A high-performance benzocyclobutene-based polynorbornene composite material and its preparation method

Abstract

The present invention discloses a high-performance benzocyclobutene-based polynorbornene composite material and its preparation method. The structural formula of the benzocyclobutene-based polynorbornene composite material is shown in Formula I, where R1, R2, and R3 are independently selected from C1-C4 alkyl or oxy groups; x is in the range of 1-100; and y is in the range of 1-100. The novel material of the present invention exhibits excellent comprehensive properties in many aspects, including excellent thermal stability (thermal decomposition temperature T d5% >440°C), good hydrophobicity (contact angle greater than 100°), and excellent mechanical properties. The molecular design method provided by this invention paves the way for the development of new low-dielectric constant materials and demonstrates an effective strategy for improving the performance of electronic packaging technology. #imgabs0# Formula I.

Description

Technical Field

[0001] The invention relates to a high-performance benzocyclobutene-based polynorbornene composite material and a preparation method thereof, belonging to the technical field of high-performance electronic packaging resins. Background Art

[0002] With the rapid development of the integrated circuit industry, chip feature sizes are shrinking while internal wiring density is increasing significantly, leading to increasingly serious problems of resistance-capacitance delay, crosstalk noise, and power loss caused by metal resistance and parasitic capacitance between wiring layers. To solve these problems, the use of low-resistance metals such as copper is crucial, but even more critical is to reduce the inherent parasitic capacitance of the dielectric layer. Therefore, it is urgent to develop new low-k dielectric constant ( D k ) insulation materials to cope with the rapid advancement of information technology.

[0003] Introducing inorganic nanopores into polymers can effectively reduce the dielectric constant of composite materials. Polyhedral oligomeric siloxanes (POSS) are considered the basis for constructing such functional nanomaterials. POSS can be considered organic-inorganic hybrid nanostructures with different geometries and symmetries. Their potential lies in their ability to reduce the dielectric constant and dielectric loss of polymers including polyimides, bismaleimide resins, polyarylethers, polybenzoxazines, benzocyclobutene resins, polyolefins, cyanate ester resins, and epoxy resins, either alone or in combination with other materials.

[0004] However, industrially producing high-purity POSS on a large scale faces difficulties. Furthermore, POSS has inherent limitations. Besides the long production cycle and high cost, increasing the number of POSS particles incorporated into the polymer matrix can lead to particle aggregation and phase separation. To address these issues, it is necessary to establish chemical linkages between POSS and polymer chains, facilitating the production of various nanocomposites in a "bottom-up" manner to overcome these challenges.

[0005] Ring-opening polymerization (ROMP) has become a powerful and widely used technique for synthesizing polymer materials. Norbornene-based monomers are widely employed due to their high ring strain, which promotes efficient polymerization propagation. Furthermore, these monomers can be easily modified with various functional groups, enabling the synthesis of polymers with unique structures and properties. Due to this versatility, polynorbornenes with pendant groups have attracted considerable attention in nanocomposite research, ensuring excellent properties such as mechanical integrity and highly dispersed inorganic nanodomains. However, systematic experimental studies are currently lacking to clarify the specific effects of topological structure and particle dispersion on dielectric properties during efficient ROMP of organic-inorganic copolymers.

[0006] Currently, there is an urgent need to develop a simple and efficient "bottom-up" synthesis strategy and carefully design the types and proportions of suspended silane groups in the ROMP main chain to optimize the chemical structure and properties of the resin material, thereby meeting the growing demand for BCB resins with different performance in the advanced electronic packaging and low dielectric composite materials markets. Summary of the Invention

[0007] The purpose of the present invention is to provide a high-performance benzocyclobutene-based polynorbornene composite material. This new material has good comprehensive dielectric material properties, including thermal stability, good hydrophobicity and good mechanical properties. The molecular method of the composite material provided by the invention paves the way for the design of new low Dk materials and demonstrates an effective strategy for improving the performance of electronic packaging technology.

[0008] The benzocyclobutene-based polynorbornene crosslinked polymer provided by the present invention has a structural formula as shown in Formula I:

[0009]

[0010] Formula I

[0011] Wherein, R1, R2, and R3 are independently selected from C1-C4 alkyl or oxy groups;

[0012] The alkyl group can be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc.

[0013] The oxy group may be a methoxy group or an ethoxy group;

[0014] The value range of x is 1-100; the value range of y is 1-100.

[0015] The relationship formula of the high-performance benzocyclobutene-based polynorbornene composite material of the present invention can be expressed as C-XD-YB or C-XT-YB;

[0016] Wherein: D / T represents a polysiloxane cross-linked polymer; B represents a benzocyclobutene polymer;

[0017] Specifically, the high-performance benzocyclobutene-based polynorbornene composite material of the present invention is any one or more of the following polymers:

[0018] 1) Polymer H-0D-100B: R1 is methyl, R2 and R3 are oxy groups, x is 0, and y is 100;

[0019] 2) Polymer H-1D-99B: R1 is methyl, R2 and R3 are oxy groups, x is 1, and y is 99;

[0020] 3) Polymer H-3D-97B: R1 is methyl, R2 and R3 are oxy groups, x is 3, and y is 97;

[0021] 4) Polymer H-5D-95B: R1 is methyl, R2 and R3 are oxy groups, x is 5, and y is 95;

[0022] 5) Polymer H-10D-90B: R1 is methyl, R2 and R3 are oxy groups, x is 10, and y is 90;

[0023] 6) Polymer H-20D-80B: R1 is methyl, R2 and R3 are oxy groups, x is 20, and y is 80;

[0024] 7) Polymer H-30D-70B: R1 is methyl, R2 and R3 are oxy groups, x is 30, and y is 70;

[0025] 8) Polymer H-0T-100B: R1, R2 and R3 are oxy groups, x is 0, and y is 100;

[0026] 9) Polymer H-1T-99B: R1, R2 and R3 are oxy groups, x is 1, and y is 99;

[0027] 10) Polymer H-3T-97B: R1, R2 and R3 are oxy groups, x is 3, and y is 97;

[0028] 11) Polymer H-5T-95B: R1, R2 and R3 are oxy groups, x is 5, and y is 95;

[0029] 12) Polymer H-10T-90B: R1, R2 and R3 are oxy groups, x is 10, and y is 90;

[0030] 13) Polymer H-20T-80B: R1, R2 and R3 are oxy groups, x is 20, and y is 80;

[0031] 14) Polymer H-30T-70B: R1, R2 and R3 are oxy groups, x is 30, and y is 70.

[0032] The present invention also provides a method for preparing the high-performance benzocyclobutene-based polynorbornene composite material, comprising the following steps:

[0033] S1 and 5-vinylbicyclo[2.2.1]hept-2-ene are subjected to hydrosilylation reaction with dimethoxysilane hydride or trimethoxysilane hydride in the presence of catalyst I to obtain siloxane precursor II and siloxane precursor III;

[0034] The structure of the 5-vinylbicyclo[2.2.1]hept-2-ene is ;

[0035] The structures of the dimethoxysilane and the trimethoxysilane monomers are respectively 、 ;

[0036] The structures of the siloxane precursor II and the siloxane precursor III are respectively 、 ;

[0037] S2, 5-vinylbicyclo[2.2.1]hept-2-ene and silylbenzenecyclobutene undergo a hydrosilylation reaction under the action of the catalyst I to obtain a norbornene-modified benzocyclobutene monomer;

[0038] The structure of the silicon hydrogen benzocyclobutene is ;

[0039] The structure of the benzocyclobutene precursor IV is ;

[0040] S3, the siloxane precursor II or the siloxane precursor III and the benzocyclobutene precursor IV undergo ROMP polymerization reaction under the action of catalyst II to obtain a linear benzocyclobutene-based polynorbornene represented by formula V;

[0041]

[0042] Formula V

[0043] In formula V, R1, R2, and R3 are selected from C1-C4 alkyl or alkoxy groups;

[0044] S4, the linear benzocyclobutenyl polynorbornene represented by formula V undergoes a condensation reaction under the action of catalyst III to obtain a benzocyclobutenyl polynorbornene cross-linked product represented by formula VI;

[0045]

[0046] Formula VI

[0047] In formula VI, R1, R2, and R3 are selected from C1-C-4 alkyl or oxy groups;

[0048] S5. The benzocyclobutene-based polynorbornene crosslinked product represented by formula VI is thermally cured at high temperature to generate the high-performance benzocyclobutene-based polynorbornene composite material.

[0049] In the preparation method of the present invention, in step S1, the molar ratio of the 5-vinylbicyclo[2.2.1]hept-2-ene to the dimethoxysilane or the trimethoxysilane is 1:1-1.5;

[0050] The catalyst I is a Karstedt catalyst;

[0051] The molar ratio of the catalyst I to the trimethoxysilane or the dimethoxysilane is 1:50-100;

[0052] The conditions of the hydrosilylation reaction are: temperature of 70-90° C. and time of 1-4 h.

[0053] In the preparation method of the present invention, in step S1, the molar ratio of the 5-vinylbicyclo[2.2.1]hept-2-ene to the silylbenzenecyclobutene is 1:1-1.5;

[0054] The molar ratio of the catalyst I to the silicon hydrogen benzocyclobutene is 1:50-60;

[0055] The conditions of the hydrosilylation reaction are: temperature of 70-90° C. and time of 1-4 h.

[0056] In the preparation method of the present invention, in step S3, the catalyst II is a Grubbs catalyst;

[0057] The molar ratio of the catalyst II to the benzocyclobutene precursor IV is 1:50-60;

[0058] The ROMP polymerization reaction is carried out in an organic solvent I, wherein the organic solvent I is one or more of tetrahydrofuran, toluene, dichloromethane and dioxane;

[0059] The conditions of the ROMP polymerization reaction are: temperature of 20-40° C. and time of 1-3 h.

[0060] According to the different types of precursors and the introduction ratios, the silsesquioxane precursors shown in Formula V include crosslinked products 0D-100B, crosslinked products 1D-99B, crosslinked products 3D-97B, crosslinked products 5D-95B, crosslinked products 10D-90B, crosslinked products 20D-80B, crosslinked products 30D-70B crosslinked products 1T-99B, crosslinked products 3T-97B, crosslinked products 5T-95B, crosslinked products 10T-90B, crosslinked products 20T-80B, and crosslinked products 30T-70B;

[0061] in:

[0062] Cross-linked compound 0D-100B: R1 is methyl, R2 and R3 are methoxy, x is 0, and y is 100;

[0063] Cross-linked compound 1D-99B: R1 is methyl, R2 and R3 are methoxy, x is 1, and y is 99;

[0064] Cross-linked compound 3D-97B: R1 is methyl, R2 and R3 are methoxy, x is 3, and y is 97;

[0065] Cross-linked compound 5D-95B: R1 is methyl, R2 and R3 are methoxy, x is 5, and y is 95;

[0066] Cross-linked compound 10D-90B: R1 is methyl, R2 and R3 are methoxy, x is 10, and y is 90;

[0067] Cross-linked compound 20D-80B: R1 is methyl, R2 and R3 are methoxy, x is 20, and y is 80;

[0068] Cross-linked compound 30D-70B: R1 is methyl, R2 and R3 are methoxy, x is 30, and y is 70;

[0069] Cross-linked compound 0T-100B: R1, R2 and R3 are methoxy, x is 0, and y is 100;

[0070] Cross-linked compound 1T-99B: R1, R2 and R3 are methoxy, x is 1, and y is 99;

[0071] Cross-linked compound 3T-97B: R1, R2 and R3 are methoxy, x is 3, and y is 97;

[0072] Cross-linked compound 5T-95B: R1, R2 and R3 are methoxy, x is 5, and y is 95;

[0073] Cross-linked compound 10T-90B: R1, R2 and R3 are methoxy, x is 10, and y is 90;

[0074] Cross-linked compound 20T-80B: R1, R2 and R3 are methoxy, x is 20, and y is 80;

[0075] Cross-linked compound 30T-70B: R1, R2 and R3 are methoxy, x is 30, and y is 70;

[0076] In the preparation method of the present invention, in step S4, the catalyst III is one or more of hydrochloric acid, sulfuric acid, nitric acid and trifluoroacetic acid;

[0077] By adding the catalyst III, the pH of the reaction system is adjusted to 3-6;

[0078] The condensation reaction is carried out in an organic solvent II; the organic solvent II is one or more of tetrahydrofuran, dioxane, acetonitrile and dimethyl sulfoxide;

[0079] The condensation reaction conditions are: temperature 20-30°C, time 12-15h;

[0080] In the preparation method of the present invention, in step S5, the temperature of the thermal curing can be 250-350°C.

[0081] The present invention further provides a packaging material, which is made of the above-mentioned benzocyclobutene-based polynorbornene composite material.

[0082] Compared with the prior art, the present invention has the following beneficial effects:

[0083] This invention uses an innovative "bottom-up" synthesis strategy to produce high-performance benzocyclobutene-based polynorbornene composites. This method uses ROMP polymerization to covalently integrate organoalkoxysilane and BCB as pendant groups of polynorbornene. After hydrolysis and programmed thermal curing, these linear polymers can be fully cross-linked to form ladder-shaped or network-like siloxane structures with inherent porosity. 0 -10 6 In the Hz frequency range, the material of the present invention exhibits a stable low dielectric constant (dielectric constant <2.25) and dielectric loss factor (dielectric loss <2.27×10⁻³). In addition, the new material of the present invention exhibits excellent comprehensive properties in many aspects, including excellent thermal stability (thermal decomposition temperature T d5% >440°C), good hydrophobicity (contact angle greater than 100°), and excellent mechanical properties. The molecular design approach provided by this invention paves the way for the development of new low-dielectric-constant materials and demonstrates an effective strategy for improving the performance of electronic packaging technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0084] Figure 1 This is the H-NMR spectrum of the trimethoxysilicon precursor (TMSi) prepared in Example 1 of the present invention;

[0085] Figure 2 This is the H NMR spectrum of the dimethoxysilicon precursor (DMSi) prepared in Example 1 of the present invention;

[0086] Figure 3 This is the H NMR spectrum of the benzocyclobutene silicon hydride precursor prepared in Example 1 of the present invention;

[0087] Figure 4 This is the H NMR spectrum of the linear 0D-100B cross-linked product prepared in Example 1 of the present invention;

[0088] Figure 5 This is a comparison chart of dielectric properties tests of 12 kinds of cured products prepared in Example 4 of the present invention;

[0089] Figure 6 This is a comparison chart of thermal stability tests of 12 cured products prepared in Example 4 of the present invention;

[0090] Figure 7 This is a comparison chart of mechanical properties tests of 12 kinds of cured products prepared in Example 4 of the present invention;

[0091] Figure 8 This is a comparison chart of contact angle tests of 12 kinds of cured products prepared in Example 4 of the present invention. DETAILED DESCRIPTION

[0092] The present invention will be further described below with reference to specific examples, but the present invention is not limited to the following examples.

[0093] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0094] Unless otherwise specified, the reagents, materials, instruments, etc. used in the following examples can be obtained from commercial sources.

[0095] Example 1. Preparation of ROMP polymer precursor

[0096] Under an inert atmosphere, Karstedt's catalyst (1.92 g, 5 mmol) was dissolved in 5-vinylbicyclo[2.2.1]hept-2-ene (69.2 g, 200 mmol) and added to a 250 mL three-necked flask. Nitrogen was bubbled in an ice / water bath for 15 min, and trialkoxysilyl hydride (24.5 g, 200 mmol) was added under nitrogen protection. The mixture was heated in an oil bath for 2 h and then cooled to room temperature. Precursor III was subsequently obtained by vacuum distillation at a fraction temperature of 120°C.

[0097] According to the above operation steps, the trialkoxysilane monomer was replaced with a dialkoxysilane monomer and a benzocyclobutenesilane monomer, and the fractionation temperatures were 110°C and 180°C, respectively. The obtained precursors were recorded as Precursors II and IV, respectively.

[0098] The nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum of the precursor prepared in this example are as follows Figure 1-3 shown

[0099] Example 2: Preparation of linear benzocyclobutene-based polynorbornene polymer

[0100] Grubbs II catalyst, precursor II, and precursor IV were dissolved in anhydrous dichloromethane at a molar ratio of 2 / 0 / 100, 2 / 1 / 99, 2 / 3 / 97, 2 / 5 / 95, 2 / 10 / 90, 2 / 20 / 80, and 2 / 30 / 70 to a concentration of 10 mmol / 80 mL. Polymerization was carried out in a nitrogen atmosphere glove box for 30 minutes. The solvent was poured into methanol and the precipitated polymer was decanted. The above "redissolve and precipitate" step was repeated twice. The product was a viscous liquid and was designated XD-YB (X+Y=100; X=0, 1, 3, 5, 10, 20, 30).

[0101] Following the above steps, replace precursor formula II with precursor formula III, while keeping other parameters unchanged. These polymers are named XT-YB (X+Y=100; X=0, 1, 3, 5, 10, 20, 30).

[0102] The H NMR spectrum of the linear benzocyclobutene-based polynorbornene polymer 0X-100B prepared in this example is as follows: Figure 4 shown.

[0103] Example 3: Preparation of Benzocyclobutene-based Polynorbornene Crosslinked Products

[0104] Polymer XD-YB (10 mmol) was dissolved in 200 mL of tetrahydrofuran. Subsequently, an appropriate amount of 0.1 mol / L hydrochloric acid and 3 mL of deionized water were added to adjust the solution's pH to approximately 3. The mixture was stirred at room temperature for 10 hours, after which the solution was dried over anhydrous magnesium sulfate (MgSO₄). Subsequently, the solution was vacuum filtered using a small amount of silica gel to remove insoluble matter, and the solvent was removed by rotary evaporation. The resulting liquid was designated H-XD-YB.

[0105] According to the above operation steps, other parameters remained unchanged to prepare polymer H-XT-YB (X+Y=100; X=0, 1, 3, 5, 10, 20, 30).

[0106] Example 4: Preparation of Benzocyclobutene-Based Polynorbornene Composite Material

[0107] The disc-shaped mold product prepared in Example 3 was cured at 280° C. in a nitrogen atmosphere for 3 h; the composite resins after curing were C-XD-YB and C-XT-YB (X+Y=100; X=0, 1, 3, 5, 10, 20, 30), respectively.

[0108] The dielectric properties and thermodynamic properties of the 12 high-performance benzocyclobutene-based polynorbornene composite materials obtained in Example 4 were tested using the following test methods:

[0109] The test method for dielectric properties is: dielectric constant tester method.

[0110] The testing method for mechanical properties is: dynamic mechanical analyzer method.

[0111] The test method for thermal properties is: thermogravimetric analyzer method.

[0112] The test method for hydrophobicity is: contact angle tester.

[0113] Table 1 is a comparison of the dielectric properties, mechanical properties and thermal properties of different cured products. Figure 5 This is a comparison chart of the dielectric properties of different cured products. Figure 6 This is a comparison chart of thermal stability tests of different cured products. Figure 7 This is a comparison chart of mechanical properties tests of different cured products. Figure 8 This is a comparison chart of contact angle tests of different cured products.

[0114] Table 1 Comparison of dielectric properties, mechanical properties and thermal properties of different cured products

[0115]

[0116] From the above test results we can see that:

[0117] (1) Dielectric properties: as shown in Table 1 and Figure 5 As shown, at low frequencies 1-10 6 In the Hz range, the dielectric constants of the 12 cured products are all less than 2.6, and in particular, the dielectric constant of the C-5T-95B cured product is only 2.25. This shows that the cured product prepared by the present invention has excellent low dielectric properties.

[0118] (2) Mechanical properties: as shown in Table 1 and Figure 7 As shown in the figure, at room temperature, the storage moduli of the six cured products are higher than 3.4 GPa, with C-10D-90B and C-20T-80B in particular reaching 3.9 GPa and 4.1 GPa, respectively. This indicates that the cured products prepared by the present invention have excellent mechanical properties.

[0119] (3) Thermal properties: as shown in Table 1 and Figure 6 As shown, the thermal decomposition temperatures of the 12 cured products are at least 429° C., and in particular, the thermal decomposition temperature of C-10T-90B is as high as 443° C. This indicates that the cured products prepared by the present invention have stable thermal properties.

[0120] (4) Hydrophobic properties: such as Figure 8 As shown in the figure, the contact angles of the 12 cured products are all greater than 95°, especially the contact angle of C-5T-95B is as high as 105°. It can be seen that the cured product prepared by the present invention has good hydrophobicity.

[0121] Although the present invention has been described in detail above using general descriptions and specific embodiments, it will be apparent to those skilled in the art that modifications and improvements may be made based on the present invention. Therefore, such modifications and improvements, which do not depart from the spirit of the present invention, are intended to be within the scope of protection claimed herein.

Claims

1. A benzocyclobutene-based polynorbornene composite material, the structural formula of which is shown in Formula I: Formula I In the formula, R1 is a C1-C4 alkyl group, R2 and R3 are methoxy or ethoxy; The x value range is 1-30; the y value range is 70-99.

2. The composite material according to claim 1, characterized in that: The benzocyclobutene-based polynorbornene composite material is any one of the following 1) to 12): 1) Composite material C-1D-99B: R1 is methyl, R2 and R3 are methoxy or ethoxy, x is 1, and y is 99; 2) Composite material C-3D-97B: R1 is methyl, R2 and R3 are methoxy or ethoxy, x is 3, and y is 97; 3) Composite material C-5D-95B: R1 is methyl, R2 and R3 are methoxy or ethoxy, x is 5, and y is 95; 4) Composite material C-10D-90B: R1 is methyl, R2 and R3 are methoxy or ethoxy, x is 10, and y is 90; 5) Composite material C-20D-80B: R1 is methyl, R2 and R3 are methoxy or ethoxy, x is 20, and y is 80; 6) Composite material C-30D-70B: R1 is methyl, R2 and R3 are methoxy or ethoxy, x is 30, and y is 70; 7) Composite material C-1T-99B: R1, R2 and R3 are methoxy or ethoxy, x is 1, and y is 99; 8) Composite material C-3T-97B: R1, R2 and R3 are methoxy or ethoxy, x is 3, and y is 97; 9) Composite material C-5T-95B: R1, R2 and R3 are methoxy or ethoxy, x is 5, and y is 95; 10) Composite material C-10T-90B: R1, R2 and R3 are methoxy or ethoxy, x is 10, and y is 90; 11) Composite material C-20T-80B: R1, R2 and R3 are methoxy or ethoxy, x is 20, and y is 80; 12) Composite material C-30T-70B: R1, R2 and R3 are methoxy or ethoxy, x is 30, and y is 70.

3. The method for preparing the benzocyclobutene-based polynorbornene composite material according to claim 1, comprising the following steps: S1 and 5-vinylbicyclo[2.2.1]hept-2-ene are subjected to hydrosilylation reaction with dimethoxysilane hydride or trimethoxysilane hydride in the presence of catalyst I to obtain siloxane precursor II and siloxane precursor III; S2, 5-vinylbicyclo[2.2.1]hept-2-ene and silylbenzenecyclobutene undergo a hydrosilylation reaction under the action of the catalyst I to obtain a benzocyclobutene precursor IV; S3, the siloxane precursor II or the siloxane precursor III and the benzocyclobutene precursor IV undergo ROMP polymerization reaction under the action of catalyst II to obtain a linear benzocyclobutene-based polynorbornene represented by formula V; Formula V In formula V, R1 is a C1-C4 alkyl group, and R2 and R3 are methoxy or ethoxy; S4, the linear benzocyclobutenyl polynorbornene represented by formula V undergoes a condensation reaction under the action of catalyst III to obtain a benzocyclobutenyl polynorbornene cross-linked product represented by formula VI; Formula VI In formula VI, R1 is a C1-C4 alkyl group, and R2 and R3 are methoxy or ethoxy; The value range of x is 1-30; the value range of y is 70-99; S5. The benzocyclobutene-based polynorbornene crosslinked product represented by formula VI is thermally cured at a high temperature to generate the benzocyclobutene-based polynorbornene composite material.

4. The preparation method according to claim 3, wherein: In step S1, the molar ratio of the 5-vinylbicyclo[2.2.1]hept-2-ene to the dimethoxysilane or the trimethoxysilane is 1:1-1.5; The catalyst I is a Karstedt catalyst; The molar ratio of the catalyst I to the trimethoxysilane or the dimethoxysilane is 1:50-100; The conditions of the hydrosilylation reaction are: temperature of 70-90° C. and time of 1-4 h.

5. The preparation method according to claim 3 or 4, characterized in that: In step S2, the molar ratio of the 5-vinylbicyclo[2.2.1]hept-2-ene to the silylbenzenecyclobutene is 1:1-1.5; The molar ratio of the catalyst I to the silicon hydrogen benzocyclobutene is 1:50-60; The conditions of the hydrosilylation reaction are: temperature of 70-90° C. and time of 1-4 h.

6. The preparation method according to claim 3 or 4, characterized in that: In step S2, the catalyst II is a Grubbs catalyst; The molar ratio of the catalyst II to the benzocyclobutene precursor IV is 1:50-60; The ROMP polymerization reaction is carried out in an organic solvent I, wherein the organic solvent I is one or more of tetrahydrofuran, toluene, dichloromethane and dioxane; The conditions of the ROMP polymerization reaction are: temperature of 20-40° C. and time of 1-3 h.

7. The preparation method according to claim 3 or 4, characterized in that: In step S3, the catalyst III is one or more of hydrochloric acid, sulfuric acid, nitric acid and trifluoroacetic acid; By adding the catalyst III, the pH of the reaction system is adjusted to 3-6; The condensation reaction is carried out in an organic solvent II; the organic solvent II is one or more of tetrahydrofuran, dioxane, acetonitrile and dimethyl sulfoxide; The conditions of the condensation reaction are: temperature of 20-30° C. and time of 12-15 h.

8. The preparation method according to claim 3 or 4, characterized in that: In step S5, the temperature of the thermal curing is 250-350°C.

9. A packaging material made from the benzocyclobutene-based polynorbornene composite material according to claim 1 or 2.

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