A high-frequency low-dielectric-loss benzocyclobutene resin and its preparation method and application

Abstract

The invention discloses a high-frequency low dielectric loss benzocyclobutene resin and its preparation method and application. The 1,3-position diene, benzocyclobutene group, vinyl compound, initiator and organic solvent are polymerized under the conditions of 5°C to 78°C and then treated to obtain a high-frequency low dielectric loss benzocyclobutene resin. The high-frequency low dielectric loss benzocyclobutene resin prepared by the present invention has excellent thermal stability, mechanical properties and dielectric properties after high-temperature curing. At a frequency of 10 GHz, its dielectric constant (Dk) is 2.35-2.60, dielectric loss (Df) is 0.0004-0.0007, T 5％ The thermal decomposition temperature is 442‑465°C, and the thermal expansion coefficient of the cured resin is 32‑88ppm / °C@50°C. Therefore, it can be used as high-temperature resistant dielectric materials, high-performance composite materials, electronic packaging materials, and aviation materials; it can be used in 5G / 6G high-frequency PCB boards and interlayer packaging of chips, etc.

Description

Technical Field

[0001] The invention relates to the field of thermosetting polyolefin materials, and in particular to a high-frequency low-dielectric-loss benzocyclobutene resin and a preparation method thereof, and an application thereof as a high-frequency low-dielectric-loss material. Background Art

[0002] Benzocyclobutene resins as thermosetting resins have the following advantages: they can be heat-cured by themselves without releasing small molecules, and the cured products have excellent heat resistance, extremely low thermal expansion coefficient, and excellent electrical and mechanical properties, making them popular in the fields of light, electricity, heat, etc., and are currently widely used in the fields of aviation, aerospace, microelectronics packaging, etc. Application scenarios include interlayer insulation materials, photoresist materials, electronic packaging materials, radar wave-transparent materials, high-density interconnection circuit boards, etc.

[0003] In recent years, due to the development demand of high frequency and high speed, the size of ultra-large-scale integrated circuits has gradually decreased, and the connection lines inside the chip have become more and more dense, resulting in a series of problems such as signal transmission delay, cross interference and increased power loss, which have a great impact on device performance. Using low-dielectric and low-loss materials as inter-electron layer dielectrics is one of the important solutions. Therefore, the design and synthesis of high-performance low-dielectric and low-loss materials has become a special concern of contemporary scientific researchers. Summary of the invention

[0004] An object of the present invention is to solve at least the above problems and / or disadvantages and to provide at least the advantages which will be described hereinafter.

[0005] The main purpose of the present invention is to provide a high-frequency low dielectric loss benzocyclobutene resin, which has better thermal stability, low thermal expansion performance and high-frequency low dielectric loss.

[0006] In order to achieve these purposes and other advantages according to the present invention, a high-frequency low dielectric loss benzocyclobutene resin is provided, and the structural formula of the benzocyclobutene resin is shown in formula (I):

[0007]

[0008] Wherein, x, y, z are all integers ≥ 1, w is an integer greater than or equal to 0; and the ratio of x+y to z+w is any value between 1:9 and 9:1;

[0009] R1 is -H or an unsubstituted alkyl group having 1 to 3 carbon atoms;

[0010] R2 is;

[0011] R3 is a substituted or unsubstituted alkyl group having 4 to 6 carbon atoms.

[0012] Preferably, the substitution in R3 refers to that one or more hydrogen atoms on the group are replaced by a substituent selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an unsubstituted phenyl group or a phenyl group in which 1 to 3 hydrogen atoms on the benzene ring are replaced by an alkyl group having 1 to 4 carbon atoms.

[0013] Preferably, R3 is replaced by one of substituted or unsubstituted phenyl, biphenyl, naphthyl, phenanthryl and anthracenyl.

[0014] Preferably, the substitution in R3 refers to that one or more hydrogen atoms on the aryl group are replaced by a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms.

[0015] The present invention also provides a method for preparing the high-frequency and low-dielectric-loss benzocyclobutene resin as described above, comprising:

[0016] The 1,3-position diene, benzocyclobutene group, vinyl compound, initiator and organic solvent are polymerized at -5 DEG C to -78 DEG C and then treated to obtain high-frequency and low-dielectric-loss benzocyclobutene resin.

[0017] Preferably, the 1,3-dienes are at least one of butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene and 2-methyl-1,3-pentadiene; and the benzocyclobutene group is 4-vinylbenzocyclobutene or 1-vinylbenzocyclobutene.

[0018] Preferably, the vinyl compound is at least one of hexene, vinyl cyclohexane, heptene, octene, styrene, 1-methylstyrene, 2-methylstyrene, p-methylstyrene, vinyl biphenyl, vinyl naphthalene and its substitutes, vinyl phenanthrene and its substitutes, vinyl anthracene and its substitutes; the initiator is at least one of n-butyl lithium, sec-butyl lithium, methyl lithium and sodium naphthalene, and the amount of the initiator is 0.001-10% of the molar number of the added material; the organic solvent is at least one of tetrahydrofuran, acetonitrile, 1,4-dioxane and n-hexane.

[0019] Preferably, the polymerization reaction time is 4-10 hours; the polymerization reaction post-treatment method is: pouring the reaction solution into 3-10 times methanol, filtering, dissolving in toluene, washing with water for multiple times, drying and concentrating to obtain high-frequency and low dielectric loss benzocyclobutene resin.

[0020] The present invention also provides an application of the high-frequency low dielectric loss benzocyclobutene resin as described above in a high-temperature resistant dielectric material. The high-frequency low dielectric loss benzocyclobutene resin has a dielectric constant Dk of 2.35-2.60, a dielectric loss Df of 0.0004-0.0007, and a T 5％The thermal decomposition temperature is 442-465°C, and the thermal expansion coefficient of the cured resin is 32-88ppm / °C@50°C.

[0021] The present invention also provides an application of the high-frequency, low-dielectric-loss benzocyclobutene resin as described above in electronic packaging materials, and the high-frequency, low-dielectric-loss benzocyclobutene resin is applied to 5G / 6G high-frequency PCB boards and interlayer packaging of chips.

[0022] The present invention has at least the following beneficial effects:

[0023] (1) The present invention provides a high-frequency, low-dielectric-loss benzocyclobutene resin having the advantages of adjustable molecular weight and adjustable glass transition temperature, which eliminates the cumbersome step of "prepolymerization" required for such resins and can be directly used in the next application, thereby greatly reducing production costs.

[0024] (2) The high-frequency and low-dielectric-loss benzocyclobutene resin prepared by the present invention has excellent thermal stability, mechanical properties and dielectric properties after high-temperature curing; at a frequency of 10 GHz, its dielectric constant (Dk) is 2.35-2.60, the dielectric loss (Df) is 0.0004-0.0007, and T 5％ The thermal decomposition temperature is 442-465℃, and the thermal expansion coefficient of the cured resin is 32-88ppm / ℃@50℃. Therefore, it can be used as high-temperature resistant dielectric materials, high-performance composite materials, electronic packaging materials and aviation materials; it can be used in 5G / 6G high-frequency PCB boards and interlayer packaging of chips, etc.

[0025] Other advantages, objectives and features of the present invention will be embodied in part through the following description, and in part will be understood by those skilled in the art through study and practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is the NMR spectrum of the polymer described in Example 1;

[0027] Figure 2 This is the GPC spectrum of the polymer described in Example 1;

[0028] Figure 3 is the rheological curve of the polymer described in Example 1;

[0029] Figure 4 This is the NMR spectrum of the polymer described in Example 2;

[0030] Figure 5 This is the GPC spectrum of the polymer described in Example 2;

[0031] Figure 6 This is the rheological curve of the polymer described in Example 2. DETAILED DESCRIPTION

[0032] It should be noted that the following detailed descriptions are exemplary and are intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.

[0033] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprising" and / or "including" are used in this specification, it indicates the presence of features, steps, operations and / or combinations thereof.

[0034] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below in conjunction with specific embodiments.

[0035] Embodiment 1:

[0036] A type of high frequency low dielectric loss benzocyclobutene resin,

[0037]

[0038] The preparation method is as follows:

[0039] In a 1L jacketed reactor, 32.5g (0.25mol) of 4-vinylbenzocyclobutene, 54g (1mol) of butadiene and 300mL of dry tetrahydrofuran were added in sequence, stirred evenly at -20°C, and then 15mL of n-butyllithium (1.6M, n-hexane solution) was added. After reacting for 6h, 3mL of methanol was added to quench the reaction. After returning to room temperature, the reaction solution was poured into 1L of methanol for precipitation and filtration. After the filter cake was dried, 500mL of toluene was added to dissolve it, and then it was washed with ultrapure water for several times, dried and concentrated to obtain a viscous benzocyclobutene resin 1 with a yield of 91%.

[0040] The structural characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.27-7.06 (3H, ArH), 6.92-6.85 (3H, =CH2), 5.-5.24 (19H, =CH2, -CH=CH-), 5.04-4.75 (12H, =CH2, -CH=CH-) 3.19 (s, 4H, -CH2-CH2-, four-membered ring), 2.25-1.82 (m, 15H, -CH1), 1.55-1 (m, 25H, -CH2CH 2- ). Figure 1This is the NMR spectrum of the polymer described in Example 1, where 3.19 is the characteristic displacement of the benzocyclobutene four-membered ring, 1-2 is the main chain methylene displacement of double bond polymerization, 4.85 and 5.2-5.7 are the main chain double bonds and side chain double bonds characteristic displacements formed by 1,2 polymerization and 1,4 polymerization of butadiene, respectively, indicating that copolymerization has been achieved. Random copolymer of benzocyclobutene resin 1, molecular weight of 5500, molecular weight distribution of 1.8.

[0041] Figure 2 This is the GPC spectrum of the polymer described in Example 1; it can be seen from the figure that it is a single peak with a narrow distribution, indicating that it is not a blend of two homopolymers.

[0042] Figure 3 This is the rheological curve of the polymer described in Example 1; it can be seen from the rheological curve that the copolymer 100 and 180°C reacted to cause a viscosity change, corresponding to the double bond and the four-membered ring, respectively.

[0043] Through feed ratio, NMR and molecular weight test, the specific molecular formula of polymer 1 can be calculated as follows:

[0044]

[0045] Through dielectric testing, the dielectric constant of the benzocyclobutene resin 1 random copolymer cured product at 10GHz is 2.51, and the dielectric loss is 0.00055; T 5％ The temperature is 453℃; the coefficient of thermal expansion is 88ppm / ℃@50-200℃.

[0046] Embodiment 2:

[0047] A type of high frequency low dielectric loss benzocyclobutene resin,

[0048]

[0049] The preparation method is as follows:

[0050] In a 1L jacketed reactor, 52g (0.4mol) of 4-vinylbenzocyclobutene, 32.4g (0.6mol) of butadiene and 300mL of dry tetrahydrofuran were added in sequence, stirred evenly at -20°C, and then 15mL of n-butyllithium (1.6M, n-hexane solution) was added. After reacting for 6h, 3mL of methanol was added to quench the reaction. After returning to room temperature, the reaction solution was poured into 1L of methanol for precipitation and filtration. After the filter cake was dried, 500mL of toluene was added to dissolve it, and then it was washed with ultrapure water for several times, dried and concentrated to obtain a viscous benzocyclobutene resin 2 with a yield of 94%.

[0051] The structural characterization is as follows: 1H NMR (400 MHz, CDCl3) δ (ppm): 7.27-7.06 (3H, ArH), 6.92-6.85 (3H, = CH2), 5.-5.24 (13H, = CH2, -CH = CH-), 5.04-4.75 (12H, = CH2, -CH = CH-) 3.19 (s, 4H, -CH2-CH2-, four-membered ring), 2.25-1.82 (m, 12H, -CH1), 1.55-1 (m, 16H, -CH2CH 2- ). Figure 4 This is the NMR spectrum of the polymer described in Example 2, where 3.19 is the characteristic displacement of the benzocyclobutene four-membered ring, 1-2 is the main chain methylene displacement of double bond polymerization, 4.85 and 5.2-5.7 are the main chain double bonds and side chain double bonds characteristic displacements formed by 1,2 polymerization and 1,4 polymerization of butadiene, respectively, indicating that copolymerization has been achieved. Random copolymer of benzocyclobutene resin 2, molecular weight of 6800, molecular weight distribution of 1.75.

[0052] Figure 5 This is the GPC spectrum of the polymer described in Example 2; it can be seen from the figure that it is a single peak and the distribution is narrow, indicating that it is not a blend of two homopolymers.

[0053] Figure 6 This is the rheological curve of the polymer described in Example 2. From the rheological curve, it can be seen that the copolymer 100 and 180°C reacted to cause a viscosity change, which corresponded to the double bond and the four-membered ring, respectively.

[0054] Through feed ratio, NMR and molecular weight test, the specific molecular formula of polymer 2 can be calculated as follows:

[0055]

[0056] Through dielectric testing, the dielectric constant of the benzocyclobutene resin 2 random copolymer cured product is 2.54 and the dielectric loss is 0.0006 at 10GHz; T 5％ The temperature is 455℃; the coefficient of thermal expansion is 48ppm / ℃@50-200℃.

[0057] Embodiment 3:

[0058] A type of high frequency low dielectric loss benzocyclobutene resin,

[0059]

[0060] The preparation method is as follows:

[0061] In a 1L jacketed reactor, 26g (0.2mol) 4-vinylbenzocyclobutene, 31.2g (0.3mol) styrene, 27g (0.5mol) butadiene and 300mL dry tetrahydrofuran were added in sequence, stirred evenly at -20°C, and then 15mL n-butyllithium (1.6M, n-hexane solution) was added. After reacting for 6h, 3mL methanol was added to quench the reaction. After returning to room temperature, the reaction solution was poured into 1L methanol for precipitation and filtration. After the filter cake was dried, 500mL toluene was added to dissolve it, and then it was washed with ultrapure water for several times, dried and concentrated to obtain viscous benzocyclobutene resin 3 with a yield of 92%.

[0062] The structural characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.27-7.06 (8H, ArH), 5.45-5.04 (7.5H, =CH2, -CH=CH-), 3.19 (s, 4H, -CH2-CH2-, four-membered ring), 2.35 (m, 5H, -CH1), 1.55 (m, 14H, -CH2CH 2- ). Benzocyclobutene resin 3 random copolymer, molecular weight is 6800, molecular weight distribution is 1.9.

[0063] The specific molecular formula of polymer 3 is:

[0064]

[0065] Through dielectric testing, the dielectric constant of the benzocyclobutene resin 3 random copolymer cured product at 10GHz is 2.56 and the dielectric loss is 0.00055; T 5％ The temperature is 458℃; the coefficient of thermal expansion is 45ppm / ℃@50-200℃.

[0066] Embodiment 4:

[0067] A type of high frequency low dielectric loss benzocyclobutene resin,

[0068]

[0069] The preparation method is as follows:

[0070] In a 1L jacketed reactor, 26g (0.2mol) of 4-vinylbenzocyclobutene, 54.6g (0.3mol) of 4-vinylbiphenyl, 27g (0.5mol) of butadiene and 300mL of dry tetrahydrofuran were added in sequence, stirred evenly at -20°C, and then 15mL of n-butyllithium (1.6M, n-hexane solution) was added. After reacting for 6h, 3mL of methanol was added to quench the reaction. After returning to room temperature, the reaction solution was poured into 1L of methanol for precipitation and filtration. After the filter cake was dried, 500mL of toluene was added to dissolve it, and then it was washed with ultrapure water for several times, dried and concentrated to obtain a viscous benzocyclobutene resin 4 with a yield of 85%.

[0071] The structural characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.27-7.06 (12H, ArH), 5.45-5.04 (7.5H, =CH2, -CH=CH-), 3.19 (s, 4H, -CH2-CH2-, four-membered ring), 2.35 (m, 5H, -CH1), 1.55 (m, 14H, -CH2CH 2- ). Benzocyclobutene resin 4 random copolymer, molecular weight is 6400, molecular weight distribution is 2.1.

[0072] The specific molecular formula of polymer 4 is:

[0073]

[0074] Through dielectric testing, the dielectric constant of benzocyclobutene resin 4 random copolymer cured product is 2.52 and the dielectric loss is 0.0006 at 10GHz; T 5％ The temperature is 461℃; the coefficient of thermal expansion is 74ppm / ℃@50-200℃.

[0075] Embodiment 5:

[0076] A type of high frequency low dielectric loss benzocyclobutene resin,

[0077]

[0078] The preparation method is as follows:

[0079] In a 1L jacketed reactor, 52g (0.4mol) 4-vinylbenzocyclobutene, 40.8g (0.6mol) isoprene and 300mL dry tetrahydrofuran were added in sequence, stirred evenly at -20°C, and then 15mL n-butyllithium (1.6M, n-hexane solution) was added. After reacting for 6h, 3mL methanol was added to quench the reaction. After returning to room temperature, the reaction solution was poured into 1L methanol for precipitation and filtration. After the filter cake was dried, 500mL toluene was added to dissolve it, and then ultrapure water was washed several times, dried and concentrated to obtain a viscous benzocyclobutene resin 5 with a yield of 86%. The structural characterization is as follows:1 H NMR (400 MHz, CDCl3) δ (ppm): 7.27-7.06 (3H, ArH), 5.45-5.04 (8.5H, =CH2, -CH=CH-), 3.19 (s, 4H, -CH2-CH2-, four-membered ring), 2.35 (m, 2.6H, -CH1), 1.88 (m, 4.5H, =CH-CH3), 1.55 (m, 12H, -CH2CH 2- ),0.88(s,4.5H,-CH3),. Benzocyclobutene resin 5 random copolymer, molecular weight is 7100, molecular weight distribution is 1.8.

[0080] Through dielectric testing, the dielectric constant of the benzocyclobutene resin 5 random copolymer cured product at 10GHz is 2.52 and the dielectric loss is 0.0006; T 5％ The temperature is 452℃; the coefficient of thermal expansion is 64ppm / ℃@50-200℃.

[0081] Embodiment 6:

[0082] A type of high frequency low dielectric loss benzocyclobutene resin,

[0083]

[0084] The preparation method is as follows:

[0085] In a 1L jacketed reactor, 26g (0.2mol) 1-vinylbenzocyclobutene, 31.2g (0.3mol) styrene, 27g (0.5mol) butadiene and 300mL dry tetrahydrofuran were added in sequence, stirred evenly at -30°C, and then 15mL n-butyllithium (1.6M, n-hexane solution) was added. After reacting for 6h, 3mL methanol was added to quench the reaction. After returning to room temperature, the reaction solution was poured into 1L methanol for precipitation and filtration. After the filter cake was dried, 500mL toluene was added to dissolve it, and then it was washed with ultrapure water for several times, dried and concentrated to obtain a viscous benzocyclobutene resin 6 with a yield of 90%.

[0086] The structural characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.27-7.06 (8H, ArH), 5.45-5.04 (7.5H, =CH2, -CH=CH-), 3.32 (s, 1H, -CH1, four-membered ring), 3.19 (dd, 2H, -CH2-CH2-, four-membered ring), 2.35 (m, 5H, -CH1), 1.55 (m, 14H, -CH2CH 2- ). Benzocyclobutene resin 6 random copolymer, molecular weight is 6900, molecular weight distribution is 2.2.

[0087] The specific molecular formula of polymer 6 is:

[0088]

[0089] Through dielectric testing, the dielectric constant of benzocyclobutene resin 6 random copolymer cured product is 2.52 and the dielectric loss is 0.00055 at 10GHz; T 5％ The temperature is 450℃; the coefficient of thermal expansion is 61ppm / ℃@50-200℃.

[0090] Embodiment 7:

[0091] A type of high frequency low dielectric loss benzocyclobutene resin,

[0092]

[0093] The preparation method is as follows:

[0094] In a 1L jacketed reactor, 52g (0.4mol) 4-vinylbenzocyclobutene, 62.4g (0.6mol) styrene, 27g (0.5mol) butadiene and 400mL dry tetrahydrofuran were added in sequence, stirred evenly at -30°C, and then 12mL n-butyllithium (1.6M, n-hexane solution) was added. After reacting for 6h, 3mL methanol was added to quench the reaction. After returning to room temperature, the reaction solution was poured into 1L methanol for precipitation and filtration. After the filter cake was dried, 500mL toluene was added to dissolve it, and then it was washed with ultrapure water for several times, dried and concentrated to obtain a viscous benzocyclobutene resin 7 with a yield of 92%.

[0095] The structural characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.27-7.06 (9H, ArH), 5.45-5.04 (7.5H, =CH2, -CH=CH-), 3.19 (s, 4H, -CH2-CH2-, four-membered ring), 2.35 (m, 5H, -CH1), 1.55 (m, 16H, -CH2CH 2- ). Benzocyclobutene resin 7 random copolymer, molecular weight is 7400, molecular weight distribution is 2.05.

[0096] The specific molecular formula of polymer 7 is:

[0097]

[0098] Through dielectric testing, the dielectric constant of the benzocyclobutene resin 7 random copolymer cured product is 2.55 and the dielectric loss is 0.0005 at 10GHz; T 5％ The temperature is 451℃; the coefficient of thermal expansion is 58ppm / ℃@50-200℃.

[0099] Embodiment 8:

[0100] A type of high frequency low dielectric loss benzocyclobutene resin,

[0101]

[0102] The preparation method is as follows:

[0103] In a 1L jacketed reactor, 26g (0.2mol) of 4-vinylbenzocyclobutene, 54.6g (0.3mol) of 4-vinylbiphenyl, 27g (0.5mol) of butadiene and 300mL of dry tetrahydrofuran were added in sequence, stirred evenly at -30°C, and then 12mL of n-butyllithium (1.6M, n-hexane solution) was added. After reacting for 8h, 3mL of methanol was added to quench the reaction. After returning to room temperature, the reaction solution was poured into 1L of methanol for precipitation and filtration. After the filter cake was dried, 500mL of toluene was added to dissolve it, and then it was washed with ultrapure water for several times, dried and concentrated to obtain a viscous benzocyclobutene resin 8 with a yield of 87%.

[0104] The structural characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.27-7.06 (12H, ArH), 5.45-5.04 (7.5H, =CH2, -CH=CH-), 3.19 (s, 4H, -CH2-CH2-, four-membered ring), 2.35 (m, 5H, -CH1), 1.55 (m, 14H, -CH2CH 2- ). Benzocyclobutene resin 8 random copolymer, molecular weight is 7600, molecular weight distribution is 1.95.

[0105] The specific molecular formula of polymer 8 is:

[0106]

[0107] Through dielectric testing, the dielectric constant of benzocyclobutene resin 8 random copolymer cured product is 2.52 and the dielectric loss is 0.0006 at 10GHz; T 5％ The temperature is 460℃; the coefficient of thermal expansion is 42ppm / ℃@50-200℃.

[0108] Embodiment 9:

[0109] A type of high frequency low dielectric loss benzocyclobutene resin,

[0110]

[0111] The preparation method is as follows:

[0112] In a 1L jacketed reactor, 26g (0.2mol) of 4-vinylbenzocyclobutene, 54.6g (0.3mol) of 4-vinylbiphenyl, 27g (0.5mol) of butadiene and 300mL of dry tetrahydrofuran were added in sequence, stirred evenly at -40°C, and then 12mL of n-butyllithium (1.6M, n-hexane solution) was added. After reacting for 8h, 3mL of methanol was added to quench the reaction. After returning to room temperature, the reaction solution was poured into 1L of methanol for precipitation and filtration. After the filter cake was dried, 500mL of toluene was added to dissolve it, and then it was washed with ultrapure water for several times, dried and concentrated to obtain a viscous benzocyclobutene resin 9 with a yield of 87%.

[0113] The structural characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.27-7.06 (12H, ArH), 5.45-5.04 (7.5H, =CH2, -CH=CH-), 3.19 (s, 4H, -CH2-CH2-, four-membered ring), 2.35 (m, 5H, -CH1), 1.55 (m, 14H, -CH2CH 2- ). Benzocyclobutene resin 9 random copolymer, molecular weight is 7400, molecular weight distribution is 1.92.

[0114] The specific molecular formula of polymer 9 is:

[0115]

[0116] Through dielectric testing, the dielectric constant of the benzocyclobutene resin 9 random copolymer cured product is 2.52 and the dielectric loss is 0.0006 at 10GHz; T 5％ The temperature is 460℃; the coefficient of thermal expansion is 40ppm / ℃@50-200℃.

[0117] Embodiment 10:

[0118] A type of high frequency low dielectric loss benzocyclobutene resin,

[0119]

[0120] The preparation method is as follows:

[0121] In a 1L jacketed reactor, 52g (0.4mol) 4-vinylbenzocyclobutene, 62.4g (0.6mol) styrene, 27g (0.5mol) butadiene and 400mL dry tetrahydrofuran were added in sequence, stirred evenly at -40°C, and then 12mL n-butyllithium (1.6M, n-hexane solution) was added. After reacting for 6h, 3mL methanol was added to quench the reaction. After returning to room temperature, the reaction solution was poured into 1L methanol for precipitation and filtration. After the filter cake was dried, 500mL toluene was added to dissolve it, and then it was washed with ultrapure water for several times, dried and concentrated to obtain a viscous benzocyclobutene resin 10 with a yield of 93%.

[0122] The structural characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.27-7.06 (9H, ArH), 5.45-5.04 (7.5H, =CH2, -CH=CH-), 3.19 (s, 4H, -CH2-CH2-, four-membered ring), 2.35 (m, 5H, -CH1), 1.55 (m, 16H, -CH2CH 2- ). Benzocyclobutene resin 10 random copolymer, molecular weight of 7800, molecular weight distribution of 1.75.

[0123] The specific molecular formula of polymer 10 is:

[0124]

[0125] Through dielectric testing, the dielectric constant of the benzocyclobutene resin 7 random copolymer cured product is 2.55 and the dielectric loss is 0.0005 at 10GHz; T 5％ The temperature is 451℃; the coefficient of thermal expansion is 58ppm / ℃@50-200℃.

[0126] Embodiment 11:

[0127] A type of high frequency low dielectric loss benzocyclobutene resin,

[0128]

[0129] The preparation method is as follows:

[0130] In a 1L jacketed reactor, 26g (0.2mol) 1-vinylbenzocyclobutene, 31.2g (0.3mol) styrene, 27g (0.5mol) butadiene and 300mL dry tetrahydrofuran were added in sequence, stirred evenly at -50°C, and then 15mL n-butyllithium (1.6M, n-hexane solution) was added. After reacting for 6h, 3mL methanol was added to quench the reaction. After returning to room temperature, the reaction solution was poured into 1L methanol for precipitation and filtration. After the filter cake was dried, 500mL toluene was added to dissolve it, and then it was washed with ultrapure water for several times, dried and concentrated to obtain a viscous benzocyclobutene resin 11 with a yield of 90%.

[0131] The structural characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.27-7.06 (8H, ArH), 5.45-5.04 (7.5H, =CH2, -CH=CH-), 3.32 (s, 1H, -CH1, four-membered ring), 3.19 (dd, 2H, -CH2-CH2-, four-membered ring), 2.35 (m, 5H, -CH1), 1.55 (m, 14H, -CH2CH 2- ). Benzocyclobutene resin 11 random copolymer, molecular weight of 7400, molecular weight distribution of 1.94.

[0132] The specific molecular formula of polymer 11 is:

[0133]

[0134] Through dielectric testing, the dielectric constant of the benzocyclobutene resin 11 random copolymer cured product at 10GHz is 2.52 and the dielectric loss is 0.00055; T 5％ The temperature is 450℃; the coefficient of thermal expansion is 61ppm / ℃@50-200℃.

[0135] Embodiment 12:

[0136] A type of high frequency low dielectric loss benzocyclobutene resin,

[0137]

[0138] The preparation method is as follows:

[0139] In a 1L jacketed reactor, 26g (0.2mol) 1-vinylbenzocyclobutene, 31.2g (0.3mol) styrene, 27g (0.5mol) butadiene and 300mL dry tetrahydrofuran were added in sequence, stirred evenly at -60°C, and then 12mL n-butyllithium (1.6M, n-hexane solution) was added. After reacting for 8h, 3mL methanol was added to quench the reaction. After returning to room temperature, the reaction solution was poured into 1L methanol for precipitation and filtration. After the filter cake was dried, 500mL toluene was added to dissolve it, and then it was washed with ultrapure water for several times, dried and concentrated to obtain viscous benzocyclobutene resin 12 with a yield of 92%.

[0140] The structural characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.27-7.06 (8H, ArH), 5.45-5.04 (7.5H, =CH2, -CH=CH-), 3.32 (s, 1H, -CH1, four-membered ring), 3.19 (dd, 2H, -CH2-CH2-, four-membered ring), 2.35 (m, 5H, -CH1), 1.55 (m, 14H, -CH2CH 2- ). Benzocyclobutene resin 12 random copolymer, molecular weight is 8100, molecular weight distribution is 1.78.

[0141] The specific molecular formula of polymer 12 is:

[0142]

[0143] Through dielectric testing, the dielectric constant of benzocyclobutene resin 12 random copolymer cured product is 2.52 and the dielectric loss is 0.00055 at 10GHz; T 5％ The temperature is 450℃; the coefficient of thermal expansion is 61ppm / ℃@50-200℃.

[0144] Embodiment 13:

[0145] A type of high frequency low dielectric loss benzocyclobutene resin,

[0146]

[0147] The preparation method is as follows:

[0148] In a 1L jacketed reactor, 52g (0.4mol) of 4-vinylbenzocyclobutene, 62.4g (0.6mol) of styrene, 27g (0.5mol) of butadiene and 400mL of dry tetrahydrofuran were added in sequence, stirred evenly at -40°C, and 10mL of sodium naphthalene solution (homemade, 2.5M) was added. After reacting for 8h, 3mL of methanol was added to quench the reaction. After returning to room temperature, the reaction solution was poured into 1L of methanol for precipitation and filtration. After the filter cake was dried, 500mL of toluene was added to dissolve it, and then it was washed with ultrapure water for several times, dried and concentrated to obtain viscous benzocyclobutene resin 13 with a yield of 81%.

[0149] The structural characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ (ppm): 7.27-7.06 (9H, ArH), 5.45-5.04 (7.5H, =CH2, -CH=CH-), 3.19 (s, 4H, -CH2-CH2-, four-membered ring), 2.35 (m, 5H, -CH1), 1.55 (m, 16H, -CH2CH 2- ). Benzocyclobutene resin 13 random copolymer, molecular weight of 5800, molecular weight distribution of 1.95.

[0150] The specific molecular formula of polymer 13 is:

[0151]

[0152] Through dielectric testing, the dielectric constant of the benzocyclobutene resin 13 random copolymer cured product at 10GHz is 2.55 and the dielectric loss is 0.0005; T 5％ The temperature is 451℃; the coefficient of thermal expansion is 58ppm / ℃@50-200℃.

[0153] Application Example 1:

[0154] An application of a high-frequency low dielectric loss benzocyclobutene resin prepared by any of the above embodiments in a high temperature resistant dielectric material, wherein the high-frequency low dielectric loss benzocyclobutene resin has a dielectric constant Dk of 2.35-2.60, a dielectric loss Df of 0.0004-0.0007, and a T 5％ The thermal decomposition temperature is 442-465℃, and the thermal expansion coefficient of the cured resin is 32-88ppm / ℃@50-200℃.

[0155] Application Example 2:

[0156] An application of a high-frequency, low-dielectric-loss benzocyclobutene resin prepared as described in any of the above embodiments in electronic packaging materials, wherein the high-frequency, low-dielectric-loss benzocyclobutene resin is applied to 5G / 6G high-frequency PCB boards and interlayer packaging of chips.

[0157] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes, and they can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and the illustrations shown and described herein.

Claims

1. A high frequency and low dielectric loss benzocyclobutene resin, characterized in that: The structural formula of the benzocyclobutene resin is shown in formula (I): Wherein, x, y, z are all integers ≥ 1, w is an integer greater than or equal to 0; and the ratio of x+y to z+w is any value between 1:9 and 9:1; R1 is -H or an unsubstituted alkyl group having 1 to 3 carbon atoms; R2 is; R3 is a substituted or unsubstituted alkyl group having 4 to 6 carbon atoms.

2. The high-frequency low dielectric loss benzocyclobutene resin according to claim 1, characterized in that: The substitution in R3 refers to that one or more hydrogen atoms on the group are replaced by a substituent selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an unsubstituted phenyl group or a phenyl group in which 1 to 3 hydrogen atoms on the benzene ring are replaced by an alkyl group having 1 to 4 carbon atoms.

3. The high-frequency low dielectric loss benzocyclobutene resin according to claim 1, characterized in that: R3 is replaced by one of substituted or unsubstituted phenyl, biphenyl, naphthyl, phenanthryl and anthracenyl.

4. The high-frequency low dielectric loss benzocyclobutene resin according to claim 3, characterized in that: The substitution in R3 refers to that one or more hydrogen atoms on the aryl group are replaced by a substituent selected from the following group: an alkyl group having 1 to 6 carbon atoms.

5. The method for preparing a high-frequency, low-dielectric-loss benzocyclobutene resin according to any one of claims 1 to 4, characterized in that: include: 1,3-diolefins, benzocyclobutene groups, vinyl compounds, The initiator and the organic solvent are polymerized at -5 DEG C to -78 DEG C and then treated to obtain a high-frequency and low-dielectric-loss benzocyclobutene resin.

6. The method for preparing a high-frequency, low-dielectric-loss benzocyclobutene resin according to claim 5, characterized in that: The 1,3-dienes are at least one of butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene and 2-methyl-1,3-pentadiene; and the benzocyclobutene group is 4-vinylbenzocyclobutene or 1-vinylbenzocyclobutene.

7. The method for preparing a high-frequency, low-dielectric-loss benzocyclobutene resin according to claim 5, characterized in that: The vinyl compound is at least one of hexene, vinyl cyclohexane, heptene, octene, styrene, 1-methylstyrene, 2-methylstyrene, p-methylstyrene, vinyl biphenyl, vinyl naphthalene and its substitutes, vinyl phenanthrene and its substitutes, vinyl anthracene and its substitutes; the initiator is at least one of n-butyl lithium, sec-butyl lithium, methyl lithium and sodium naphthalene, and the amount of the initiator is 0.001-10% of the molar number of the added material; the organic solvent is at least one of tetrahydrofuran, acetonitrile, 1,4-dioxane and n-hexane.

8. The method for preparing a high-frequency, low-dielectric-loss benzocyclobutene resin according to claim 5, characterized in that: The polymerization reaction time is 4-10 hours; the polymerization reaction post-treatment method is: pouring the reaction solution into 3-10 times methanol, filtering, dissolving in toluene, washing with water for multiple times, drying and concentrating to obtain high-frequency and low dielectric loss benzocyclobutene resin.

9. Use of a high-frequency, low-dielectric-loss benzocyclobutene resin as claimed in any one of claims 1 to 4 in a high-temperature resistant dielectric material, characterized in that: The high-frequency low dielectric loss benzocyclobutene resin has a dielectric constant Dk of 2.35-2.60, a dielectric loss Df of 0.0004-0.0007, and a T 5％ The thermal decomposition temperature is 442-465°C, and the thermal expansion coefficient of the cured resin is 32-88ppm / °C@50°C.

10. Use of the high-frequency, low-dielectric-loss benzocyclobutene resin as claimed in any one of claims 1 to 4 in electronic packaging materials, characterized in that: This high-frequency, low-dielectric-loss benzocyclobutene resin is used in 5G / 6G high-frequency PCB boards and interlayer packaging of chips.

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