Preparation method of super-hydrophobic hybrid photosensitive resin

Abstract

The invention discloses a preparation method of super-hydrophobic hybrid photosensitive resin. The preparation method specifically comprises the following steps: step 1, preparing eugenol epoxide; 2, carrying out a hydrosilylation reaction on the eugenol epoxide, tetramethyldisiloxane and tetramethyldiphenyltrisiloxane to prepare two eugenol-based organosilicon epoxy compounds, and carrying out a hydrosilylation reaction on the eugenol epoxide, tetramethyldisiloxane and tetramethyldiphenyltrisiloxane; 3, DGEBA, OTX, TMP3EOTA, a photoinitiator 1176 and an initiator 184 are added into a light-proof bottle and stirred for 1 h, and the evenly-mixed photosensitive resin is poured into a silica gel mold and cured for 30 min under ultraviolet light. According to the preparation method of the super-hydrophobic hybrid photosensitive resin provided by the invention, the high-strength rigid photosensitive resin is prepared by regulating and controlling the proportion of the components and investigating indexes such as tensile strength, tensile modulus, bending strength, volume shrinkage, gel content, fracture growth rate, toughness and the like of the material.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of photosensitive resin preparation, and in particular to a preparation method of super-hydrophobic hybrid photosensitive resin. BACKGROUND

[0002] At present, a large number of literatures focus on the research of bio-based organosilicon epoxy resin to obtain similar performance to petroleum-based compounds. Researchers continue to explore renewable materials containing aromatic fragments (such as eugenol) as sustainable alternatives to DGEBA. Eugenol obtained from clove oil and lignin is a bio-based raw material with low price and high reactivity.

[0003] Siloxane compounds have attracted attention due to their excellent high-temperature resistance, stable chemical properties, good biocompatibility and flexibility. Dai Jin designed and synthesized three bio-based epoxy resin precursors SIE-EP, SIEP-EP and D4E-EP from eugenol, siloxane compounds and epoxy chloropropane, and compared the performance with DGEBA in the field of thermal curing.

[0004] However, whether the eugenol-based organosilicon epoxy resin can match the performance of DGEBA in photocuring 3D printing has not been explored so far. SUMMARY

[0005] The application discloses a preparation method of super-hydrophobic hybrid photosensitive resin, and aims to solve the technical problems in the background art.

[0006] In order to achieve the above-mentioned purpose, the application adopts the following technical scheme:

[0007] The preparation method of the super-hydrophobic hybrid photosensitive resin comprises the following steps:

[0008] Step one: preparing eugenol epoxide;

[0009] Step two: preparing two eugenol-based organosilicon epoxides through the silicon-hydrogen addition reaction of eugenol epoxide, tetramethyldisiloxane and tetramethyldiphenyltrisiloxane;

[0010] Step three: adding DGEBA, OTX, TMP3EOTA, a photoinitiator 1176 and an initiator 184 into a light-proof bottle, stirring for 1 h, pouring the mixed photosensitive resin into a silica gel mold, and curing for 30 min under ultraviolet light.

[0011] In a preferred embodiment, the step one specifically comprises the following steps: under nitrogen atmosphere, eugenol and epichlorohydrin are added into a 500 mL three-neck flask with a thermometer and reflux condenser in a molar ratio of 1:10, and TBAB is added, the temperature is raised to 80℃, and the reaction is carried out for 2 hours, then g NaOH is added in multiple portions, the reaction is carried out for three hours, then the excess epichlorohydrin is removed by vacuum distillation, then the pH is adjusted to 7 with dilute hydrochloric acid, and the product is extracted with ethyl acetate, the combined organic layers are washed with brine, dried with sodium sulfate, filtered, and then vacuum distilled to obtain a light yellow solid, and finally the white crystalline solid can be obtained by recrystallization in a methanol solution at 4℃.

[0012] In a preferred embodiment, the step two comprises the following steps: under nitrogen atmosphere, the obtained eugenol epoxide-EUEP is added into a 50 mL three-neck flask with a thermometer and reflux condenser, the reaction system is heated to 70℃, after the reaction system in the step two is heated to 70℃, the reaction system is heated to 70℃, then KARSTEDT catalyst is added, and then 1,1,3,3-tetramethyldisiloxane or 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane is slowly added dropwise, and the mixture is reacted at 70℃ for 4 hours to obtain a light yellow liquid.

[0013] In a preferred embodiment, the sample after the step three solidification can be tested by infrared spectrum, nuclear magnetic resonance hydrogen spectrum, viscosity, gel rate test and solvent resistance test, in the gel rate test, the solidified sample M1 is taken, the solidified sample is placed in a Soxhlet extractor, and acetone is used for 24 hours of immersion, after the immersion is completed, the sample is dried at 65℃ for 2 hours, and then the dried mass M2 is determined, and the gel rate is calculated according to the following formula: gel rate: (M2 / M1) × 100%;

[0014] In the solvent resistance test, the solvent resistance of the solidified sample in water, ethanol, toluene, 10wt% HCl solution, and 10wt% NaOH solution is tested respectively, the mass M0 of the solidified sample is immersed in a sealed glass bottle of different solvents, and the sample is soaked at room temperature for 48 hours, then the wet sample is taken out and placed in a 60℃ drying oven for drying for 2 hours to obtain a constant weight of the dried sample, and the mass M A is calculated according to the following formula:

[0015] WR = M A / M0 × 100%.

[0016] From the above, a preparation method of a super-hydrophobic hybrid photosensitive resin, specifically comprising the following steps: step one: preparing eugenol epoxide; step two: preparing two eugenol-based organosilicon epoxides by the silicon-hydrogen addition reaction of eugenol epoxide with tetramethyldisiloxane and tetramethyl diphenyl trisiloxane; step three: adding DGEBA, OTX, TMP3EOTA, photoinitiator 1176 and initiator 184 into a light-proof bottle and stirring for 1h, pouring the uniformly mixed photosensitive resin into a silica gel mold and curing under ultraviolet light for 30min. The preparation method of the super-hydrophobic hybrid photosensitive resin provided by the application selects DGEBA and OTX as cation components; TMP3EOTA as a free radical component; initiator 1176 and initiator 184 as initiators of cation and free radical components respectively, and through proportion control among the components, the tensile strength, tensile modulus, bending strength, volume shrinkage rate, gel content, fracture growth rate and toughness of the material are investigated, and a high-strength rigid photosensitive resin is prepared. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 The synthesis path diagram of SIEEP / SIDPEEP for the preparation method of the super-hydrophobic hybrid photosensitive resin proposed by the application.

[0018] Figure 2 The infrared spectrum (a) and nuclear magnetic resonance hydrogen spectrum (b) diagram of EUEP, SIEEP and SIDPEEP for the preparation method of the super-hydrophobic hybrid photosensitive resin proposed by the application.

[0019] Figure 3 The cation and free radical different component proportion diagram for the preparation method of the super-hydrophobic hybrid photosensitive resin proposed by the application.

[0020] Figure 4 The shell side structure sectional view for the preparation method of the super-hydrophobic hybrid photosensitive resin proposed by the application.

[0021] Figure 5 The DGEBA and OTX different proportion comparison diagram for the preparation method of the super-hydrophobic hybrid photosensitive resin proposed by the application.

[0022] Figure 6 The initiator different content diagram for the preparation method of the super-hydrophobic hybrid photosensitive resin proposed by the application.

[0023] Figure 7 The initiator 1176 and initiator 184 proportion comparison diagram for the preparation method of the super-hydrophobic hybrid photosensitive resin proposed by the application.

[0024] Figure 8A performance chart of different contents of SIEEP for a preparation method of a super-hydrophobic hybrid photosensitive resin according to the present application.

[0025] Figure 9 A performance chart of different contents of SIDPEEP for a preparation method of a super-hydrophobic hybrid photosensitive resin according to the present application. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments.

[0027] Referring to Figures 1-9 A preparation method of a super-hydrophobic hybrid photosensitive resin, specifically comprising the following steps:

[0028] Step one: preparing eugenol epoxide;

[0029] Step two: preparing two eugenol-based organosilicon epoxides through a silicon-hydrogen addition reaction of eugenol epoxide with tetramethyldisiloxane and tetramethyl diphenyl trisiloxane;

[0030] Step three: adding DGEBA, OTX, TMP3EOTA, a photoinitiator 1176 and an initiator 184 into a light-proof bottle and stirring for 1 hour, pouring the mixed photosensitive resin into a silica gel mold, and curing for 30 minutes under ultraviolet light.

[0031] In a preferred embodiment, the step one specifically comprises the following steps: under a nitrogen atmosphere, eugenol (50g, 0.30mol) and epichlorohydrin (281.73g, 3mol) are added into a 500mL three-necked flask with a thermometer and a reflux condenser in a molar ratio of 1:10, 0.97g of TBAB (3mmol) is added, the temperature is raised to 80℃, and the reaction is carried out for 2 hours, then 14.64g of NaOH (0.37mol) is added in multiple portions, the reaction is carried out for three hours, then filtration is performed, excess epichlorohydrin is removed through reduced pressure distillation, then the pH is adjusted to 7 with dilute hydrochloric acid, and extraction is performed with ethyl acetate (3×60mL).

[0032] In a preferred embodiment, the combined organic layers in the extraction are washed with brine, dried with sodium sulfate, filtered, and then subjected to reduced pressure distillation to obtain a light yellow solid, and finally, white crystalline solid can be obtained through recrystallization in a 4℃ methanol solution.

[0033] In a preferred embodiment, the step two comprises the following steps: the obtained eugenol epoxide-EUEP (10 g, 45.40 mmol) is added into a three-neck flask with a thermometer and a reflux condenser under nitrogen atmosphere, and the reaction system is heated to 70°C.

[0034] In a preferred embodiment, after the reaction system in the step two is heated to 70°C, the reaction system is heated to 70°C, then the KARSTEDT catalyst (0.026 g, 10 ppm) is added, and 1,1,3,3-tetramethyldisiloxane (3.05 g, 22.70 mmol) or 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (7.55 g, 22.70 mmol) is slowly added dropwise, and the mixture is reacted at 70°C for 4 hours to obtain a light yellow liquid.

[0035] In a preferred embodiment, the sample after curing in the step one can be tested by infrared spectroscopy, nuclear magnetic resonance hydrogen spectrum, viscosity, gel rate test, solvent resistance test and volume shrinkage rate test.

[0036] Volume shrinkage rate test: the density p of the photosensitive resin at room temperature is first determined with distilled water as a reference 前 , then the solid volume is measured by Archimedes drainage method and the density p is calculated 后 . According to this, the volume shrinkage rate is calculated:

[0037]

[0038] In the formula: p 后 is the density of the photosensitive resin after curing, g / cm 3 ; p 前 is the density of the photosensitive resin, g / cm 3 .

[0039] The tensile and bending tests are carried out according to the GB / T 1040.1-2008 and GB / T 9341-2008 standards respectively on a universal tensile testing machine, wherein the tensile speed and bending speed are both set to 5 mm / min.

[0040] According to the GB / T 1843-2008 standard, the notched impact strength of the sample is determined at room temperature, and the following formula is used for calculation:

[0041]

[0042] In the formula: s is the notched impact strength, kJ / m 2 ; W is the impact amount absorbed by the sample, J; h is the thickness of the sample, mm; b is the remaining width of the sample, mm.

[0043] Shore D hardness tester was used to measure the hardness of the cured sample according to GB / T2411-2008 standard, each sample bar was measured at 5 different points and the average value was calculated.

[0044] In a preferred embodiment, in the gel fraction test, a certain amount of photosensitive resin was taken and placed in a silica gel mold, and cured under ultraviolet light irradiation. After curing, the initial mass M1 of the sample was measured. Then, the cured sample was placed in a Soxhlet extractor and soaked with acetone for 24 hours. After soaking, the sample was dried at 65°C for 2 hours, and then the dried mass M2 was measured. The gel fraction was calculated according to the following formula:

[0045] Gel fraction = (M2 / M1) x 100% (2-1)

[0046] In a preferred embodiment, in the solvent resistance test, the solvent resistance of the cured sample in water, ethanol, toluene, 10wt% HC1 solution, 10wt% NaOH solution was tested respectively. The cured sample with a mass of M0 was immersed in a sealed glass bottle containing different solvents, and soaked at room temperature for 48h. Then the wet sample was taken out and placed in a 60°C drying oven for 2h to obtain a constant weight of dry sample with a mass of M A The mass change percentage (WR) was calculated according to the following formula:

[0047]

[0048] The synthesis steps of eugenol epoxy (EUEP) are as follows: under nitrogen atmosphere, eugenol (50g, 0.30mol) and epichlorohydrin (281.73g, 3mol) were added to a 500mL three-necked flask with a thermometer and reflux condenser in a ratio of 1:10 by mole, and 0.97g TBAB (3mmol) was added, and the temperature was raised to 80°C, and the reaction was carried out for 2 hours, then 14.64g NaOH (0.37mol) was added in several portions, and the reaction was carried out for three hours, then filtered, and the excess epichlorohydrin was removed by reduced pressure distillation, then the pH was adjusted to 7 with dilute hydrochloric acid, and extracted with ethyl acetate (3x60mL). The combined organic layer was washed with brine, dried over sodium sulfate, filtered, and then distilled under reduced pressure to obtain a light yellow solid. Finally, white crystalline solid EUEP can be obtained by recrystallization in a methanol solution at 4°C, and the epoxy value is detected (epoxy value is 0.44mol / 100g). The yield of this step is 98%, and the purity can be as high as 99%;

[0049] The synthesis procedure of the eugenol-based silicone epoxy resin (SIEEP / SIDPEEP) is as follows: under a nitrogen atmosphere, the obtained EUEP (10 g, 45.40 mmol) is added to a three-necked flask with a thermometer and a reflux condenser. Thereafter, the reaction system is heated to 70°C, and then 1,1,3,3-tetramethyldisiloxane (3.05 g, 22.70 mmol) or 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (7.55 g, 22.70 mmol) is slowly added dropwise after the addition of KARSTEDT catalyst (0.026 g, 10 ppm). The mixture is reacted at 70°C for 4 hours to obtain a light yellow liquid SIEEP / SIDPEEP. The yield of this step is 99%, and the reaction equation is shown in Figure 1 ;

[0050] As shown in Figure 2 , the structural characterization of EUEP, SIEEP and SIDPEEP is carried out by using the method of infrared analysis. The product EUEP obtained by the nucleophilic substitution reaction of eugenol and epichlorohydrin can be found to have a characteristic peak of an epoxy group at 910 cm -1 . In SIEEP and SIDPEEP obtained by the hydrosilylation reaction of EUEP and hydrogen-containing silicone oil, the Si-H peak at 2100 cm -1 and the C=C peak at 1630 cm -1 disappear, in addition, the hydrogen spectrum analysis of the above three products is carried out; in the hydrogen spectrum of EUEP, the characteristic peak of epoxy at 2.6-3.3 ppm appears, indicating that EUEP is successfully synthesized; in the hydrogen spectrum of SIEEP and SIDPEEP, the characteristic peak of double bond at 6.5-7 ppm appears, indicating that SIEEP and SIDPEEP are successfully synthesized.

[0051] The DGEBA, OTX, TMP3EOTA, photoinitiator 1176, and initiator 184 are mixed according to the formulations shown in the following table, the proportion of the above compounds is optimized by single factor test, and different formulations are named as SFA-n (n is a positive integer) according to the experimental order. Taking the SFA-4 formulation as an example, the preparation method is as follows: 26.72 g of DGEBA, 8.91 g of OTX, 11.87 g of TMP3EOTA, 1.67 g of initiator 1176, and 0.84 g of initiator 184 are added to a light-tight bottle, and stirred for 1 h. The uniformly mixed photosensitive resin is poured into a silica gel mold, and cured under ultraviolet light for 30 min;

[0052]

[0053] The curing process diagram is as shown in Figure 3As shown, the polymerization principle of the hybrid photosensitive resin is as follows: initiator 1176 forms carbocations under ultraviolet light and initiates the cationic polymerization of DGEBA and OTX. Initiator 184 forms free radicals under ultraviolet light and initiates the free radical polymerization of TMP3EOTA. Therefore, the hybrid photocurable resin can polymerize into a cross-linked interpenetrating network (IPN) structure after UV irradiation, exhibiting excellent comprehensive properties.

[0054] like Figure 4 As shown: TMP3EOTA is a fast-polymerizing, photocrosslinkable monomer, and the resulting polymer provides high mechanical strength. However, the more free radical components there are, the greater the volume shrinkage caused by double bond polymerization. Therefore, to investigate the optimal ratio of free radical components, three ratios of 2:1, 3:1, and 4:1 were set up, and experiments were conducted using three formulations: SFA-1, SFA-2, and SFA-3 (the 3:1 component is m). (DGEBA+OTX) :m TMP3EOTA =3:1). As the free radical component content increases, tensile strength, elongation at break, and notched impact strength all increase. However, when the ratio of cationic to free radical components is less than 3:1, the increase is slow. A 2:1 ratio of cationic to free radical components can bring higher strength and toughness, but the volume shrinkage caused by double bond solidification reaches 6.29%. A high volume shrinkage rate is detrimental to printing and molding, leading to warping and shrinkage deformation of the molded parts. The results showed that SFA-1 exhibited significant volume shrinkage and warping. In conclusion, a 3:1 ratio of cationic to free radical components is the optimal formulation. This formulation achieves a tensile strength of 56.84 MPa, a fracture elongation of 10.10%, and a toughness of 4.30 KJ / m. 2 All are at a relatively high level. The volume shrinkage is only 5.77.

[0055] like Figure 5 As shown, OTX exhibits high reactivity due to its strong cyclostrain and high nucleophilicity, and possesses low viscosity, making it widely used in cationic photocuring reactions. Based on the determination that SFA-2 was the optimal formulation, the ratio of DGEBA to OTX was further optimized. Experiments designed for SFA-4 and SFA-5 were compared with those for SFA-2, and the results were as follows: DGEBA :m OTX The ratios were 3:1, 4:1, and 2:1. In the three groups of experiments, tensile strength and fracture growth rate remained almost unchanged. When the DGEBA to OTX ratio was 3:1, the gel content and toughness were significantly improved, reaching 85.62% and 5.14 KJ / m, respectively. 2In addition, the viscosity of the system reaches the minimum value under this formulation, and the smaller viscosity helps the resin to level during the 3D printing process, which directly affects the printing speed. OTX as a diluent, too little will cause the material viscosity to increase and the brittleness to increase, too much will also affect the crosslinking density of the material, resulting in increased brittleness. Therefore, when the ratio of DGEBA to OTX is 3:1, it has good mechanical properties;

[0056] As shown in Figure 6 : On the basis of SFA-4, the initiator content is also optimized. Three groups of experiments with initiator contents of 4%, 5% and 6% are set, respectively, as experiments SFA-6, SFA-4 and SFA-7. When the initiator content is 5%, it has the optimal tensile strength, volume shrinkage and viscosity. In addition, the remaining properties are also in the middle value. The amount of initiator determines the curing speed of the photosensitive resin. Too little initiator will result in slow curing speed, while too much initiator will also promote the chain termination reaction, and the cost is relatively high (the price of initiator is relatively high). Therefore, the curing rate of epoxy groups and double bond groups will first increase and then decrease with the increase of the amount of initiator. Considering comprehensively, the initiator content of 5% is the optimal formulation;

[0057] As shown in Figure 7 : Finally, three groups of experiments SFA-4, SFA-10 and SFA-11 are carried out, in which the initiator 1176 and the initiator 184 are 2:1, 2.5:1 and 3:1 respectively. When the initiator 1176: initiator 184 = 2:1, the shrinkage is the lowest; the elongation at break and the gel content are the largest; the tensile strength and the toughness are in the middle. Therefore, SFA-4 is determined as the optimal formulation;

[0058] As shown in Figure 8 : With the addition of SIEEP, the mechanical strength decreases, the elongation at break and the notched impact strength first increase and then decrease. In addition, with the addition of SIEEP, the viscosity of the system decreases significantly, which is very beneficial to the light-cured 3D printing. The main reason for this phenomenon is that the silicone segment in SIEEP provides good flexibility and toughness, thereby increasing the elongation at break and impact strength. In addition, the molecular weight of SIEEP is greater than that of DGEBA, so with the addition of SIEEP, the number of epoxy groups participating in curing decreases, resulting in a decrease in crosslinking density and tensile strength. When the addition amount of SIEEP is 75wt%, it exhibits excellent flexibility and toughness. At this time, the elongation at break reaches 84%, and the notched impact strength reaches 9.78KJ / m 2 , which is 730% and 90.3% higher than SFA-4, respectively;

[0059] As shown in Figure 9It is shown that with the addition of SIDPEEP, the tensile strength gradually decreases, the elongation at break and the notched impact strength gradually increase. The gel content also gradually decreases with the addition of SIDPEEP, while the viscosity and the shrinkage are significantly reduced. SIDPEEP has two more benzene ring structures compared to SIEEP, however, the curing efficiency of SIDPEEP is reduced due to the steric hindrance of benzene ring and the lower epoxy value. Therefore, the addition of SIDPEEP results in lower tensile strength and lower gel content. But SIDPEEP has more excellent impact strength and lower volume shrinkage. This is due to the large steric hindrance of benzene ring structure, which reduces the shrinkage caused by curing. In addition, the conjugated system provided by the benzene ring structure enhances the toughness of the material. When adding 75wt% SIDPEEP, the notched impact strength reaches 12.3KJ / m 2 , increasing by 139%; the volume shrinkage decreases to 3%, decreasing by 49%. Therefore, for improving toughness and shrinkage, SIDPEEP is obviously better, while for improving elongation at break, SIEEP is better.

[0060] In the present application, DGEBA and OTX are selected as the cationic component; TMP3EOTA is selected as the free radical component; initiator 1176 and initiator 184 are selected as the initiators of cationic and free radical components, respectively. By adjusting the ratio of each component, the tensile strength, tensile modulus, bending strength, volume shrinkage, gel content, fracture growth rate, toughness and other indicators of the material are investigated, and a high-strength rigid photosensitive resin is prepared. For the optimization of the formula of the hybrid system, SFA-4 is the optimal formula, and the performance is relatively good. At this time, the tensile strength of SFA-4 is 56.72MPa, the elongation at break is 10.12%, the notched impact strength is 5.14KJ / m 2 , the gel content is 85.62%, the volume shrinkage is 5.85%, and the viscosity is 360cps. In addition, high-precision chess models are printed in this paper. These results show that the hybrid curing photosensitive resin has 3D printing potential, and the performance is not inferior to that of commercially available photosensitive resin.

[0061] The present application obtains high-purity eugenol epoxide by nucleophilic substitution reaction of bio-based raw material eugenol with epichlorohydrin. Then, two eugenol-based organosilicon epoxide compounds (SIEEP, SIDPEEP) are prepared in high yield by hydrosilylation reaction of eugenol epoxide with tetramethyldisiloxane and tetramethyl-diphenyltrisiloxane. The mechanical properties of SIEEP and SIDPEEP are studied by replacing the DGEBA component in the SFA formula. The results show that SIEEP focuses on the improvement of elongation at break; while SIDPEEP focuses on the improvement of impact strength and volume shrinkage, but the addition of both will sacrifice the tensile strength. When the addition amount of SIEEP / SIDPEEP is 75wt%, the performance is optimal. When the addition amount of SIEEP is 75wt%, excellent flexibility and toughness are exhibited. At this time, the elongation at break reaches 84%, the notched impact strength reaches 9.78KJ / m 2 , which is increased by 730% and 90.3% respectively compared with SFA-4. When 75wt% SIDPEEP is added, the notched impact strength reaches 12.3KJ / m 2 , which is increased by 139%; the volume shrinkage is reduced to 3%, which is decreased by 49%.

[0062] The above is only the preferred specific embodiment of the present application, but the protection scope of the present application is not limited thereto, any skilled person in the art can make equivalent replacement or change according to the technical solution and inventive concept of the present application within the technical range disclosed by the present application, which should be covered in the protection scope of the present application.

Claims

1. A method for preparing a superhydrophobic hybrid photosensitive resin, characterized by, Specifically comprising the following steps: Step one: preparation of eugenol epoxide; Step two: preparation of two eugenol-based organosilicon epoxides by hydrosilylation reaction of eugenol epoxide with tetramethyldisiloxane and tetramethyl diphenyl trisiloxane; Step three: DGEBA, OTX, TMP3EOTA, photoinitiator 1176 and initiator 184 are added to an opaque bottle and stirred for 1 h, and the uniformly mixed photosensitive resin is poured into a silica gel mold and cured under ultraviolet light for 30 min.

2. The method for preparing a superhydrophobic hybrid photosensitive resin according to claim 1, characterized in that, The step one specifically comprises the following steps: under a nitrogen atmosphere, eugenol and epichlorohydrin are added to a 500 mL three-necked flask with a thermometer and reflux condenser in a molar ratio of 1:10, and TBAB is added, and the temperature is raised to 80℃, and the reaction is carried out for 2 hours, then gNaOH is added in multiple times, and the reaction is carried out for three hours, then filtered, and the excess epichlorohydrin is removed by reduced pressure distillation, then the pH is adjusted to 7 with dilute hydrochloric acid, and extracted with ethyl acetate.

3. The method for preparing a superhydrophobic hybrid photosensitive resin according to claim 2, characterized in that, The combined organic layer in the extraction is washed with brine, dried with sodium sulfate, filtered, and then distilled under reduced pressure to obtain a light yellow solid, and finally white crystalline solid can be obtained by recrystallization in a 4℃ methanol solution.

4. The method for preparing a superhydrophobic hybrid photosensitive resin according to claim 1, characterized in that, The step two comprises the following steps: under a nitrogen atmosphere, the obtained eugenol epoxide-EUEP is added to a 50 mL three-necked flask with a thermometer and reflux condenser, and the reaction system is heated to 70℃.

5. The method for preparing a superhydrophobic hybrid photosensitive resin according to claim 4, characterized in that, After the reaction system in the step two is heated to 70℃, the reaction system is heated to 70℃, then KARSTEDT catalyst is added, and then 1,1,3,3-tetramethyldisiloxane or 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane is slowly added dropwise, and the mixture is reacted at 70℃ for 4 hours to obtain a light yellow liquid.

6. The method for preparing a superhydrophobic hybrid photosensitive resin according to claim 1, characterized in that, The sample after curing in the step three can be tested by infrared spectroscopy, nuclear magnetic resonance hydrogen spectrum, viscosity, gel rate test and solvent resistance test.

7. The method for preparing a superhydrophobic hybrid photosensitive resin according to claim 6, characterized in that, In the gel rate test, take the cured sample M1, put the cured sample into a Soxhlet extractor, and use acetone for 24 hours of immersion, after the immersion is completed, the sample is dried at 65℃ for 2 hours, then the dried mass M2 is measured, and the gel rate is calculated according to the following formula: gel rate: (M2 / M1) × 100%.

8. A method for preparing a superhydrophobic hybrid photosensitive resin according to claim 7, characterized in that, In the solvent resistance test, the solvent resistance of the cured sample in water, ethanol, toluene, 10wt% HC1 solution, and 10wt% NaOH solution was tested respectively. The cured sample with a mass of M0 was immersed in a sealed glass bottle containing different solvents, and soaked at room temperature for 48h. Then the wet sample was taken out and placed in a 60°C drying oven for drying for 2h to obtain a dried sample with a constant mass of M A The mass change percentage WR was calculated according to the following formula: WR = M A / M0 x 100%.

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