phosphine oxide is 1:(0.8-2).

[0023] The present application study found that the phosphine ligands are trivalent phosphine and trivalent phosphine oxide, and the molar ratio of trivalent phosphine to trivalent phosphine oxide is 1:(0.5-4), which can improve the selectivity and product yield of the reaction. When the trivalent phosphine compound is used as a catalyst, its nucleophilicity and alkalinity may help stabilize the reaction intermediates and accelerate the reaction process. When combined with a trivalent phosphorus oxygen-containing compound, the latter may further promote the reaction through the activity of its P=O double bond, thereby improving the selectivity and product yield of the reaction.

[0024] The hydroformylation reaction is carried out under a pressure of 5-10 MPa, a temperature of 120-200° C. and a time of 8-48 h.

[0025] Preferably, the hydroformylation reaction is carried out under a pressure of 5-8 MPa, a temperature of 140-150° C. and a time of 8-15 h.

[0026] Further preferably, the hydroformylation reaction is carried out under a pressure of 6 MPa, a temperature of 145° C. and a time of 12 h.

[0027] The S1 includes a reaction solvent, which includes at least one of aromatic hydrocarbons, alkanes, tetrahydrofuran, DMF, NMP, and alcohol ethers, preferably at least one of toluene, tetrahydrofuran, and cyclohexane.

[0028] The catalyst used for hydrogenation in the S2 is selected from a nickel-based catalyst, a copper-based catalyst, and a ruthenium-based catalyst.

[0029] The nickel-based catalyst is selected from one of Raney nickel, alumina-loaded nickel, silica-loaded nickel, and diatomaceous earth-loaded nickel; the copper-based catalyst is selected from one of copper oxide, alumina-loaded copper, and silica-loaded copper; the ruthenium-based catalyst is selected from one of activated carbon-loaded ruthenium, alumina-loaded ruthenium, or silica-loaded ruthenium.

[0030] The step S2 is carried out in a fixed bed or a stirred tank; preferably, the step is carried out in a trickle flow manner in a fixed bed, and the volume space velocity of the intermediate aldehyde relative to the hydrogenation catalyst is 0.1 to 5 h -1 When the reaction is carried out in a stirred tank, the mass of the hydrogenation catalyst accounts for 0.1% to 5% of the mass of the intermediate aldehyde.

[0031] The second aspect of the present invention provides an application of a method for preparing tricyclodecane monomethanol, which is applied to the preparation of photocurable coatings.

[0032] Beneficial Effects

[0033] 1. In the present application, dicyclopentadiene is used as a raw material to prepare tricyclodecane monomethanol, and the reaction raw materials are easily available, thereby reducing the synthesis cost.

[0034] 2. The molar ratio of the trivalent phosphine to the ruthenium catalyst is (0.1-5):1, which can increase the conversion rate of dicyclopentadiene to more than 70%.

[0035] 3. The phosphine ligands are trivalent phosphine and trivalent phosphine oxide, and the molar ratio of trivalent phosphine to trivalent phosphine oxide is 1:(0.5-4), which can improve the selectivity and product yield of the reaction.

[0036] 4. The molar ratio of the trivalent phosphine to the ruthenium catalyst is (0.3-3):1, and the content of tricyclodecane monoformaldehyde can reach

[0037] More than 60%.

[0038] 5. The method for preparing tricyclodecane monomethanol of the present application has mild conditions and simple steps. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is the H NMR spectrum of tricyclodecane monoformaldehyde prepared in Example 1. DETAILED DESCRIPTION

[0040] Example 1

[0041] A method for preparing tricyclodecane monomethanol, as shown in Formula 1, comprises the following steps:

[0042] S1, 30g (0.227mol) dicyclopentadiene, 97mg (0.00015mol) Ru 3 (CO) 12 , 0.272 g (0.00013 mol) of ligand L1, 50 mg (0.00018 mol) of triphenylphosphine oxide and 100 mL of toluene were added to a 250 mL autoclave and replaced with nitrogen three times, followed by synthesis gas (volume ratio, H 2 :CO=1:1) for three times, the pressure in the autoclave was replenished to 5MPa, and then the stirring and heating program were started, the reaction pressure was about 6MPa, the reaction temperature was controlled at about 145°C, the reaction time was 12h, and the intermediate tricyclodecane carboxaldehyde was obtained after distillation;

[0043]

[0044] S2, add 30g of intermediate tricyclodecane monoformaldehyde, 2g of Raney nickel catalyst and 100mL of tetrahydrofuran to a 250mL autoclave. After nitrogen replacement three times, replace with hydrogen three times, add hydrogen pressure to 2MPa, stir and heat to 120°C, maintain the hydrogen pressure in the autoclave at 2.5MPa, sample and analyze after 8h reaction, aldehyde conversion rate is 98%, and tricyclodecane monomethanol TCDM 28.5g is obtained after vacuum distillation.

[0045] Example 2

[0046] S1, 30g (0.227mol) dicyclopentadiene, 97mg (0.00015mol) Ru 3 (CO) 12 , 0.215 g (0.00018 mol) of ligand L2, 50 mg (0.00018 mol) of triphenylphosphine oxide and 100 mL of toluene were added to a 250 mL autoclave and replaced with nitrogen three times, followed by synthesis gas (volume ratio, H 2 :CO=1:1) for three times, the pressure in the autoclave was replenished to 5MPa, and then the stirring and heating program were started, the reaction pressure was about 6MPa, the reaction temperature was controlled at about 145°C, the reaction time was 12h, and the intermediate tricyclodecane carboxaldehyde was obtained after distillation;

[0047] S2, using a set of 50mL jacket-heated fixed-bed hydrogenation reactor, filled with 40mL of loaded nickel catalyst, the tetrahydrofuran solution (30wt%) of the intermediate tricyclodecane carboxaldehyde was hydrogenated from top to bottom in a trickle bed manner at a flow rate of 20mL / h, the hydrogen flow rate was 0.04L / h, the hydrogen pressure was maintained at 5MPa, the reaction temperature was 160°C, after 5h of continuous reaction, sampling and analysis at the outlet, the aldehyde conversion rate was 99%.

[0048] Example 3

[0049] A method for preparing tricyclodecane monomethanol comprises the following steps:

[0050] S1, 30g (0.227mol) dicyclopentadiene, 97mg (0.00015mol) Ru 3 (CO) 12 , 0.544 g (0.00027 mol) of ligand L1, 110 mg (0.00040 mol) of triphenylphosphine oxide and 100 mL of cyclohexane were added to a 250 mL autoclave and replaced with nitrogen three times, followed by synthesis gas (volume ratio, H 2 :CO=1:1) for three times, the pressure in the autoclave was replenished to 5MPa, and then the stirring and heating program were started, the reaction pressure was about 6MPa, the reaction temperature was controlled at about 145°C, the reaction time was 12h, and the intermediate tricyclodecane carboxaldehyde was obtained after distillation;

[0051] S2, same as Example 1.

[0052] Example 4

[0053] A method for preparing tricyclodecane monomethanol comprises the following steps:

[0054] S1, 30g (0.227mol) dicyclopentadiene, 97mg (0.00015mol) Ru 3 (CO) 12 , 0.43 g (0.00036 mol) of ligand L2, 90 mg (0.00030 mol) of tri(p-tolylphenyl)phosphine oxide and 100 mL of tetrahydrofuran were added to a 250 mL autoclave and replaced with nitrogen three times, followed by synthesis gas (volume ratio, H 2 :CO=1:1) for three times, the pressure in the autoclave was replenished to 5MPa, and then the stirring and heating program were started, the reaction pressure was about 6MPa, the reaction temperature was controlled at about 145°C, the reaction time was 12h, and the intermediate tricyclodecane carboxaldehyde was obtained after distillation;

[0055] S2, same as Example 1.

[0056] Example 5

[0057] A method for preparing tricyclodecane monomethanol comprises the following steps:

[0058] S1, 30g (0.227mol) dicyclopentadiene, 97mg (0.00015mol) Ru 3 (CO) 12 , 0.544 g (0.00027 mol) of ligand L1, 120 mg (0.00036 mol) of 2-(diphenylphosphinyl)-biphenyl and 100 mL of tetrahydrofuran were added to a 250 mL autoclave and replaced with nitrogen three times, followed by synthesis gas (volume ratio, H 2 :CO=1:1) for three times, the pressure in the autoclave was replenished to 5MPa, and then the stirring and heating program were started, the reaction pressure was about 6MPa, the reaction temperature was controlled at about 145°C, the reaction time was 12h, and the intermediate tricyclodecane carboxaldehyde was obtained after distillation;

[0059] S2, same as Example 1.

[0060] Comparative Example 1

[0061] A method for preparing an intermediate tricyclodecane carboxaldehyde comprises the following steps: 30 g (0.227 mol) of dicyclopentadiene, 97 mg (0.00015 mol) of Ru 3 (CO) 12 , 120 mg (0.00043 mol) triphenylphosphine oxide and 100 mL toluene were added to a 250 mL autoclave and replaced with nitrogen three times, followed by synthesis gas (volume ratio, H 2 :CO=1:1) replacement three times, the pressure in the autoclave was replenished to 5MPa, and then the stirring and heating program were started. The reaction pressure was about 6MPa, the reaction temperature was controlled at about 145°C, the reaction time was 12h, and the intermediate tricyclodecane carboxaldehyde was obtained after distillation.

[0062] Comparative Example 2

[0063] A method for preparing an intermediate tricyclodecane carboxaldehyde comprises the following steps: 30 g (0.227 mol) of dicyclopentadiene, 97 mg (0.00015 mol) of Ru 3 (CO) 12 , 126 mg (0.00043 mol) triphenylphosphine oxide and 100 mL toluene were added to a 250 mL autoclave and replaced with nitrogen three times, followed by synthesis gas (volume ratio, H 2:CO=1:1) replacement three times, the pressure in the autoclave was replenished to 5MPa, and then the stirring and heating program were started. The reaction pressure was about 6MPa, the reaction temperature was controlled at about 145°C, the reaction time was 12h, and the intermediate tricyclodecane carboxaldehyde was obtained after distillation.

[0064] Performance Testing Methods

[0065] 1. The tricyclodecane monomethanol prepared in Example 1 was subjected to nuclear magnetic hydrogen spectrum detection, and the spectrum was as follows: Figure 1 shown.

[0066] 2. The conversion rate of dicyclopentadiene and the content of tricyclodecane monoformaldehyde were detected by gas chromatography for the intermediate tricyclodecane carboxaldehyde in the examples and comparative examples. The conversion rate of tricyclodecane monoformaldehyde in Examples 1 and 2 was detected. The test data are listed in Table 1, where "-" indicates no detection.

[0067] 3. The tricyclodecane monomethanol prepared in Example 1 is used to prepare tricyclodecane monomethanol acrylate and tricyclodecane monomethanol methacrylate, and tricyclodecane monomethanol is used to prepare tricyclodecane monomethanol acrylate and tricyclodecane monomethanol methacrylate:

[0068] Take 100g of tricyclodecane monomethanol, 48g of acrylic acid (or 56g of methacrylic acid), 100g of n-heptane, 1g of inhibitor hydroquinone, and 2.8g of catalyst p-toluenesulfonic acid and place them in a flask. Reflux and dehydrate for about 12 hours. After the reaction is completed, the reaction solution is washed with alkali, vacuum-removed solvents, and distilled to obtain tricyclodecane monomethanol (meth)acrylate product. Performance test was conducted, and resin (resin formula: 48% SD-7546 resin + 48% tricyclodecane monomethanol (meth)acrylate + 4wt% D-1173; scraping thickness: 50μm; irradiation source: medium pressure mercury lamp; curing atmosphere: air atmosphere) was prepared to test the adhesion of different substrates. The adhesion was tested by the 100-grid test method. The 100-grid test standard refers to "GBT9286-1998 Scratch Test of Paint and Varnish Film". A blade was used to scratch the completely cured film, and the number of cuts in each direction was 6; the interval width between the lines was 1.5mm. After scratching, tape was attached to the scratched position, and the tape was pressed down with fingers to attach it tightly, and then the tape was torn off with an instantaneous force to visually observe whether the sample fell off. Adhesion is expressed by ASTM standard grade. The results are shown in Table 2.

[0069] Performance test data

[0070] Table 1

[0071]

[0072]

[0073] Table 2

[0074]

Claims

1. A method for preparing tricyclodecane monomethanol, characterized in that: The following steps are involved: S1, dicyclopentadiene is subjected to hydroformylation reaction catalyzed by a ruthenium catalyst and a phosphine ligand to obtain an intermediate tricyclodecane carboxaldehyde; S2. The intermediate tricyclodecane carboxaldehyde is subjected to catalytic hydrogenation reaction to obtain tricyclodecane monomethanol.

2. The method for preparing tricyclodecane monomethanol according to claim 1, characterized in that: The ruthenium catalyst is selected from at least one of triruthenium dodecacarbonyl, ruthenium acetylacetonate, tetrakis(dimethyl sulfoxide) ruthenium dichloride, ruthenium trichloride, ruthenium acetate, and cyclooctadiene ruthenium dichloride.

3. The method for preparing tricyclodecane monomethanol according to claim 2, characterized in that: The molar ratio of the dicyclopentadiene to the ruthenium catalyst is 1:(0.0001-0.05).

4. The method for preparing tricyclodecane monomethanol according to claim 3, characterized in that: The phosphine ligands are trivalent phosphine and trivalent phosphine oxide.

5. The method for preparing tricyclodecane monomethanol according to claim 4, characterized in that: The structure of the trivalent phosphine includes formula L1 or formula L2:

6. The method for preparing tricyclodecane monomethanol according to claim 5, characterized in that: The trivalent phosphine oxide is selected from at least one of triphenylphosphine oxide, tri(alkyl substituted)phenylphosphine oxide such as tri(p-tolyl)phosphine oxide, tri(p-methoxyphenyl)phosphine oxide, tri(m-tolyl)phosphine oxide, etc., tricyclohexylphosphine oxide, and 2-diphenylphosphine oxide-biphenyl.

7. The method for preparing tricyclodecane monomethanol according to claim 6, characterized in that: The molar ratio of the trivalent phosphine to the ruthenium catalyst is (0.1-5):

1.

8. The method for preparing tricyclodecane monomethanol according to claim 7, characterized in that: The molar ratio of the trivalent phosphine to the trivalent phosphine oxide is 1:(0.05-0.2).

9. The method for preparing tricyclodecane monomethanol according to claim 8, characterized in that: The hydroformylation reaction is carried out under a pressure of 5-10 MPa, a temperature of 120-200° C. and a time of 8-48 h.

10. An application of the method for preparing tricyclodecane monomethanol according to any one of claims 1 to 9, characterized in that: Used in the preparation of light-curing coatings.

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