Low-dielectric high-heat-resistance hydrocarbon resin as well as preparation method and application thereof

Abstract

The invention discloses hydrocarbon resin with low dielectric constant and high heat resistance as well as a preparation method and application thereof, and the preparation method of the hydrocarbon resin with low dielectric constant and high heat resistance comprises the following steps: S1, in an organic solvent, adding a polycyclic aromatic hydrocarbon compound and a chlorinated hydrocarbon compound for reaction; s2, adjusting the pH value of a reaction system to be neutral, and removing a water phase; s3, part of the organic solvent is removed through distillation till the set solid content is achieved, and a low-dielectric high-heat-resistance hydrocarbon resin solution is obtained after cooling. The low-dielectric high-heat-resistance hydrocarbon resin solves the problems that traditional hydrocarbon resin is insufficient in rigidity, low in strength, poor in heat resistance and low in glass transition temperature after being cured.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of carbon hydrogen resin, in particular to a low dielectric high heat-resistant carbon hydrogen resin and a preparation method and application thereof. BACKGROUND

[0002] With the rapid development of modern communication and information industry, electronic products are moving towards high density, safety and high functionality, especially in the field of mobile communication and high frequency microwave, the rapid development of high performance electronic computer, electronic switch, microwave antenna and satellite communication equipment and other technologies puts forward higher requirements for the signal propagation speed and transmission efficiency of electronic system.

[0003] Carbon hydrogen resin has low molecular polarity, so it exhibits good dielectric properties in high molecular materials, and thus has broad application prospects in the fields of 5G communication, vehicle millimeter wave radar, Internet of Things and copper-clad plate. However, the flexible and non-polar carbon chain structure of traditional carbon hydrogen resin leads to the problems of insufficient rigidity, low strength, poor heat resistance and low glass transition temperature of the cured product, which limits its application range. SUMMARY

[0004] In view of the above defects, the purpose of the present application is to provide a low dielectric high heat-resistant carbon hydrogen resin and a preparation method and application thereof, which solve the problems of insufficient rigidity, low strength, poor heat resistance and low glass transition temperature of the traditional carbon hydrogen resin after curing.

[0005] To achieve this purpose, the technical scheme adopted by the present application is as follows: A low dielectric high heat-resistant carbon hydrogen resin, the structure general formula of the low dielectric high heat-resistant carbon hydrogen resin is as follows: ; Among them, n=0-30, R is selected from at least one of hydrogen atom, aliphatic hydrocarbon group, aryl group, aralkyl group and the following structural formula: ; R1 is selected from at least one of hydrogen atom, aliphatic alkenyl group and aralkenyl group; A is selected from Or .

[0006] A preparation method of a low dielectric high heat-resistant carbon hydrogen resin, for preparing the above-mentioned low dielectric high heat-resistant carbon hydrogen resin, comprising the following steps: S1, in an organic solvent, adding a condensed ring aromatic compound and a chlorinated hydrocarbon compound to react; S2, after adjusting the pH value of the reaction system to neutral, removing the aqueous phase; S3, distilling to remove part of the organic solvent to a set solid content, and obtaining a low dielectric high heat-resistant carbon hydrogen resin solution after cooling.

[0007] Preferably, in step S1, the molar ratio of the condensed ring aromatic compound to the chlorinated hydrocarbon compound is 1: (1.5-3.0).

[0008] Preferably, in step S1, the reaction temperature is 40-85℃, and the reaction time is 6-30h.

[0009] Preferably, the condensed ring aromatic compound is selected from at least one of fluorene, indene and benzindene; The chlorinated hydrocarbon compound is selected from at least one of dichlorobenzene, chloropropylene, methyl chloropropylene, chlorobutene, chloropentene, biphenyl dichlorobenzyl, p-dichlorobenzyl, chloromethyl styrene and p-chlorostyrene.

[0010] Preferably, the condensed ring aromatic compound is a mixture of fluorene and indene.

[0011] Preferably, the chlorinated hydrocarbon compound is selected from at least one of dichlorobenzene, chloropropylene, methyl chloropropylene, biphenyl dichlorobenzyl, p-dichlorobenzyl and chloromethyl styrene.

[0012] Preferably, in step S1, the organic solvent is one of toluene, xylene and cyclohexane.

[0013] Preferably, in step S1, a base solution is also added for reaction, and the base solution is a sodium hydroxide solution or a potassium hydroxide solution.

[0014] A low dielectric high heat-resistant carbon hydrogen resin composition comprises the low dielectric high heat-resistant carbon hydrogen resin described above.

[0015] The technical solution provided by the present application can include the following beneficial effects: The present application introduces condensed ring aromatic structure and multi-functional structure formed by condensed ring aromatic and chlorinated hydrocarbon into the structure under the premise of ensuring that the carbon hydrogen resin has lower molecular polarity, improves the crosslinking density of the resin, and thus effectively improves the heat resistance of the product after curing. The styrene and aliphatic alkenyl in the structure are matched with appropriate crosslinking density to improve the glass transition temperature, and a more compact three-dimensional network structure is formed to effectively improve the strength of the product. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 is the GPC graph of the low dielectric high heat-resistant carbon hydrogen resin prepared in Example 1 of the present application. DETAILED DESCRIPTION

[0017] The technical solution of the present application is further illustrated by the specific embodiments below.

[0018] For the purpose of facilitating the understanding of the present application, a more comprehensive description of the present application is provided below. The present application can be realized in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so as to make the disclosure of the present application more thorough and comprehensive.

[0019] Unless otherwise specified in the embodiments, the techniques or conditions are carried out according to the techniques or conditions described in the literature in the field or according to the product instructions. Unless otherwise specified, the reagents or instruments used are all conventional products that can be obtained commercially.

[0020] A low-dielectric high-heat-resistant hydrocarbon resin, the structural general formula of which is as follows: ; In the formula, n = 0-30, and R is selected from at least one of a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, an aralkyl group, and a group represented by the following structural formula: ; R1 is selected from at least one of a hydrogen atom, an aliphatic alkenyl group, and an aralkenyl group; A is selected from or .

[0021] To solve the problems existing in the prior art, the present application provides a low-dielectric high-heat-resistant hydrocarbon resin. The low-dielectric high-heat-resistant hydrocarbon resin belongs to a multifunctional polymer and contains a heat-curable alkenyl structure in the molecular chain structure. The heat-curable alkenyl structure is an indene ring double bond, a styryl group, a propenyl group, a methacryl group, a butenyl group, and a pentenyl group, etc. in the resin structure. The hydrocarbon resin limits the polymerization degree n to 0-30 and introduces a condensed aromatic hydrocarbon and a multifunctional structure formed by the condensed aromatic hydrocarbon and a chlorinated hydrocarbon in the structure. The introduction of the condensed aromatic hydrocarbon can improve the rigidity and stability of the molecular chain, reduce the movement of the molecular chain, and provide multiple reaction sites. The introduction of the multifunctional structure can further increase the number of crosslinking points. The condensed aromatic hydrocarbon and the multifunctional structure together improve the crosslinking density of the hydrocarbon resin, so that a tighter three-dimensional network structure is formed during the curing process of the resin, effectively increasing the average molecular weight of the resin. In addition, the active hydrogen on the condensed aromatic hydrocarbon structure is consumed during the curing process, which can effectively reduce the dielectric loss of the finished product. The hydrocarbon resin can be used for crosslinking and curing with many unsaturated substances such as ene-yne, which can further improve the crosslinking density, increase the heat resistance after curing, reduce brittleness, and improve the performance of the product.

[0022] Therefore, the low-dielectric high-heat-resistant hydrocarbon resin has the advantages that the resin has low molecular polarity and good dielectric performance, the cross-linking density of the resin is improved through the fused ring aromatic structure and the multi-functional structure formed by the fused ring aromatic compound and the chlorinated hydrocarbon compound, the heat resistance of the cured product is effectively improved, the glass transition temperature is improved through the appropriate cross-linking density of the styrene and aliphatic alkenyl in the structure, the strength of the product is effectively improved through the closer three-dimensional network structure, and the problems of low heat resistance, low glass transition temperature, insufficient rigidity and low strength of the traditional hydrocarbon resin after curing are solved.

[0023] A preparation method of a low-dielectric high-heat-resistant hydrocarbon resin, which is used for preparing the low-dielectric high-heat-resistant hydrocarbon resin, comprises the following steps: S1, reacting a fused ring aromatic compound and a chlorinated hydrocarbon compound in an organic solvent; S2, removing the water phase after adjusting the pH value of the reaction system to neutral; S3, distilling part of the organic solvent to a set solid content, and obtaining a low-dielectric high-heat-resistant hydrocarbon resin solution after cooling.

[0024] The chlorinated hydrocarbon compound and the fused ring aromatic compound are bridged to form a main chain and a branch chain, and the chain ends have a reactive double bond, that is, the molecular chain contains multiple active functional groups that can participate in curing, so that a multi-functional resin is obtained, the multi-functional groups provide more reaction sites, the reaction is more complete, the cross-linking network formed by the reaction is more dense, that is, the cross-linking density of the resin is improved, the average molecular weight is increased, the structure characteristics of the multi-functional group branching promote the formation of a high-density cross-linking network, effectively inhibit the molecular chain movement, increase the heat resistance of the cured product and reduce the brittleness, the fused ring aromatic structure is introduced, the group is difficult to break at high temperature, further improves the heat resistance of the cured product, and through the consumption of active hydrogen on the fused ring aromatic structure, the dielectric loss of the finished product can be effectively reduced, the strength and heat resistance of the hydrocarbon resin after curing are improved under the premise of ensuring excellent dielectric performance, and the problems of insufficient rigidity, low strength, poor heat resistance and low glass transition temperature of the traditional hydrocarbon resin after curing are solved.

[0025] And, the present application uses the reaction of the alkylization of the condensed ring aromatic compound containing active hydrogen and the alkenyl halide under the catalyst without metal, compared with the conventional method of preparing the hydrocarbon resin, i.e. the synthetic method of copolymerization, the present application is easier to control the reaction speed and the molecular weight; and the hydrocarbon resin is prepared by the Suzuki coupling reaction, the cross-coupling reaction of the boronic acid or borate ester of aryl or alkenyl and halogenated hydrocarbon under the zero-valent palladium catalysis, the function of the alkali in the reaction is mainly to promote the metal transfer, the raw materials are limited to the boronic acid or borate ester and halogenated hydrocarbon, and the boronic acid or borate ester needs to be excessive in the reaction, and the use of strong alkali will also cause the self-coupling reaction of the halogenated hydrocarbon to generate by-products, and the present application will add the alkali solution in the reaction, the function of the alkali solution is to absorb the hydrochloric acid formed in the reaction process, and the alkali solution does not need to be limited to weak alkali, so that the waste water and waste solvent generated in the preparation process of the present application are easier to be harmlessly treated.

[0026] It is worth noting that in step S1, the reaction of the condensed ring aromatic compound and the chlorinated hydrocarbon compound, first, the condensed ring aromatic compound reacts with the bifunctional chlorinated hydrocarbon compound to generate the main chain and the branch, and then the unsaturated halogenated hydrocarbon is added to cap to obtain the required resin.

[0027] In step S3, part of the organic solvent is removed by distillation to reach the set solid content, specifically, the normal solid content is set to be between 50-80%, and within this solid content range, the subsequent processing needs can be well met.

[0028] It is worth noting that in step S3, the distillation temperature is 40-70℃.

[0029] Preferably, in step S1, the molar ratio of the condensed ring aromatic compound to the chlorinated hydrocarbon compound is 1: (1.5-3.0).

[0030] Specifically, according to the number of active hydrogen of the condensed ring aromatic compound that can react with the chlorinated hydrocarbon compound, the ratio is limited to effectively avoid the residual active hydrogen or residual chlorinated hydrocarbon, so as to ensure the performance of the product after solidification.

[0031] Preferably, in step S1, the reaction temperature is 40-85℃, and the reaction time is 6-30h.

[0032] Specifically, at this temperature, it is ensured that the reaction of the condensed ring aromatic compound and the chlorinated hydrocarbon can proceed normally, avoiding too long reaction time, and at the same time avoiding the case that part of the active hydrogen of the condensed ring aromatic compound cannot react with the chlorinated hydrocarbon due to insufficient activation energy, so as to obtain the target product.

[0033] Furthermore, excessively high temperatures can exacerbate the hydrolysis of chlorinated hydrocarbons in an alkaline environment, leading to the formation of non-reactive raw material structures, thereby reducing the proportion of the target structure and introducing byproducts. Unsaturated double bonds in the structure are prone to polymerization at high temperatures to form macromolecular products. Limiting the reaction temperature ensures better performance of the finished product.

[0034] Preferably, the polycyclic aromatic hydrocarbon compound is selected from at least one of fluorene, indene, and benzo[a]indene; The chlorinated hydrocarbon compound is selected from at least one of dichlorobenzene, chloropropene, methylchloropropene, chlorobutene, chloropentene, biphenyl dichlorobenzyl, p-dichlorobenzyl, chloromethylstyrene, and p-chlorostyrene.

[0035] Specifically, the above-mentioned polycyclic aromatic hydrocarbons react with bifunctional chlorinated hydrocarbons to generate a main chain and branches, and then the compounds are capped with unsaturated haloalkanes to obtain the desired product.

[0036] Preferably, the polycyclic aromatic hydrocarbon is a mixture of fluorene and indene.

[0037] Specifically, using a mixture of fluorene and indene ensures that the molecular chain length is moderate and that no molecular structure with excessively high functionality is generated. This results in a resin with good crosslinking density, ensuring complete curing in the later stages without affecting dielectric properties and heat resistance, and facilitating application.

[0038] Preferably, the chlorinated hydrocarbon compound is selected from at least one of dichlorobenzene, allyl chloride, methylchloropropene, biphenyl dichlorobenzyl, p-dichlorobenzyl, and chloromethylstyrene.

[0039] Specifically, the chains of chloroprene and chloropentene are relatively long, resulting in longer flexible chains during subsequent curing, which lowers the glass transition temperature of the finished product. Furthermore, their reactivity with chlorostyrene is relatively low, leading to a lower yield under this preparation method.

[0040] Preferably, in step S1, the organic solvent is one of toluene, xylene, and cyclohexane.

[0041] Specifically, the purpose of adding organic solvents is to dissolve raw materials and finished products.

[0042] Preferably, in step S1, an alkaline solution is added to carry out the reaction, wherein the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution.

[0043] Specifically, in the preparation method of the present invention, a fused-ring aromatic compound containing active hydrogen and an alkenyl halide are used to carry out an alkylation reaction in the presence of a metal-free catalyst. The role of the base in the reaction is to absorb the hydrochloric acid formed during the reaction. The addition of the base solution is to neutralize the acid produced in the reaction. At the same time, the water in the base solution is used to dissolve the salt generated by the acid-base neutralization. Therefore, the amount of base used should be greater than the amount of acid produced, and the amount of water in the base should be sufficient to completely dissolve the salt produced.

[0044] Using the aforementioned alkaline solution offers safety, eliminates side reactions, and facilitates subsequent wastewater treatment. For example, neutralization of carbonate or bicarbonate-based alkalis generates large amounts of carbon dioxide, posing a risk of material spillage and safety hazards during production; organic and inorganic alkalis such as sodium alkoxide are easily hydrolyzed in water; organic alkalis such as DBU may trigger side reactions, result in difficult wastewater treatment, and are not economically viable. Overall, the current option offers good economic benefits and more convenient post-treatment.

[0045] A low-dielectric, high-heat-resistant hydrocarbon resin composition comprising the aforementioned low-dielectric, high-heat-resistant hydrocarbon resin.

[0046] It is convenient to apply to various fields. While retaining the characteristics of high strength and good heat resistance of the low dielectric and high heat resistant hydrocarbon resin, it can add other components to synergistically optimize and improve the overall performance to meet the needs of different fields.

[0047] The technical solution of the present invention will be further illustrated below through specific embodiments.

[0048] Example group Example 1 S1. Using toluene as the reaction solvent, 1 mol of biphenyl dichlorobenzyl, 0.5 mol of fluorene, 0.5 mol of indene, 500 g of 25% sodium hydroxide solution and 1000 g of toluene were added to the reactor for reaction. The reaction temperature was 65℃ and the reaction time was 6 h. Then, 0.5 mol of chloromethylstyrene was added dropwise and the reaction was carried out for 8 h. S2. After adjusting the pH of the reaction system to neutral, remove the aqueous phase; S3. Gradually increase the temperature and distill to remove vacuum within 40-70℃ to remove some toluene until the solid content is 70%. After cooling, a low dielectric and high heat-resistant hydrocarbon resin solution is obtained.

[0049] The obtained low-dielectric, high-heat-resistant hydrocarbon resin solution was analyzed by permeation gel chromatography, and the characteristic chromatogram, i.e., GPC chromatogram, was obtained as follows: Figure 1 As shown.

[0050] Following standard procedures, the obtained low-dielectric, high-heat-resistant hydrocarbon resin was cured into a sheet. Dielectric loss was tested at a frequency of 10 GHz, and the dielectric loss of the cured sheet was found to be 0.0013. Simultaneously, DMA testing was performed on the cured sheet, and the glass transition temperature was found to be greater than 300℃.

[0051] Example 2 S1. Using toluene as the reaction solvent, 1 mol of p-dichlorobenzyl, 0.5 mol of fluorene, 0.5 mol of indene, 500 g of 25% sodium hydroxide solution and 1000 g of toluene were added to the reactor for reaction. The reaction temperature was 65℃ and the reaction time was 6 h. Then, 0.5 mol of chloromethylstyrene was added dropwise and the reaction was carried out for 8 h. S2. After adjusting the pH of the reaction system to neutral, remove the aqueous phase; S3. Gradually increase the temperature and distill to remove vacuum within 40-70℃ to remove some toluene until the solid content is 70%. After cooling, a low dielectric and high heat-resistant hydrocarbon resin solution is obtained.

[0052] Following standard procedures, the obtained low-dielectric, high-heat-resistant hydrocarbon resin was cured into a sheet. Dielectric loss was tested at a frequency of 10 GHz, and the dielectric loss of the cured sheet was found to be 0.0015. Simultaneously, DMA testing was performed on the cured sheet, and the glass transition temperature was measured to be 290℃.

[0053] Example 3 S1. Using xylene as the reaction solvent, 1 mol of biphenyl dichlorobenzyl, 0.5 mol of fluorene, 0.6 mol of indene, 500 g of 25% sodium hydroxide solution and 1000 g of xylene were added to the reactor for reaction. The reaction temperature was 65℃ and the reaction time was 6 h. Then, 0.7 mol of chloromethylstyrene was added dropwise and the reaction was carried out for 8 h. S2. After adjusting the pH of the reaction system to neutral, remove the aqueous phase; S3. Gradually increase the temperature and distill to remove vacuum within 40-70℃ to remove some toluene until the solid content is 70%. After cooling, a low dielectric and high heat-resistant hydrocarbon resin solution is obtained.

[0054] Following standard procedures, the obtained low-dielectric, high-heat-resistant hydrocarbon resin was cured into a sheet. Dielectric loss was tested at a frequency of 10 GHz, and the dielectric loss of the cured sheet was found to be 0.0014. Simultaneously, DMA testing was performed on the cured sheet, and the glass transition temperature was found to be greater than 300℃.

[0055] Example 4 S1. Using toluene as the reaction solvent, 0.8 mol of p-dichlorobenzyl, 0.5 mol of fluorene, 0.6 mol of indene, 700 g of 20% sodium hydroxide solution and 1000 g of toluene were added to a reactor for reaction at 65°C for 6 hours. Then, 0.6 mol of chloromethylstyrene and 0.6 mol of chloropropene were added dropwise, and the reaction was allowed to continue for 8 hours. S2. After adjusting the pH of the reaction system to neutral, remove the aqueous phase; S3. Gradually increase the temperature and distill to remove vacuum within 40-70℃ to remove some toluene until the solid content is 70%. After cooling, a low dielectric and high heat-resistant hydrocarbon resin solution is obtained.

[0056] Following standard procedures, the obtained low-dielectric, high-heat-resistant hydrocarbon resin was cured into a sheet. Dielectric loss was tested at a frequency of 10 GHz, and the dielectric loss of the cured sheet was found to be 0.0015. Simultaneously, DMA testing was performed on the cured sheet, and the glass transition temperature was found to be greater than 300℃.

[0057] Example 5 S1. Using toluene as the reaction solvent, 0.75 mol of biphenyl dichlorobenzyl, 1 mol of fluorene, 500 g of 25% sodium hydroxide solution and 1000 g of toluene were added to the reactor for reaction. The reaction temperature was 65℃ and the reaction time was 6 h. Then, 0.5 mol of chloromethylstyrene was added dropwise and the reaction was carried out for 8 h. S2. After adjusting the pH of the reaction system to neutral, remove the aqueous phase; S3. Gradually increase the temperature and distill to remove vacuum within 40-70℃ to remove some toluene until the solid content is 70%. After cooling, a low dielectric and high heat-resistant hydrocarbon resin solution is obtained.

[0058] Following standard procedures, the obtained low-dielectric, high-heat-resistant hydrocarbon resin was cured into a sheet. Dielectric loss was tested at a frequency of 10 GHz, and the dielectric loss of the cured sheet was found to be 0.0017. Simultaneously, DMA testing was performed on the cured sheet, and the glass transition temperature was measured to be 260℃.

[0059] Example 6 S1. Using toluene as the reaction solvent, 1 mol of biphenyl dichlorobenzyl, 1 mol of indene, 500 g of 25% sodium hydroxide solution and 1000 g of toluene were added to the reactor for reaction. The reaction temperature was 65℃ and the reaction time was 6 h. Then, 0.5 mol of chloromethylstyrene was added dropwise and the reaction was carried out for 8 h. S2. After adjusting the pH of the reaction system to neutral, remove the aqueous phase; S3. Gradually increase the temperature and distill to remove vacuum within 40-70℃ to remove some toluene until the solid content is 70%. After cooling, a low dielectric and high heat-resistant hydrocarbon resin solution is obtained.

[0060] Following standard procedures, the obtained low-dielectric, high-heat-resistant hydrocarbon resin was cured into a sheet. Dielectric loss was tested at a frequency of 10 GHz, and the dielectric loss of the cured sheet was found to be 0.0017. Simultaneously, DMA testing was performed on the cured sheet, and the glass transition temperature was found to be greater than 360°C.

[0061] Comparative group Comparative Example 1 S1. Using toluene as the reaction solvent, 1 mol of biphenyl dichlorobenzyl, 0.5 mol of fluorene, 0.5 mol of indene, 500 g of 25% sodium hydroxide solution and 1000 g of toluene were added to the reactor for reaction. The reaction temperature was 30℃ and the reaction time was 6 h. Then, 0.5 mol of chloromethylstyrene was added dropwise and the reaction was carried out for 8 h. S2. After adjusting the pH of the reaction system to neutral, remove the aqueous phase; S3. Gradually increase the temperature and distill to remove vacuum within the range of 40-70℃ to remove some toluene until the solid content is 70%. After cooling, a hydrocarbon resin solution is obtained.

[0062] The obtained hydrocarbon resin was made into a cured sheet according to the conventional process. The dielectric loss was tested at a frequency of 10G, and the dielectric loss of the cured sheet was found to be 0.0025. At the same time, the glass transition temperature was measured to be 186℃ by DMA test.

[0063] Comparative Example 2 S1. Using toluene as the reaction solvent, 1 mol of biphenyl dichlorobenzyl, 0.5 mol of fluorene, 0.5 mol of indene, 500 g of 25% sodium hydroxide solution and 1000 g of toluene were added to the reactor for reaction. The reaction temperature was 90℃ and the reaction time was 6 h. Then, 0.5 mol of chloromethylstyrene was added dropwise and the reaction was carried out for 8 h. S2. After adjusting the pH of the reaction system to neutral, remove the aqueous phase; S3. Gradually increase the temperature and distill to remove vacuum within the range of 40-70℃ to remove some toluene until the solid content is 70%. After cooling, a hydrocarbon resin solution is obtained.

[0064] The obtained hydrocarbon resin was made into a cured sheet according to the conventional process. The dielectric loss was tested at a frequency of 10G, and the dielectric loss of the cured sheet was found to be 0.0018. At the same time, the glass transition temperature was measured to be greater than 300℃ by DMA test.

[0065] Comparative Example 3 S1. Using toluene as the reaction solvent, 2 mol of biphenyl dichlorobenzyl, 0.5 mol of fluorene, 0.5 mol of indene, 500 g of 25% sodium hydroxide solution and 1000 g of toluene were added to the reactor for reaction. The reaction temperature was 65℃ and the reaction time was 6 h. Then, 2 mol of chloromethylstyrene was added dropwise and the reaction was carried out for 8 h. S2. After adjusting the pH of the reaction system to neutral, remove the aqueous phase; S3. Gradually increase the temperature and distill to remove vacuum within the range of 40-70℃ to remove some toluene until the solid content is 70%. After cooling, a hydrocarbon resin solution is obtained.

[0066] The obtained hydrocarbon resin was made into a cured sheet according to the conventional process. The dielectric loss was tested at a frequency of 10G, and the dielectric loss of the cured sheet was found to be 0.0025. At the same time, the glass transition temperature was measured to be 267℃ by DMA test.

[0067] Comparative Example 4 S1. Using toluene as the reaction solvent, 1 mol of biphenyl dichlorobenzyl, 0.5 mol of fluorene, 0.5 mol of indene, 500 g of 25% sodium hydroxide solution and 1000 g of toluene were added to the reactor for reaction. The reaction temperature was 65℃ and the reaction time was 6 h. Then, 0.3 mol of chloromethylstyrene was added dropwise and the reaction was carried out for 8 h. S2. After adjusting the pH of the reaction system to neutral, remove the aqueous phase; S3. Gradually increase the temperature and distill to remove vacuum within the range of 40-70℃ to remove some toluene until the solid content is 70%. After cooling, a hydrocarbon resin solution is obtained.

[0068] The obtained hydrocarbon resin was made into a cured sheet according to the conventional process. The dielectric loss was tested at a frequency of 10G, and the dielectric loss of the cured sheet was found to be 0.00186. At the same time, the glass transition temperature was measured to be 273℃ by DMA test.

[0069] Comparative Example 5 100g of divinylbenzene, 100g of styrene, and 150g of solvent (100g of butyl acetate + 50g of toluene) were added to a reaction vessel, stirred, heated to 60℃, and kept at that temperature for 30 minutes to obtain a first mixture. 1.5g of catalyst (boron trifluoride diethyl ether solution) was added to the first mixture, and the mixture was stirred to obtain a second mixture. 0.5g of chain transfer agent (dodecyl mercaptan) was added to the second mixture, and the temperature was maintained at 60℃ for 30 hours. After the reaction was completed, sodium bicarbonate aqueous solution was added to separate the phases. The organic phase was collected, washed four times with deionized water, and the solvent was removed under reduced pressure to obtain a white viscous substance, which is the traditional hydrocarbon resin.

[0070] The obtained hydrocarbon resin was made into a cured sheet according to the conventional process. The dielectric loss was tested at a frequency of 10G, and the dielectric loss of the cured sheet was found to be 0.0015. At the same time, the glass transition temperature was measured to be 180℃ by DMA test.

[0071] All of the above-described embodiments conform to the limitations of this invention. The dielectric loss factor of the resulting cured sheets is between 0.0013 and 0.0016, indicating low dielectric loss and excellent dielectric properties. At the same time, the glass transition temperature is greater than 290°C, indicating high temperature, good heat resistance, and good strength, which is far superior to the performance parameters of the traditional hydrocarbon resin in Comparative Example 5.

[0072] Compared to Example 1, Comparative Examples 1 and 2 had reaction temperatures exceeding 40-85°C. In Comparative Example 1, the temperature was below 40°C, making the reaction between polycyclic aromatic hydrocarbons (PAHs) and chlorinated hydrocarbons difficult. Because different activation energies are required to generate different structures, some active hydrogen atoms from PAHs could not react with chlorinated hydrocarbons, resulting in a low content of the target product. Therefore, the dielectric loss of Comparative Example 1 (0.0025) was higher than that of Example 1, and its glass transition temperature (186°C) was much lower than that of Example 1, indicating higher dielectric loss and lower glass transition temperature, making it less rigid than Example 1. In Comparative Example 2, the temperature was above 85°C, which exacerbated the hydrolysis of chlorinated hydrocarbons in an alkaline environment, leading to the formation of non-reactive raw material structures, thus reducing the proportion of the target structure and introducing byproducts. Furthermore, unsaturated double bonds were prone to polymerization at high temperatures, forming large molecular products, which affected the performance of the final product. Although the glass transition temperature of Comparative Example 2 was also above 300°C, it was higher than that of Example 1 (0.0018) due to the affected dielectric loss.

[0073] Compared with Example 1, Comparative Examples 3 and 4 had a molar ratio of polycyclic aromatic hydrocarbons to chlorinated hydrocarbons that exceeded the specified range, resulting in residual active hydrogen or chlorinated hydrocarbons, which affected the performance of the finished product. The dielectric loss of Comparative Examples 3 and 4 was higher than that of Example 1, and the glass transition temperature was lower than 300°C, indicating that Comparative Examples 3 and 4 had insufficient rigidity.

[0074] Comparative Example 5 is a traditional hydrocarbon resin, which does have good dielectric properties with a dielectric loss of 0.0015. However, its glass transition temperature is 180℃, which is low and results in insufficient rigidity.

[0075] In summary, the examples demonstrate that the hydrocarbon resin obtained by the present invention has good dielectric properties, a high glass transition temperature, and good rigidity and strength.

[0076] The technical principles of the present invention have been described above with reference to specific embodiments. These descriptions are merely for explaining the principles of the invention and should not be construed as limiting the scope of protection of the invention in any way. Based on this explanation, those skilled in the art can readily conceive of other specific embodiments of the invention without inventive effort, and these embodiments will all fall within the scope of protection of the present invention.

Claims

1. A low dielectric high heat resistant hydrocarbon resin, characterized by, The low dielectric high heat-resistant hydrocarbon resin has a general structure as shown in the following formula: ； wherein n=0-30, and R is selected from at least one of a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, an aralkyl group, and a group shown in the following formula: ； R1 is selected from at least one of a hydrogen atom, an aliphatic alkenyl group, and an aralkenyl group. A is selected from or .

2. A method for preparing a low dielectric high heat resistant hydrocarbon resin, characterized by, A low dielectric high heat-resistant hydrocarbon resin as claimed in claim 1 is prepared by the following steps: S1. reacting a condensed aromatic hydrocarbon compound with a chlorinated hydrocarbon compound in an organic solvent; S2. removing the aqueous phase after adjusting the pH value of the reaction system to neutral; S3. distilling part of the organic solvent to a set solid content, and obtaining a low dielectric high heat-resistant hydrocarbon resin solution after cooling.

3. The method for preparing a low-dielectric, high-heat-resistant hydrocarbon resin according to claim 2, characterized in that: In step S1, the molar ratio of the condensed aromatic hydrocarbon compound to the chlorinated hydrocarbon compound is 1: (1.5-3.0).

4. The method for preparing a low-dielectric, high-heat-resistant hydrocarbon resin according to claim 2, characterized in that: In step S1, the reaction temperature is 40-85°C, and the reaction time is 6-30h.

5. The method for preparing a low-dielectric, high-heat-resistant hydrocarbon resin according to claim 2, characterized in that: The condensed aromatic hydrocarbon compound is selected from at least one of fluorene, indene, and benzindene. The chlorinated hydrocarbon compound is selected from at least one of dichlorobenzene, chloropropene, methyl chloropropene, chlorobutene, chloropentene, biphenyl dichlorobenzyl, p-dichlorobenzyl, chloromethyl styrene, and p-chlorostyrene.

6. The method for preparing a low-dielectric, high-heat-resistant hydrocarbon resin according to claim 2, characterized in that: The condensed aromatic hydrocarbon compound is a mixture of fluorene and indene.

7. The method for preparing a low-dielectric, high-heat-resistant hydrocarbon resin according to claim 2, characterized in that: The chlorinated hydrocarbon compound is selected from at least one of dichlorobenzene, chloropropene, methyl chloropropene, biphenyl dichlorobenzyl, p-dichlorobenzyl, and chloromethyl styrene.

8. The method for preparing a low-dielectric, high-heat-resistant hydrocarbon resin according to claim 2, characterized in that: In step S1, the organic solvent is one of toluene, xylene, and cyclohexane.

9. The method for preparing a low-dielectric, high-heat-resistant hydrocarbon resin according to claim 2, characterized in that: In step S1, a base solution is further added for reaction, and the base solution is a sodium hydroxide solution or a potassium hydroxide solution.

10. A low dielectric high heat resistant hydrocarbon resin composition, characterized by comprising: The low dielectric high heat-resistant hydrocarbon resin as claimed in claim 1.

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