Alicyclic polyetherimide high-performance photocuring material and preparation method thereof

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to an alicyclic polyetherimide high-performance photocuring material and a preparation method thereof. The preparation method comprises the following steps: synthesizing an alicyclic methacrylate acrylate monomer through a ring-opening reaction of an alicyclic epoxy monomer and carboxyl, preparing an alicyclic imide monomer through a Michael addition reaction of the alicyclic methacrylate acrylate, carrying out an epoxidation reaction of the alicyclic imide monomer and an oxidant to generate an alicyclic epoxy imide monomer, and carrying out a polymerization reaction of the alicyclic epoxy imide monomer and the alicyclic epoxy imide monomer. And carrying out ring opening polymerization on the alicyclic epoxy imide monomer to obtain the alicyclic polyetherimide material. The material can be used for preparing a cyclic polyetherimide high-performance light-cured film through ultraviolet light curing. The main chain and the side chain of the alicyclic polyetherimide high-performance photocuring material are both of an alicyclic polyether rigid structure, meanwhile, the alicyclic polyetherimide high-performance photocuring material contains acrylate groups, has good toughness, heat resistance, weather resistance and electrical performance, and can be used in the fields of IC carrier solder resist ink, electronic packaging, flexible display substrates, photoresist and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to an alicyclic polyetherimide high-performance photocurable material and a preparation method thereof. Background Art

[0002] UV curing has a wide range of applications in coatings and inks, adhesives, the electronics industry, and biomedicine. Photocurable materials have a fast curing speed, high production efficiency, contain little or no organic solvents, reduce environmental pollution, and can adjust the formula according to requirements to obtain materials with different properties.

[0003] Currently, in the manufacturing and packaging processes of many electronic devices, high-performance sealants, special inks and other polymer materials are involved, including circuit inks required for the production of printed circuit boards and PCB photosensitive developing solder resist inks. With the increasing precision of electronic device manufacturing, the performance requirements for packaging materials and PCB inks are becoming more and more stringent. Traditional aromatic packaging materials and solder resist materials can no longer meet the performance requirements. The biggest defect is that it is difficult to improve the key properties of traditional packaging materials such as water and oxygen barrier properties, coefficient of thermal expansion, and yellowing resistance. For the photosensitive developing solder resist ink used in IC substrates (a new generation of chip packaging technology), it is also very difficult for traditional aromatic epoxy-based materials to obtain sufficient development resolution, low CTE, high T g 、high hardness and other properties. In view of the current situation, it is necessary to develop an alicyclic polyetherimide high-performance photocurable material to improve the comprehensive performance of the photocurable film and meet the requirements of more complex future applications. Summary of the Invention

[0004] In order to overcome the deficiencies of the above-mentioned prior art, the present invention provides a preparation method of an alicyclic polyetherimide high-performance photocurable material with a new structure. The present invention introduces an alicyclic structure into the polymer molecular chain, and through Michael addition reaction, epoxidation reaction, and ring-opening polymerization reaction, a multifunctional alicyclic polyetherimide photocurable resin is generated. This resin contains acrylate groups and can be cured into a film after being irradiated with UV light for dozens of seconds. Moreover, both the main chain and the side chain of the resin contain alicyclic structures, which improves the transparency and rigidity of the cured film and enhances the optical properties, mechanical properties, etc. of the cured resin.

[0005] The object of the present invention can be achieved through the following technical solutions:

[0006] In the first aspect, the present invention provides a preparation method of an alicyclic polyetherimide high-performance photocurable material, comprising the following steps:

[0007] S1. React the epoxy group of an alicyclic epoxy monomer with the carboxyl group of acrylic acid or an acrylic acid derivative in the presence of an inhibitor and a catalyst to synthesize an alicyclic methacrylate acrylate monomer;

[0008] S2. Dissolve the alicyclic methacrylate acrylate monomer synthesized in step S1 and the imide ring monomer with a cyclic double bond at the end group in a solvent, add a catalyst, and perform a Michael addition reaction between the N-H structure of the imide ring monomer and the acrylate double bond structure to synthesize an alicyclic imide monomer;

[0009] S3. Dissolve the alicyclic imide monomer synthesized in step S2, an oxidant, and sodium bicarbonate in a solvent. After the reaction, wash and purify to obtain an alicyclic epoxy imide monomer;

[0010] S4. Dissolve the alicyclic epoxy imide monomer synthesized in step S3 in a solvent, add an initiator, and dropwise add a catalyst to perform a ring-opening polymerization reaction. After the reaction, wash and purify to obtain an alicyclic polyether imide monomer;

[0011] S5. Mix the alicyclic polyether imide monomer synthesized in step S4 and a photoinitiator, and then cure it by ultraviolet light to prepare an alicyclic polyether imide high-performance photocurable film.

[0012] In the present invention, first, an alicyclic methacrylate acrylate monomer is synthesized by reacting the epoxy group of an alicyclic epoxy monomer with the carboxyl group of acrylic acid or an acrylic acid derivative. This step introduces an acrylate group and a methacrylate group. The former is used for the Michael addition reaction, and the latter is used for the photopolymerization reaction. Then, the synthesized alicyclic methacrylate acrylate monomer and the imide ring monomer with a cyclic double bond at the end group are subjected to a Michael addition reaction between the N-H structure of the imide monomer and the acrylate double bond structure to synthesize an alicyclic imide monomer. This reaction avoids the cumbersome steps and long reaction time of thermal imidization, greatly improving the reaction efficiency. After that, the terminal double bond is epoxidized by an oxidant to obtain an alicyclic epoxy imide monomer. The alicyclic epoxy imide monomer is converted into an alicyclic polyether imide monomer through a ring-opening polymerization reaction, and the polyether main chain can improve the comprehensive performance of the material. Finally, the alicyclic polyether imide monomer and the photoinitiator are mixed and cured by ultraviolet light to prepare a photocurable film. This step uses a free radical photocuring method, which is efficient and more suitable for industrial production. The alicyclic polyether imide high-performance photocurable material prepared by the present invention has excellent toughness, heat resistance, weather resistance, and electrical properties, and has broad application prospects in the fields of IC substrate solder resist inks, electronic packaging, flexible display substrates, photoresists, etc.

[0013] Preferably, in step S1, the alicyclic epoxy monomer includes but is not limited to methyl 3,4-epoxycyclohexylmethacrylate and 4-vinylcyclohexene oxide; the acrylic acid derivative includes but is not limited to methacrylic acid and β-acryloyloxypropionic acid; the alicyclic methacrylate acrylate monomer has both an acrylate group and a methacrylate group. The former is used for the Michael addition reaction, and the latter is used for the photopolymerization reaction.

[0014] Preferably, in step S1, the reaction temperature between the carboxyl group and the epoxy group is 105 °C, and the reaction time is 10 to 12 h. Preferably, in step S1, the polymerization inhibitors for the reaction include, but are not limited to, dibutylhydroxytoluene (BHT) and methylhydroquinone (MEHQ).

[0015] Preferably, in step S1, the catalyst includes, but is not limited to, chromium octoate.

[0016] Preferably, in step S1, the molar ratio of the alicyclic epoxy monomer to acrylic acid or the alicyclic epoxy monomer to methacrylic acid is 1.1:1.

[0017] Preferably, in step S2, the imide ring monomer with a cyclic double bond at the end group includes, but is not limited to, 1,2,3,6-tetrahydrophthalimide and 5-norbornene-2,3-dicarboximide.

[0018] Preferably, in step S2, the solvent includes, but is not limited to, dichloromethane and ethyl acetate.

[0019] Preferably, in step S2, the catalyst includes, but is not limited to, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0020] Preferably, in step S2, the reaction temperature of the Michael addition reaction is 70 °C to 80 °C, and the reaction time is 8 to 10 h.

[0021] Preferably, in step S2, the molar ratio of the alicyclic methacrylate acrylate monomer to the imide ring monomer with a cyclic double bond at the end group is 1.1:1.

[0022] Preferably, in step S2, the product obtained after the reaction is washed with pickling solution and saturated NaCl solution to obtain a viscous and transparent alicyclic imide monomer.

[0023] Preferably, in step S3, the oxidants include, but are not limited to, m-chloroperbenzoic acid and hydrogen peroxide.

[0024] Preferably, in step S3, the solvent includes, but is not limited to, dichloromethane and dichloroethane.

[0025] Preferably, in step S3, the molar ratio of the oxidant to the alicyclic imide monomer is 3 - 3.5:1, and the molar ratio of sodium bicarbonate to the oxidant is 1:1.

[0026] More preferably, in step S3, the reaction temperature is room temperature, and the reaction time is 20 to 24 h.

[0027] Preferably, in step S3, the product obtained after the reaction is washed with alkali and then with NaCl solution to obtain a viscous and transparent alicyclic epoxy imide monomer.

[0028] Preferably, in step S4, the solvent includes but is not limited to ethyl acetate and dichloromethane.

[0029] Preferably, in step S4, the initiator includes but is not limited to trimethylolpropane (TMP), methanol, and glycerol.

[0030] Preferably, in step S4, the catalyst is boron trifluoride diethyl etherate.

[0031] Preferably, in step S4, the reaction temperature of the ring-opening polymerization reaction is 45-60 °C, and the reaction time is 4-6 h.

[0032] More preferably, in step S4, the molar ratio of the initiator to the alicyclic epoxy imide monomer is 1:5, and the molar ratio of the catalyst to the alicyclic epoxy imide monomer is 1:25.

[0033] Preferably, in step S4, the product obtained after the reaction is washed with water to obtain a viscous and transparent alicyclic polyether imide monomer.

[0034] Preferably, in step S5, the photoinitiator includes but is not limited to α,α-dimethoxy-α-phenylacetophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone (D1173), 1-hydroxy-cyclohexyl phenyl ketone, 2-methyl-1-[4-methylthiophenyl]-2-morpholinopropanone-1, 2-phenyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), or bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (BAPO).

[0035] Preferably, in step S5, the dosage of the photoinitiator is 0.5-2% by weight of the alicyclic polyether imide monomer.

[0036] Preferably, in step S5, the ultraviolet light intensity is 30-40 mw / cm 2 , and the irradiation time is 60-80 s.

[0037] Preferably, in step S5, after the ultraviolet irradiation, it is placed in an oven and dried at 80 °C for 6-10 h.

[0038] In a second aspect, the present invention provides an alicyclic polyether imide high-performance photocurable material prepared by the above preparation method, and the structure of the alicyclic polyether imide high-performance photocurable material is as follows:

[0039]

[0040] In the formula, n is any integer from 2 to 5; the group R is the acrylate double bond in the alicyclic methacrylate acrylate monomer The residue after transformation, the other structures of the alicyclic methacrylate acrylate monomer remain unchanged. The alicyclic methacrylate acrylate monomer has both a methacrylate group and an acrylate group. The structure of the methacrylate group is as shown in I, and the structure of the acrylate group is as shown in II:

[0041]

[0042] In a third aspect, the present invention provides an application of the above-mentioned alicyclic polyetherimide high-performance photocurable material in the field of optoelectronic devices.

[0043] The alicyclic polyetherimide high-performance photocurable film prepared by the method of the present invention has better toughness, heat resistance, weather resistance, and electrical properties, providing a new method for the application and development in the fields of IC carrier board solder resist ink, electronic packaging, flexible display substrate, photoresist, etc.

[0044] The beneficial effects that can be produced by this application are as follows:

[0045] (The present invention discloses a preparation method of an alicyclic polyetherimide high-performance photocurable material. First, an alicyclic methacrylate acrylate monomer is synthesized by the ring-opening reaction of an alicyclic epoxy monomer and a carboxyl group. Then, an alicyclic imide monomer is prepared from the alicyclic methacrylate acrylate monomer through a Michael addition reaction. The alicyclic imide monomer is subjected to an epoxidation reaction with an oxidant to generate an alicyclic epoxy imide monomer. Finally, the alicyclic epoxy imide monomer is subjected to ring-opening polymerization to obtain an alicyclic polyetherimide material. This material can be ultraviolet-cured to prepare a high-performance photocurable film of cyclic polyetherimide. The alicyclic polyetherimide high-performance photocurable material prepared by the method of the present invention not only has a rigid alicyclic polyether main chain structure, but also has an alicyclic rigid structure in the side chain, and at the same time contains acrylate groups, endowing the material with excellent toughness, heat resistance, weather resistance, and electrical properties, and can be used in the fields of IC carrier board solder resist ink, electronic packaging, flexible display substrate, photoresist, etc. Description of the Drawings

[0046] Figure 1 It is a reaction route diagram for preparing the alicyclic polyetherimide high-performance photocurable film in Example 1.

[0047] Figure 2 It is a physical diagram of the alicyclic polyetherimide high-performance photocurable films prepared in Example 1, Example 2, and Comparative Example 1.

[0048] Figure 3Thermogravimetric curves of the high-performance photocurable films of alicyclic polyetherimide prepared in Example 1, Example 2, and Comparative Example 1.

[0049] Figure 4 DSC curves of the high-performance photocurable films of alicyclic polyetherimide prepared in Example 1, Example 2, and Comparative Example 1. Detailed implementation manners

[0050] Next, the technical solutions in the embodiments of the present application will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present application without creative efforts shall fall within the protection scope of the present application.

[0051] Unless otherwise specified, the experimental methods in the following embodiments are all conventional methods, and the test materials used in the following embodiments can all be obtained through conventional commercial channels unless otherwise specified.

[0052] Example 1

[0053] Preparation method of high-performance photocurable material of alicyclic polyetherimide. The specific preparation method includes the following steps:

[0054] (1) Preparation of alicyclic methacrylate acrylate monomer

[0055] The synthesis reaction formula is as follows:

[0056]

[0057] The specific preparation method is as follows:

[0058] Add 0.72 g (0.01 mol) of acrylic acid (AA), 0.0018 g (0.25 wt% relative to AA) of dibutylhydroxytoluene (BHT), and 0.0018 g (0.25 wt% relative to AA) of methoxyphenol (MEHQ) to a three-necked flask equipped with a reflux condenser, a thermometer, mechanical stirring, and continuously introducing nitrogen. Slowly heat up to 105 °C, add 0.00648 g (0.9 wt% relative to AA) of chromium isooctanoate, and then dropwise add 2.16 g (0.011 mol) of 3,4-epoxycyclohexylmethyl methacrylate at 105 °C for about 6 h. After that, keep the temperature constant at 105 °C ± 2 °C. After the reaction is completed, a colorless and transparent product is obtained, named CHOMA-AA.

[0059] The CHOMA-AA prepared in this step was subjected to nuclear magnetic resonance hydrogen spectroscopy, infrared absorption spectroscopy, and mass spectrometry analysis. The chemical shifts in the 400 MHz nuclear magnetic resonance hydrogen spectrum in DMSO-d6 solvent were 6.33 - 5.91 ppm (3H, -CH=CH2), 6.03 ppm, and 5.65 ppm (2H, -C=CH2), 5.03 - 4.77 ppm (1H, alicyclic O=C-O-CH-), 3.95 ppm (2H, -CH2-O-C=O), 3.75 and 3.65 ppm (1H, alicyclic -CH-O-), 1.88 ppm (3H, -CH3), 2.09 - 1.31 ppm (7H, alicyclic -CH-, alicyclic -CH2-); the peak positions in the infrared absorption spectrum were respectively: 3400 cm -1 (O-H stretching vibration), 2935 cm -1 and 2863 cm -1 (alicyclic C-H stretching vibration), 1714 cm -1 (C=O stretching vibration), 1666 cm -1 (C=C stretching vibration); the relative molecular mass of CHOMA-AA was 268.13.

[0060] (2) Preparation of alicyclic imide monomer

[0061] The synthesis reaction formula is as follows:

[0062]

[0063] The specific preparation method is as follows:

[0064] The product CHOMA-AA (2.95 g, 0.011 mol) obtained in step (1), 1,2,3,6-tetrahydrophthalimide (1.51 g, 0.01 mol), and the catalyst DBU (1 mL) were successively added to a flask, and then stirred in an oil bath at 75 °C for 8 h. The obtained product was dissolved in dichloromethane, washed 3 times with 1 mol / L dilute hydrochloric acid aqueous solution, washed once with saturated sodium chloride aqueous solution, and then the dichloromethane was removed by rotary evaporation. The product was placed in an oven and vacuum dried at 40 °C for 8 h to obtain a relatively pure pale yellow viscous product, which was the alicyclic imide monomer PIM-2.

[0065] The product PIM-2 was analyzed by nuclear magnetic resonance hydrogen spectroscopy, infrared absorption spectroscopy and mass spectrometry. The chemical shifts in the 400 MHz nuclear magnetic resonance hydrogen spectrum in DMSO-d6 solvent were: 6.03 ppm and 5.65 ppm (2H, -C=CH2), 5.83 ppm (2H, cyclic -C=C-), 3.95 ppm (2H, -CH2-O-C=O), 3.60 ppm (2H, -N-CH2), 3.10 ppm (2H, -CH-C-O-), 2.52 ppm (2H, -CH2-C-O-), 2.28 ppm (4H, -CH2-C=C-), 1.88 ppm (3H, -CH3), 2.09 - 1.31 ppm (7H, alicyclic -CH-, alicyclic -CH2-); The peak positions in the infrared absorption spectrum were: 3488 cm -1 (O-H stretching vibration), 696 cm -1 (out-of-plane bending vibration of cyclic C=C), 813 cm -1 and 1635 cm -1 (C=C stretching vibration), the characteristic absorption peak of -NH- at the original 3212 cm -1 disappeared; The relative molecular mass of PIM-2 was 419.19.

[0066] (3) Preparation of alicyclic epoxyimide monomer

[0067] The synthesis reaction formula is as follows:

[0068]

[0069] The specific preparation method is as follows:

[0070] Dissolve the product PIM-2 (4.19 g, 0.01 mol) from step (2) in 50 mL of dichloroethane, then add m-chloroperbenzoic acid (2.59 g, 0.015 mol) and sodium bicarbonate (1.26 g, 0.015 mol), and stir and react at room temperature for 24 h. Wash the obtained solution 3 times with saturated sodium bicarbonate aqueous solution and once with saturated sodium chloride aqueous solution, then rotary evaporate to remove dichloroethane, and put the product in an oven to dry in vacuum at 40 °C for 8 h to obtain a relatively pure light yellow viscous product, which is the alicyclic epoxyimide monomer EPIM-2.

[0071] The product EPIM-2 was analyzed by nuclear magnetic resonance hydrogen spectroscopy, infrared absorption spectroscopy and mass spectrometry. The chemical shifts in the 400 MHz nuclear magnetic resonance hydrogen spectrum in DMSO-d6 solvent were: 6.03 ppm and 5.65 ppm (2H, -C=CH2), 3.95 ppm (2H, -CH2-O-C=O), 3.60 ppm (2H, -N-CH2), 3.10 ppm (2H, -CH-C-O-), 2.82 ppm (2H, epoxy-CH-), 2.52 ppm (2H, -CH2-C-O-), 2.28 ppm (4H, -CH2-C=C-), 1.88 ppm (3H, -CH3), 2.09 - 1.31 ppm (7H, alicyclic-CH-, alicyclic-CH2-); The peak positions in the infrared absorption spectrum were: 813 cm -1 and 1635 cm -1 (C=C stretching vibration), 796 cm -1 (characteristic absorption peak of epoxy C-O-C), the out-of-plane bending vibration peak of the terminal C=C double bond at the original 696 cm -1 disappeared; The relative molecular mass of EPIM-2 was 435.19.

[0072] (4) Preparation of alicyclic polyetherimide monomer

[0073] The synthesis reaction formula is as follows:

[0074]

[0075] The specific preparation method is as follows:

[0076] 4.35 g (0.01 mol) of the product EPIM-2 from step (3), 50 ml of ethyl acetate, and 0.27 g (0.002 mol) of trimethylolpropane were successively added to a three-necked flask equipped with a reflux condenser, a thermometer, mechanical stirring and continuously purged with nitrogen. The temperature was raised to 55 °C, and then a mixed solution of 0.1 ml of boron trifluoride etherate and 10 ml of ethyl acetate was dropped in from a constant pressure funnel. The dropping was completed within 0.5 h, and the reaction was continued for 6 h. After the reaction was completed, the obtained solution was washed three times with deionized water, and then the ethyl acetate was removed by rotary evaporation. The product was placed in an oven and vacuum dried at 40 °C for 8 h to obtain a relatively pure viscous product, which was the alicyclic polyetherimide monomer PEPIM-2.

[0077] The product PEPIM-2 was analyzed by 1H NMR and IR absorption spectroscopy. The chemical shifts in the 400 MHz 1H NMR spectrum in DMSO-d6 solvent were: 6.03 ppm and 5.65 ppm (2H, -C=CH2), 3.95 ppm (2H, -CH2-O-C=O), 3.60 ppm (2H, -N-CH2), 3.05 - 2.81 ppm (8H, -CH- and -CH2- on the polyether main chain), 2.52 ppm (2H, -CH2-C-O-), 1.88 ppm (3H, -CH3), 2.09 - 1.31 ppm (7H, alicyclic -CH- and alicyclic -CH2-); The peak positions in the IR absorption spectrum were: 813 cm -1 and 1635 cm -1 (C=C stretching vibration), and the characteristic absorption peak of the original epoxy C-O-C at 796 cm-1 disappeared.

[0078] (5) Preparation of photocured film

[0079] 1 g of the above-prepared PEPIM-2 was mixed with 0.01 g of 1 wt% free radical photoinitiator D1173. After ultrasonic dissolution and homogenization at 55 °C, the solution was then applied to a tinplate, coated with a 700 μm film applicator, placed in an oven at 60 °C for heat leveling for 2 h, and then exposed under a UV light intensity of 38 mW / cm 2 for 60 - 90 s to obtain a high-performance photocured film of alicyclic polyetherimide.

[0080] The high-performance photocured film of alicyclic polyetherimide was subjected to infrared testing using an ATR module. From the infrared spectrum analysis of the UV-cured film, it can be seen that the characteristic absorption peak of the acrylate double bond near 810 cm -1 has basically disappeared, and the prepolymer has changed from a resin state to a cured film form, indicating complete curing.

[0081] Example 2

[0082] Preparation of high-performance photocured material of alicyclic polyetherimide

[0083] The specific preparation method includes the following steps:

[0084] (1) Preparation of alicyclic methacrylate acrylate monomer

[0085] The synthesis reaction formula is as follows:

[0086]

[0087] The specific preparation method is as follows:

[0088] Add 0.86 g (0.01 mol) of methacrylic acid (MAA), 0.00215 g (0.25 wt% relative to MAA) of dibutylhydroxytoluene (BHT), and 0.00215 g (0.25 wt% relative to MAA) of methyl p-hydroxybenzoate (MEHQ) into a three-necked flask equipped with a reflux condenser, a thermometer, mechanical stirring, and continuously purged with nitrogen. Slowly heat up to 105 °C, add 0.00774 g (0.9 wt% relative to MAA) of chromium isooctanoate, and then dropwise add 2.00 g (0.011 mol) of (3,4-epoxycyclohexyl) methyl acrylate at 105 °C. The dropping process takes about 6 h. After that, keep the temperature constant at 105 °C ± 2 °C. After the reaction is completed, a transparent product is obtained and named CHOA-MAA.

[0089] Perform nuclear magnetic resonance hydrogen spectrum, infrared absorption spectrum, and mass spectrometry analysis on the CHOA-MAA prepared in this step. The chemical shifts in the 400 MHz nuclear magnetic resonance hydrogen spectrum in DMSO-d6 solvent are 6.33 - 5.91 ppm (3H, -CH=CH2), 6.03 ppm and 5.65 ppm (2H, -C=CH2), 5.03 - 4.77 ppm (1H, alicyclic O=C-O-CH-), 3.95 ppm (2H, -CH2-O-C=O), 3.75 and 3.65 ppm (1H, alicyclic -CH-O-), 1.88 ppm (3H, -CH3), 2.09 - 1.31 ppm (7H, alicyclic -CH-, alicyclic -CH2-); The characteristic peaks of the infrared absorption spectrum are 3400 cm -1 (O-H stretching vibration), 2935 cm -1 and 2863 cm -1 (alicyclic C-H stretching vibration), 1714 cm -1 (C=O stretching vibration), 1666 cm -1 (C=C stretching vibration); The relative molecular mass of CHOA-MAA is 268.13.

[0090] (2) Preparation of alicyclic imide monomer

[0091] The synthesis reaction formula is as follows:

[0092]

[0093] The specific preparation method is as follows:

[0094] The product CHOA-MAA (2.95 g, 0.011 mol) obtained in step (1), phthalimide (1.51 g, 0.01 mol), and the catalyst DBU (1 mL) were successively added to a flask, and then stirred in an oil bath at 75 °C for 8 h. The resulting product was dissolved in dichloromethane, washed three times with 1 mol / L dilute hydrochloric acid aqueous solution, and once with saturated sodium chloride aqueous solution. Then, dichloromethane was removed by rotary evaporation, and the product was placed in an oven and dried under vacuum at 40 °C for 8 h to obtain a relatively pure pale yellow viscous product, which was the alicyclic imide monomer PIM-3.

[0095] The product PIM-3 was analyzed by nuclear magnetic resonance hydrogen spectrum, infrared absorption spectrum, and mass spectrum. The chemical shifts in the 400 MHz nuclear magnetic resonance hydrogen spectrum in DMSO-d6 solvent were: 6.03 ppm and 5.65 ppm (2H, -C=CH2), 5.83 ppm (2H, cyclic -C=C-), 3.95 ppm (2H, -CH2-O-C=O), 3.60 ppm (2H, -N-CH2), 3.10 ppm (2H, -CH-C-O-), 2.52 ppm (2H, -CH2-C-O-), 2.28 ppm (4H, -CH2-C=C-), 1.88 ppm (3H, -CH3), 2.09 - 1.31 ppm (7H, alicyclic -CH-, alicyclic -CH2-); The peak positions in the infrared absorption spectrum were: 3488 cm -1 (O-H stretching vibration), 696 cm -1 (out-of-plane bending vibration of cyclic C=C), 813 cm -1 and 1635 cm -1 (C=C stretching vibration), and the characteristic absorption peak of -NH- at the original 3212 cm -1 disappeared. The relative molecular mass of PIM-3 was 419.19.

[0096] (3) Preparation of alicyclic epoxyimide monomer

[0097] The synthesis reaction formula is as follows:

[0098]

[0099] The specific preparation method is as follows:

[0100] Dissolve the product PIM-3 (4.19 g, 0.01 mol) from step (2) in 50 mL of dichloroethane, then add m-chloroperbenzoic acid (2.59 g, 0.015 mol) and sodium bicarbonate (1.26 g, 0.015 mol), and stir the reaction at room temperature for 24 h. Wash the resulting solution three times with saturated aqueous sodium bicarbonate solution and once with saturated aqueous sodium chloride solution, then rotary evaporate to remove dichloroethane. Put the product in an oven and dry it under vacuum at 40 °C for 8 h to obtain a relatively pure pale yellow viscous product, which is the alicyclic epoxyimide monomer EPIM-3.

[0101] Perform nuclear magnetic resonance hydrogen spectrum, infrared absorption spectrum and mass spectrometry analysis on the product EPIM-3. The chemical shifts in the 400 MHz nuclear magnetic resonance hydrogen spectrum in DMSO-d6 solvent are: 6.03 ppm and 5.65 ppm (2H, -C=CH2), 3.95 ppm (2H, -CH2-O-C=O), 3.60 ppm (2H, -N-CH2), 3.10 ppm (2H, -CH-C-O-), 2.82 ppm (2H, epoxy-CH-), 2.52 ppm (2H, -CH2-C-O-), 2.28 ppm (4H, -CH2-C=C-), 1.88 ppm (3H, -CH3), 2.09 - 1.31 ppm (7H, alicyclic-CH-, alicyclic-CH2-); The peak positions in the infrared absorption spectrum are: 813 cm -1 and 1635 cm -1 (C=C stretching vibration), 796 cm-1 (characteristic absorption peak of epoxy C-O-C), and the out-of-plane bending vibration peak of the terminal C=C double bond at the original 696 cm-1 disappears. The relative molecular mass of EPIM-3 is 435.19.

[0102] (4) Preparation of alicyclic polyetherimide monomer

[0103] The synthesis reaction formula is as follows:

[0104]

[0105] The specific preparation method is as follows:

[0106] To a three-necked flask equipped with a reflux condenser, a thermometer, a mechanical stirrer, and a continuous nitrogen flow, 4.35 g (0.01 mol) of the product EPIM-3 from step (3), 50 ml of ethyl acetate, and 0.27 g (0.002 mol) of trimethylolpropane were added in sequence. The temperature was raised to 55°C, and then a mixed solution of 0.1 ml of boron trifluoride etherate and 10 ml of ethyl acetate was added dropwise from a constant pressure funnel. The addition was completed within 0.5 h, and the reaction was continued for 6 h. After the reaction was completed, the resulting solution was washed three times with deionized water, and then the ethyl acetate was removed by rotary evaporation. The product was placed in an oven at 40°C under vacuum and dried for 8 h to obtain a relatively pure viscous product, namely, the alicyclic polyetherimide monomer PEPIM-3.

[0107] The product PEPIM-3 was analyzed by H NMR and IR. The chemical shifts in the 400 MHz H NMR spectrum in DMSO-d6 solvent were: 6.03 ppm and 5.65 ppm (2H, -C=CH2), 3.95 ppm (2H, -CH2-OC=O), 3.60 ppm (2H, -N-CH2), 3.05-2.81 ppm (8H, -CH-, -CH2- on the polyether backbone), 2.52 ppm (2H, -CH2-CO-), 1.88 ppm (3H, -CH3), 2.09-1.31 ppm (7H, alicyclic -CH-, alicyclic -CH2-); in the IR absorption spectrum: 813 cm -1 and 1635cm -1 (C=C stretching vibration), the original characteristic absorption peak of epoxy COC at 796cm-1 disappeared.

[0108] (5) Preparation of photocurable films

[0109] The prepared PEPIM-3 (1 g) was mixed with 1 wt% free radical photoinitiator D1173 (0.01 g), and after being uniformly dissolved by ultrasonication at 55 ° C, the solution was applied on a tinplate sheet and coated with a 700 μm film applicator. The film was placed in an oven at 60 ° C for 2 h to heat and level it. Then, the film was dried under a light intensity of 38 mW / cm 2 The product was exposed to UV light of high intensity for 60 to 90 seconds to obtain a high-performance photocurable film of alicyclic polyetherimide.

[0110] The high performance photocurable film of alicyclic polyetherimide was tested by infrared spectroscopy using ATR components. The infrared spectrum analysis of the UV cured film showed that after the prepolymer was UV cured, the 810 cm -1 The characteristic absorption peak of the nearby acrylate double bond has basically disappeared, and the prepolymer has transformed from a resin state to a cured film state, indicating that the curing is complete.

[0111] Comparative Example 1

[0112] Preparation of High-performance Photocurable Alicyclic Polyetherimide Materials

[0113] (1) Preparation of Alicyclic Imide Monomers

[0114] The synthesis reaction formula is as follows:

[0115]

[0116] The specific preparation method is as follows:

[0117] 1,2,3,6-Tetrahydrophthalimide (1.51 g, 0.01 mol), 3-(acryloyloxy)-2-hydroxypropyl methacrylate (2.36 g, 0.011 mol) and the catalyst DBU (1 mL) were successively added to a flask, and then stirred in an oil bath at 75 °C for 8 h. The obtained product was dissolved in dichloromethane, washed three times with 1 mol / L dilute hydrochloric acid aqueous solution and once with saturated sodium chloride aqueous solution, and then the dichloromethane was removed by rotary evaporation. The product was placed in an oven and vacuum dried at 40 °C for 8 h to obtain a relatively pure pale yellow viscous product, which is the alicyclic imide monomer PIM.

[0118] The product PIM was analyzed by 1H NMR, IR and MS. The chemical shifts in the 400 MHz 1H NMR spectrum in DMSO-d6 solvent are: 6.06 ppm and 5.67 ppm (2H, -C=CH2), 5.83 ppm (2H, cyclo-C=C-), 4.12 - 3.93 ppm (6H, -CH2-), 3.60 ppm (H, -CH-O-), 3.11 ppm (2H, -CH-C=O-), 2.52 ppm (2H, -CH2-C=O-), 2.36 and 2.20 ppm (4H, -CH2-C=C-), 1.88 ppm (3H, -CH3); the peak positions in the IR spectrum are: 3482 cm -1 (O-H stretching vibration), 696 cm -1 (out-of-plane bending vibration of cyclo C=C), 809 cm -1 and 1633 cm -1 (C=C stretching vibration), and the characteristic absorption peak of -NH- at the original 3212 cm -1 disappeared; the relative molecular mass of PIM is 365.38.

[0119] (2) Preparation of Alicyclic Epoxy Imide Monomers

[0120] The synthesis reaction formula is as follows:

[0121]

[0122] The specific preparation method is as follows:

[0123] Dissolve the product PIM (3.65 g, 0.01 mol) from step (1) in 50 mL of dichloroethane, then add m-chloroperbenzoic acid (2.59 g, 0.015 mol) and sodium bicarbonate (1.26 g, 0.015 mol), and stir the reaction at room temperature for 24 h. Wash the resulting solution three times with saturated aqueous sodium bicarbonate solution and once with saturated aqueous sodium chloride solution, then rotary evaporate to remove dichloroethane. Place the product in an oven and dry it under vacuum at 40 °C for 8 h to obtain a relatively pure pale yellow viscous product, which is the alicyclic epoxyimide monomer EPIM.

[0124] Perform nuclear magnetic resonance hydrogen spectrum, infrared absorption spectrum and mass spectrometry analysis on the product EPIM. The chemical shifts in the 400 MHz nuclear magnetic resonance hydrogen spectrum in DMSO-d6 solvent are: 6.06 ppm and 5.67 ppm (2H, -C=CH2), 4.12 - 3.93 ppm (6H, -CH2-), 3.60 ppm (H, -CH-O-), 3.11 ppm (2H, -CH-C=O-), 2.82 ppm (2H, epoxy-CH-), 2.52 ppm (2H, -CH2-C=O-), 2.36 and 2.20 ppm (4H, -CH2-C=C-), 1.88 ppm (3H, -CH3); the peak positions in the infrared absorption spectrum are: 813 cm -1 and 1635 cm -1 (C=C stretching vibration), 797 cm -1 (characteristic absorption peak of epoxy C-O-C), and the out-of-plane bending vibration peak of the terminal C=C double bond at the original 696 cm -1 disappears; the relative molecular mass of EPIM is 381.38.

[0125] (3) Preparation of alicyclic polyetherimide monomer

[0126] The synthesis reaction formula is as follows:

[0127]

[0128] The specific preparation method is as follows:

[0129] Into a three-necked flask equipped with a reflux condenser, a thermometer, mechanical stirring, and continuously purged with nitrogen, 3.81 g (0.01 mol) of the product EPIM from step (2), 50 ml of ethyl acetate, and 0.27 g (0.002 mol) of trimethylolpropane were successively added. The temperature was raised to 55 °C, and then a mixed solution of 0.1 ml of boron trifluoride diethyl ether and 10 ml of ethyl acetate was dropped in from a constant pressure funnel. The dropping was completed within 0.5 h, and the reaction was continued for 6 h. After the reaction was completed, the resulting solution was washed three times with deionized water, and then the ethyl acetate was removed by rotary evaporation. The product was placed in an oven and vacuum dried at 40 °C for 8 h to obtain a relatively pure viscous product, which is the alicyclic polyetherimide monomer PEPIM.

[0130] The product PEPIM was analyzed by 1H NMR and IR absorption spectroscopy. The chemical shifts in the 400 MHz 1H NMR in DMSO-d6 solvent are: 6.06 ppm and 5.67 ppm (2H, -C=CH2), 4.12~3.93 ppm (6H, -CH2-), 3.60 ppm (H, -CH-O-), 3.11 ppm (2H, -CH-C=O-), 3.05 - 2.81 ppm (8H, -CH- and -CH2- on the polyether main chain), 2.52 ppm (2H, -CH2-C=O-), 2.36 and 2.20 ppm (4H, -CH2-C=C-), 1.88 ppm (3H, -CH3); in the IR absorption spectrum: 813 cm -1 and 1635 cm -1 (C=C stretching vibration), and the characteristic absorption peak of the original 796 cm-1 epoxy C-O-C disappeared.

[0131] (4) Preparation of photocurable film

[0132] The above-prepared PEPIM (1 g) was mixed with 1 wt% free radical photoinitiator D1173 (0.01 g). After ultrasonic dissolution and homogenization at 55 °C, the solution was then coated on a tinplate, and coated with a 700 μm film applicator, and placed in an oven at 60 °C for 2 h to heat and level. Subsequently, it was exposed under a UV light intensity of 38 mW / cm 2 for 60 - 90 s to obtain an alicyclic polyetherimide high-performance photocurable film.

[0133] The alicyclic polyetherimide high-performance photocurable film was subjected to infrared testing using an ATR component. Through the infrared spectrum analysis of the UV-cured film, it can be seen that after the prepolymer was UV-cured, the characteristic absorption peak of the acrylate double bond near 810 cm -1 had basically disappeared, and the prepolymer had changed from a resin state to a cured film form, indicating complete curing.

[0134] Performance analysis

[0135] (1) Appearance of the cured film

[0136] Figure 1 It is a physical picture of the high-performance photocurable films of alicyclic polyetherimide prepared in Example 1, Example 2 and Comparative Example 1. The serial numbers 1 to 3 in the figure are PEPIM-2, PEPIM-3, and PEPIM respectively. It can be seen from the figure that the cured film is light yellow, has high transparency and relatively high overall hardness.

[0137] (2) Pencil hardness and thermal stability analysis

[0138] The prepared photocurable films were subjected to performance tests. The test methods are as follows: (1) The pencil hardness was tested according to GB / T6739—2006; (2) The TG test was carried out using Netzsch's TG 209F1 thermogravimetric analyzer to test the thermal stability of the UV-cured film. The heating rate was 10 °C / min, and the temperature range was 25 to 700 °C. (3) The DSC test was carried out using Netzsch's DSC-204F1 Phoenix differential scanning calorimeter to determine the glass transition temperature (T g ) of the UV-cured film. The heating rate was 10 °C / min, and the temperature range was 25 to 250 °C. Figure 2 、 Figure 3 They are the thermogravimetric and DSC diagrams of the high-performance photocurable films of alicyclic polyetherimide prepared in Example 1, Example 2 and Comparative Example 1. The data of 5%, 10% thermogravimetric loss, glass transition temperature and pencil hardness of the photocurable films in nitrogen and air are shown in Table 1 below.

[0139] Table 1 Properties of different resin cured films

[0140]

[0141] It can be seen from Table 1 that the pencil hardness of these thermally cured films is greater than 3H, and the hardness of PEPIM-2 and PEPIM-3 is greater than that of PEPIM; the temperatures at which the cured films PEPIM-2 and PEPIM-3 in Examples 1 and 2 have 5% and 10% thermogravimetric loss are higher than those of the cured film PEPIM in Comparative Example 1. The reason may be that in addition to the polyether structure in the main chain, PEPIM-2 and PEPIM-3 also have an alicyclic structure introduced in the side chain, with a large steric hindrance, which increases their rigidity and has better heat resistance; the glass transition temperatures of the cured films PEPIM-2 and PEPIM-3 in Examples 1 and 2 are higher than that of PEPIM in the comparative example. The reason may be that the side chain of PEPIM does not introduce an alicyclic structure and contains more alkane side groups, and the molecular chain is more flexible. Thus, it can be seen that the preparation method of a high-performance photocurable material of alicyclic polyetherimide proposed by the present invention is feasible, and this implementation scheme has good industrial prospects.

[0142] The above is a specific description of the preferred embodiment of the present invention. However, the present invention is not limited to the described embodiment. Those skilled in the art can make various equivalent deformations or substitutions without departing from the spirit of the present invention, and these equivalent deformations or substitutions are all included within the scope defined by the claims of this application.

Claims

1. A preparation method of an alicyclic polyetherimide high-performance photocurable material, characterized in that, Including the following steps: S1. Synthesize an alicyclic methacrylate acrylate monomer by reacting the epoxy group of an alicyclic epoxy monomer with the carboxyl group of acrylic acid or an acrylic acid derivative in the presence of an inhibitor and a catalyst; S2. Dissolve the alicyclic methacrylate acrylate monomer synthesized in step S1 and an imide ring monomer with a cyclic double bond at the end group in a solvent, and add a catalyst. Synthesize an alicyclic imide monomer through a Michael addition reaction between the N-H structure of the imide ring monomer and the acrylate double bond structure; S3. Dissolve the alicyclic imide monomer synthesized in step S2, an oxidant, and sodium bicarbonate in a solvent. After the reaction, wash and purify to obtain an alicyclic epoxy imide monomer; S4. Dissolve the alicyclic epoxy imide monomer synthesized in step S3 in a solvent, add an initiator, and dropwise add a catalyst to carry out a ring-opening polymerization reaction. After the reaction, wash and purify to obtain an alicyclic polyether imide monomer; S5. Mix the alicyclic polyether imide monomer synthesized in step S4 and a photoinitiator, and then prepare a high-performance photocurable film of alicyclic polyether imide through ultraviolet curing.

2. The preparation method of an alicyclic polyetherimide high-performance photocurable material according to claim 1, wherein, In step S1, the alicyclic epoxy monomer is at least one of methyl 3,4-epoxycyclohexylmethacrylate and 4-vinylcyclohexene oxide; the acrylic acid derivative is at least one of methacrylic acid and β-acryloyloxypropionic acid; the alicyclic methacrylate acrylate monomer has both an acrylate group and a methacrylate group. The former is used for the Michael addition reaction, and the latter is used for the photopolymerization reaction.

3. The preparation method of an alicyclic polyetherimide high-performance photocurable material according to claim 1, characterized in that, In step S1, the reaction temperature for the reaction between the carboxyl group and the epoxy group is 105 °C, the reaction time is 12 h, the inhibitor is at least one of dibutylhydroxytoluene and p-hydroxyanisole, and the catalyst is chromium isooctanoate.

4. The preparation method of an alicyclic polyetherimide high-performance photocurable material according to claim 1, characterized in that, In step S2, the imide ring monomer with a cyclic double bond at the end group is at least one of 1,2,3,6-tetrahydrophthalimide and 5-norbornene-2,3-dicarboximide; the solvent is at least one of dichloromethane and ethyl acetate; the catalyst is 1,8-diazabicyclo[5.4.0]undec-7-ene.

5. The preparation method of an alicyclic polyetherimide high-performance photocurable material according to claim 1, wherein In step S2, the reaction temperature for the Michael addition reaction is 70 °C to 80 °C, and the reaction time is 8 to 10 h.

6. The preparation method of an alicyclic polyetherimide high-performance photocurable material according to claim 1, characterized in that, In step S3, the oxidant is at least one of m-chloroperbenzoic acid and hydrogen peroxide; the solvent is at least one of dichloromethane and dichloroethane.

7. The preparation method of an alicyclic polyetherimide high-performance photocuring material according to claim 1, characterized in that, In step S3, the reaction temperature is room temperature, and the reaction time is 20 to 24 h.

8. The preparation method of an alicyclic polyetherimide high-performance photocurable material according to claim 1, characterized in that In step S4, the solvent is at least one of ethyl acetate and dichloromethane; the initiator is at least one of trimethylolpropane, methanol, and glycerol; the catalyst is boron trifluoride diethyl ether; the reaction temperature for the ring-opening polymerization reaction is 45 to 60 °C, and the reaction time is 4 to 6 h.

9. The preparation method of an alicyclic polyetherimide high-performance photocurable material according to claim 1, wherein, In step S5, the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone and 1-hydroxycyclohexyl phenyl ketone; the UV light intensity is 38 mw / cm 2 , and the light irradiation time is 60 to 80 s.

10. A high-performance photocurable material of alicyclic polyetherimide prepared by the preparation method according to any one of claims 1-9, characterized in that, The structure of the high-performance photocurable material of alicyclic polyether imide is as follows: Wherein, n is any integer from 2 to 5; the group R is the acrylate double bond in the alicyclic methacrylate acrylate monomer The residue after transformation, and the other structures of the alicyclic methacrylate acrylate monomer remain unchanged. The alicyclic methacrylate acrylate monomer has both a methacrylate group and an acrylate group. The structure of the methacrylate group is as shown in I, and the structure of the acrylate group is as shown in II:

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