Methyl isobutyl ketone acetal ester compound as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of synthesis of organic compounds, and particularly relates to a methyl isobutyl ketone acetal ester compound as well as a preparation method and application thereof. The methyl isobutyl ketone acetal ester compound provided by the invention can be used as a diluent when being used for a photocuring product, on one hand, the methyl isobutyl ketone acetal ester compound provided by the invention has relatively high molecular weight and boiling point and relatively low volatility; compared with the prior art, the polymer has the advantages that the polymer has low irritation to the skin (the skin irritation index P.I.I is 1.0) on the other hand, when the polymer is used for a photocuring material, the polymer can be cross-linked with other photocuring materials under the illumination condition to quickly form a film, and the film has good adhesive force on a substrate.

Description

Technical Field

[0001] The invention belongs to the technical field of organic compound synthesis, and particularly relates to a methyl isobutyl ketone glycerol ester compound, a preparation method and an application thereof. Background Art

[0002] The most common photocurable products are UV coatings, UV inks, and UV adhesives, which are generally composed of photocurable oligomers, photocurable reactive diluents, photoinitiators, additives, and the like. Conventional photocurable diluents include tetrahydrofurfuryl alcohol acrylate, phenoxyethanol acrylate, and isobornyl acrylate. These photocurable reactive diluents have good dilution ability and adhesion, but they also suffer from strong odor and skin irritation. The skin irritation index (PII) of tetrahydrofurfuryl alcohol acrylate is 5.0. Phenoxyethanol acrylate and isobornyl acrylate have lower skin irritation indices, but they have a very strong odor. Industrial workers usually need to take very strict protective measures when using these reactive diluents, otherwise they may suffer from health problems such as skin redness, rotting, and swollen eyes. Summary of the Invention

[0003] The present invention aims to provide a methyl isobutyl glycerol ketal acrylate compound, a preparation method and an application thereof. The methyl isobutyl glycerol ketal acrylate compound provided by the present invention has a low skin irritation index and low volatility.

[0004] In order to achieve the above object, the present invention provides the following technical solutions:

[0005] The present invention provides a methyl isobutyl ketone glycerol ester compound having a structure shown in Formula I:

[0006] In formula I, R is H or CH3.

[0007] The present invention also provides a method for preparing the methyl isobutyl ketone glycerol ester compound described in the above technical solution, comprising the following steps:

[0008] Hydrolyze the glyceryl acetonate compound having the structure of formula I-1 with water under acidic catalyst conditions to obtain compound 2;

[0009] In formula I-1, R is H or CH3;

[0010] The compound 2, methyl isobutyl ketone, a water-carrying agent and a polymerization inhibitor are mixed and then subjected to a condensation reaction to obtain the methyl isobutyl ketone glycerol acrylate compound.

[0011] Preferably, the molar ratio of the glyceryl acetonate acrylate compound to water is 100:10 to 1:100.

[0012] Preferably, the acidic catalyst comprises one or more of a strong acid, an acid salt and a strong acid cation exchange resin.

[0013] Preferably, the acidic catalyst is 0.1 to 20% of the total mass of the glyceryl acetonate compound and water.

[0014] Preferably, the hydrolysis temperature is 30-80° C., the time is 1-24 h, and the vacuum degree is ≤0.02 MPa.

[0015] Preferably, the molar ratio of the compound 2 to methyl isobutyl ketone may be 10:1 to 1:1.

[0016] Preferably, the water-carrying agent includes toluene, benzene, petroleum ether and C6-C 10 One or more alkanes; the polymerization inhibitor includes one or more of phenothiazine, p-hydroxyanisole, hydroquinone and tert-butylhydroquinone.

[0017] Preferably, the condensation reaction is carried out under reflux conditions; the condensation reaction time is 6 to 48 hours.

[0018] The present invention also provides the use of the methyl isobutyl acrylate glycerol ketal compound described in the above technical solution or the methyl isobutyl acrylate glycerol ketal compound prepared by the preparation method described in the above technical solution in light-curing inks or light-curing adhesives.

[0019] The present invention provides a methyl isobutyl ketone glycerol ester compound having a structure shown in Formula I:

[0020] In formula I, R is H or CH3.

[0021] The methyl isobutyl acrylate glycerol ketal compound provided by the present invention can be used as a diluent when used in a photocurable product. On the one hand, the methyl isobutyl acrylate glycerol ketal compound provided by the present invention has low skin irritation and low volatility. On the other hand, when used in a photocurable material, it can cross-link with other photocurable materials under light conditions, quickly forming a film, and the film layer has good adhesion to the substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0023] Figure 1 Gas chromatogram of the methyl isobutyl ketone glyceryl acrylate ester prepared in Example 1;

[0024] Figure 2 Infrared spectrum of the methyl isobutyl ketone glyceryl acrylate ester prepared in Example 1;

[0025] Figure 3 Nuclear magnetic resonance hydrogen spectrum of the methyl isobutyl ketone glyceryl acrylate ester prepared in Example 1;

[0026] Figure 4 Gas chromatogram of the hydrolysis reaction solution of the propionone glyceryl acrylate ester;

[0027] Figure 5 Hydrogen spectrum of the methyl isobutyl ketone glyceryl methacrylate ester prepared in Example 2. DETAILED DESCRIPTION

[0028] The present application provides a methyl isobutyl ketone glyceryl acrylate ester compound having the structure shown in Formula I:

[0029] In Formula I, R is H or CH3.

[0030] The present application provides a preparation method of a methyl isobutyl ketone glyceryl acrylate ester, comprising the following steps:

[0031] The propionone glyceryl acrylate ester compound having the structure of Formula I-1 is hydrolyzed with water under the condition of an acid catalyst to obtain compound 2.

[0032] In Formula I-1, R is H or CH3.

[0033] The compound 2, methyl isobutyl ketone, a water-carrying agent and a polymerization inhibitor are mixed and then subjected to a condensation reaction to obtain the methyl isobutyl ketone glyceryl acrylate ester compound.

[0034] The present application hydrolyzes the propionone glyceryl acrylate ester compound having the structure of Formula I-1 with water under an acid condition to obtain compound 2.

[0035] As an embodiment of the present application, the molar ratio of the propionone glyceryl acrylate ester compound and water can be 100:10-1:100, and specifically can be 1:2.

[0036] In one embodiment of the present invention, the acidic catalyst comprises one or more of a strong acid, an acid salt, and a strong-acid cation exchange resin. In another embodiment of the present invention, the strong acid comprises one or more of concentrated sulfuric acid, concentrated phosphoric acid, hydrobromic acid, and aminosulfonic acid; the acid salt comprises sodium bisulfate; and the strong-acid cation exchange resin is primarily a sulfonic acid-type strong-acid cation exchange resin with a polystyrene backbone. In another embodiment of the present invention, the mass of the acidic catalyst is 0.1-20% of the total mass of the glyceryl acrylate compound and water, and specifically can be 0.45%.

[0037] As an embodiment of the present invention, the hydrolysis temperature can be 30-80°C, specifically 30°C, 40°C, 50°C, 60°C, 70°C or 50°C; the time can be 1-24h, specifically 6h, and the vacuum degree is ≤0.02MPa.

[0038] As an embodiment of the present invention, the hydrolysis is preferably carried out in a four-necked round-bottom flask connected to a distillation head, a condenser and a vacuum pump. During the reaction, by-products are removed in real time to promote the forward reaction.

[0039] After obtaining compound 2, the present invention mixes compound 2, methyl isobutyl ketone, a water-carrying agent and a polymerization inhibitor, and then performs a condensation reaction to obtain the methyl isobutyl ketone glycerol acrylate compound.

[0040] As an embodiment of the present invention, the molar ratio of the compound 2 to methyl isobutyl ketone can be 10:1 to 1:2, specifically 3:1 to 1:2.

[0041] As an embodiment of the present invention, the water-carrying agent includes toluene, benzene, petroleum ether and C6-C 10 One or more alkanes. As one embodiment of the present invention, the polymerization inhibitor includes one or more of phenothiazine, p-hydroxyanisole, hydroquinone, and tert-butylhydroquinone. As one embodiment of the present invention, the mass ratio of the methyl isobutyl ketone to the water-carrying agent can be 1 to 1.5:3, specifically 1.1 to 1.2:3; the mass ratio of the methyl isobutyl ketone to the polymerization inhibitor can be 100 to 150:2, specifically 105 to 115:2.

[0042] As an embodiment of the present invention, the condensation reaction is preferably carried out under reflux conditions; the condensation reaction time can be 6 to 48 hours, specifically 24 hours.

[0043] As an embodiment of the present invention, after the condensation reaction, the condensation reaction liquid is further neutralized, the neutralized reaction liquid is filtered to remove inorganic compounds, and the filtrate is subjected to reduced pressure distillation to obtain the methyl isobutyl ketone glyceride compound.

[0044] The present invention also provides the use of the methyl isobutyl acrylate glycerol ketal compound described in the above technical solution or the methyl isobutyl acrylate glycerol ketal compound prepared by the preparation method described in the above technical solution in light-curing inks or light-curing adhesives.

[0045] In order to further illustrate the present invention, the scheme of the present invention is described in detail below with reference to the accompanying drawings and embodiments, but they should not be understood as limiting the scope of protection of the present invention.

[0046] Example 1

[0047] (1) Add glyceryl acetone acrylate (186.2 g, 1 mol), water (36.0 g, 2 mol), and concentrated sulfuric acid (1.0 g) to a four-necked round-bottom flask. Add a magnet and start magnetic stirring. Install the distillation head, condenser, and tail pipe, connect and start the vacuum pump, and control the vacuum degree to ≤0.02 MPa. After 6 hours of reaction, the reaction solution changes from a turbid milky white state to a clear and transparent state, obtaining glyceryl monoacrylate and acetone. The acetone is removed from the reaction system under vacuum conditions.

[0048] (2) Add methyl isobutyl ketone (110.2 g, 1.1 mol), toluene (300 g) and phenothiazine (2 g) to the reaction solution obtained in step (1) (containing 1 mol of compound 2). Start stirring, heat the reaction solution to reflux, and separate the water produced by the system. React for 24 hours, monitor the reaction degree by gas chromatography, and stop the reaction when the conversion of glycerol monoacrylate is complete. Then add 10 g of NaOH powder to the reaction system for neutralization, and neutralize to a pH value of 7. After neutralization, filter the reaction system, and purify the filtrate by vacuum distillation to obtain 195 g of methyl isobutyl ketone glycerol ester.

[0049] Figure 1 This is a gas chromatogram of methyl isobutyl acrylate glycerol ketal prepared in Example 1. The test method is as follows: the gas chromatographic column is a KB-624 weak polar bonded cross-linked stationary phase chromatographic column, the carrier gas is nitrogen, the vaporization chamber temperature is 240°C, the detector is an FDI flame ionization detector, and the detector temperature is 240°C. The column oven temperature program is 120°C for 5 minutes, then the temperature is increased at a rate of 10°C / min for 10 minutes to 220°C, and finally the temperature is maintained at 220°C for 15 minutes. Figure 1 It can be seen that the retention time of methyl isobutyl acrylate glycerol ketal is 7.648 min.

[0050] Figure 2 This is the infrared spectrum of methyl isobutyl acrylate ketal prepared in Example 1. The spectrum information is: 2871.78cm -1 、2955.57cm -1 、2983.00cm -1 It is the absorption peak of the CH symmetric and asymmetric stretching vibration of the CH2 and CH3 groups in the isobutyl group. 1376.60cm -1 、1454.89cm -1 、1468.23cm -1 It is the absorption peak of the CH symmetric and asymmetric bending vibration of the CH2 and CH3 groups in the isobutyl group. 1619.73cm -1 、1653.62cm -1 It is the stretching vibration absorption peak of C=C double bond. 1731.53cm -1 It is the stretching vibration absorption peak of the carbonyl C=O double bond. 1185.29cm -1 It is the stretching vibration absorption peak of the oxygen five-membered ring COC.

[0051] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of methyl isobutyl glycerol ketal prepared in Example 1.

[0052] Figure 4 This is a gas chromatogram of the hydrolysis reaction liquid of glyceryl acetone acrylate. The test conditions are as follows: the gas chromatography column is a KB-624 weak polar bonded cross-linked stationary phase column, the carrier gas is nitrogen, the vaporization chamber temperature is 240°C, the detector is an FDI flame ionization detector, and the detector temperature is 240°C. The column oven temperature program is 120°C for 5 minutes, then the temperature is increased at a rate of 10°C / min for 10 minutes to 220°C, and finally the temperature is maintained at 220°C for 15 minutes. Figure 4 It can be seen that the retention time of the hydrolysis reaction product of glyceryl acetonate (Compound 2) is 7.093 min.

[0053] Figure 5 This is the gas chromatogram of glyceryl acetone acrylate. The test conditions are as follows: the gas chromatography column is a KB-624 weak polar bonded cross-linked stationary phase column, the carrier gas is nitrogen, the vaporization chamber temperature is 240°C, the detector is an FDI flame ionization detector, and the detector temperature is 240°C. The column oven temperature program is to keep it at 120°C for 5 minutes, then increase the temperature at a rate of 10°C / min for 10 minutes to 220°C, and finally keep it at 220°C for 15 minutes. Figure 5 It can be seen that the retention time of glyceryl acrylate acetone acetal is 2.427 min.

[0054] Example 2

[0055] (1) Add methyl methacrylate acetone glycerol ester (200.25 g, 1 mol), water (90 g, 5 mol), and concentrated sulfuric acid (2 g) to a four-necked round-bottom flask. Add a magnet and start magnetic stirring. Install the distillation head, condenser, and tail pipe, connect and start the vacuum pump, and control the vacuum degree to ≤0.02 MPa. After 6 hours of reaction, the reaction solution changes from a turbid milky white state to a clear and transparent state, obtaining glycerol monomethacrylate and acetone. The acetone is removed from the reaction system under vacuum conditions.

[0056] (2) Add methyl isobutyl ketone (200.3 g, 2 mol), toluene (500 g) and phenothiazine (4 g) to the reaction solution obtained in (1) (containing 1 mol of compound 2). Start stirring, heat the reaction solution to reflux, and separate the water produced by the system. React for 24 hours, monitor the reaction degree by gas chromatography, and stop the reaction when the conversion of glycerol monomethacrylate is complete. Then add 10 g of NaOH powder to the reaction system for neutralization until the pH value of the reaction system reaches 7. After neutralization, filter the reaction system, and purify the obtained filtrate by vacuum distillation to obtain 198 g of methyl isobutyl ketone glycerol methacrylate.

[0057] The present invention conducted a photocuring performance test on the methyl isobutyl glycerol ketal acrylate prepared in Example 1. The test was as follows: 100 g of the methyl isobutyl glycerol ketal acrylate prepared in Example 1 was added with 1 g of photoinitiator 1171, and stirred evenly to obtain a mixed solution; 2 g of the mixed solution was spread evenly on a PET film, and irradiated under a mercury lamp for 1 minute. The methyl isobutyl glycerol ketal acrylate polymerized into a viscoelastic cured film layer, and the film layer had good adhesion to the surface of the PET film.

[0058] Although the above embodiment provides a detailed description of the present invention, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the scope of protection of the present invention.

Claims

1. A methyl isobutyl ketone glycerol ester compound having the structure shown in Formula I: In formula I, R is H or CH3.

2. The method for preparing the methyl isobutyl ketal glycerol acrylate compound according to claim 1, comprising the following steps: Hydrolyze the glyceryl acetonate compound having the structure of formula I-1 with water under acidic catalyst conditions to obtain compound 2; In formula I-1, R is H or CH3; The compound 2, methyl isobutyl ketone, a water-carrying agent and a polymerization inhibitor are mixed and then subjected to a condensation reaction to obtain the methyl isobutyl ketone glycerol acrylate compound.

3. The preparation method according to claim 2, wherein The molar ratio of the glyceryl acetonate acrylate compound to water is 100:10 to 1:

100.

4. The preparation method according to claim 2, wherein The acidic catalyst includes one or more of a strong acid, an acid salt and a strong acid cation exchange resin.

5. The preparation method according to claim 4, wherein The mass of the acidic catalyst is 0.1 to 20% of the total mass of the glyceryl acetonate compound and water.

6. The preparation method according to claim 2, wherein The hydrolysis temperature is 30-80° C., the time is 1-24 hours, and the vacuum degree is ≤0.02 MPa.

7. The preparation method according to claim 2, wherein The molar ratio of the compound 2 to methyl isobutyl ketone can be 10:1 to 1:

1.

8. The preparation method according to claim 2, wherein The water-carrying agent includes toluene, benzene, petroleum ether and C6-C 10 One or more alkanes; the polymerization inhibitor includes one or more of phenothiazine, p-hydroxyanisole, hydroquinone and tert-butylhydroquinone.

9. The preparation method according to claim 2, wherein The condensation reaction is carried out under reflux conditions; the condensation reaction time is 6 to 48 hours.

10. Use of the methyl isobutyl acrylate glycerol ketal compound according to claim 1 or the methyl isobutyl acrylate glycerol ketal compound prepared by the preparation method according to any one of claims 2 to 9 in light-curing inks or light-curing adhesives.

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