A multifunctional alicyclic epoxy monomer and its preparation method and application

Abstract

The present invention discloses a multifunctional alicyclic epoxy monomer, a preparation method and application thereof. The structure of the multifunctional alicyclic epoxy monomer is shown in formula (I): #imgabs0##imgabs1# The multifunctional alicyclic epoxy monomer prepared by the present invention has good light transmittance. At the same time, the monomer can initiate free radical polymerization under ultraviolet light irradiation to prepare a multifunctional alicyclic epoxy polymer. The obtained multifunctional alicyclic epoxy polymer has good light transmittance, light color, good flexibility and high thermal decomposition temperature, which solves the problem of poor flexibility of bisphenol A epoxy resin. The polymer has great application prospects in the fields of solder mask ink, light and heat dual curing system, electronic manufacturing, coating protection, etc., and has very good application value.

Description

Technical Field

[0001] The present invention belongs to the field of polymer materials, and in particular relates to a multifunctional alicyclic epoxy monomer and a preparation method and application thereof. Background Art

[0002] Epoxy polymers, also known as epoxy resins, are a class of high-molecular-weight organic compounds with at least two epoxy groups in their molecular structure. They exhibit excellent bonding properties, superior chemical resistance, excellent mechanical properties, good heat resistance, and electrical insulation. Furthermore, the greatest advantage of epoxy resins lies in their adaptability. They can be formed into rigid potting compounds or highly elastic soft adhesives, making them widely used in fields such as electronics manufacturing and aerospace. However, the brittleness and high shrinkage of epoxy resins have hindered many of their potential applications.

[0003] The most widely used variety in the world is bisphenol A epoxy resin, but due to its poor flexibility, it is difficult to apply to electronic packaging and UV packaging of flat panels and flexible display devices. Alicyclic epoxy resin is a branch of epoxy resin. Since the epoxy groups of alicyclic epoxy resin are directly connected to the alicyclic ring, a tight rigid molecular structure can be formed. After curing, the crosslinking density is large, resulting in a high heat deformation temperature, a small curing shrinkage, and a high tensile strength. At the same time, since it does not contain chlorine and sodium ions during the synthesis process, alicyclic epoxy resin has good dielectric properties and is now widely used in industries such as photocurable coatings, electronic adhesives, insulating materials, LED packaging adhesives, and 3D printing. In particular, when used in electronic industries such as LED packaging, it can exert excellent electrical insulation properties. Therefore, the present invention has developed a multifunctional alicyclic epoxy monomer and used it to prepare a multifunctional alicyclic epoxy polymer, which is expected to broaden the application field of epoxy resin. Summary of the Invention

[0004] In response to the technical problems existing in the prior art, the present invention provides a multifunctional alicyclic epoxy monomer. The prepared multifunctional alicyclic epoxy monomer has good light transmittance. At the same time, the monomer can initiate free radical polymerization under ultraviolet light irradiation to prepare a multifunctional alicyclic epoxy polymer. The obtained multifunctional alicyclic epoxy polymer has good light transmittance, light color, good flexibility and high thermal decomposition temperature, which solves the problem of poor flexibility of bisphenol A epoxy resin. It has great application prospects in the fields of solder mask ink, light and thermal dual-curing system, electronic manufacturing, coating protection, etc., and has very good application value.

[0005] The object of the present invention is to provide a multifunctional alicyclic epoxy monomer, the structure of which is shown in formula (I):

[0006]

[0007] Where R is C 1～12alkyl,

[0008]

[0009] In some embodiments of the present invention, R is ethyl.

[0010] Another object of the present invention is to provide a multifunctional alicyclic epoxy polymer, which is prepared by polymerization of the multifunctional alicyclic epoxy monomer and an auxiliary agent.

[0011] In some embodiments of the present invention, the auxiliary agent consists of a cationic photoinitiator, a photosensitizer and a reactive diluent.

[0012] Another object of the present invention is to provide a method for preparing a multifunctional alicyclic epoxy monomer, comprising the following steps:

[0013] S1. Diketene, an alcohol compound, a first catalyst and a first solvent are mixed, reacted, and purified to obtain an acetoacetate compound;

[0014] S2. The acetoacetate compound is mixed with 7-oxabicyclo[4.1.0]hept-3-yl methacrylate, a second catalyst, and a second solvent, and reacted to obtain a multifunctional alicyclic epoxy monomer.

[0015] In some embodiments of the present invention, in S1, the alcohol compound is selected from C 1～7 Monohydric alcohol, C 2～12 diols, C 3～6 triol, C 3～6 At least one of pentaerythritol and polyether polyol.

[0016] In some embodiments of the present invention, in S1, the alcohol compound is selected from at least one of methanol, ethanol, isopropanol, n-butanol, cyclohexanol, cyclohexylmethanol, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, glycerol, trimethylolpropane, and pentaerythritol.

[0017] In some embodiments of the present invention, in S1, the first catalyst is selected from triethylamine.

[0018] In some embodiments of the present invention, in S1, the first solvent is selected from dichloromethane.

[0019] In some embodiments of the present invention, in S1, the molar ratio of diketene, alcohol compound and first catalyst is 1-4:1:0.075-0.3.

[0020] In some embodiments of the present invention, in S1, the reaction temperature is 20-40° C., and the reaction time is 8-12 h.

[0021] In some embodiments of the present invention, in S2, the structure of 7-oxabicyclo[4.1.0]hept-3-yl methacrylate is as follows:

[0022]

[0023] In some embodiments of the present invention, in S2, the second catalyst is selected from quaternary ammonium salts.

[0024] In some embodiments of the present invention, in S2, the quaternary ammonium salt is selected from tetrabutylammonium bromide.

[0025] In some embodiments of the present invention, in S2, the second solvent is selected from ethyl acetate.

[0026] In some embodiments of the present invention, in S2, the molar ratio of the acetoacetate compound to 7-oxabicyclo[4.1.0]hept-3-yl methacrylate to the second catalyst is 1:2-8:0.15-0.60.

[0027] In some embodiments of the present invention, in S2, the reaction temperature is 60-100° C., and the reaction time is 3-8 h.

[0028] Another object of the present invention is to provide a method for preparing a multifunctional alicyclic epoxy polymer, comprising the following steps:

[0029] The multifunctional alicyclic epoxy monomer, cationic photoinitiator, photosensitizer and reactive diluent are mixed and photocured to obtain a multifunctional alicyclic epoxy polymer.

[0030] In some embodiments of the present invention, by mass percentage, the multifunctional alicyclic epoxy monomer is 80-85%, the cationic photoinitiator is 3-5%, the photosensitizer is 0.2-0.3%, and the reactive diluent is 10-15%.

[0031] In some embodiments of the present invention, the cationic photoinitiator is selected from at least one of diphenyliodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, 4,4'-ditolyliodonium hexafluorophosphate, and diphenyliodonium hexafluoroarsenate. The cationic photoinitiator employed in the present invention can effectively avoid the oxygen inhibition problem caused by oxygen in free radical photocuring during the photocuring process.

[0032] In some embodiments of the present invention, the photosensitizer is selected from at least one of naphthalene, anthracene, phenanthrene, phenothiazine, and 2-isopropylthioxanthone.

[0033] In some embodiments of the present invention, the reactive diluent is selected from at least one of bis(3,4-epoxycyclohexylmethyl)adipate, tetrahydrofuran acrylate, bisoxetane and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate.

[0034] In some embodiments of the present invention, the light curing temperature is 80-100°C, the time is 5-15 minutes, and the light intensity is 30-40 mw / cm 2 .

[0035] Another object of the present invention is to provide a multifunctional alicyclic epoxy polymer for use in solder resist inks, photothermal dual-curing systems, electronic manufacturing, and coating protection.

[0036] The synthetic route of multifunctional alicyclic epoxy monomers is as follows:

[0037]

[0038] An alcohol compound reacts with diketene in the presence of a catalyst to generate an acetoacetate compound intermediate, which then undergoes a Michael addition reaction with 7-oxabicyclo[4.1.0]hept-3-yl methacrylate to obtain a multifunctional alicyclic epoxy monomer having an alicyclic epoxy group at the molecular end, which is then photocured using a cationic photoinitiator to obtain a multifunctional alicyclic epoxy polymer.

[0039] Compared with the prior art, the present invention has the following beneficial effects:

[0040] (1) The multifunctional alicyclic epoxy monomer prepared by the present invention has good light transmittance. At the same time, the monomer can initiate free radical polymerization under ultraviolet light to prepare a multifunctional alicyclic epoxy polymer. The obtained multifunctional alicyclic epoxy polymer has good light transmittance, light color, good flexibility and high thermal decomposition temperature, which solves the problem of poor flexibility of bisphenol A epoxy resin. It has great application prospects in the fields of solder mask ink, photothermal dual-curing system, electronic manufacturing, coating protection, etc. and has very good application value.

[0041] (2) The reaction conditions for preparing multifunctional alicyclic epoxy monomers in the present invention are mild, environmental pollution is small, and it is suitable for industrial production.

[0042] (3) The present invention uses a cationic photoinitiator for photocuring when preparing a multifunctional alicyclic epoxy polymer, thereby avoiding problems such as oxygen inhibition. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 This is the appearance of the multifunctional alicyclic epoxy resin film PE-1 of Example 7.

[0044] Figure 2This is the appearance of the multifunctional alicyclic epoxy resin film PE-2 of Example 8.

[0045] Figure 3 This is the appearance of the multifunctional alicyclic epoxy resin film PE-3 of Example 9.

[0046] Figure 4 This is the appearance of the multifunctional alicyclic epoxy resin film PE-4 of Example 10.

[0047] Figure 5 This is the appearance of the multifunctional alicyclic epoxy resin film PE-5 of Example 11.

[0048] Figure 6 This is the appearance of the multifunctional alicyclic epoxy resin film PE-6 of Example 12.

[0049] Figure 7 These are the thermogravimetric test graphs of multifunctional alicyclic epoxy resin films PE-1, PE-3, PE-4, and PE-6.

[0050] Figure 8 These are the optical transmittance test charts of multifunctional alicyclic epoxy resin films PE-1, PE-2, PE-3, PE-4, PE-5, and PE-6.

[0051] Figure 9 This is a test chart of the flexibility of the multifunctional alicyclic epoxy resin film PE-1.

[0052] Figure 10 This is a test chart of the flexibility of the multifunctional alicyclic epoxy resin film PE-2.

[0053] Figure 11 This is a test chart of the flexibility of the multifunctional alicyclic epoxy resin film PE-3.

[0054] Figure 12 This is a test chart of the flexibility of the multifunctional alicyclic epoxy resin film PE-4.

[0055] Figure 13 This is a test chart of the flexibility of the multifunctional alicyclic epoxy resin film PE-5.

[0056] Figure 14 This is a test chart of the flexibility of the multifunctional alicyclic epoxy resin film PE-6. DETAILED DESCRIPTION

[0057] In order to enable those skilled in the art to better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts should fall within the scope of protection of the present invention.

[0058] The experimental methods in the following examples are conventional methods unless otherwise specified, and the experimental materials used in the following examples are commercially available unless otherwise specified.

[0059] Example 1

[0060] This embodiment provides a multifunctional alicyclic epoxy monomer E-1, and the specific process is as follows:

[0061] S1. Ethyl acetoacetate (0.02 mol), 7-oxabicyclo[4.1.0]hept-3-yl methacrylate (0.04 mol), and 0.30 g of tetrabutylammonium bromide were added to a 100 ml flask, followed by 50 ml of ethyl acetate. The mixture was reacted in a 65°C oil bath for 3 h. After the reaction, the mixture was acid-washed 3-5 times with a 1 mol / L dilute hydrochloric acid solution, separated, and the dichloromethane was removed by rotary evaporation to obtain a polyfunctional alicyclic epoxy monomer E-1. The chemical structure of the polyfunctional alicyclic epoxy monomer E-1 is as follows:

[0062]

[0063] The nuclear magnetic resonance structure and infrared structure of the multifunctional alicyclic epoxy monomer E-1 are as follows:

[0064] The chemical shifts in the 400 MHz H-NMR spectrum of DMSO d6 solvent are 4.18-4.10 ppm (2H, aliphatic O-CH2-), 4.05-4.00 ppm (4H, aliphatic -CH2-O), 3.83-3.76 ppm (8H, aliphatic C(O)-CH2-CH2-), 3.17-3.05 ppm (4H, alicyclic CH-O-CH), 2.18-2.08 ppm (3H, aliphatic C(O)-CH3), 2.09-1.29 ppm (14H, alicyclic CH and CH2), 1.22-1.13 ppm (3H, aliphatic C(O)-CH3); the peak positions in the infrared absorption spectrum are 1733 and 1713 cm -1 (ester C=O), 789 cm -1 (alicyclic CH-O-CH).

[0065] Example 2

[0066] This embodiment provides a multifunctional alicyclic epoxy monomer E-2, and the specific process is as follows:

[0067] S1. Add 1,3-propylene glycol (0.02 mol), diketene (0.04 mol), and 0.5 ml of triethylamine to a 100 ml flask, then add 40 ml of dichloromethane and react in an oil bath at 35°C for 10 h. After the reaction, wash with 1 mol / L dilute hydrochloric acid and then with distilled water, separate the liquids, dry over anhydrous magnesium sulfate, filter, and rotary evaporate to obtain a light yellow liquid, i.e., acetoacetate compound DK-2.

[0068] S2. Add acetoacetate compound DK-2 (0.02 mol), 7-oxabicyclo[4.1.0]hept-3-yl methacrylate (0.08 mol) and 0.58 g tetrabutylammonium bromide into a 100 ml beaker, then add 40 ml ethyl acetate and react at 75 ° C for 3 hours. After the reaction is completed, wash with 1 mol / L dilute hydrochloric acid and then with distilled water. Separate the liquid, dry with anhydrous magnesium sulfate, filter, and rotary evaporate to obtain a viscous liquid, i.e., the multifunctional alicyclic epoxy monomer E-2.

[0069] The chemical structural formula of the acetoacetate compound DK-2 is as follows:

[0070]

[0071] The NMR structure and IR structure of the acetoacetate compound DK-2 are as follows:

[0072] The chemical shifts in the 400 MHz H-NMR spectrum of DMSO d6 solvent are 4.20-4.11 ppm (4H, aliphatic O-CH2), 3.48-3.36 ppm (4H, aliphatic C(O)-CH2-C(O)), 2.27-2.13 ppm (6H, aliphatic C(O)-CH3), and 2.02-1.90 ppm (2H, aliphatic CH2); the peak positions in the infrared absorption spectrum are 1739 and 1705 cm -1 (Ester C=O).

[0073] The chemical structural formula of the multifunctional alicyclic epoxy monomer E-2 is as follows:

[0074]

[0075] The nuclear magnetic resonance structure and infrared structure of the multifunctional alicyclic epoxy monomer E-2 are as follows:

[0076] The chemical shifts in the 400 MHz H NMR spectrum of DMSO d6 solvent are 4.21-4.12 ppm (4H, aliphatic O-CH2-), 4.10-3.99 ppm (8H, aliphatic-C H2 -O), 3.97-3.73ppm (16H, aliphatic C(O)-CH2-CH2-), 3.17-3.05ppm (8H, alicyclic CH-O-CH), 2.20-2.03ppm (6H, aliphatic C(O)-CH3), 2.03-1.89ppm (2H, alicyclic CH2), 1.86-0.88ppm (28H, alicyclic CH and CH2); the peak positions in the infrared absorption spectrum are 1739 and 1705cm respectively. -1 (ester C=O) and 784 cm -1 (alicyclic CH-O-CH).

[0077] Example 3

[0078] This embodiment provides a multifunctional alicyclic epoxy monomer E-3, and the specific process is as follows:

[0079] S1. Neopentyl glycol (0.02 mol), diketene (0.04 mol), and 0.5 ml of triethylamine were added to a 100 ml flask, followed by 40 ml of dichloromethane. The mixture was reacted in an oil bath at 25°C for 12 h. After the reaction, the mixture was washed with 1 mol / L dilute hydrochloric acid and then with distilled water. The mixture was separated, dried over anhydrous magnesium sulfate, filtered, and rotary evaporated to obtain the acetoacetate compound DK-3.

[0080] S2. Add acetoacetate compound DK-3 (0.02 mol), 7-oxabicyclo[4.1.0]hept-3-yl methacrylate (0.08 mol) and 0.60 g tetrabutylammonium bromide into a 100 ml beaker, then add 40 ml ethyl acetate and react at 75 ° C for 6 hours. After the reaction is completed, wash with 1 mol / L dilute hydrochloric acid and then with distilled water, separate the liquid, dry with anhydrous magnesium sulfate, filter, and rotary evaporate to obtain a viscous liquid, i.e., multifunctional alicyclic epoxy monomer E-3.

[0081] The chemical structural formula of the acetoacetate compound DK-3 is as follows:

[0082]

[0083] The NMR structure and IR structure of the acetoacetate compound DK-2 are as follows:

[0084] The chemical shifts in the 400 MHz H-NMR spectrum of DMSO d6 solvent are 3.94-3.85 ppm (4H, aliphatic O-CH2), 3.48-3.36 ppm (4H, aliphatic C(O)-CH2-C(O)), 2.27-2.13 ppm (6H, aliphatic C(O)-CH3), and 0.98-0.87 ppm (6H, aliphatic CH3); the peak positions in the infrared absorption spectrum are 1736 and 1708 cm -1 (Ester C=O).

[0085] The chemical structural formula of the multifunctional alicyclic epoxy monomer E-3 is as follows:

[0086]

[0087] The nuclear magnetic resonance structure and infrared structure of the multifunctional alicyclic epoxy monomer E-3 are as follows:

[0088] The chemical shifts in the 400 MHz H-NMR spectrum of DMSO d6 solvent are 4.14-4.02 ppm (4H, aliphatic O-CH2-), 3.91-3.83 ppm (8H, aliphatic -CH2-O), 3.82-3.73 ppm (16H, aliphatic C(O)-CH2-CH2-), 3.17-3.05 ppm (8H, alicyclic CH-O-CH), 2.24-2.07 ppm (6H, aliphatic C(O)-CH3), 2.05-1.04 ppm (28H, alicyclic six-membered ring hydrogen), 1.02-0.87 ppm (6H, alicyclic CH3); the peak positions in the infrared absorption spectrum are 1736 and 1708 cm -1 (ester C=O) and 787 cm -1 (alicyclic CH-O-CH).

[0089] Example 4

[0090] This embodiment provides a multifunctional alicyclic epoxy monomer E-4, and the specific process is as follows:

[0091] S1. Add glycerol (0.02 mol), diketene (0.06 mol), and 0.75 ml of triethylamine to a 100 ml flask, followed by 40 ml of dichloromethane. Incubate in an oil bath at 25°C for 12 h. After completion of the reaction, wash with 1 mol / L dilute hydrochloric acid and then with distilled water. Separate the liquid, dry over anhydrous magnesium sulfate, filter, and rotary evaporate to obtain a pale yellow liquid, namely, the acetoacetate compound DK-4.

[0092] S2. Add acetoacetate compound DK-4 (0.02 mol), 7-oxabicyclo[4.1.0]hept-3-yl methacrylate (0.12 mol) and 0.86 g tetrabutylammonium bromide into a 100 ml beaker, then add 40 ml ethyl acetate and react at 75 ° C for 5 hours. After the reaction is completed, wash with 1 mol / L dilute hydrochloric acid and then with distilled water, separate the liquid, dry with anhydrous magnesium sulfate, filter, and rotary evaporate to obtain a viscous liquid, i.e., multifunctional alicyclic epoxy monomer E-4.

[0093] The chemical structural formula of the acetoacetate compound DK-4 is as follows:

[0094]

[0095] The NMR structure and IR structure of the acetoacetate compound DK-4 are as follows:

[0096] The chemical shifts in the 400 MHz H-NMR spectrum of DMSO d6 solvent are 4.45-4.08 ppm (5H, aliphatic CH and CH2), 3.48-3.36 ppm (6H, aliphatic C(O)-CH2-C(O)), and 2.25-2.12 ppm (9H, aliphatic C(O)-CH3); the peak positions in the infrared absorption spectrum are 1743 cm -1 and 1705cm -1 (Ester C=O).

[0097] The chemical structural formula of the multifunctional alicyclic epoxy monomer E-4 is as follows:

[0098]

[0099] The nuclear magnetic resonance structure and infrared structure of the multifunctional alicyclic epoxy monomer E-4 are as follows:

[0100] The chemical shifts in the 400 MHz H-NMR spectrum of DMSO d6 solvent are 4.17-3.99 ppm (5H, aliphatic O-CH2- and O-CH-), 3.91-3.83 ppm (12H, aliphatic -CH2-O), 3.82-3.73 ppm (24H, aliphatic C(O)-CH2-CH2-), 3.21-3.05 ppm (12H, alicyclic CH-O-CH), 2.24-2.07 ppm (9H, aliphatic C(O)-CH3), 2.05-1.04 ppm (42H, alicyclic CH2 and CH); the peak positions in the infrared absorption spectrum are 1743 cm -1 and 1705cm -1 (ester C=O) and 787 cm -1 (alicyclic CH-O-CH).

[0101] Example 5

[0102] This embodiment provides a multifunctional alicyclic epoxy monomer E-5, and the specific process is as follows:

[0103] S1. Add 1,4-cyclohexanediol (0.02 mol), diketene (0.04 mol), and 0.5 ml of triethylamine to a 100 ml flask, followed by 40 ml of dichloromethane. React in an oil bath at 40°C for 8 h. After the reaction, wash with 1 mol / L dilute hydrochloric acid and then with distilled water. Separate the liquid, dry over anhydrous magnesium sulfate, filter, and rotary evaporate to obtain a pale yellow liquid, acetoacetate compound DK-5.

[0104] S2. Add acetoacetate compound DK-5 (0.02 mol), 7-oxabicyclo[4.1.0]hept-3-yl methacrylate (0.08 mol) and 0.61 g tetrabutylammonium bromide into a 100 ml beaker, then add 40 ml ethyl acetate and react at 75 °C for 8 h. After the reaction, wash with 1 mol / L dilute hydrochloric acid and then with distilled water, separate the liquids, dry with anhydrous magnesium sulfate, filter, and rotary evaporate to obtain a viscous liquid, i.e., the multifunctional alicyclic epoxy monomer E-5.

[0105] The chemical structural formula of the acetoacetate compound DK-5 is as follows:

[0106]

[0107] The NMR structure and IR structure of the acetoacetate compound DK-5 are as follows:

[0108] The chemical shifts in the 400 MHz H-NMR spectrum of DMSO d6 solvent are 4.63-4.59 ppm (2H, alicyclic CH-O, 3.48-3.36 ppm (4H, aliphatic C(O)-CH2-C(O)), 2.28-2.12 ppm (6H, aliphatic C(O)-CH3), 1.80-1.55 ppm (8H, alicyclic six-membered ring hydrogen); the peak positions in the infrared absorption spectrum are 1740 cm -1 and 1708cm -1 (Ester C=O).

[0109] The chemical structural formula of the multifunctional alicyclic epoxy monomer E-5 is as follows:

[0110]

[0111] The nuclear magnetic resonance structure and infrared structure of the multifunctional alicyclic epoxy monomer E-5 are as follows:

[0112] The chemical shifts in the 400 MHz H-NMR spectrum of DMSO d6 solvent are 4.67-4.62 ppm (2H, aliphatic O-CH-), 4.02-3.83 ppm (8H, aliphatic -CH2-O), 3.90-3.73 ppm (16H, aliphatic C(O)-CH2-CH2-), 3.21-3.05 ppm (8H, alicyclic CH-O-CH), 2.20-2.05 ppm (6H, aliphatic C(O)-CH3), 2.05-1.04 ppm (36H, hydrogen on the alicyclic six-membered ring); the peak positions in the infrared absorption spectrum are 1743 cm -1 and 1705cm -1 (ester C=O) and 790 cm -1 (alicyclic CH-O-CH).

[0113] Example 6

[0114] This embodiment provides a multifunctional alicyclic epoxy monomer E-6, and the specific process is as follows:

[0115] S1. Add tricyclodecane dimethanol (0.02 mol), diketene (0.04 mol), and 0.5 ml of triethylamine to a 100 ml flask, followed by 40 ml of dichloromethane. Incubate in an oil bath at 35°C for 8 h. After completion of the reaction, wash with 1 mol / L dilute hydrochloric acid and then with distilled water. Separate the mixture, dry over anhydrous magnesium sulfate, filter, and rotary evaporate to obtain a pale yellow liquid, acetoacetate compound DK-6.

[0116] S2. Add acetoacetate compound DK-6 (0.02 mol), 7-oxabicyclo[4.1.0]hept-3-yl methacrylate (0.08 mol) and 0.66 g tetrabutylammonium bromide into a 100 ml beaker, then add 40 ml ethyl acetate and react at 80 ° C for 6 hours. After the reaction is completed, wash with 1 mol / L dilute hydrochloric acid and then with distilled water, separate the liquid, dry with anhydrous magnesium sulfate, filter, and rotary evaporate to obtain a viscous liquid, i.e., multifunctional alicyclic epoxy monomer E-6.

[0117] The chemical structural formula of the acetoacetate compound DK-6 is as follows:

[0118]

[0119] The NMR structure and IR structure of the acetoacetate compound DK-6 are as follows:

[0120] The chemical shifts in the 400 MHz H-NMR spectrum of DMSO d6 solvent are 4.38-4.17 ppm (4H, aliphatic CH2), 3.48-3.36 ppm (4H, aliphatic C(O)-CH2-C(O)), 2.25-2.12 ppm (6H, aliphatic C(O)-CH3), 1.90-1.14 ppm (14H, alicyclic CH and CH2); the peak positions in the infrared absorption spectrum are 1743 cm -1 and 1705cm -1 (Ester C=O).

[0121] The chemical structural formula of the multifunctional alicyclic epoxy monomer E-6 is as follows:

[0122]

[0123] The nuclear magnetic resonance structure and infrared structure of the multifunctional alicyclic epoxy monomer E-6 are as follows:

[0124] The chemical shifts in the 400 MHz H-NMR spectrum of DMSO d6 solvent are 4.51-4.40 ppm (4H, aliphatic O-CH2-), 4.08-3.95 ppm (8H, aliphatic -CH2-O), 3.91-3.80 ppm (16H, aliphatic C(O)-CH2-CH2-), 3.27-3.05 ppm (8H, alicyclic CH-O-CH), 2.25-2.08 ppm (6H, aliphatic C(O)-CH3), 2.07-1.05 ppm (42H, alicyclic CH and CH2); the peak positions in the infrared absorption spectrum are 1742 cm -1 and 1708cm -1 (ester C=O) and 790 cm -1 (alicyclic CH-O-CH).

[0125] Example 7

[0126] This embodiment provides a multifunctional alicyclic epoxy polymer PE-1, and the specific process is as follows:

[0127] Weigh the multifunctional alicyclic epoxy monomer E-1 (82.86 wt%) and di(3,4-epoxycyclohexylmethyl) adipate (12.75 wt%), add bis(4-tert-butylphenyl)iodonium hexafluorophosphate (4.14 wt%) and 2-isopropylthioxanthone (0.249 wt%), place the mixed sample in an ultrasonic bath and mix evenly, then pour it onto tinplate, and then place it on a constant temperature heating table at 90 ° C and irradiate it with ultraviolet light for about 10 min (light intensity 35 mw / cm 2), after 10 minutes of light exposure, the film was placed in a vacuum oven and cured for several hours to obtain a multifunctional alicyclic epoxy resin film PE-1, i.e., a multifunctional alicyclic epoxy polymer PE-1.

[0128] Example 8

[0129] This embodiment provides a multifunctional alicyclic epoxy polymer PE-2, and the specific process is as follows:

[0130] Weigh the multifunctional alicyclic epoxy monomer E-2 (83.04 wt%), di(3,4-epoxycyclohexylmethyl) adipate (12.58 wt%), add bis(4-tert-butylphenyl)iodonium hexafluorophosphate (4.14 wt%), 2-isopropylthioxanthone (0.242 wt%), place the mixed sample in an ultrasonic bath for uniform mixing, pour it onto tinplate, and then place it on a constant temperature heating table at 90 ° C for about 10 min under ultraviolet light (light intensity 35 mw / cm 2 ), after 10 minutes of light exposure, the film was placed in a vacuum oven and cured for several hours to obtain a multifunctional alicyclic epoxy resin film PE-2, i.e., a multifunctional alicyclic epoxy polymer PE-2.

[0131] Example 9

[0132] This embodiment provides a multifunctional alicyclic epoxy polymer PE-3, and the specific process is as follows:

[0133] Weigh the multifunctional alicyclic epoxy monomer E-3 (81.88 wt%), di(3,4-epoxycyclohexylmethyl) adipate (13.73 wt%), add bis(4-tert-butylphenyl)iodonium hexafluorophosphate (4.13 wt%), 2-isopropylthioxanthone (0.248 wt%), place the mixed sample in an ultrasonic immersion chamber for uniform mixing, pour it onto tinplate, and then place it on a constant temperature heating table at 90 ° C for about 10 min under ultraviolet light (light intensity 35 mw / cm 2 ), after 10 minutes of light exposure, the film was placed in a vacuum oven and cured for several hours to obtain a multifunctional alicyclic epoxy resin film PE-3, i.e., a multifunctional alicyclic epoxy polymer PE-3.

[0134] Example 10

[0135] This embodiment provides a multifunctional alicyclic epoxy polymer PE-4, and the specific process is as follows:

[0136] Weigh the multifunctional alicyclic epoxy monomer E-4 (83.07 wt%), di(3,4-epoxycyclohexylmethyl) adipate (12.51 wt%), add bis(4-tert-butylphenyl)iodonium hexafluorophosphate (4.16 wt%), 2-isopropylthioxanthone (0.25 wt%), place the mixed sample in an ultrasonic bath for uniform mixing, pour it onto tinplate, and then place it on a constant temperature heating table at 90 ° C for about 7 minutes under ultraviolet light (light intensity 35 mw / cm 2 ), after seven minutes of light exposure, the film was placed in a vacuum oven and cured for several hours to obtain a multifunctional alicyclic epoxy resin film PE-4, i.e., a multifunctional alicyclic epoxy polymer PE-4.

[0137] Example 11

[0138] This embodiment provides a multifunctional alicyclic epoxy polymer PE-5, and the specific process is as follows:

[0139] Weigh the multifunctional alicyclic epoxy monomer E-5 (81.36 wt%), di(3,4-epoxycyclohexylmethyl) adipate (14.32 wt%), add bis(4-tert-butylphenyl)iodonium hexafluorophosphate (4.07 wt%), 2-isopropylthioxanthone (0.243 wt%), place the mixed sample in an ultrasonic immersion chamber for uniform mixing, pour it onto tinplate, and then place it on a constant temperature heating table at 90 ° C for about 10 min under ultraviolet light (light intensity 35 mw / cm 2 ), after 10 minutes of light exposure, the film was placed in a vacuum oven and cured for several hours to obtain a multifunctional alicyclic epoxy resin film PE-5, i.e., a multifunctional alicyclic epoxy polymer PE-5.

[0140] Example 12

[0141] This embodiment provides a multifunctional alicyclic epoxy polymer PE-6, and the specific process is as follows:

[0142] Weigh the multifunctional alicyclic epoxy monomer E-6 (82.44 wt%), di(3,4-epoxycyclohexylmethyl) adipate (13.19 wt%), add bis(4-tert-butylphenyl)iodonium hexafluorophosphate (4.12 wt%), 2-isopropylthioxanthone (0.247 wt%), place the mixed sample in an ultrasonic bath for uniform mixing, pour it onto tinplate, and then place it on a constant temperature heating table at 90 ° C for about 10 min under ultraviolet light (light intensity 35 mw / cm 2 ), after 10 minutes of light exposure, the film was placed in a vacuum oven and cured for several hours to obtain a multifunctional alicyclic epoxy resin film PE-6, i.e., a multifunctional alicyclic epoxy polymer PE-6.

[0143] Pencil hardness test of multifunctional alicyclic epoxy resin film: the test method refers to GB-T6739-2022.

[0144] Table 1. Pencil hardness test results of multifunctional alicyclic epoxy resin films.

[0145]

[0146]

[0147] As can be seen from Table 1, the multifunctional alicyclic epoxy resin films PE-1, PE-2, PE-3, PE-4, PE-5 and PE-6 prepared in Examples 7 to 12 of the present invention have low hardness and good flexibility, while the hardness of bisphenol A epoxy resin is generally above 4H. It can be seen that the multifunctional alicyclic epoxy resin prepared in the present invention solves the problem of poor flexibility of bisphenol A epoxy resin.

[0148] The thermogravimetric properties of multifunctional alicyclic epoxy resin films PE-1, PE-3, PE-4, and PE-6 were tested. The test results are as follows: Figure 7 .Depend on Figure 7 It can be seen that the 5% thermal weight loss temperatures of the multifunctional alicyclic epoxy resin films PE-1, PE-3, PE-4, and PE-6 are all around 200°C, among which the 5% thermal decomposition temperature of PE-6 is 216°C, which is the highest thermal decomposition temperature.

[0149] The optical transmittance of multifunctional alicyclic epoxy resin films PE-1, PE-2, PE-3, PE-4, PE-5 and PE-6 was tested. The test results are as follows: Figure 8 The transmittance of the multifunctional alicyclic epoxy resin films PE-1, PE-2, PE-3, PE-4, PE-5 and PE-6 of the present invention is about 75%, and the light transmittance performance is good. Among them, PE-3 has the best optical transmittance, and the transmittance in the range of 700 to 900 nm is always above 75%.

[0150] The flexibility of multifunctional alicyclic epoxy resin films PE-1, PE-2, PE-3, PE-4, PE-5 and PE-6 was tested. The test results are shown in Figures 9-14 ,Depend on Figures 9-14 It can be seen that the multifunctional alicyclic epoxy resin films PE-1, PE-2, PE-3, PE-4, PE-5 and PE-6 can be bent without breaking, among which PE-1 has the best flexibility.

[0151] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in the relevant field should understand that after reading the specification of this application, technicians can still modify or replace the specific implementation methods of the present invention with equivalents, but these modifications or changes do not depart from the scope of protection of the pending claims of the present application.

Claims

1. A multifunctional alicyclic epoxy monomer, characterized in that The structure of the multifunctional alicyclic epoxy monomer is shown in formula (I): Formula (I) Where R is C 1~12 alkyl, 、 、 、 or .

2. The multifunctional alicyclic epoxy monomer according to claim 1, wherein The R is an ethyl group.

3. A multifunctional alicyclic epoxy polymer, characterized in that The invention is prepared by polymerizing the multifunctional alicyclic epoxy monomer according to any one of claims 1 to 2 and an auxiliary agent.

4. The multifunctional alicyclic epoxy polymer according to claim 3, wherein The auxiliary agent consists of a cationic photoinitiator, a photosensitizer and an active diluent.

5. The method for preparing a multifunctional alicyclic epoxy monomer according to any one of claims 1 to 2, characterized in that: The steps include: S1. Diketene, an alcohol compound, a first catalyst and a first solvent are mixed, reacted, and purified to obtain an acetoacetate compound; S2. The acetoacetate compound is mixed with 7-oxabicyclo[4.1.0]hept-3-yl methacrylate, a second catalyst, and a second solvent, and reacted to obtain a multifunctional alicyclic epoxy monomer; The alcohol compound is selected from C 1~7 Monohydric alcohol, C 2~12 diols, C 3~6 triol, C 3~6 At least one of pentaerythritol and polyether polyol; The first catalyst is selected from triethylamine; The second catalyst is selected from quaternary ammonium salts.

6. The method for preparing a multifunctional alicyclic epoxy monomer according to claim 5, wherein: The first solvent is selected from dichloromethane; The second solvent is selected from ethyl acetate.

7. The method for preparing a multifunctional alicyclic epoxy monomer according to claim 5, wherein: In S1, the molar ratio of diketene, alcohol compound and first catalyst is 1-4:1:0.075-0.3; The reaction temperature is 20-40° C., and the reaction time is 8-12 hours.

8. The method for preparing a multifunctional alicyclic epoxy monomer according to claim 5, wherein: In S2, the molar ratio of the acetoacetate compound to 7-oxabicyclo[4.1.0]hept-3-yl methacrylate and the second catalyst is 1:2-8:0.15-0.60; The reaction temperature is 60-100° C., and the reaction time is 3-8 hours.

9. A method for preparing a multifunctional alicyclic epoxy polymer, characterized in that: The steps include: The multifunctional alicyclic epoxy monomer according to any one of claims 1 to 2, a cationic photoinitiator, a photosensitizer and a reactive diluent are mixed and photocured to obtain a multifunctional alicyclic epoxy polymer.

10. The method for preparing a multifunctional alicyclic epoxy polymer according to claim 9, wherein: In terms of mass percentage, the multifunctional alicyclic epoxy monomer according to any one of claims 1 to 2 is 80-85%, the cationic photoinitiator is 3-5%, the photosensitizer is 0.2-0.3%, and the reactive diluent is 10-15%; The cationic photoinitiator is selected from at least one of diphenyliodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, 4,4'-ditolyliodonium hexafluorophosphate and diphenyliodonium hexafluoroarsenate; The photosensitizer is selected from at least one of naphthalene, anthracene, phenanthrene, phenothiazine, and 2-isopropylthioxanthone; The reactive diluent is selected from at least one of di(3,4-epoxycyclohexylmethyl)adipate, tetrahydrofuran acrylate, dioxetane and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate; The light curing temperature is 80-100°C, the time is 5-15 minutes, and the light intensity is 30-40 mw / cm 2 .

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