Triazine biphenyl compound, composition and condensate as well as preparation method and application of triazine biphenyl compound

Abstract

The invention discloses a triazine biphenyl compound, a composition, a cured product as well as a preparation method and application of the triazine biphenyl compound, the composition and the cured product. The compound is phenolic resin with a triazine biphenyl structure obtained through condensation polymerization of p-cyanobiphenol; the phenolic resin respectively reacts with an epichlorohydrin compound and an acyl chloride compound to obtain epoxy resin and active ester with a triazine biphenyl structure, and the epoxy resin and the active ester can be self-cured or cured under the action of an imidazole accelerator; in the preparation process, triazine ring (containing nitrogen) is introduced as a node, trifunctional epoxy resin with a rigid aromatic structure as an arm and an active ester curing agent (the same skeleton) are prepared into a thermosetting cross-linked network by adopting a non-polar cross-linking scheme, and a three-dimensional network intrinsic microporous structure is formed through in-situ cross-linking regulation and control of a rigid long-arm branched unit. Further, the bottlenecks of low dielectric property, high temperature resistance, flame retardance and the like are broken through, and the cured material has the characteristics of excellent flame retardance, high temperature resistance and low dielectric property.

Description

Technical Field

[0001] The invention belongs to the field of thermosetting resin materials, and specifically relates to a triazine biphenyl compound, a composition, a cured product, and a preparation method and application thereof. Background Art

[0002] Thermosetting resin is a kind of high molecular polymer material. The molecular chains are chemically cross-linked together to form a rigid three-dimensional network structure. This cross-linked structure cannot be repeatedly processed and molded during the polymerization process. It has excellent comprehensive performance. Commonly used thermosetting resins include epoxy resin, polyester resin, vinyl ester, bismaleimide, thermosetting polyimide, cyanate ester, etc. However, there are some performance deficiencies such as poor high temperature resistance, high dielectric constant and dielectric loss, large thermal expansion coefficient, and flammability. These deficiencies limit its application field to a certain extent.

[0003] Epoxy resin refers to an organic polymer compound containing two or more epoxy groups in the molecule. Because its molecular structure contains active epoxy groups, it can undergo cross-linking reaction with curing agent to form an insoluble, infusible polymer with a three-dimensional network structure. This structure contains a large number of polar groups such as hydroxyl, ether, amino, etc., which gives the material many excellent properties, such as excellent adhesion, high temperature resistance, insulation, corrosion resistance and low shrinkage, and the cost is relatively low. However, a large number of polar groups will increase the dielectric loss and water absorption of the cured product, which cannot meet the requirements of the new generation of low dielectric thermosetting resin materials. Summary of the invention

[0004] The object of the present invention is to provide a triazine biphenyl compound and a preparation method thereof, wherein the triazine biphenyl compound is obtained by cyclotrimerization of a p-cyano biphenol compound to obtain a phenolic resin, and then the phenolic resin is reacted with an epichlorohydrin compound and an acyl chloride compound to obtain an epoxy resin and an active ester of a triazine biphenyl structure, wherein not only the epoxy resin is a trifunctional epoxy with a rigid aromatic structure as an arm, but also the active ester has the same skeleton structure. The active ester has the following advantages: after reacting with an epoxy group, a hydroxyl group is not formed on the side chain, but an ester group with a smaller polarity and a larger volume is produced, which is conducive to reducing dielectric loss and water absorption, and reducing curing shrinkage and internal stress. Although the ester group can reduce Tg as an epoxy curing agent traditionally, the active ester of the present invention can keep the heat resistance of the cured product to a certain extent by significantly improving the skeleton rigidity and functionality. The epoxy resin prepared from the epoxy resin and active ester based on triazine biphenyl structure has obvious improvements in high temperature resistance, low dielectric and low thermal expansion coefficient compared with the traditional bisphenol A type and tetraglycidylamine type epoxy resins on the basis of ensuring flame retardant performance. In addition, the preparation method provided by the present invention is simple, easy to implement, and suitable for large-scale industrial production.

[0005] In order to achieve the above object, in the first aspect, the present invention provides a compound having the structure of the compound represented by the following general formula (I):

[0006]

[0007] In the general formula (I), R1-R3 each independently represent a linear or branched alkyl group having 0 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. 27 R each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. 28 -R 30 Each independently represents one of the following groups of general formula (I'),

[0008]

[0009] In the general formula (I'), R a , R b Each independently represents a linear or branched alkyl group having 0 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms; preferably a linear or branched alkyl group having 1 to 10 carbon atoms.

[0010] In a second aspect, the present invention provides a method for preparing the above-mentioned compound, which comprises the following steps: dissolving a cyanobiphenol compound in a solvent, adding a catalyst, and preparing R of the compound represented by the general formula (I) 28 -R 30 The phenolic resin represents -H; the p-cyanobiphenol compound is preferably 4-hydroxybiphenyl-4-carbonitrile; the solvent is preferably dichloromethane or ethylene dichloride; the catalyst is preferably a protonic acid or a metal halide, and further preferably one or a combination of sulfuric acid, p-toluenesulfonic acid, hydrochloric acid and ZnCl2.

[0011] In a third aspect, the present invention provides a method for preparing the above-mentioned compound, comprising the following steps: (1) dissolving a cyanobiphenol compound in a solvent, adding a catalyst, and preparing R of the compound represented by the general formula (I) 28 -R 30 The phenolic resin represents -H; the p-cyanobiphenol compound is preferably 4-hydroxybiphenyl-4-carbonitrile; the solvent is preferably dichloromethane or ethylene dichloride; the catalyst is preferably a protonic acid or a metal halide, and further preferably one or a combination of sulfuric acid, p-toluenesulfonic acid, hydrochloric acid and ZnCl2.

[0012] (2) reacting the phenolic resin, epichlorohydrin compound and phase transfer catalyst described in step (1) to obtain R of the compound represented by general formula (I) 28 -R 30 express The epoxy resin preferably has an epoxy value of 0.266-0.387.

[0013] Optionally, the phase transfer catalyst is one or a combination of trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetrabenzyltrimethylammonium chloride, methylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium bromide and tetrabutylammonium hydrogen sulfate; and the epichlorohydrin compound is epichlorohydrin.

[0014] In a fourth aspect, the present invention provides a method for preparing the above-mentioned compound, comprising the following steps: (1) dissolving a cyanobiphenol compound in a solvent, adding a catalyst, and preparing R of the compound represented by the general formula (I) 28 -R 30 The phenolic resin represents -H; the p-cyanobiphenol compound is preferably 4-hydroxybiphenyl-4-carbonitrile; the solvent is preferably dichloromethane or ethylene dichloride; the catalyst is preferably a protonic acid or a metal halide, and further preferably one or a combination of sulfuric acid, p-toluenesulfonic acid, hydrochloric acid and ZnCl2.

[0015] (2) dissolving the phenolic resin in step (1) in a solvent, adding an acyl chloride compound and an amine compound in sequence, and reacting to obtain R of the compound represented by general formula (I) 28 -R 30 express Active esters of

[0016] Optionally, in step (2), the solvent is tetrahydrofuran or ethyl acetate; the acyl chloride compound is acetyl chloride or benzoyl chloride; and the amine compound is triethylamine.

[0017] In a fifth aspect, the present invention provides a curable composition comprising the compound as described above or the compound obtained by the preparation method as described above.

[0018] Optionally, the curable composition comprises the epoxy resin described above and the active ester described above.

[0019] In a sixth aspect, the present invention provides a cured product obtained by curing the curable composition as described above.

[0020] In a seventh aspect, the present invention provides a method for preparing the above-mentioned cured product, comprising the following steps: the above-mentioned curable composition is melted by heating and cured by heating in sequence to obtain a triazine biphenyl epoxy cured product.

[0021] Optionally, the method for preparing the cured product comprises the following steps: mixing the epoxy resin and the active ester according to a ratio, adding an accelerator, and obtaining a triazine biphenyl epoxy cured product after curing.

[0022] Optionally, the accelerator is an imidazole accelerator; the imidazole accelerator is preferably 2-methyl imidazoline (2MZL), 2-heptadecylimidazole (C17Z), 2-ethyl-4-methylimidazole (2E4MZ), 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN), the imidazole accelerator is selected from 2-methylimidazole (2MZ), 1-dodecyl-2-methyl-3-benzylimidazole chloride (SFZ), 1-cyanoethyl-2-undecylimidazole (C11Z-CN), 1-cyanoethyl-2-phenylimidazole (2PZ-CN), 1,3-dibenzyl-2-methylimidazole chloride (FFZ), 2-ethyl-4-methylimidazole (2E4MZ), 1-cyanoethyl-2 -methylimidazole (2MZ-CN), 2-undecylimidazole (C11Z), 1-cyanoethyl-2-phenylimidazole trimellitate (2PZ-CNS), 1-benzyl-2-methylimidazole (1B2MZ), 2-phenyl-4-methylimidazole (2P4MZ), 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-undecylimidazole trimellitate (C11Z-CNS), 2-phenylimidazole (2PZ), 1-cyanoethyl-2-ethyl-4-methylimidazole trimellitate (2E4MZ-CNS), trimellitate (2MZ-CNS) and 2,4-diamino-6[2'-methylimidazole-(1')]ethyl-S-triazine (2MZ-A) or a combination thereof.

[0023] In an eighth aspect, the present invention provides an application of a solidified material obtained by the preparation method as described above, which is applied in the fields of electronics, aerospace, automobile industry, construction or coatings.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] (1) The present invention provides a triazine biphenyl compound and a preparation method thereof, wherein a phenolic resin with a triazine biphenyl structure is obtained by polycondensation of p-cyanobiphenol, and then the phenolic resin is reacted with an epichlorohydrin compound and an acyl chloride compound to obtain an epoxy resin and an active ester with a triazine biphenyl structure, and under the action of an imidazole accelerator, a triazine ring (containing nitrogen) is introduced as a node, and a thermosetting cross-linked network is prepared by a non-polar cross-linking scheme using a trifunctional epoxy resin with a rigid aromatic structure as an arm and an active ester curing agent (same skeleton), and a three-dimensional network intrinsic microporous structure is formed by in-situ cross-linking of rigid long-arm branching units, thereby breaking through bottlenecks such as low dielectric, high temperature resistance, and flame retardancy, and the cured material has excellent flame retardancy, high temperature resistance, and low dielectric properties. This technology has pioneered a preparation method for fully rigid epoxy compounds, which is of great significance for the construction of high-performance thermosetting resin materials.

[0026] (2) The preparation method of the present invention introduces triazine rings and biphenyl structures into epoxy resin and active ester, and ensures the rigidity and high symmetry of the structure through "π-π" conjugation to ensure the formation of an ordered pore structure. The epoxy and active ester molecules are alternately ringed to form a nanometer-level microporous structure; and the active ester and epoxy resin are cross-linked without generating hydroxyl groups, which further improves the dielectric properties of the epoxy resin.

[0027] (2) The epoxy resin containing triazine biphenyl structure provided by the present invention has excellent flame retardancy and high temperature resistance, good low dielectric properties and low thermal expansion coefficient; the comprehensive performance is significantly improved compared with traditional epoxy and phenolic resins. The high-performance epoxy resin can be widely used as a thermosetting resin material in many fields such as electronics, aerospace, automobile industry, construction and coatings.

[0028] (3) The preparation method of the present invention is simple and efficient, has good controllability, is easy to operate, has high product purity, and is suitable for large-scale industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is the infrared spectrum of the triazine biphenyl epoxy resin and phenolic resin and active ester of Examples 1 and 2.

[0030] Figure 2 This is the curing kinetics diagram of triazine biphenyl epoxy resin and active ester in Example 2.

[0031] Figure 3 This is the TGA diagram of the epoxy active ester cured product in Examples 1 and 2.

[0032] Figure 4 DMA diagram of epoxy active ester cured product in Examples 1 and 2.

[0033] Figure 51 and 2 are the relationship between the dielectric constant, dielectric loss and frequency of the epoxy active ester cured product.

[0034] Figure 6 This is the BET diagram of the epoxy active ester cured product of Example 2. DETAILED DESCRIPTION

[0035] In order to make the above-mentioned objects, features and advantages of the invention more obvious and easy to understand, the specific embodiments of the invention are described in detail below.

[0036] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein, and those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0037] A method for preparing an epoxy resin containing a triazine biphenyl structure, comprising the following steps:

[0038] (1) Preparation of phenolic resin: dissolve a cyanobiphenol compound in a solvent to maintain a concentration of 10%-35% g / ml, stir and reflux at 0°C for 10 minutes, add a catalyst in a molar ratio of cyanobiphenol compound: catalyst = 1:3, stir for 30 minutes until the liquid phase is uniform, then slowly heat the system to room temperature (25°C) and react for 12 hours, add ice water, add ammonia water dropwise to adjust the pH value to neutral, filter and wash with water 3-6 times, and vacuum dry to obtain a phenolic resin containing a triazine biphenyl structure, the structural formula of which is as follows:

[0039]

[0040] (2) Preparation of epoxy resin: The phenolic resin and epichlorohydrin compound prepared in step (1) are stirred under nitrogen reflux at 65° C. until they are homogeneous, a phase transfer catalyst is added, and the molar ratio of the phenolic resin: epichlorohydrin compound: phase transfer catalyst is 1:30:0.1565. After reacting for 10 minutes, sodium hydroxide is added, and the molar ratio of sodium hydroxide: phenolic resin is 3.6:1. The reaction is continued for 3 hours. After the reaction is completed, the filtrate is filtered, and the filtrate is washed with hot water for 3 times, and dehydrated with anhydrous sodium sulfate for more than 6 hours. The filtrate is filtered again and the solvent is removed by rotary evaporation. The product is placed in a vacuum oven and dried to obtain an epoxy resin containing a triazine biphenyl structure, and the epoxy value thereof is 0.266-0.387. The structural formula is as follows:

[0041]

[0042] (3) Preparation of active ester: The phenolic resin obtained in step (1) is stirred with a solvent under nitrogen reflux at 0°C until it becomes homogeneous, maintaining its concentration at 5%-30% g / ml, adding an acyl chloride compound, wherein the molar ratio is phenolic resin: acyl chloride compound = 1:1.5-2, keeping the temperature for 10 minutes, then slowly adding an amine compound dropwise, wherein the molar ratio is phenolic resin: amine compound = 1:1.5-2, reacting for 2 hours, then heating to 25°C for 2 hours, then heating to 60°C for 2 hours, filtering to remove the generated amine compound salt, rotary distilling the filtrate to remove the solvent, adding ethyl acetate to dissolve it again, washing with hot water until neutral, removing water with anhydrous sodium sulfate, and rotary distilling to remove the solvent, and drying the product in a vacuum oven to obtain an active ester containing a triazine biphenyl structure, the structural formula of which is as follows:

[0043]

[0044] (4) Preparation of epoxy active ester curing material: After epoxy resin and active ester are uniformly mixed at 140°C according to the ratio, an accelerator is added and stirred rapidly. The molar ratio is epoxy resin: active ester: accelerator = 6:5:0.11. The mixture is poured into a mold and cured in three stages according to the curing process: 200°C / 2h, 225°C / 2h, and 250°C / 4h. After natural cooling, a triazine biphenyl epoxy active ester curing material is obtained.

[0045] In one embodiment of the present invention, the p-cyanobiphenol compound in step (1) is 4-hydroxybiphenyl-4-carbonitrile.

[0046] In one embodiment of the present invention, the solvent in step (1) is dichloromethane or ethylene dichloride.

[0047] In one embodiment of the present invention, the catalyst in step (1) is a protonic acid or a metal halide, preferably one or a combination of sulfuric acid, p-toluenesulfonic acid, hydrochloric acid and ZnCl2.

[0048] In one embodiment of the present invention, the phase transfer catalyst in step (2) is one or a combination of trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetrabenzyltrimethylammonium chloride, methylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium bromide or tetrabutylammonium hydrogen sulfate.

[0049] In one embodiment of the present invention, the epichlorohydrin compound in step (2) is epichlorohydrin.

[0050] In one embodiment of the present invention, the solvent in step (3) is tetrahydrofuran and ethyl acetate.

[0051] In one embodiment of the present invention, the acyl chloride compound in step (3) is acetyl chloride or benzoyl chloride.

[0052] In one embodiment of the present invention, the amine compound in step (3) is triethylamine

[0053] In one embodiment of the present invention, the accelerator of step (4) is 2-methyl imidazoline (2MZL), 2-heptadecylimidazole (C17Z), 2-ethyl-4-methylimidazole (2E4MZ), 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN), the imidazole accelerator is selected from 2-methylimidazole (2MZ), 1-dodecyl-2-methyl-3-benzylimidazole chloride (SFZ), 1-cyanoethyl-2-undecylimidazole (C11Z-CN), 1-cyanoethyl-2-phenylimidazole (2PZ-CN), 1,3-dibenzyl-2-methylimidazole chloride (FFZ), 2-ethyl-4-methylimidazole (2E4MZ), 1-cyanoethyl -2-methylimidazole (2MZ-CN), 2-undecylimidazole (C11Z), 1-cyanoethyl-2-phenylimidazole trimellitate (2PZ-CNS), 1-benzyl-2-methylimidazole (1B2MZ), 2-phenyl-4-methylimidazole (2P4MZ), 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-undecylimidazole trimellitate (C11Z-CNS), 2-phenylimidazole (2PZ), 1-cyanoethyl-2-ethyl-4-methylimidazole trimellitate (2E4MZ-CNS), trimellitate (2MZ-CNS) and 2,4-diamino-6[2'-methylimidazole-(1')]ethyl-S-triazine (2MZ-A).

[0054] The triazine biphenyl compound, composition, cured product and preparation method thereof of the present invention are specifically described below by way of examples. Main raw materials and equipment used: Unless otherwise specified, the raw materials and equipment of each embodiment and comparative example are the same; materials without specific models or types are purchased from the market or commonly available through common channels of the same model, and are not specifically limited.

[0055] Example 1

[0056] (1) Synthesis of phenolic resin (TZDP): In a 250 ml four-necked flask equipped with a mechanical stirrer, condensation reflux, and nitrogen introduction device, add 10.2375 g of 4-hydroxybiphenyl-4-carbonitrile (HBC) and 150 ml of dichloromethane, and stir and mix under condensation reflux in a water bath at 0°C. After the temperature stabilizes at 0°C, add 23.65 g of p-toluenesulfonic acid and stir for 30 min until the liquid phase is uniform and the temperature is stable. Then, the system is slowly heated to room temperature (25°C) and reacted for 12 h. Ice water is added, and ammonia water is added dropwise to adjust the pH value to neutral. The mixture is filtered and washed with water 3-6 times, and dried in vacuo to obtain phenolic resin with a yield of 91%.

[0057] (2) Synthesis of triazine biphenyl epoxy (TZDP-EP): In a 250 ml four-necked flask equipped with mechanical stirring, condensation reflux, and nitrogen introduction device, add 10 g of phenolic resin (TZDP) and 94.82 g of epichlorohydrin, and heat to 65°C under a nitrogen atmosphere. After the temperature stabilizes, add 0.618 g of tetramethylammonium bromide, react for 10 min, then add 3.69 g of sodium hydroxide and react for 3 h. After the reaction is completed, filter and wash the filtrate with hot water for 3 times, remove water with anhydrous sodium sulfate for more than 6 h, filter again and remove the solvent by rotary evaporation. The product is placed in a vacuum oven and dried to obtain triazine biphenyl epoxy resin (TZDP-EP) with a yield of 88%.

[0058] (3) Self-curing of triazine biphenyl epoxy resin (TZDP-EP): The obtained TZDP-EP epoxy resin is added into a mold, and the epoxy is heated and melted at 140°C. After filling the mold, three-stage curing is carried out according to the curing process: 190°C / 2h, 215°C / 2h, and 240°C / 2h. Due to the presence of tertiary ammonium (-N=) in the structure of TZDP-EP epoxy resin, it can promote the self-curing of epoxy, and finally a cured product of triazine biphenyl epoxy resin (TZDP-EP) is obtained.

[0059] The properties of the cured product of triazine biphenyl epoxy resin (TZDP-EP) are as follows: the 5% thermal weight loss temperature under nitrogen atmosphere is 304°C, the residual carbon rate at 800°C is 32%, the glass transition temperature is 188.5°C, the dielectric constant (10 7 HZ) is 3.47, and it has flame retardant and self-extinguishing properties, reaching the UL-94 test V-0 level.

[0060] Example 2

[0061] (1) Synthesis of triazine biphenyl active ester (TZDP-AE): In a 250 ml four-necked flask equipped with a mechanical stirrer, condensation reflux, and nitrogen introduction device, 10 g of phenolic resin (TZDP, the synthesis steps are the same as in Example 1) and 60 g of tetrahydrofuran were added, and the mixture was stirred and mixed in a water bath at 0°C under condensation reflux until a homogeneous phase was obtained. After the temperature stabilized, 6.03 g of acetyl chloride was added and the mixture was stirred evenly. After the temperature stabilized, 7.78 g of triethylamine was added, and attention was paid to preventing temperature surge. The mixture was stirred for 2 h, and the temperature was raised to 25°C and the reaction was continued for 2 h. The temperature was then raised to 60°C and the reaction was continued for 2 h. After the reaction was completed, the generated amine compound salt was removed by suction filtration, the filtrate was evaporated to remove the solvent, ethyl acetate was added at 60°C to dissolve the mixture again, the mixture was washed with hot water several times until the mixture was neutral, the mixture was dehydrated with anhydrous sodium sulfate for more than 6 h, and the solvent was removed by evaporation again. The product was dried in a vacuum oven to obtain triazine biphenyl active ester (TZDP-AE) with a yield of 85%.

[0062] (2) Curing of TZDP-EP and TZDP-AE: After 5.36 g of TZDP-EP and 6.675 g of TZDP-AE were mixed evenly at 140°C, 0.12 g of 2-ethyl-4-methylimidazole was added and stirred rapidly. The mixture was poured into a mold and cured in three stages according to the curing process: 200°C / 2h, 225°C / 2h, and 250°C / 4h. After natural cooling, an epoxy active ester cured product (TZDP-AE / EP) containing a triazine ring and a biphenyl structure was obtained.

[0063] The properties of the epoxy active ester cured product are as follows: the 5% thermal weight loss temperature under nitrogen atmosphere is 337°C, the residual carbon rate at 800°C is 51.37%, the glass transition temperature is 252°C, the dielectric constant (10 7 HZ) is 2.57, and has flame retardant and self-extinguishing properties, reaching UL-94 test V-0 level. Figure 6 It can be seen from the BET test curve that TZDP-EP and TZDP-AE have micropores (<2nm) after curing, which significantly improves the dielectric properties.

[0064] Comparative Example 1

[0065] E51 / DDM: Take 10g of epoxy resin E51 and 2.5g of diaminodiphenylmethane (DDM), mix them evenly at 120℃, pour them into the mold and cure them at 130℃ / 2h+160℃ / 2h+190℃ / 2h.

[0066] Performance Testing

[0067] Test method:

[0068] TGA: N2 was selected as the protective gas, the heating rate was 10°C / min, the test range was 25°C to 800°C, and the test was performed using a TA Instruments Q500 TGA instrument.

[0069] TMA: The coefficient of linear expansion (CTE) of the samples was measured using a TMA402 F1 / F3 Hyperion Thermomechanical Analyzer in compression mode at a heating rate of 5°C / min.

[0070] Determination of dielectric constant and loss: Dielectric tester Keysight E5071C and precision impedance analyzer Agilent4294A are used to test the dielectric constant and loss of epoxy resin at high and low frequencies respectively.

[0071] DMA: The test was performed using a TA Instruments Q800 DMA instrument in tensile mode with a frequency of 1 Hz and a heating rate of .

[0072] Vertical burning test (UL-94): It is carried out on a M607B vertical burning test machine. The test is carried out according to the standard ASTM D3801-10, and the test sample size is 125×13X3mm.

[0073] The performance test results are shown in Table 1.

[0074] Table 1

[0075]

[0076] from Figure 1-6 It can be seen from the test data that, compared with the E51 / DDM epoxy resin cured product of Comparative Example 1, the epoxy active ester cured product (TZDP-AE / EP) containing triazine rings and biphenyl structures of Example 2 of the present invention has greatly improved high temperature resistance (Tg), dimensional stability (TMA), dielectric properties, flame retardancy, etc.

[0077] Although some specific embodiments of the present invention have been described in detail by way of example, it will be appreciated by those skilled in the art that the above examples are for illustration only and are not intended to limit the scope of the present invention. It will be appreciated by those skilled in the art that the above embodiments may be modified without departing from the scope and spirit of the present invention. The scope of the present invention is defined by the appended claims.

Claims

1. A compound, characterized in that It has the structure of the compound represented by the following general formula (I), In the general formula (I), R1-R3 each independently represent a linear or branched alkyl group having 0 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. 27 R each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. 28 -R 30 Each independently represents the following general formula (I ’ ), In the general formula (I ’ ) where R a , R b Each independently represents a linear or branched alkyl group having 0 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

2. The method for preparing the compound according to claim 1, characterized in that: The following steps are involved: The p-cyanobiphenol compound is dissolved in a solvent, and a catalyst is added to prepare the compound represented by the general formula (I). 28 -R 30 It represents a phenolic resin of -H.

3. The method for preparing the compound according to claim 1, characterized in that: The following steps are involved: (1) dissolving a cyanobiphenol compound in a solvent, adding a catalyst, and preparing R of a compound represented by the general formula (I) 28 -R 30 It represents a phenolic resin of -H. (2) reacting the phenolic resin, epichlorohydrin compound and phase transfer catalyst described in step (1) to obtain R of the compound represented by general formula (I) 28 -R 30 express The epoxy resin has an epoxy value of 0.266-0.

387.

4. The method for preparing the compound as claimed in claim 3, characterized in that: The phase transfer catalyst is one or a combination of trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetrabenzyltrimethylammonium chloride, methylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium bromide and tetrabutylammonium hydrogen sulfate; and the epichlorohydrin compound is epichlorohydrin.

5. The method for preparing the compound according to claim 1, characterized in that: The following steps are involved: (1) dissolving a cyanobiphenol compound in a solvent, adding a catalyst, and preparing R of a compound represented by the general formula (I) 28 -R 30 Phenolic resin representing -H; (2) dissolving the phenolic resin in step (1) in a solvent, adding an acyl chloride compound and an amine compound in sequence, and reacting to obtain R of the compound represented by general formula (I) 28 -R 30 express of active esters.

6. A method for preparing a compound according to any one of claims 2 to 5, characterized in that: In claim 2 or step (1) of claims 3-5, the p-cyanobiphenol compound is 4-hydroxybiphenyl-4-carbonitrile, the solvent is dichloromethane or ethylene dichloride, and the catalyst is a protonic acid or a metal halide.

7. A curable composition, characterized in that The invention comprises the compound according to claim 1 or the compound obtained by the preparation method according to any one of claims 2 to 6.

8. A solidified product, characterized in that: The curable composition according to claim 7 is cured.

9. A method for preparing a solidified product as claimed in claim 8, characterized in that: The method comprises the following steps: the curable composition according to claim 7 is melted by heating and cured by heating in sequence to obtain a triazine biphenyl epoxy cured product.

10. Use of a solidified material obtained by the preparation method according to claim 8 or claim 9, characterized in that: Used in the fields of electronics, aerospace, automotive industry, construction or coatings.

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