An aluminum hydroxide-filled hydrocarbon resin for copper clad laminates and its preparation method

Abstract

The present invention relates to the technical field of copper clad laminates, and specifically relates to an aluminum hydroxide-filled hydrocarbon resin for copper clad laminates and a preparation method thereof. The aluminum hydroxide-filled hydrocarbon resin comprises the following components by weight: 80-100 parts of epoxidized 1,2-polybutadiene, 20-30 parts of aluminum hydroxide, 10-15 parts of boron nitride, 12-18 parts of curing agent, 0.1-0.3 parts of curing accelerator, and 90-110 parts of solvent. By mixing epoxidized 1,2-polybutadiene with aluminum hydroxide and boron nitride and combining the co-action of various additives, the prepared aluminum hydroxide-filled hydrocarbon resin has excellent heat resistance and flame retardancy, thereby prolonging the service life of the copper clad laminate.

Description

Technical Field

[0001] The present invention relates to the technical field of copper clad laminates, and specifically to an aluminum hydroxide-filled hydrocarbon resin for copper clad laminates and a preparation method thereof. Background Art

[0002] With the continuous development of electronic communication technologies, higher requirements are also put forward for copper clad laminates in high-frequency electronic information transmission. Due to its excellent dielectric properties and comprehensive properties, hydrocarbon resin is considered an ideal material for preparing high-frequency copper clad laminates. However, the flexible and non-polar carbon chain structure of hydrocarbon resin leads to problems such as insufficient rigidity, low strength, poor heat resistance, and low peel strength of the cured product, which limit the application of hydrocarbon resin. At the same time, the flame retardant performance of hydrocarbon resin is poor, it is easily affected by fire, producing harmful gases and smoke, and it is difficult to meet the flame retardant requirements of copper clad laminates for high-frequency electronic information transmission.

[0003] Therefore, we propose an aluminum hydroxide-filled hydrocarbon resin for copper clad laminates and a preparation method thereof. Summary of the Invention

[0004] The purpose of the present invention is to provide an aluminum hydroxide-filled hydrocarbon resin for copper clad laminates and a preparation method thereof, so as to solve the problems raised in the above background art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] A preparation method of an aluminum hydroxide-filled hydrocarbon resin for copper clad laminates, comprising the following steps:

[0007] Step S1: Mix 1,2-polybutadiene, a photoinitiator, and 1-thioglycerol evenly, and after ultraviolet light irradiation, obtain hydroxylated 1,2-polybutadiene;

[0008] Step S2: Mix hydroxylated 1,2-polybutadiene, epichlorohydrin, and tetrabutylammonium bromide evenly, heat up to 65 - 75 °C, reflux and react for 3 - 4 h, cool down to 45 - 55 °C, add sodium hydroxide solution, and continue to react for 3 - 4 h. After filtration, washing, and vacuum distillation, obtain epoxidized 1,2-polybutadiene;

[0009] Step S3: Mix epoxidized 1,2-polybutadiene and a solvent evenly, heat up to 50 - 60 °C, add aluminum hydroxide, boron nitride, a curing agent, and a curing accelerator and mix evenly to obtain an aluminum hydroxide-filled hydrocarbon resin.

[0010] In the above technical solution, through the thiol-ene click chemical reaction between the vinyl double bond in the side chain of 1,2-polybutadiene and the thiol group in 1-thioglycerol, a hydroxyl group is introduced to generate hydroxylated 1,2-polybutadiene; then the hydroxylated 1,2-polybutadiene is reacted with epichlorohydrin to epoxidize the hydroxyl group to generate epoxidized 1,2-polybutadiene; finally, through the mixing of epoxidized 1,2-polybutadiene with aluminum hydroxide and boron nitride and the combined action of various additives, the prepared aluminum hydroxide-filled hydrocarbon resin has excellent heat resistance and flame retardancy.

[0011] Further, in step S1, the mass ratio of 1,2-polybutadiene, photoinitiator and 1-thioglycerol is 1:(0.01 - 0.03):(1 - 2).

[0012] Further, in step S1, the photoinitiator is 2-hydroxy-2-methylpropiophenone.

[0013] Further, the process conditions for ultraviolet irradiation in step S1 are: irradiated with ultraviolet rays of 360 - 380 nm for 5 - 7 h, and the irradiation intensity is 20 - 25 mW / cm 2 。

[0014] Further, in step S2, the mass ratio of hydroxylated 1,2-polybutadiene, epichlorohydrin and tetrabutylammonium bromide is 1:(2 - 3):(0.01 - 0.03).

[0015] Further, in step S2, the concentration of the sodium hydroxide solution is 40 - 45 wt%, and its dosage is 3 - 4 times the mass of hydroxylated 1,2-polybutadiene.

[0016] Further, the aluminum hydroxide-filled hydrocarbon resin includes the following weight components: 80 - 100 parts of epoxidized 1,2-polybutadiene, 20 - 30 parts of aluminum hydroxide, 10 - 15 parts of boron nitride, 12 - 18 parts of curing agent, 0.1 - 0.3 parts of curing accelerator, and 90 - 110 parts of solvent.

[0017] Further, the aluminum hydroxide is subjected to a modification treatment, and the specific modification process is as follows:

[0018] Step (1): Mix hexamethylenediaminetetramethylenephosphonic acid and deionized water evenly, add aluminum hydroxide, heat up to 90 - 100 °C, react for 6 - 8 h, cool to room temperature, and after filtration, washing and drying, obtain compound A;

[0019] Step (2): Mix melamine and deionized water evenly, heat up to 90 - 100 °C, adjust the pH of the system to 5 - 6 with hydrochloric acid solution, add compound A, continue to react for 6 - 8 h, and after filtration, washing and drying, cool to room temperature to obtain modified aluminum hydroxide.

[0020] In the above technical solution, by reacting hexamethylenediaminetetramethylenephosphonic acid with aluminum hydroxide, P-OH active groups are introduced on the surface of aluminum hydroxide, and then reacting it with melamine to introduce -NH2 active groups, which can further react with epoxidized 1,2-polybutadiene to form a network structure, thereby improving the thermal stability and flame retardancy of the material.

[0021] Further, in step (1), the mass ratio of hexamethylenediaminetetramethylenephosphonic acid to deionized water is 1:(25 - 30).

[0022] Further, in step (1), the mass of aluminum hydroxide is 10 - 20% of the mass of hexamethylenediaminetetramethylenephosphonic acid.

[0023] Further, in step (2), the mass ratio of melamine to deionized water is 1:(25 - 30).

[0024] Further, in step (2), the concentration of the hydrochloric acid solution is 1.0 - 1.2 mol / L.

[0025] Further, in step (2), the mass of compound A is 0.3 - 0.5 times the mass of melamine.

[0026] Further, the preparation method of the curing agent is as follows:

[0027] Mix triethylenetetramine, diphenylvinyl ethoxysilane, and tetrahydrofuran evenly, heat up to 70 - 80 °C, react for 4 - 6 h, and obtain the curing agent through vacuum distillation.

[0028] In the above technical solution, by carrying out a Michael addition reaction between the amino group at one end of triethylenetetramine and the double bond in diphenylvinyl ethoxysilane, a rigid benzene ring structure is introduced; the amino group at the other end can react with epoxidized 1,2-polybutadiene, thereby improving the mechanical properties and thermal stability of the material.

[0029] Further, the mass ratio of triethylenetetramine, diphenylvinyl ethoxysilane, and tetrahydrofuran is 1:

[0030] (1.7 - 1.8):(5 - 10).

[0031] Further, the curing agent accelerator is 2-methylimidazole.

[0032] Further, the solvent is composed of 60 - 70 parts of toluene and 30 - 40 parts of xylene.

[0033] An application of aluminum hydroxide-filled hydrocarbon resin for a copper clad laminate, comprising the following steps:

[0034] The glass fiber cloth is completely impregnated in the aluminum hydroxide-filled hydrocarbon resin for 3 - 12 minutes, taken out, and baked at 150 - 180 °C for 10 - 20 minutes to obtain a prepreg; 3 - 9 prepregs are stacked together to obtain a composite multi-layer sheet, and a copper foil is placed on each of the upper and lower surfaces of the composite multi-layer sheet, and a copper clad laminate is obtained through a lamination process.

[0035] Further, the lamination process conditions are: lamination temperature 180 - 260 °C, lamination pressure 2 - 5 MPa, and lamination time 3 - 7 h.

[0036] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0037] 1. In the aluminum hydroxide-filled hydrocarbon resin for a copper clad laminate and its preparation method of the present invention, the side chain vinyl double bond of 1,2-polybutadiene reacts with the mercapto group in 1-thioglycerol through a thiol-ene click chemical reaction to introduce a hydroxyl group and generate hydroxylated 1,2-polybutadiene; then the hydroxylated 1,2-polybutadiene reacts with epichlorohydrin to epoxidize the hydroxyl group and generate epoxidized 1,2-polybutadiene; finally, through the mixing of epoxidized 1,2-polybutadiene with aluminum hydroxide and boron nitride and the combined action of various additives, the prepared aluminum hydroxide-filled hydrocarbon resin has excellent heat resistance and flame retardancy.

[0038] 2. In the aluminum hydroxide-filled hydrocarbon resin for a copper clad laminate and its preparation method of the present invention, the epoxy group in epoxidized 1,2-polybutadiene reacts with the amino group in the curing agent to form a three-dimensional network structure, enhancing the mechanical properties and thermal stability of the material; at the same time, the epoxy group in epoxidized 1,2-polybutadiene can also react with the amino group of the modified aluminum hydroxide, which can not only effectively improve the flame retardancy of the material and make it have better fire resistance under high-temperature conditions, but also further enhance the interfacial bonding between the materials, thereby improving the peel strength of the copper clad laminate. Detailed implementation manners

[0039] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Apparently, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0040] In this embodiment, 1,2-polybutadiene: average molecular weight 3×10 5, sourced from Shanghai Macklin Biochemical Co., Ltd.; Aluminum hydroxide: grade AH-1, particle size of 5000 mesh, sourced from Jiangyin Guangyuan Superfine Powder Co., Ltd.; Boron nitride: hexagonal boron nitride, particle size of 10 - 45μm, sourced from Zhejiang Asia-America Nano-Tech Co., Ltd.; Fiberglass cloth: specification 2116, thickness 0.08mm, grammage 105g / m 2 , sourced from Guangzhou Hetai Silk Composite Materials Co., Ltd.; Copper foil: T2 pure copper, sourced from Shanghai Xinyie Metal Products Co., Ltd.

[0041] In the following examples and comparative examples, 1 part is equal to 10g.

[0042] Example 1: A preparation method of an aluminum hydroxide-filled hydrocarbon resin for copper clad laminates, comprising the following processes:

[0043] Step S1: Mix 80 parts of 1,2-polybutadiene, 0.8 part of photoinitiator, and 80 parts of 1-thioglycerol evenly, irradiate with 360nm ultraviolet light for 5h, and the irradiation intensity is 20mW / cm 2 , to obtain hydroxylated 1,2-polybutadiene;

[0044] Step S2: Mix 80 parts of hydroxylated 1,2-polybutadiene, 160 parts of epichlorohydrin, and 0.8 part of tetrabutylammonium bromide evenly, heat up to 65°C, reflux for 3h, cool down to 45°C, add 240 parts of 40wt% sodium hydroxide solution, continue to react for 3h, filter, wash, and perform vacuum distillation to obtain epoxidized 1,2-polybutadiene;

[0045] Step S3: Mix 80 parts of epoxidized 1,2-polybutadiene, 60 parts of toluene, and 30 parts of xylene evenly, heat up to 50°C, add 20 parts of aluminum hydroxide, 10 parts of boron nitride, 12 parts of curing agent, and 0.1 part of curing accelerator, and mix evenly to obtain aluminum hydroxide-filled hydrocarbon resin;

[0046] The aluminum hydroxide is subjected to a modification treatment, and the specific modification process is as follows:

[0047] Step (1): Mix 200 parts of hexamethylenediaminetetramethylenephosphonic acid and 5000 parts of deionized water evenly, add 20 parts of aluminum hydroxide, heat up to 90°C, react for 6h, cool to room temperature, filter, wash, and dry to obtain compound A;

[0048] Step (2): Mix 70 parts of melamine and 1750 parts of deionized water evenly, heat up to 90°C, adjust the pH of the system to 5 with 1.0mol / L hydrochloric acid solution, add 21 parts of compound A, continue to react for 6h, filter, wash, and dry, and then cool to room temperature to obtain modified aluminum hydroxide;

[0049] The preparation method of the curing agent is as follows:

[0050] Mix 12 parts of triethylenetetramine, 20.4 parts of diphenylethenyl ethoxysilane, and 60 parts of tetrahydrofuran evenly, heat up to 70 °C, react for 4 h, and obtain a curing agent through vacuum distillation.

[0051] An application of aluminum hydroxide-filled hydrocarbon resin for a copper clad laminate, comprising the following steps:

[0052] Completely impregnate a glass fiber cloth in the aluminum hydroxide-filled hydrocarbon resin for 3 min, take it out, and bake it at 150 °C for 10 min to obtain a prepreg; stack 3 prepregs together to obtain a composite multi-layer sheet, place a copper foil on each of the upper and lower surfaces of the composite multi-layer sheet, and obtain a copper clad laminate through a lamination process (lamination temperature 180 °C, lamination pressure 2 MPa, lamination time 3 h).

[0053] Example 2: A preparation method of aluminum hydroxide-filled hydrocarbon resin for a copper clad laminate, comprising the following processes:

[0054] Step S1: Mix 90 parts of 1,2-polybutadiene, 1.8 parts of a photoinitiator, and 135 parts of 1-thioglycerol evenly, irradiate with 370 nm ultraviolet light for 6 h, and the irradiation intensity is 22 mW / cm 2 to obtain hydroxylated 1,2-polybutadiene;

[0055] Step S2: Mix 90 parts of hydroxylated 1,2-polybutadiene, 225 parts of epichlorohydrin, and 1.8 parts of tetrabutylammonium bromide evenly, heat up to 70 °C, reflux and react for 3.5 h, cool down to 50 °C, add 315 parts of 42 wt% sodium hydroxide solution, continue to react for 3.5 h, filter, wash, and perform vacuum distillation to obtain epoxidized 1,2-polybutadiene;

[0056] Step S3: Mix 90 parts of epoxidized 1,2-polybutadiene, 65 parts of toluene, and 35 parts of xylene evenly, heat up to 55 °C, add 25 parts of aluminum hydroxide, 12 parts of boron nitride, 16 parts of a curing agent, and 0.2 part of a curing accelerator and mix evenly to obtain aluminum hydroxide-filled hydrocarbon resin;

[0057] The aluminum hydroxide is subjected to a modification treatment, and the specific modification process is as follows:

[0058] Step (1): Mix 150 parts of hexamethylenediaminetetramethylenephosphonic acid and 4200 parts of deionized water evenly, add 25 parts of aluminum hydroxide, heat up to 95 °C, react for 7 h, cool down to room temperature, filter, wash, and dry to obtain compound A;

[0059] Step (2): Mix 62.5 parts of melamine and 1750 parts of deionized water evenly, heat up to 95 °C, adjust the pH of the system to 5.5 with 1.1 mol / L hydrochloric acid solution, add 25 parts of Compound A, continue the reaction for 7 h, after filtration, washing, and drying, cool to room temperature to obtain modified aluminum hydroxide;

[0060] The preparation method of the curing agent is as follows:

[0061] Mix 16 parts of triethylenetetramine, 28 parts of diphenylethenyl ethoxysilane, and 128 parts of tetrahydrofuran evenly, heat up to 75 °C, react for 5 h, and obtain the curing agent through vacuum distillation;

[0062] An application of aluminum hydroxide-filled hydrocarbon resin for a copper clad laminate includes the following steps:

[0063] Completely immerse the glass fiber cloth in the aluminum hydroxide-filled hydrocarbon resin for 10 min, take it out, bake it at 160 °C for 15 min to obtain a prepreg; stack 5 prepregs together to obtain a composite multi-layer sheet, place a copper foil on each of the upper and lower surfaces of the composite multi-layer sheet, and obtain the copper clad laminate through a lamination process (lamination temperature 220 °C, lamination pressure 3 MPa, lamination time 5 h).

[0064] Example 3: A preparation method of aluminum hydroxide-filled hydrocarbon resin for a copper clad laminate includes the following processes:

[0065] Step S1: Mix 100 parts of 1,2-polybutadiene, 3 parts of photoinitiator, and 200 parts of 1-thioglycerol evenly, irradiate with 380 nm ultraviolet light for 7 h, and the irradiation intensity is 25 mW / cm 2 , to obtain hydroxylated 1,2-polybutadiene;

[0066] Step S2: Mix 100 parts of hydroxylated 1,2-polybutadiene, 300 parts of epichlorohydrin, and 3 parts of tetrabutylammonium bromide evenly, heat up to 75 °C, reflux and react for 4 h, cool down to 55 °C, add 400 parts of 45 wt% sodium hydroxide solution, continue the reaction for 4 h, after filtration, washing, and vacuum distillation, obtain epoxidized 1,2-polybutadiene;

[0067] Step S3: Mix 100 parts of epoxidized 1,2-polybutadiene, 70 parts of toluene, and 40 parts of xylene evenly, heat up to 60 °C, add 30 parts of aluminum hydroxide, 15 parts of boron nitride, 18 parts of curing agent, and 0.3 part of curing accelerator and mix evenly to obtain aluminum hydroxide-filled hydrocarbon resin;

[0068] The aluminum hydroxide is modified, and the specific modification process is:

[0069] Step (1): Mix 150 parts of hexamethylenediamine tetramethylenephosphonic acid and 4500 parts of deionized water evenly, add 30 parts of aluminum hydroxide, heat up to 100 °C, react for 8 h, cool to room temperature, and obtain compound A after filtration, washing, and drying;

[0070] Step (2): Mix 60 parts of melamine and 1800 parts of deionized water evenly, heat up to 100 °C, adjust the pH of the system to 6 with 1.2 mol / L hydrochloric acid solution, add 30 parts of compound A, continue to react for 8 h, cool to room temperature after filtration, washing, and drying, and obtain modified aluminum hydroxide;

[0071] The preparation method of the curing agent is as follows:

[0072] Mix 18 parts of triethylenetetramine, 32.4 parts of diphenylethenyl ethoxysilane, and 180 parts of tetrahydrofuran evenly, heat up to 80 °C, react for 6 h, and obtain the curing agent through vacuum distillation;

[0073] An application of aluminum hydroxide-filled hydrocarbon resin for a copper clad laminate includes the following steps:

[0074] Completely impregnate the glass fiber cloth in the aluminum hydroxide-filled hydrocarbon resin for 12 min, take it out, bake it at 180 °C for 20 min to obtain a prepreg; stack 9 prepregs together to obtain a composite multi-layer sheet, place a copper foil on each of the upper and lower surfaces of the composite multi-layer sheet, and obtain a copper clad laminate through a lamination process (lamination temperature 260 °C, lamination pressure 5 MPa, lamination time 7 h).

[0075] Comparative Example 1: The aluminum hydroxide-filled hydrocarbon resin includes the following weight components: 80 parts of epoxidized 1,2-polybutadiene, 20 parts of aluminum hydroxide, 10 parts of boron nitride, 5 parts of curing agent, 0.1 part of curing accelerator, and 90 parts of solvent; compared with Example 1, Comparative Example 1 reduces the addition amount of the curing agent, and other steps and processes are the same as those in Example 1.

[0076] Comparative Example 2: The aluminum hydroxide-filled hydrocarbon resin includes the following weight components: 80 parts of 1,2-polybutadiene, 20 parts of aluminum hydroxide, 10 parts of boron nitride, 12 parts of curing agent, 0.1 part of curing accelerator, and 90 parts of solvent; compared with Example 1, Comparative Example 2 replaces epoxidized 1,2-polybutadiene with the same mass of 1,2-polybutadiene, and other steps and processes are the same as those in Example 1.

[0077] Comparative Example 3: The aluminum hydroxide-filled hydrocarbon resin includes the following weight components: 80 parts of epoxidized 1,2-polybutadiene, 50 parts of aluminum hydroxide, 10 parts of boron nitride, 12 parts of curing agent, 0.1 part of curing accelerator, and 90 parts of solvent; compared with Example 1, Comparative Example 3 adds 50 parts of aluminum hydroxide, and other steps and processes are the same as those in Example 1.

[0078] Comparative Example 4: A preparation method of an aluminum hydroxide-filled hydrocarbon resin for a copper clad laminate, comprising the following processes:

[0079] The aluminum hydroxide is subjected to a modification treatment, and the specific modification process is as follows:

[0080] Step (1): Mix 150 parts of hexamethylenediaminetetramethylenephosphonic acid and 4200 parts of deionized water evenly, add 25 parts of aluminum hydroxide, heat up to 95 °C, react for 7 h, cool to room temperature, and after filtration, washing, and drying, obtain Compound A;

[0081] Step (2): Mix 62.5 parts of melamine and 1750 parts of deionized water evenly, heat up to 95 °C, adjust the pH of the system to 5.5 with a 1.1 mol / L hydrochloric acid solution, add 6.25 parts of Compound A, continue to react for 7 h, and after filtration, washing, and drying, cool to room temperature to obtain modified aluminum hydroxide;

[0082] Compared with Example 2, in Step (2) of Comparative Example 4, the mass of Compound A is 0.1 times the mass of melamine; other steps are the same as those in Example 2.

[0083] Experiment: Take the copper clad laminates obtained in Examples 1-3 and Comparative Examples 1-4, prepare specimens, and detect and record the performance of each of them:

[0084] The flame retardancy is determined by the vertical burning method according to the UL-94 standard. Experimental steps: Cut the copper clad laminate into specimens with a size of 125 mm in length × 13 mm in width × 0.7 mm in thickness, ignite the lower end thereof, record the combustion process of the specimen, and classify it into different grades according to the performance: The V-0 grade indicates that the material does not drip sparks, the combustion process time is less than 10 seconds, and the flame height is less than 50 mm; The V-1 grade indicates that during the combustion process of the material, the flame height is less than 75 mm, the combustion time does not exceed 30 seconds, and there are no obvious dripping sparks.

[0085] The heat resistance test is carried out using a lead-free soldering furnace. Experimental steps: Cut the copper clad laminate into specimens with a size of 10 cm × 10 cm, place them in a 288 °C tin furnace for tin floating 3 times, 10 s each time, dip tin for 120 s, take out, cool to room temperature, observe whether there are phenomena such as bubble delamination, cracking, or fading on the surface of the specimen, and record the data.

[0086] The peel strength was determined according to the "Test Method for Peel and Impact of Copper Clad Laminate" in IPC-TM-650, Edition 2.4.8. Experimental procedure: The copper clad laminate was cut into strips with a size of 100 mm in length and 10 mm in width. The copper foil at one end of the strip was peeled off from the substrate by a distance of 12 mm, and the peeled copper foil was clamped with a specimen clip to test the peel strength between the copper foil and the substrate. During the test, the peel speed was set at 50 mm / min, the peel angle was 90°, and the peel distance was 25 mm.

[0087] Test results

[0088]

[0089] According to the data in the above table, the following conclusions can be clearly obtained:

[0090] 1. Compared with Examples 1-3, the heat resistance and peel strength of the products obtained in Comparative Examples 1, 2, and 3 decreased, indicating that the performance of the aluminum hydroxide-filled hydrocarbon resin prepared by the present invention is affected by its composition and ratio. By selecting the components and ratios within the specified range, materials with excellent thermal stability and mechanical properties can be prepared.

[0091] 2. Compared with Examples 1-3, the flame retardancy of the product obtained in Comparative Example 4 decreased. It can be seen that the performance of the modified aluminum hydroxide prepared by the present invention is affected by the ratio of each reagent in its preparation process. By selecting the mass ratio within the specified range, the prepared modified aluminum hydroxide has excellent flame retardancy, thus providing an excellent flame retardant effect for the copper clad laminate.

[0092] It should be noted that in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variant thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not expressly listed, or elements inherent to such process, method, article or device.

[0093] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A preparation method of an aluminum hydroxide-filled hydrocarbon resin for a copper clad laminate, characterized in that: It includes the following steps: Step S1: Mix 1,2-polybutadiene, photoinitiator and 1-thioglycerol evenly, and after ultraviolet irradiation, hydroxylated 1,2-polybutadiene is obtained; Step S2: Mix hydroxylated 1,2-polybutadiene, epichlorohydrin and tetrabutylammonium bromide evenly, heat up to 65 - 75 °C, reflux for 3 - 4 h, cool down to 45 - 55 °C, add sodium hydroxide solution, continue to react for 3 - 4 h, and after filtration, washing and vacuum distillation, epoxidized 1,2-polybutadiene is obtained; Step S3: Mix epoxidized 1,2-polybutadiene and solvent evenly, heat up to 50 - 60 °C, add aluminum hydroxide, boron nitride, curing agent and curing accelerator and mix evenly to obtain aluminum hydroxide-filled hydrocarbon resin; The aluminum hydroxide-filled hydrocarbon resin includes the following weight components: 80 - 100 parts of epoxidized 1,2-polybutadiene, 20 - 30 parts of aluminum hydroxide, 10 - 15 parts of boron nitride, 12 - 18 parts of curing agent, 0.1 - 0.3 parts of curing accelerator, and 90 - 110 parts of solvent; The aluminum hydroxide is subjected to a modification treatment, and the specific modification process is as follows: Step (1): Mix hexamethylenediaminetetramethylenephosphonic acid and deionized water evenly, add aluminum hydroxide, heat up to 90 - 100 °C, react for 6 - 8 h, cool to room temperature, and after filtration, washing and drying, compound A is obtained; Step (2): Mix melamine and deionized water evenly, heat up to 90 - 100 °C, adjust the pH of the system to 5 - 6 with hydrochloric acid solution, add compound A, continue to react for 6 - 8 h, and after filtration, washing and drying, cool to room temperature to obtain modified aluminum hydroxide; In step (2), the mass of compound A is 0.3 - 0.5 times the mass of melamine; The preparation method of the curing agent is as follows: Mix triethylenetetramine, diphenylethenyl ethoxysilane and tetrahydrofuran evenly, heat up to 70 - 80 °C, react for 4 - 6 h, and after vacuum distillation, the curing agent is obtained.

2. The preparation method of the aluminum hydroxide-filled hydrocarbon resin for copper clad laminate according to claim 1, characterized in that: In step S1, the mass ratio of 1,2-polybutadiene, photoinitiator and 1-thioglycerol is 1:(0.01 - 0.03):(1 - 2).

3. The preparation method of the aluminum hydroxide-filled hydrocarbon resin for a copper clad laminate according to claim 1, wherein: In step (1), the mass of aluminum hydroxide is 0.10 - 0.12 times the mass of hexamethylenediaminetetramethylenephosphonic acid.

4. An aluminum hydroxide-filled hydrocarbon resin for a copper clad laminate prepared by the preparation method according to any one of claims 1 - 3.

5. Use of the aluminum hydroxide-filled hydrocarbon resin for a copper clad laminate according to claim 4, characterized in that: It includes the following steps: Fully immerse the glass fiber cloth in the aluminum hydroxide-filled hydrocarbon resin for 3 - 12 min, take it out, bake it at 150 - 180 °C for 10 - 20 min to obtain a prepreg; stack 3 - 9 prepregs together to obtain a composite multi-layer sheet, place a copper foil on each of the upper and lower surfaces of the composite multi-layer sheet, and through a lamination process, a copper clad laminate is obtained.

6. The application of aluminum hydroxide-filled hydrocarbon resin for copper clad laminates according to claim 5, characterized in that: The lamination process conditions are: lamination temperature 180 - 260 °C, lamination pressure 2 - 5 MPa, and lamination time 3 - 7 h.

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