A copper-clad laminate resin composition with ultra-low transmission loss and preparation method thereof

Abstract

The invention discloses a copper-clad laminate resin composition with ultra-low transmission loss and a preparation method thereof, and relates to the technical field of electronic materials. The invention mixes a modified bismaleimide resin, a modified polyphenylene ether resin and an epoxy resin E-51 to obtain a mixed resin. The modified polyphenylene ether resin uses tin tetrachloride as a catalyst, toluene as an organic solvent, and polyphenylene ether and 2-chloroethanol undergo a nucleophilic substitution reaction to prepare a polyphenylene ether resin containing a hydroxyl group; the copper-clad laminate resin composition prepared by the invention has the advantages of low transmission loss, good thermal stability and high mechanical strength.

Description

Technical Field

[0001] The invention relates to the technical field of electronic materials, and in particular to a copper-clad laminate resin composition with ultra-low transmission loss and a preparation method thereof. Background Art

[0002] With the rapid development of communication substrates, communication networks, data centers, cloud computing and other fields, electronic products are moving towards high speed and high frequency. Their market expansion has also driven the new development of high-speed copper clad laminates, which are substrate materials for high-speed printed circuit boards, in product varieties and technologies. The copper clad laminate substrate is a plate-like material formed by impregnating the reinforcing material with resin glue, covering one or both sides with copper foil, and finally hot pressing. Among the three major components of the copper clad laminate, the main resin plays a decisive role in the performance of the copper clad laminate. The main resin has a very important influence on the electrical properties, mechanical properties and thermal properties of the copper clad laminate. According to the requirements of terminal equipment manufacturers for low signal transmission loss of copper clad laminates, substrate materials can be divided into standard loss substrate materials, medium loss substrate materials, low loss substrate materials, and extremely low loss substrate materials.

[0003] With the development trend of server products, the transmission rate of the main ports will be significantly improved, which will further increase the loss requirements of the substrate. How to prepare copper clad laminate resin materials with ultra-low transmission loss is a technical problem that needs to be solved urgently.

[0004] Patent application CN117384354A discloses a resin composition for copper clad laminates and its application. A trifunctional polyetheramine and 2-phenylsulfane succinic acid are subjected to amidation reaction to obtain a modified trifunctional polyetheramine; epoxy resin, modified difunctional polyetheramine and modified trifunctional polyetheramine are mixed and multifunctionally cross-linked to improve the strength of the resin composition for copper clad laminates. However, the above preparation process fails to reduce the transmission loss of the resin composition for copper clad laminates. Summary of the invention

[0005] The object of the present invention is to provide a method for preparing a copper clad laminate resin composition with ultra-low transmission loss, by using 3-mercaptopropyltriethoxysilane to modify bismaleimide resin, and by using chlorinated polyphenylene ether and epoxy resin for cross-linking, so as to prepare a copper clad laminate resin composition with low transmission loss, high mechanical strength and good thermal stability.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A copper-clad laminate resin composition with ultra-low transmission loss, the copper-clad laminate resin composition with ultra-low transmission loss comprising the following components in parts by weight;

[0008] 10-20 parts of modified bismaleimide resin, 10-20 parts of modified polyphenylene ether resin and 20-30 parts of epoxy resin E-51.

[0009] Furthermore, the preparation method of the modified bismaleimide resin comprises the following steps:

[0010] A1. Add (3-chloropropyl)trimethoxysilane and tetrabutylammonium bromide to a pressure reactor, and introduce H 2 S gas, until H 2 The partial pressure of S gas is 300-320KPa / 345KPa, and a reaction mixture is obtained;

[0011] A2, heating the pressure reactor to 60-70°C, then adding NaHS, mixing and reacting at 70-80°C for 5 hours, and then cooling to room temperature to generate an organic liquid; phase-separating the organic liquid to obtain 3-mercaptopropyltriethoxysilane;

[0012] A3. Mix 3-mercaptopropyltriethoxysilane, toluene and azobisisobutyronitrile and stir to obtain a premix; add bismaleimide resin to the premix, heat to 100-110° C., mechanically stir and react for 10-12 hours; after the reaction is completed, perform post-processing to obtain a solid modified bismaleimide resin.

[0013] Azobisisobutyronitrile was used as a free radical initiator, and the organosilane 3-mercaptopropyltriethoxysilane and bismaleimide resin underwent a mercapto-double bond click reaction to prepare a modified bismaleimide resin.

[0014] The reaction formula of bismaleimide resin and 3-mercaptopropyltriethoxysilane is as follows:

[0015]

[0016] Furthermore, in step A1, the usage ratio of (3-chloropropyl)trimethoxysilane and tetrabutylammonium bromide is 200-300 g:10-20 g.

[0017] Furthermore, in step A2, the amount of NaHS used is 120-140 g.

[0018] Furthermore, in step A3, the usage ratio of 3-mercaptopropyltriethoxysilane, toluene, azobisisobutyronitrile and bismaleimide resin is 20-30 g:100 mL:1-2 g:30-40 g.

[0019] Furthermore, in step A3, the post-processing step includes: removing the toluene solvent by distillation under reduced pressure to obtain the remaining organic solvent; adding the remaining organic solvent into anhydrous ethanol for precipitation, filtering and drying the precipitate to obtain a modified bismaleimide resin.

[0020] Furthermore, the preparation method of the modified polyphenylene ether resin comprises the following steps:

[0021] B1. In a three-necked flask equipped with a stirrer and a dropping funnel, polyphenylene ether and toluene are mixed evenly, and then tin tetrachloride is added, and the mixture is mixed and stirred; under a nitrogen atmosphere and at 0-5° C., 2-chloroethanol is added dropwise to the three-necked flask through the dropping funnel. After the addition is completed, the mixture is kept at a constant temperature of 0-5° C. for 4-5 hours to obtain a reaction product;

[0022] B2. The reaction product was washed three times with a 10%wt NaOH solution to remove the unreacted organic solvent 2-chloroethanol, and then anhydrous ethanol was added to the reaction product for precipitation to obtain a solid; the solid was placed in a vacuum oven at 80°C and dried until constant weight was obtained to obtain a modified polyphenylene ether resin.

[0023] The polyphenylene ether resin containing hydroxyl groups is prepared by using tin tetrachloride as a catalyst and toluene as an organic solvent to react polyphenylene ether and 2-chloroethanol to undergo a nucleophilic substitution reaction.

[0024] Furthermore, in step B1, the usage ratio of polyphenylene ether, toluene, tin tetrachloride and 2-chloroethanol is 15-20 g:100 mL:1-3 g:20-30 mL.

[0025] A method for preparing a copper-clad laminate resin composition with low transmission loss comprises the following steps:

[0026] S1, take the raw materials by weight of the formula;

[0027] S2. Evenly mix the modified bismaleimide resin, the modified polyphenylene ether resin and the epoxy resin E-51 to obtain a copper clad laminate resin composition with ultra-low transmission loss.

[0028] The present invention has the following beneficial effects:

[0029] 1. The copper-clad laminate resin composition prepared by the present invention is specifically a composition of modified bismaleimide resin, modified polyphenylene ether resin and epoxy resin E-51. Among them, bismaleimide resin and 3-mercaptopropyltriethoxysilane undergo a mercapto-double bond click reaction to prepare a modified bismaleimide resin; bismaleimide resin is a bifunctional polymer with maleimide group as the active end group, and has good thermal stability and radiation resistance, but the dielectric loss of bismaleimide resin is high and the processing performance is poor; using silicone resin to modify bismaleimide resin can significantly improve the dielectric properties of modified bismaleimide resin and reduce the loss factor.

[0030] 2. As another component of the copper-clad laminate resin composition, the large number of aromatic rings on the main chain of polyphenyl ether hinder the rotation of the molecular chain, increase the rigidity of the molecular chain, and make the polyphenyl ether have a higher glass transition temperature and melting temperature; when preparing the copper-clad laminate resin composition, adding a certain amount of polyphenyl ether is beneficial to improving the thermal stability of the copper-clad laminate resin composition; and in the later preparation of the copper-clad laminate curing process, the hydroxyl-containing polyphenyl ether can react with the epoxy group of the epoxy resin E-51, thereby improving the mechanical properties and stability of the prepared resin composition. The copper-clad laminate resin composition prepared by the above-mentioned modified resin has the characteristics of low transmission loss, high mechanical strength and high thermal stability. DETAILED DESCRIPTION

[0031] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] Example 1

[0033] This embodiment provides a method for preparing a modified bismaleimide resin for a copper-clad laminate resin composition with ultra-low transmission loss, comprising the following steps:

[0034] A1. Add 200 g of (3-chloropropyl)trimethoxysilane and 10 g of solid tetrabutylammonium bromide as a phase transfer catalyst into a pressure reactor, and introduce H 2 S gas, until H 2 The partial pressure of S gas is 300KPa / 345KPa to obtain a reaction mixture; the pressure reactor is then heated to 60°C; 120g of NaHS is then added to the pressure reactor using a pressure injection pump, mixed and reacted at 70°C for 5h, and then cooled to room temperature to obtain an organic liquid; the generated organic liquid is phase-separated to obtain 3-mercaptopropyltriethoxysilane.

[0035] A2. Add 20g of 3-mercaptopropyltriethoxysilane, 100mL of toluene and 1g of azobisisobutyronitrile to a 250mL four-necked flask, mix and stir at 100r / min for 30min to obtain a premix; add 30g of bismaleimide resin to the premix, heat to 100°C, and react for 10h with mechanical stirring at 100r / min; after the reaction, remove the toluene solvent by vacuum distillation to obtain the remaining organic solvent. Then, add the remaining organic solvent to anhydrous ethanol for precipitation, filter and dry the precipitate to obtain a modified bismaleimide resin.

[0036] Example 2

[0037] This embodiment provides a method for preparing a modified bismaleimide resin for a copper-clad laminate resin composition with ultra-low transmission loss, comprising the following steps:

[0038] A1. Add 250 g of (3-chloropropyl)trimethoxysilane and 16 g of solid tetrabutylammonium bromide as a phase transfer catalyst into a pressure reactor, and introduce H 2 S gas, until H 2 The partial pressure of S gas is 310KPa / 345KPa, and a reaction mixture is obtained; the pressure reactor is then heated to 67°C; 130g of NaHS is then added to the pressure reactor using a pressure injection pump, mixed and reacted at 75°C for 5h, and then cooled to room temperature to generate an organic liquid; the generated organic liquid is phase-separated to obtain 3-mercaptopropyltriethoxysilane.

[0039] A2. Add 25 g of 3-mercaptopropyltriethoxysilane, 100 mL of toluene and 1 g of azobisisobutyronitrile into a 250 mL four-necked flask, mix and stir at 150 r / min for 30 min to obtain a premix; add 36 g of bismaleimide resin to the premix, heat to 105 ° C, and react for 11 h with mechanical stirring at 130 r / min; after the reaction is completed, remove the toluene solvent by vacuum distillation, and then add the remaining organic solvent into anhydrous ethanol for precipitation, filter and dry the precipitate to obtain a modified bismaleimide resin.

[0040] Example 3

[0041] This embodiment provides a method for preparing a modified bismaleimide resin for a copper-clad laminate resin composition with ultra-low transmission loss, comprising the following steps:

[0042] A1. Add 300 g of (3-chloropropyl)trimethoxysilane and 20 g of solid tetrabutylammonium bromide as a phase transfer catalyst into a pressure reactor, and introduce H 2 S gas, until H2 The partial pressure of S gas is 300KPa / 345KPa to obtain a reaction mixture; the pressure reactor is then heated to 70°C; 140g of NaHS is then added to the pressure reactor using a pressure injection pump, mixed and reacted at 80°C for 5h, and then cooled to room temperature to obtain an organic liquid; the generated organic liquid is phase-separated to obtain 3-mercaptopropyltriethoxysilane.

[0043] A2. Add 30 g of 3-mercaptopropyltriethoxysilane, 100 mL of toluene and 2 g of azobisisobutyronitrile into a 250 mL four-necked flask, mix and stir at 200 r / min for 30 min to obtain a premix; add 40 g of bismaleimide resin to the premix, heat to 110° C., and react for 12 h with mechanical stirring at 200 r / min; after the reaction is completed, remove the toluene solvent by distillation under reduced pressure, and then add the remaining organic solvent into anhydrous ethanol for precipitation, filter and dry the precipitate to obtain a modified bismaleimide resin.

[0044] Example 4

[0045] This embodiment provides a method for preparing a modified polyphenylene ether resin for a copper-clad laminate resin composition with ultra-low transmission loss, comprising the following steps:

[0046] B1. Add 15 g of polyphenylene ether and 100 mL of toluene into a three-necked flask equipped with a stirrer at 100 r / min, then add 1 g of tin tetrachloride, and stir at 500 r / min for 5 min; nitrogen is introduced into one end of the three-necked flask and a dropping funnel is set at the other end. At 0°C, 20 mL of 2-chloroethanol is added dropwise into the three-necked flask through the dropping funnel. After the addition is completed, react at a constant temperature for 4 h to obtain a reaction product.

[0047] B2. Wash the reaction product three times with a 10%wt NaOH solution to remove the unreacted organic solvent 2-chloroethanol; then add anhydrous ethanol to the reaction product for precipitation to obtain a solid; place the solid in a vacuum oven at 80°C and dry until constant weight is obtained to obtain a modified polyphenylene ether resin.

[0048] Example 5

[0049] This embodiment provides a method for preparing a modified polyphenylene ether resin for a copper-clad laminate resin composition with ultra-low transmission loss, comprising the following steps:

[0050] B1. Add 18 g of polyphenylene ether and 100 mL of toluene into a three-necked flask equipped with a stirrer at 100 r / min, then add 2 g of tin tetrachloride, and stir at 550 r / min for 6 min; nitrogen is introduced into one end of the three-necked flask and a dropping funnel is set at the other end. At 2°C, 25 mL of 2-chloroethanol is added dropwise into the three-necked flask through the dropping funnel. After the addition is completed, react at a constant temperature for 4.5 h to obtain a reaction product.

[0051] B2. Wash the reaction product three times with a 10%wt NaOH solution to remove the unreacted organic solvent 2-chloroethanol; then add anhydrous ethanol to the reaction product for precipitation to obtain a solid; place the solid in a vacuum oven at 80°C and dry until constant weight is obtained to obtain a modified polyphenylene ether resin.

[0052] Example 6

[0053] This embodiment provides a method for preparing a modified polyphenylene ether resin for a copper-clad laminate resin composition with ultra-low transmission loss, comprising the following steps:

[0054] B1. Add 20 g of polyphenylene ether and 100 mL of toluene into a three-necked flask equipped with a stirrer at 100 r / min, then add 30 g of tin tetrachloride, and stir at 500 r / min for 5 min; nitrogen is introduced into one end of the three-necked flask and a dropping funnel is set at the other end. At 0°C, 20 mL of 2-chloroethanol is added dropwise into the three-necked flask through the dropping funnel. After the addition is completed, react at a constant temperature for 4 h to obtain a reaction product.

[0055] B2. Wash the reaction product three times with a 10%wt NaOH solution to remove the unreacted organic solvent 2-chloroethanol; then add anhydrous ethanol to the reaction product for precipitation to obtain a solid; place the solid in a vacuum oven at 80°C and dry until constant weight is obtained to obtain a modified polyphenylene ether resin.

[0056] Example 7

[0057] This embodiment provides a method for preparing a copper-clad laminate resin composition with ultra-low transmission loss, comprising the following steps:

[0058] 10 g of the modified bismaleimide resin prepared in Example 1, 10 g of the modified polyphenylene ether resin prepared in Example 4 and 10 g of epoxy resin E-51 were weighed and mixed evenly to obtain a copper clad laminate resin composition with ultra-low transmission loss.

[0059] Example 8

[0060] This embodiment provides a method for preparing a copper-clad laminate resin composition with ultra-low transmission loss, comprising the following steps:

[0061] S1. Weigh 15 g of the modified bismaleimide resin prepared in Example 2, 15 g of the modified polyphenylene ether resin prepared in Example 5, and 15 g of epoxy resin E-51, and mix them evenly to obtain a copper-clad laminate resin composition with ultra-low transmission loss.

[0062] Example 9

[0063] This embodiment provides a method for preparing a copper-clad laminate resin composition with ultra-low transmission loss, comprising the following steps:

[0064] S1. Weigh 20 g of the modified bismaleimide resin prepared in Example 3, 20 g of the modified polyphenylene ether resin prepared in Example 6, and 20 g of epoxy resin E-51, and mix them evenly to obtain a copper-clad laminate resin composition with ultra-low transmission loss.

[0065] Comparative Example 1

[0066] Compared with Example 9, the bismaleimide resin was not modified with 3-mercaptopropyltriethoxysilane, and the modified bismaleimide resin was replaced with bismaleimide resin of equal mass.

[0067] Comparative Example 2

[0068] Compared with Example 9, the polyphenylene ether resin was not modified with 2-chloroethanol, and the modified polyphenylene ether resin was replaced with a polyphenylene ether resin of equal mass.

[0069] Comparative Example 3

[0070] Compared with Example 9, in step 1, when preparing the mixed resin, epoxy resin E-51 was not added.

[0071] Application examples and performance tests:

[0072] 1. Preparation of copper clad laminate

[0073] 1. At room temperature, 100 parts of the ultra-low transmission loss copper clad laminate resin composition prepared in Example 4 and 150 parts of toluene were mixed and stirred for 120 minutes, and then 30 parts of a crosslinking aid TAIC and 0.3 parts of an initiator BIPB-96 were added and stirred for 60 minutes; then 100 parts of spherical silica powder were added and stirred for 120 minutes to obtain a glue solution.

[0074] 2. Use 2116 glass fiber cloth with a size of 31cm×35cm to completely soak the glue, bake it in the impregnation machine at 140℃ for 3 minutes to make PP, cut it to 28.5cm×28.5cm, weigh and calculate the copper clad laminate resin composition. The content of the copper clad laminate resin composition is generally controlled at 55%±2%. If it exceeds the standard, increase the viscosity adjustment solvent or repeat the impregnation step after a certain amount of solvent volatilization to make PP. Test the physical properties of PP. After rubbing the powder, use the powder to press the cylinder of 1.805±0.005g, set the starting temperature of the dynamic viscosity machine to 100℃, adjust the heating rate to 4.0℃ / min, and set the end temperature to 180℃. After the dynamic viscosity cavity temperature reaches the set value, the instrument reminds the program to start and the test can be started; after the test, confirm the minimum dynamic viscosity value to see if it meets the target requirements (if the test result is OK, repeat the impregnation step to make 6 semi-cured sheets to be pressed. If it is unqualified, increase the impregnation time or reduce the impregnation time to confirm the minimum dynamic viscosity until it is qualified.

[0075] 3. After 6 impregnated prepregs are stacked crosswise up and down, copper foils are covered on the top and bottom, and the prepregs are attached to the surface of the copper foils. A press is used for pressing. The maximum pressing and curing temperature is 250°C ± 10°C, and the pressing time is 150 ± 10 minutes. After the pressing process is completed, when the press is cooled to below 100°C, the substrate is taken out to obtain a copper clad laminate, which is marked as Example 7. The ultra-low transmission loss copper clad laminate resin compositions of Examples 5 and 6 are prepared according to the above-mentioned operating steps to obtain copper clad laminates, which are marked as Examples 8 and 9 respectively.

[0076] 2. Performance Testing

[0077] According to IPC-TM-650 / 2.4.25, the Tg190 program (50-250°C) was selected with a heating rate of 10°C / min to test the glass transition temperature. After the test, the half-height method was used to analyze the Tg point.

[0078] According to IPC-TM-650 / 2.4.24, the delamination time of the copper clad laminates prepared in Examples 7-9 and Comparative Examples 1-3 at 288° C. was analyzed.

[0079] According to IPC-TM-650 / 2.4.24, use a mechanical thermal analyzer, select the TMA program, and heat up at a rate of 10°C / min. When the temperature reaches 288°C, keep the temperature constant for 60 minutes. Select 60-100°C to analyze z-CTE1; select 200-250°C to analyze z-CTE2; select 50-260°C to analyze z-CTE3.

[0080] A universal tensile testing machine was used to prepare a 2.5 cm × 12.5 cm copper-containing sample. Two 3.5-4.0 mm wide copper strips were cut on the copper-containing surface using a cutter to test the peel strength of the copper foil.

[0081] Df was tested using a network analyzer equipped with a 10 GHz SPDR (split cavity resonator).

[0082] The specific test results are shown in the table below:

[0083] Table 1. Sample performance test data

[0084]

[0085] Data Analysis:

[0086] The copper clad laminates prepared in Examples 7-9 of the present invention all have good heat resistance and stability, as shown by the glass transition temperature (Tg) values ​​of the copper clad laminates prepared in Examples 7-9 being relatively high. However, in Comparative Example 2, since the polyether resin is not modified with 2-chloroethanol, the non-functionalized polyether resin reduces the degree of crosslinking with the epoxy resin, thereby reducing the heat resistance and stability of the prepared copper clad laminate resin composition and the copper clad laminate, as shown by the low glass transition temperature values ​​of the copper clad laminate prepared in Comparative Example 2. In Comparative Example 3, no epoxy resin component is added to the mixed resin, which correspondingly reduces the thermal stability of the prepared copper clad laminate resin composition and the copper clad laminate.

[0087] Accordingly, since the copper clad laminates prepared in Examples 7-9 have excellent stability and heat resistance, their delamination time at 288°C is greater than 60 minutes; however, the heat resistance time of the copper clad laminate prepared in Comparative Example 2 is maintained at 15 minutes, and the heat resistance time of the copper clad laminate prepared in Comparative Example 3 is maintained at 30 minutes. The thermal expansion coefficient (z-CTE value) of the copper clad laminates prepared in Examples 7-9 is higher than that of the copper clad laminates prepared in Examples 1-3.

[0088] In the copper clad laminates prepared in Examples 7 to 9, the copper clad laminate resin composition and the copper foil have excellent bonding strength, which is manifested in that the peel strength values ​​of the copper clad laminates prepared in Examples 7 to 9 are relatively large. However, in Comparative Example 3, when preparing the copper clad laminate resin composition, epoxy resin E-51 was not added, which reduced its own bonding strength, which was manifested in a reduction in the peel strength value.

[0089] The copper clad laminates prepared in Examples 7-9 all have lower dielectric loss, which is manifested in lower dielectric constant values; however, in Comparative Example 1, the bismaleimide resin was not silicon-oxidized and failed to reduce its own dielectric loss and transmission loss, which is manifested in an increase in the dielectric constant value.

[0090] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can manage and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A copper-clad laminate resin composition with ultra-low transmission loss, characterized in that: The ultra-low transmission loss copper-clad laminate resin composition comprises the following components in parts by weight: 10-20 parts of modified bismaleimide resin, 10-20 parts of modified polyphenylene ether resin and 20-30 parts of epoxy resin E-51; The preparation method of the modified bismaleimide resin, The steps include: A1. (3-chloropropyl)trimethoxysilane and tetrabutylammonium bromide are added to a pressure reactor, and H2S gas is introduced into the pressure reactor until the partial pressure of the H2S gas is 300-320 KPa / 345 KPa, to obtain a reaction mixture; A2, heating the pressure reactor to 60-70°C, then adding NaHS, mixing and reacting at 70-80°C for 5 hours, and then cooling to room temperature to generate an organic liquid; phase-separating the organic liquid to obtain 3-mercaptopropyltriethoxysilane; A3, 3-mercaptopropyltriethoxysilane, toluene and azobisisobutyronitrile are mixed and stirred to obtain a premix; bismaleimide resin is added to the premix, the temperature is raised to 100-110° C., mechanically stirred, and reacted for 10-12 hours; after the reaction is completed, a post-process treatment is performed to obtain a solid modified bismaleimide resin; The preparation method of the modified polyphenylene ether resin comprises the following steps: B1. In a three-necked flask equipped with a stirrer and a dropping funnel, polyphenylene ether and toluene are mixed evenly, and then tin tetrachloride is added, and the mixture is mixed and stirred; under a nitrogen atmosphere and at 0-5° C., 2-chloroethanol is added dropwise to the three-necked flask through the dropping funnel. After the addition is completed, the mixture is kept at a constant temperature of 0-5° C. for 4-5 hours to obtain a reaction product; B2. The reaction product was washed three times with a 10%wt NaOH solution to remove the unreacted organic solvent 2-chloroethanol, and then anhydrous ethanol was added to the reaction product for precipitation to obtain a solid; the solid was placed in a vacuum oven at 80°C and dried until constant weight was obtained to obtain a modified polyphenylene ether resin.

2. The copper-clad laminate resin composition with ultra-low transmission loss according to claim 1, characterized in that: In step A1, the usage ratio of (3-chloropropyl)trimethoxysilane and tetrabutylammonium bromide is 200-300 g:10-20 g.

3. The copper-clad laminate resin composition with ultra-low transmission loss according to claim 1, characterized in that: In step A2, the amount of NaHS used is 120-140 g.

4. The copper-clad laminate resin composition with ultra-low transmission loss according to claim 1, characterized in that: In step A3, the usage ratio of 3-mercaptopropyltriethoxysilane, toluene, azobisisobutyronitrile and bismaleimide resin is 20-30 g:100 mL:1-2 g:30-40 g.

5. The copper-clad laminate resin composition with ultra-low transmission loss according to claim 1, characterized in that: In step A3, the post-processing step includes: removing the toluene solvent by distillation under reduced pressure to obtain the remaining organic solvent; adding the remaining organic solvent into anhydrous ethanol for precipitation, filtering and drying the precipitate to obtain a modified bismaleimide resin.

6. The copper-clad laminate resin composition with ultra-low transmission loss according to claim 1, characterized in that: In step B1, the usage ratio of polyphenylene ether, toluene, tin tetrachloride and 2-chloroethanol is 15-20 g:100 mL:1-3 g:20-30 mL.

7. A method for preparing the copper-clad laminate resin composition with ultra-low transmission loss according to any one of claims 1 to 6, characterized in that: The steps include: S1, take the raw materials by weight of the formula; S2. Evenly mix the modified bismaleimide resin, the modified polyphenylene ether resin and the epoxy resin E-51 to obtain a copper clad laminate resin composition with ultra-low transmission loss.

Images