An acrylate compound containing a benzotriazole group, and a preparation method and application thereof

Abstract

This invention discloses an acrylate compound containing a benzotriazole group, its preparation method, and its application, relating to the field of electronic packaging technology. The compound has the structure shown in general formula (I): (I) wherein X1, X2, X3, and X4 are each independently C1 or N; R1 is selected from hydrogen, methyl, or ethyl; Y is selected from absent, O, or S; Z is selected from O or S; G is selected from C1-C 20 R1 is a straight-chain or branched alkylene group; R2 is selected from hydrogen or methyl. The compounds of this invention can act as efficient molecular bridges, chemically crosslinking one end to a polymer network and strongly complexing the other end to a metal substrate during curing, thereby fundamentally improving interfacial adhesion strength. Experiments show that adding 1% can increase the room temperature shear strength of the electronic encapsulation adhesive composition by approximately 35% and the high-temperature shear strength at 200°C by approximately 25%.

Description

Technical Field

[0001] This invention relates to the field of electronic packaging technology, specifically to an acrylate compound containing benzotriazole groups, its preparation method, and its application. Background Technology

[0002] In the field of electronic packaging, shear strength is a fundamental indicator of whether an adhesive can fulfill its core structural functions, and its importance extends throughout the product design, manufacturing, testing, and entire lifecycle. Electronic packaging adhesives need to possess high bond strength, heat resistance, and stability. Existing acrylic-based packaging adhesives have relatively weak bond strength to substrates (especially metals), and may have fatal weaknesses in terms of mechanical integrity, long-term reliability, thermal management efficiency, and environmental sealing.

[0003] To improve adhesion performance, the art typically employs methods such as adding adhesion promoters like silane coupling agents to the formulation, thereby enhancing adhesion by strengthening the interaction between the encapsulant and the substrate surface. However, as electronic devices evolve towards miniaturization, higher power, and higher density, the requirements for the adhesive strength of encapsulants are becoming increasingly stringent. The improvement effects of existing technologies have reached their limits, making it difficult to meet the higher reliability and lifespan requirements of next-generation electronic products.

[0004] It is worth noting that benzotriazole (BTA) and its derivatives are recognized metal complexing agents, with nitrogen atoms in their structure forming strong coordination bonds with metal surfaces. We envision that if benzotriazole could be molecularly modified and combined with polymerizable acrylate groups via a linking group, the resulting compound could be introduced as a functional additive into encapsulant formulations. During curing, the acrylate end groups of this compound can participate in the polymerization reaction, covalently integrating into the crosslinking network of the acrylate resin; simultaneously, its benzotriazole end groups undergo strong complexation with the metal substrate surface. This design is equivalent to constructing a robust "molecular bridge" at the polymer matrix-metal interface, potentially fundamentally solving the problem of insufficient interfacial adhesion strength and thus greatly improving the overall performance of the encapsulant. Furthermore, the nitrogen atoms in the benzotriazole molecule can form a dense monolayer complex film with the metal surface (especially copper and its alloys), isolating the metal from the corrosive medium and protecting it from moisture, oxygen, halide ions, etc. in the environment. This effectively inhibits electrochemical corrosion, oxidation discoloration and dendrite growth, making it particularly suitable for encapsulation protection in high humidity or high temperature environments.

[0005] However, the application of benzotriazole compounds to enhance the adhesive strength of electronic encapsulation adhesives through the aforementioned molecular design and "molecular bridging" mechanism is rarely reported in existing technologies. Therefore, developing such novel compounds and expanding their applications is of great significance for overcoming current technological bottlenecks. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of the aforementioned background technology and provide an acrylate compound containing benzotriazole groups, its preparation method, and its application. The molecule simultaneously contains polymerizable acrylate groups and metal-complexable benzotriazole groups, which are applied to acrylate encapsulants to improve their adhesive properties. Experiments have shown that adding 1% of the compound of this invention can significantly improve the shear strength of the encapsulant, enabling the product to withstand long-term stress cycles, reducing the likelihood of fatigue microcracks and their propagation, thus ensuring high quality, high reliability, and long lifespan of electronic products. Achieving the same or even better fixing effect with a smaller bonding area provides possibilities for miniaturization and weight reduction in electronic design.

[0007] To achieve the above objectives, the present invention adopts the following technical solution: In a first aspect, the present invention provides an acrylate compound containing a benzotriazole group, said compound having the structure shown in general formula (I): (I) in, X1, X2, X3, and X4 are each independently CR1 or N; R1 is selected from hydrogen, methyl, or ethyl; Y is selected from non-existent, O, or S; Z is selected from O or S; G is selected from C1-C 20 Straight-chain or branched alkylene groups; R2 is selected from hydrogen or methyl.

[0008] When Y is present (as O or S), the structure of compound (I) corresponds to (Ia). (Ia), When Y is absent, the structure of compound (I) corresponds to (Ib), where the N atom of the benzotriazole ring is directly bonded to G. (Ib).

[0009] Preferred acrylate compounds containing benzotriazole groups, when Y is O, wherein compound (I) is selected from any of the following structures: , , .

[0010] Preferred acrylate compounds containing benzotriazole groups, when Y is absent, have the following structure: .

[0011] Preferred acrylate compounds containing benzotriazole groups, wherein X1, X2, and X3 are all CR1, X4 is CR1 or N, R1 is hydrogen; and Y is O or absent.

[0012] Secondly, the present invention provides a method for preparing acrylate compounds containing benzotriazole groups as described above, the synthetic route of which is as follows: The synthesis steps include: a. In an organic solvent environment, a benzotriazole compound having the structure of formula (II) is subjected to a substitution reaction with a haloalcohol / thiol having the structure of formula (III) under basic conditions to generate an intermediate having the structure of formula (IV); Wherein, X1, X2, X3, X4, Y, G, and Z are defined as described in claim 1; X represents Cl, Br, or I; b. In an organic solvent environment, the intermediate (IV) obtained in step a is esterified with an acyl chloride compound having the structure of formula (V) in the presence of an acid-binding agent to obtain the target compound of general formula (I); R2 is defined as described in claim 1.

[0013] The haloalcohols / thiols of formula (III) are specifically represented as follows: when Z is O, the structure of formula (III) is a haloalcohol; when Z is S, the structure of formula (III) is a halothiol.

[0014] Preferably, when Y is present (either O or S), formula (II) corresponds to formula (II-a), formula (IV) corresponds to formula (IV-a), and the target product is formula (Ia). The specific synthetic route is as follows: .

[0015] Preferably, when Y is absent, formula (II) corresponds to formula (II-b), formula (IV) corresponds to formula (IV-b), and the specific target product is formula (Ib).

[0016] .

[0017] In a preferred method for preparing acrylate compounds containing benzotriazole groups, in step a, the alkaline conditions are provided by an inorganic or organic base; Wherein, the inorganic base is one or more of potassium carbonate, sodium carbonate, cesium carbonate, or sodium hydroxide; and / or, the organic base is triethylamine, diisopropylethylamine, or pyridine; The molar ratio of benzotriazole compound (II): haloalcohol / thiol (III): inorganic base or organic base is 1:1~1.25:1.2~1.5. The reaction temperature in step a is room temperature, and the reaction time is 12~48h.

[0018] A preferred method for preparing acrylate compounds containing benzotriazole groups, wherein in step b, the acid-binding agent is selected from one or more of triethylamine, diisopropylethylamine, or pyridine. In step b, the acyl chloride compound (V) is added dropwise under ice bath conditions, maintaining the reaction temperature ≤10℃, and the reaction time is 3–6 h. The molar ratio of feed material to benzotriazole intermediate (IV): acyl chloride compound (V): acid binder is 1:1~1.2:1.2~1.5.

[0019] A preferred method for preparing acrylate compounds containing benzotriazole groups, wherein in step a, the organic solvent is selected from one or more of N,N'-dimethylformamide, acetone, acetonitrile, dichloromethane, tetrahydrofuran, or 2-methyltetrahydrofuran; and in step b, the organic solvent is selected from one or more of toluene, dichloromethane, tetrahydrofuran, or 2-methyltetrahydrofuran.

[0020] Thirdly, the present invention provides an electronic encapsulation adhesive composition comprising an acrylate compound containing benzotriazole groups as described in any one of the above claims and a base adhesive liquid, wherein the amount of the acrylate compound containing benzotriazole groups added is 0.5 to 2.5 wt% of the mass of the base adhesive.

[0021] The base adhesive of the electronic encapsulation adhesive composition contains conventional components in the art, such as, but not limited to: acrylate oligomers, acrylate reactive diluents, free radical initiators, fillers (such as silica powder, core-shell rubber), thixotropic agents (such as fumed silica), and other additives (such as silane coupling agents, polymerization inhibitors), etc.

[0022] More preferably, the base adhesive comprises, by weight, 50 parts of acrylate oligomer (epoxy acrylate oligomer), 20 parts of acrylate reactive diluent (hexylene dimethacrylate), 8 parts of core-shell rubber, 20 parts of silica powder, 1 part of free radical initiator (tert-butyl peroxide (2-ethylhexanoate)), 0.4 parts of thixotropic agent (fumed silica), 0.59 parts of silane coupling agent (KH-560), and 0.01 parts of polymerization inhibitor (hydroquinone monomethyl ether).

[0023] Fourthly, the present invention provides the application of acrylate compounds containing benzotriazole groups as described above or electronic encapsulation adhesive compositions as described above in semiconductor electronic packaging.

[0024] Compared with the prior art, the present invention has the following beneficial effects: 1. This invention is the first to design and synthesize a bifunctional compound that simultaneously possesses polymerizable acrylate groups and strong metal complex benzotriazole groups, exhibiting a novel structure.

[0025] 2. The compound of this invention can act as a highly efficient "molecular bridge," chemically cross-linking one end to the polymer network and strongly complexing the other end to the metal substrate during curing, thereby fundamentally improving the interfacial bonding strength. Experiments show that adding 1% by weight of the base adhesive can increase the room temperature shear strength by about 35% and the 200°C high-temperature shear strength by about 25%.

[0026] 3. The addition of this compound significantly enhances the mechanical integrity and long-term reliability of packaged devices, and provides a material basis for the miniaturization and lightweight design of electronic products. It exhibits good compatibility with existing acrylate encapsulant systems, is easy to use, and is readily applicable. Detailed Implementation

[0027] The following will describe the concept and technical effects of the present invention clearly and completely with reference to the embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0028] To improve the adhesive strength of electronic encapsulation adhesives, this invention provides an acrylate compound containing benzotriazole groups, the compound structure of which is shown in general formula (I). (I) in, X1, X2, X3, and X4 are each independently CR1 or N; R1 is selected from hydrogen, methyl, or ethyl; Y is selected from the absence of O or S; Z is selected from O or S; G is selected from C1-C 20 Straight-chain or branched alkylene groups; R2 is selected from hydrogen or methyl.

[0029] When Y is present (as O or S), the structure of compound (I) corresponds to (Ia). (Ia).

[0030] When Y is absent, the structure of compound (I) corresponds to (Ib). (Ib).

[0031] In some embodiments of the present invention, X1, X2, and X3 are all preferably CH; X4 is preferably CH or N; Y is preferably O; and G is preferably Cl-C. 20 Straight-chain or branched alkylene groups.

[0032] The following four structures are preferred for compounds of general formula (Ia). , , The preferred specific structure of the compound of general formula (Ib) is as follows: .

[0033] This invention also provides a method for preparing compounds of the above general formula (I), the synthetic route of which is as follows: When Y exists, the synthesis route is as follows: When Y is absent, the synthesis route is as follows: .

[0034] a. In an organic solvent environment, benzotriazole compounds having the structure of formula (II-a) or (II-b) are subjected to a substitution reaction with haloalcohols / thiols having the structure of formula (III) under basic conditions to generate benzotriazole intermediates having the structure of formula (IV-a) or (IV-b); The alkaline conditions are provided by an inorganic or organic base, wherein the inorganic base is one or more of potassium carbonate, sodium carbonate, cesium carbonate, or sodium hydroxide; and the organic base is triethylamine, pyridine, or diisopropylethylamine; the reaction temperature in step a is at room temperature.

[0035] b. In an organic solvent environment, the compound of formula (IV-a) or (IV-b) obtained in step a is subjected to an esterification reaction with an acyl chloride compound having the structure of formula (V) in the presence of an acid-binding agent to obtain the target compound of general formula (Ia) or (Ib). The acyl chloride compound (V) is added dropwise under ice bath conditions, and the reaction temperature in step b is ≤10℃.

[0036] The following specific embodiments will provide a more detailed description of the present invention.

[0037] Example 1 This embodiment provides the specific formula (Ia) structure when X1, X2, X3, and X4 are all CH; Y is O; G is a C2 straight-chain alkylene group, i.e., ethylene; Z is O; and R2 is H, i.e., the following compound P1: The preparation route of compound P1 is as follows: The specific steps are as follows: 13.5 g (0.1 mol) of the substrate 1-hydroxybenzotriazole (structure (II-a)) and 12.5 g (0.1 mol) of the haloalcohol (III), 2-bromoethanol (12.5 g, 0.1 mol), were dissolved in 300 mL of acetone. Potassium carbonate (16.6 g, 0.12 mol) was added, and the mixture was stirred at room temperature for 12 hours. The mixture was filtered, and the filter cake was washed with 100 mL of acetone. The filtrates were combined, concentrated under reduced pressure to remove the solvent, dissolved in 200 mL of ethyl acetate, washed with 50 mL of saturated brine, and dried over anhydrous sodium sulfate. The concentrate was then used to obtain 16.8 g of benzotriazole intermediate (IV-a), with a yield of 93.8%.

[0038] The above-mentioned product, benzotriazole intermediate (IV-a) (16.1 g, 0.09 mol), and triethylamine (12.1 g, 0.12 mol) were dissolved in 200 mL of anhydrous dichloromethane. Acrylamide chloride (V), i.e., acryloyl chloride (9.05 g, 0.1 mol), was added dropwise under ice bath conditions, maintaining the reaction temperature ≤10 °C, and stirring for 3 hours. 100 mL of water was added, and the mixture was stirred for 10 min, then allowed to stand. The liquid phase was separated, and the aqueous phase was extracted with 100 mL of dichloromethane. The combined organic phases were dried over sodium sulfate-free solution and concentrated under reduced pressure to obtain crude target compound P1. This crude compound was purified by column chromatography (using n-hexane / ethyl acetate = 10:1 as eluent) to give 18.4 g of pure P1 as a pale yellow solid, with a yield of 87.6%.

[0039] In this embodiment, the molar ratio of benzotriazole compound (1-hydroxybenzotriazole): haloalcohol (2-bromoethanol): base (potassium carbonate) = 1:1:1.2; intermediate: acyl chloride compound (acryloyl chloride): acid binder (triethylamine) = 1:1.11:1.33.

[0040] The chemical structure of compound P1 was tested, and the NMR characterization results are as follows: 1H NMR (400MHz, CDCl3) δ: 8.01-8.02 (d, 1H, J=4Hz), 7.50-7.57 (m, 2H), 7.37-7.40 (m, 1H), 6.43-6.46 (d, 1H, J=12Hz), 6.09-6.14 (m, 1H), 5.82-5.85 (d, 1H, J=12Hz), 4.54-4.56 (m, 2H), 4.16-4.19 (m, 2H).

[0041] Example 2 This embodiment provides the specific formula (Ia) structure when X1, X2, X3, and X4 are all CH; Y is O; G is a C3 straight-chain alkylene group, i.e., propylene; Z is O; and R2 is methyl, i.e., the following compound P2. The preparation route of compound P2 is as follows: The specific steps are as follows: 13.5 g (0.1 mol) of the substrate 1-hydroxybenzotriazole (structure (II-a)) and 9.45 g (0.1 mol) of the haloalcohol (III), 3-chloropropanol, were dissolved in 300 mL of acetone. Potassium carbonate (16.6 g, 0.12 mol) was added, and the reaction was carried out at room temperature for 48 hours. The mixture was filtered, and the filter cake was washed with 100 mL of acetone. The filtrates were combined, concentrated under reduced pressure to remove the solvent, dissolved in 200 mL of ethyl acetate, washed with 50 mL of saturated brine, and dried over anhydrous sodium sulfate. The organic phase was concentrated to give 19.2 g of benzotriazole intermediate (IV), with a yield of 99.4%.

[0042] The above-mentioned product, benzotriazole intermediate (IV) (19 g, 0.098 mol), was dissolved in 200 mL of anhydrous dichloromethane. Acyl chloride compound (V), namely methacryloyl chloride (10.45 g, 0.1 mol), was added dropwise under ice bath conditions, maintaining the reaction temperature ≤10 °C, and stirring for 3 hours. 100 mL of water was added, and the mixture was stirred for 10 min, then allowed to stand. The liquid phase was separated, and the aqueous phase was extracted with 100 mL of dichloromethane. The combined organic phases were dried over sodium sulfate-free solution and concentrated under reduced pressure to obtain crude target compound P2. This crude compound was purified by column chromatography (using n-hexane / ethyl acetate = 10:1 as eluent) to give 12 g of pure P2 as a pale yellow solid, with a yield of 46.7%.

[0043] In this embodiment, the molar ratio of hydroxybenzotriazole compound (1-hydroxybenzotriazole): haloalcohol (3-chloropropanol): base (potassium carbonate) = 1:1:1.2; intermediate: acyl chloride compound (methacryloyl chloride): acid binder (triethylamine) = 1:1.02:1.22.

[0044] The chemical structure of compound P2 was tested, and the NMR characterization results are as follows: 1H NMR (400MHz, CDCl3) δ: 8.01-8.03 (d, 1H, J=8Hz), 7.51-7.57 (m, 2H), 7.37-7.40 (m, 1H), 6.09 (s, 1H), 5.57 (s, 1H), 4.54-4.56 (m, 2H), 4.16-4.19 (m, 2H), 1.93-2.11 (m, 5H).

[0045] Example 3 This embodiment provides the specific formula (Ia) structure when X1, X2, and X3 are all CH; X4 is N; Y is O; G is a C5 branched alkylene group, i.e., 2-dimethyl-1,3-propylene; Z is O; and R2 is hydrogen, which is the following compound P3. The preparation route of compound P3 is as follows: The specific steps are as follows: The substrate N-hydroxy-7-azabenzotriazole (13.6 g, 0.1 mol) with structural formula (II-a) was dissolved in 300 mL of acetone with a haloalcohol (III), namely 3-chloro-2,2-dimethyl-1-propanol (12.26 g, 0.1 mol). Potassium carbonate (16.6 g, 0.12 mol) was added, and the reaction was carried out at room temperature for 48 hours. The mixture was filtered, and the filter cake was washed with 100 mL of acetone. The filtrates were combined, concentrated under reduced pressure to remove the solvent, dissolved in 200 mL of ethyl acetate, washed with 50 mL of saturated brine, and dried over anhydrous sodium sulfate. The organic phase was concentrated to give 21.8 g of pyridotriazole intermediate (IV), with a yield of 98.1%.

[0046] The above-mentioned product, pyridotriazole intermediate (IV) (20 g, 0.09 mol), was dissolved in 200 mL of anhydrous dichloromethane with triethylamine (12.1 g, 0.12 mol). Acryloyl chloride (9.05 g, 0.1 mol) was added dropwise under ice bath conditions, maintaining the reaction temperature ≤10℃, and stirring for 3 hours. 100 mL of water was added, and the mixture was stirred for 10 min, then allowed to stand. The liquid phase was separated, and the aqueous phase was extracted with 100 mL of dichloromethane. The organic phases were combined, dried over sodium sulfate-free solution, and concentrated under reduced pressure to obtain crude target compound P3. Crude P3 was purified by column chromatography (using n-hexane / ethyl acetate = 10:1 as eluent) to give 10.5 g of pure P3 pale yellow liquid, with a yield of 42.3%.

[0047] In this embodiment, the molar ratio of hydroxybenzotriazole compound (N-hydroxy-7-azabenzotriazole): haloalcohol (3-chloro-2,2-dimethyl-1-propanol): base (potassium carbonate) is 1:1:1.2; the molar ratio of pyridotriazole intermediate: acyl chloride compound (acryloyl chloride): acid binder (triethylamine) is 1:1.11:1.33.

[0048] The chemical structure of compound P3 was tested, and the NMR characterization results are as follows: 1H NMR (400MHz, CDCl3) δ: 8.10-8.12 (m, 1H), 7.62-7.67 (m, 1H), 7.36-7.38 (s, 1H), 6.42-6.45 (d, 1H, J=12Hz), 6.09-6.14 (m, 1H), 5.81-5.84 (d, 1H, J=12Hz), 4.44-4.47 (m, 2H), 4.11-4.14 (m, 2H), 1.10 (s, 3H) 1.08 (s, 3H).

[0049] Example 4 This embodiment provides the specific formula (Ia) structure when X1, X2, X3, and X4 are all CH; Y is O; G is a C3 straight-chain alkylene group, i.e., propylene; Z is S; and R2 is methyl, i.e., the following compound P4. The preparation route of compound P4 is as follows: The specific steps are as follows: The substrate 1-hydroxybenzotriazole (5.4 g, 0.04 mol) with structural formula (II-a) was dissolved in 100 mL of acetone with a halothiol (III), namely 3-chloro-1-propanethiol (5.5 g, 0.05 mol). Potassium carbonate (6.9 g, 0.05 mol) was added, and the reaction was carried out at room temperature for 48 hours. After filtration and concentration, the solution was dissolved in 100 mL of ethyl acetate, washed with 30 mL of saturated brine, dried over anhydrous sodium sulfate, and concentrated to give 7.13 g of benzotriazole intermediate (IV-a), with a yield of 85.2%.

[0050] The above-mentioned product, benzotriazole intermediate (IV-a) (7.13 g, 0.034 mol), was dissolved in 100 mL of anhydrous dichloromethane. Acyl chloride compound (V), namely methacryloyl chloride (4.2 g, 0.04 mol), was added dropwise under ice bath conditions, maintaining the reaction temperature ≤10 °C, and stirring for 3 hours. 100 mL of water was added, and the mixture was stirred for 10 min, then allowed to stand. The liquid phase was separated, and the aqueous phase was extracted with 50 mL of dichloromethane. The combined organic phases were dried over sodium sulfate-free solution and concentrated under reduced pressure to obtain crude target compound P4. This crude compound was purified by column chromatography (using n-hexane / ethyl acetate = 10:1 as eluent) to give 6.7 g of pure P4 as a pale yellow liquid, with a yield of 70.9%.

[0051] In this embodiment, the molar ratio of hydroxybenzotriazole compound (1-hydroxybenzotriazole): halothiol (3-chloro-1-propanethiol): base (potassium carbonate) = 1:1.25:1.25; benzotriazole intermediate: acyl chloride compound (methacryloyl chloride): acid binder (triethylamine) = 1:1.18:1.47.

[0052] The chemical structure of compound P4 was tested, and the NMR characterization results are as follows: 1H NMR (400MHz, CDCl3) δ: 8.01-8.02 (d, 1H, J=4Hz), 7.50-7.57 (m, 2H), 7.37-7.40 (m, 1H), 6.05 (s, 1H), 5.52 (s, 1H), 4.54-4.56 (m, 2H), 3.97-4.03 (m, 2H), 1.93-2.11 (m, 5H).

[0053] Example 5 In this embodiment, X1, X2, X3, and X4 are all CH; Y is non-existent; and G is C. 18 The specific formula (Ib) for a straight-chain alkylene group, i.e., an octadecylene group; where Z is O and R2 is methyl, is shown in compound P5 below. The preparation route of compound P5 is as follows: The specific steps are as follows: Benzotriazole (1.35 g, 0.01 mol) with structural formula (II-b) was dissolved in 20 mL of acetone with a haloalcohol (III), namely 18-bromo-1-octadecanool (4.19 g, 0.012 mol), and potassium carbonate (1.66 g, 0.012 mol) was added. The reaction was carried out at room temperature for 48 hours. The product was purified by column chromatography (using n-hexane / ethyl acetate = 7:1 as eluent) to give 1.78 g of pure benzotriazole intermediate (IV-b), with a yield of 45.9%.

[0054] The above-mentioned product, benzotriazole intermediate (IV-b) (1.5 g, 3.87 mmol), was dissolved in 20 mL of anhydrous dichloromethane with triethylamine (0.47 g, 4.64 mmol). Methacrylamide chloride (0.48 g, 4.64 mmol) was added dropwise under ice bath conditions, maintaining the reaction temperature ≤10 °C, and stirring for 3 hours. 30 mL of water was added, and the mixture was stirred for 10 min, then allowed to stand. The liquid phase was separated, and the aqueous phase was extracted with 30 mL of dichloromethane. The combined organic phases were dried over sodium sulfate-free solution and concentrated under reduced pressure to obtain crude target compound P5. Crude P5 was purified by column chromatography (using n-hexane / ethyl acetate = 10:1 as eluent) to give 1.23 g of pure P5 as a pale yellow liquid, with a yield of 69.7%.

[0055] In this embodiment, the ratio of benzotriazole compound (benzotriazole): haloalcohol (18-bromo-1-octadecanool): base (potassium carbonate) = 1:1.2:1.2: intermediate (IV-b): acyl chloride compound (methacryloyl chloride): acid binder (triethylamine); molar ratio of feed = 1:1.2:1.2.

[0056] The chemical structure of compound P5 was tested, and the NMR characterization results are as follows: 1H NMR (400MHz, CDCl3) δ: 7.99-8.00 (d, 1H, J=4Hz), 7.47-7.53 (m, 2H), 7.32-7.36 (m, 1H), 6.08 (s, 1H), 5.54 (s, 1H), 4.42-4.45 (m, 2H), 3.94-3.97 (m, 2H), 2.03 (s, 3H), 1.94-1.96 (m, 2H), 1.61-1.65 (m, 2H), 1.27-1.53 ​​(m, 28H).

[0057] Application Test Example: Shear Strength Test of Electronic Encapsulation Adhesive Weigh each component in Table 1 according to its mass percentage, mix thoroughly, and degas to prepare the base adhesive. Then add compounds P1-P5 to the base adhesive at 1 wt% of the base adhesive mass, mix thoroughly, and degas to prepare the modified adhesive, using the original base adhesive as a control.

[0058] Table 1. Acrylic Base Adhesive Formulation Six encapsulant samples were prepared separately, with a chip size of 0.65mm × 0.65mm, substrate: Cu, and curing conditions of 150℃ for 1 hour. The adhesive strength was evaluated using a push-pull test. The specific steps were as follows: The encapsulant sample was precisely applied to a designated location on the copper substrate using a dispensing device. The chip (size: 0.65mm × 0.65mm) was then mounted on the adhesive, and cured in a 150℃ oven for 1 hour to prepare the test sample. The prepared sample was then fixed on the test platform of a push-pull force testing machine (DAGE Series 4000 or equivalent). Using a specific shearing fixture, the sample was pushed vertically towards the chip sidewall at a constant and slow rate (e.g., 100 μm / s) until the adhesive interface between the chip and the substrate was damaged. The instrument automatically recorded the maximum force value during this process, which was then divided by the chip's adhesive area (0.4225 mm²). 2 The shear strength of the sample is given by (unit: MPa). Each sample was tested in parallel 12 times, and the final result was the average value. The results are shown in Table 2 below.

[0059] Table 2 Shear strength data of encapsulating adhesive The above results show that the encapsulating adhesives with only 1% of the compounds P1-P5 of this invention exhibit stable room temperature shear strengths above 30 MPa. This contrasts sharply with the comparative example (23.1 MPa) without the added compounds, demonstrating the fundamental enhancement of interfacial adhesion by the compounds of this invention. Taking P1 as the best performing example, its room temperature shear strength (32.2 MPa) is increased by 39.4% compared to the comparative example. Even considering P3, which shows the smallest improvement, the improvement rate reaches 32.9%. This indicates that this series of compounds can generally and stably improve the room temperature adhesion performance of existing encapsulating adhesives by approximately 35%, with extremely significant effects.

[0060] Under harsh high-temperature conditions of 200℃, the shear strength of the comparative sample dropped sharply to 0.74 MPa, nearing the failure threshold. However, all samples containing the compound of this invention maintained a strength above 0.9 MPa, demonstrating excellent heat resistance and hot-state adhesion retention. Taking P1 as an example, its high-temperature performance at 200℃ showed a 31.1% improvement in shear strength (0.97 MPa) compared to the comparative sample. This data strongly demonstrates that the "molecular bridge" constructed by the compound of this invention remains stable at high temperatures, effectively transferring stress and preventing interfacial adhesion failure caused by softening of the resin matrix.

[0061] Although the compounds of this invention differ in their substituents (such as X, Y, Z, G) (e.g., P1 is an oxyether linkage, P4 is a thioether linkage, P5 is a methylene linkage; P3 is an azircontriazole structure), all five compounds exhibit highly consistent and excellent enhancement effects. This demonstrates the universality of the molecular design concept of this invention: as long as the molecular structure simultaneously contains polymerizable (meth)acrylate groups and metal-complexable benzotriazole groups, and these groups are linked in series with suitable connecting chains, the technical effect of improving adhesive performance can be achieved.

[0062] In summary, this invention, through innovative molecular design, successfully combines the excellent metal-complexing ability of benzotriazole with the polymerizability of acrylates. The prepared compound, at an extremely low addition level (1 wt%), can act as a highly efficient "molecular bridge," forming a robust covalent-coordination synergistic interface layer between the polymer matrix and the metal substrate. This not only significantly improves the room-temperature shear strength of the encapsulant but also substantially enhances its adhesive reliability under high-temperature conditions, providing a key material solution for high-end semiconductor packaging and meeting the industry's urgent need for highly reliable, long-life electronic products.

Claims

1. An acrylate compound containing a benzotriazole group, characterized in that, The compound has the structure shown in general formula (I): (I) in, X1, X2, X3, and X4 are each independently CR1 or N; R1 is selected from hydrogen, methyl, or ethyl; Y is selected from non-existent, O, or S; Z is selected from O or S; G is selected from C1-C 20 Straight-chain or branched alkylene groups; R2 is selected from hydrogen or methyl.

2. The acrylate compound containing a benzotriazole group according to claim 1, characterized in that, When Y is O, the compound (I) is selected from any of the following structures: 、 、 。 3. The acrylate compound containing a benzotriazole group according to claim 1, characterized in that, When Y is absent, the structure of compound (I) is as follows: 。 4. The acrylate compound containing a benzotriazole group according to claim 1, characterized in that, X1, X2, and X3 are all CR1, X4 is CR1 or N, and R1 is hydrogen; Y is O or does not exist.

5. A method for preparing an acrylate compound containing a benzotriazole group as described in any one of claims 1 to 4, characterized in that, The synthetic route is as follows: The synthesis steps include: a. In an organic solvent environment, a benzotriazole compound having the structure of formula (II) is subjected to a substitution reaction with a haloalcohol / thiol having the structure of formula (III) under basic conditions to generate an intermediate having the structure of formula (IV); Wherein, X1, X2, X3, X4, Y, G, and Z are defined as described in claim 1; X represents Cl, Br, or I; b. In an organic solvent environment, the intermediate (IV) obtained in step a is esterified with an acyl chloride compound having the structure of formula (V) in the presence of an acid-binding agent to obtain the target compound of general formula (I); R2 is defined as described in claim 1.

6. The method for preparing acrylate compounds containing benzotriazole groups according to claim 5, characterized in that, In step a, the alkaline conditions are provided by an inorganic or organic base; The inorganic base is one or more of potassium carbonate, sodium carbonate, cesium carbonate, or sodium hydroxide; the organic base is triethylamine, diisopropylethylamine, or pyridine. The molar ratio of benzotriazole compounds (II): haloalcohols / thiols (III): inorganic bases or organic bases is 1:1 ~1.25:1.2~1.

5.

7. The method for preparing acrylate compounds containing benzotriazole groups according to claim 5, characterized in that, In step b, the acid-binding agent is selected from one or more of triethylamine, diisopropylethylamine, or pyridine; the acyl chloride compound (V) is added dropwise under ice bath conditions to maintain the reaction temperature ≤10℃; The molar ratio of intermediate (IV): acyl chloride compound (V): acid binder is 1:1~1.2:1.2~1.

5.

8. The method for preparing acrylate compounds containing benzotriazole groups according to claim 5, characterized in that, In step a, the organic solvent is selected from one or more of N,N'-dimethylformamide, acetone, acetonitrile, dichloromethane, tetrahydrofuran, or 2-methyltetrahydrofuran; in step b, the organic solvent is selected from one or more of toluene, dichloromethane, tetrahydrofuran, or 2-methyltetrahydrofuran.

9. An electronic encapsulating adhesive composition, characterized in that, The mixture comprises an acrylate compound containing a benzotriazole group as described in any one of claims 1 to 4 and a base adhesive, wherein the amount of the acrylate compound containing the benzotriazole group added is 0.5 to 2.5 wt% of the base adhesive.

10. The use of the compound as described in any one of claims 1 to 4 or the electronic encapsulating adhesive composition as described in claim 9 in semiconductor electronic packaging.

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