A low-dielectric hydrocarbon resin, its synthesis method and application

Abstract

The present invention discloses a low-dielectric hydrocarbon resin, its synthesis method and application, relating to the technical field of organic synthesis. The synthesis method of the low-dielectric hydrocarbon resin of the present invention comprises the following steps: (1) Mix divinylbenzene and a solvent, and heat to 30-100 °C to obtain a first mixture; (2) Add a catalyst to the first mixture and stir evenly to obtain a second mixture; (3) Add a chain transfer agent to the second mixture, react at 30-100 °C for 1-60 h, after the reaction is completed, add an aqueous sodium bicarbonate solution for phase separation, and collect the organic phase; (4) Wash the organic phase and then remove the solvent to obtain the low-dielectric hydrocarbon resin. The synthesis method of the present invention uses the solvent method for synthesis, and can synthesize a low-dielectric hydrocarbon resin with a low dielectric constant and a high glass transition temperature.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and specifically to a low-dielectric hydrocarbon resin, a synthesis method thereof, and an application thereof. Background Art

[0002] Divinylbenzene is a highly reactive double-bond aromatic compound with the molecular formula C 10 H 10 . Currently, divinylbenzene is often used to synthesize high molecular polymers, and the high molecular polymers synthesized therefrom are mainly used as the skeleton of ion exchangers. For example, divinylbenzene and styrene are reacted to form a copolymer styrene-divinylbenzene, S-DVB (copolymer of divinylbenzene and styrene), or Sty-DVB (copolymer of styrene and divinylbenzene). The formed cross-linked polymer is mainly used for producing ion exchange resins, mainly in the field of adsorption separation materials, such as in the fields of adsorbing and removing carbon dioxide and separating and purifying water.

[0003] Currently, there is little research on synthesizing polymers with low dielectric constants using divinylbenzene as a raw material. Summary of the Invention

[0004] In view of the above deficiencies of the prior art, the object of the present invention is to propose a synthesis method of a low-dielectric hydrocarbon resin, which is synthesized by a solvent method and can synthesize a low-dielectric hydrocarbon resin with a low dielectric constant and a high glass transition temperature.

[0005] Another object of the present invention is to propose a low-dielectric hydrocarbon resin, which is synthesized by the above synthesis method, has a low dielectric constant and a high glass transition temperature, and can be applied to the field of copper clad laminates.

[0006] Another object of the present invention is to propose the application of the low-dielectric hydrocarbon resin in the preparation of high-frequency copper clad laminates, and to develop a new application field for divinylbenzene polymers.

[0007] To achieve this purpose, the present invention adopts the following technical solutions:

[0008] A synthesis method of a low-dielectric hydrocarbon resin, comprising the following steps:

[0009] (1) Mix divinylbenzene and a solvent, and heat to 30-100 °C to obtain a first mixture;

[0010] (2) Add a catalyst to the first mixture and stir evenly to obtain a second mixture;

[0011] (3) Add a chain transfer agent to the second mixture, react at 30-100 °C for 1-60 h, after the reaction is completed, add an aqueous sodium bicarbonate solution for phase separation, and collect the organic phase;

[0012] (4) After washing the organic phase, the solvent is removed to obtain a low dielectric hydrocarbon resin.

[0013] Preferably, the mass of the solvent is 10-1000% of the mass of the divinylbenzene;

[0014] The mass of the catalyst is 0.01%-10% of the mass of the divinylbenzene;

[0015] The mass of the chain transfer agent is 0.1%-10% of the mass of the divinylbenzene.

[0016] Preferably, in step (4), after washing the organic phase, the solvent is removed by vacuum distillation to obtain a low dielectric hydrocarbon resin.

[0017] Preferably, the solvent is any one or a combination of lipid compounds, ketone compounds and aromatic compounds.

[0018] Preferably, the catalyst is an acidic catalyst.

[0019] Preferably, the acidic catalyst is an organic acid or a Lewis acid.

[0020] Preferably, the chain transfer agent includes 2,4-diphenyl-4-methyl-1-pentene and / or dodecyl mercaptan.

[0021] A low dielectric hydrocarbon resin is synthesized by the above-mentioned synthesis method of the low dielectric hydrocarbon resin. The weight average molecular weight of the low dielectric hydrocarbon resin is 9500-28000, and the dielectric loss ≤0.0045.

[0022] An application of a low dielectric hydrocarbon resin in preparing a high-frequency copper clad laminate, using the above-mentioned low dielectric hydrocarbon resin.

[0023] The technical solution provided by the embodiments of the present application may include the following beneficial effects:

[0024] 1. Divinylbenzene is a substance with bifunctional groups, which contains two unsaturated bonds. The synthesis method of the present technical solution uses divinylbenzene as a raw material and is synthesized by a solvent method. During the synthesis process, the molecular weight of the reaction product is controlled by controlling process conditions, and partial double bonds of divinylbenzene are retained, so that a low dielectric hydrocarbon resin with a low dielectric constant and a high glass transition temperature can be synthesized.

[0025] 2. The low-dielectric hydrocarbon resin of this technical solution is a small-molecule divinylbenzene polymer, which is a low-dielectric constant resin containing unsaturated double-bond functional groups. It has the advantages of easy solubility, low-dielectric properties, high glass transition temperature, and simple product production process. The low-dielectric hydrocarbon resin of this technical solution can meet the requirements of the high-speed and high-frequency copper clad laminate field and can be used in the field of high-speed and high-frequency copper clad laminate materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is the chemical structural formula of the low-dielectric hydrocarbon resin prepared in Example 1 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0027] To facilitate the understanding of the present invention, the present invention will be described more comprehensively below. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0028] For those not specified in the embodiments, the techniques or conditions are described according to the techniques or conditions described in the literature in this field or according to the product specifications. For raw materials not specified for the manufacturer, they are all conventional products that can be obtained through commercial purchases.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0030] The technical solution of the present invention will be further described below in conjunction with the specific embodiments.

[0031] A synthesis method of a low-dielectric hydrocarbon resin, comprising the following steps:

[0032] (1) After mixing divinylbenzene and a solvent, heat to 30-100 °C to obtain a first mixture;

[0033] (2) Add a catalyst to the first mixture and stir evenly to obtain a second mixture;

[0034] (3) Add a chain transfer agent to the second mixture, react at 30-100 °C for 1-60 h, after the reaction is completed, add an aqueous sodium bicarbonate solution for phase separation, and collect the organic phase;

[0035] (4) After washing the organic phase, remove the solvent to obtain a low-dielectric hydrocarbon resin.

[0036] It should be noted that divinylbenzene is a substance with bifunctional groups, which contains two unsaturated bonds. The synthesis method of this technical solution uses divinylbenzene as the raw material and is synthesized by the solvent method. During the synthesis process, the molecular weight of the reaction product is controlled by process conditions, and partial double bonds of divinylbenzene are retained, so that a low-dielectric hydrocarbon resin with a low dielectric constant and a high glass transition temperature can be synthesized. The low-dielectric hydrocarbon resin of this technical solution is a small-molecule divinylbenzene polymer, which is a low-dielectric constant resin containing unsaturated double bond functional groups, and has the advantages of easy solubility, low dielectric properties, high glass transition temperature and simple product production process. The chemical structure of the low-dielectric hydrocarbon resin of this technical solution is shown as follows:

[0037]

[0038] Since the low-dielectric hydrocarbon resin synthesized by this technical solution has a low dielectric constant and a high glass transition temperature, the low-dielectric hydrocarbon resin can be used in the fields of electronic packaging materials, high-performance resins and high-performance composite materials. Moreover, due to the low dielectric constant of the low-dielectric hydrocarbon resin of this technical solution, the dielectric loss ≤ 0.0045, the low-dielectric hydrocarbon resin of this technical solution can meet the requirements of the high-speed high-frequency copper clad laminate field.

[0039] Further explanation, divinylbenzene is a substance with bifunctional groups (containing two unsaturated bonds). During the synthesis process, through process condition control, some of its double bonds are retained, which can increase the crosslinking density during the later curing process, so that the synthesized low-dielectric hydrocarbon resin has a higher glass transition temperature. At the same time, during the synthesis process, by controlling process conditions such as reaction temperature to control the molecular weight of the reaction product and making the reaction product retain some double bonds, a hydrocarbon resin with a certain molecular weight is synthesized, and the hydrocarbon resin has a low dielectric constant, and the dielectric loss ≤ 0.0045.

[0040] Specifically, during the synthesis of the low-dielectric hydrocarbon resin in this technical solution, adding a catalyst in step (2) is beneficial to controlling the reaction rate, and adding a chain transfer agent in step (3) is beneficial to integrating the molecular weight to obtain a low-dielectric hydrocarbon resin with a certain molecular weight. At the same time, during the whole reaction process of this technical solution, the reaction temperature needs to be controlled at 30 - 100 °C, which is beneficial to synthesizing a hydrocarbon resin with a low dielectric constant and a high glass transition temperature. At the same time, it can reduce the reaction cycle and is beneficial to controlling the reaction rate, which is beneficial to production, and avoids too long reaction cycle and difficult control of reaction rate, so as to avoid safety problems.

[0041] There is no limit to the concentration of the sodium bicarbonate aqueous solution used in this technical solution. Preferably, the mass concentration of the sodium bicarbonate aqueous solution at room temperature is 1 - 7%.

[0042] Further explanation: The mass of the solvent is 10% to 1000% of the mass of divinylbenzene;

[0043] The mass of the catalyst is 0.01% to 10% of the mass of divinylbenzene;

[0044] The mass of the chain transfer agent is 0.1% to 10% of the mass of divinylbenzene.

[0045] In this technical solution, by controlling the dosages of the catalyst and the chain transfer agent, as well as controlling the reaction temperature and reaction time, the reaction rate and the molecular weight of the reaction product are controlled, so that the whole reaction process is safe and controllable, and part of the double bonds are retained in the reaction product, obtaining a low-dielectric hydrocarbon resin with a certain molecular weight.

[0046] Further explanation: In step (4), after washing the organic phase, the solvent is removed by vacuum distillation to obtain the low-dielectric hydrocarbon resin.

[0047] It should be noted that since the low-dielectric hydrocarbon resin synthesized by this technical solution is prone to self-polymerization at high temperatures, the double bonds of the product cannot be retained, and the low-dielectric property is lost. Therefore, in step (4), this technical solution uses vacuum distillation to remove the solvent. The method of vacuum distillation can reduce the boiling point of the solvent, making it easier to be evaporated and removed. During the vacuum distillation process, the solvent is evaporated at a lower temperature, so as to be separated from the product. Since the evaporation temperature is low, it can prevent the low-dielectric hydrocarbon resin from self-polymerizing, ensuring that the obtained product has a lower dielectric constant. In addition, vacuum distillation can also reduce the loss and volatilization of the solvent, improve the recovery rate of the solvent, and reduce the production cost. At the same time, vacuum distillation can also remove other volatile impurities in the product, improving the purity and quality of the product.

[0048] It should be noted that it is not easy to use heating to remove the solvent in this technical solution. Atmospheric heating requires a relatively high temperature, and at high temperatures, the product is prone to self-polymerization.

[0049] Further explanation: The solvent is any one or a combination of more of lipid compounds, ketone compounds, and aromatic compounds.

[0050] More preferably, the solvent in this technical solution is any one or a combination of more of butyl acetate, methyl acetate, butanone, and toluene.

[0051] Further explanation: The catalyst is an acidic catalyst.

[0052] Further explanation: The acidic catalyst is an organic acid or a Lewis acid.

[0053] Preferably, the acidic catalyst is an organic acid or a Lewis acid. For example, organic acids such as methanesulfonic acid and p-toluenesulfonic acid can be used, and Lewis acids such as tin tetrachloride and aluminum trichloride can also be used. Using these acidic catalysts can promote the reaction and is beneficial to controlling the reaction rate. If other catalysts are used, it is difficult for the reaction to occur or for the reaction rate to be controlled.

[0054] Further illustration, the chain transfer agent includes 2,4-diphenyl-4-methyl-1-pentene and / or dodecyl mercaptan.

[0055] Specifically, during the synthesis of the low dielectric hydrocarbon resin, the chain transfer agent can control the polymerization activity of the polymerization reaction, thereby being able to control the molecular weight and molecular weight distribution of the polymer in the polymerization reaction. In this technical solution, the chain transfer agent includes 2,4-diphenyl-4-methyl-1-pentene and / or dodecyl mercaptan, so that the chain transfer agent will not remain in the product and affect the self-performance of the final product. If other chain transfer agents are used, it is easy for the chain transfer agent to remain in the product and affect the performance of the product itself.

[0056] Specifically, dodecyl mercaptan is also called lauryl mercaptan, and its chemical formula is C 12 H 26 S.

[0057] A low dielectric hydrocarbon resin is synthesized by the above-mentioned synthesis method of the low dielectric hydrocarbon resin. The weight average molecular weight of the low dielectric hydrocarbon resin is 9,500 - 28,000, and the dielectric loss ≤ 0.0045.

[0058] This technical solution uses divinylbenzene as the raw material and is synthesized by the solvent method. After removing the volatile components, a low dielectric hydrocarbon resin with a weight average molecular weight of 9,500 - 28,000 and a dielectric loss ≤ 0.0045 can be synthesized. The dielectric loss (Df) mainly affects the quality of signal transmission. The smaller the dielectric loss, the smaller the loss in signal transmission. The Df of high-frequency copper clad laminates is usually required to be less than 0.005. In addition, to meet the development needs of 5G technology, high-frequency and high-speed copper clad laminates have the characteristic of low signal loss, which also puts forward strict requirements for low dielectric loss of their substrates. The dielectric loss of the low dielectric hydrocarbon resin synthesized in this technical solution is ≤ 0.0045. For example, in some embodiments of this technical solution, low dielectric hydrocarbon resins with dielectric losses (Df) of 0.0032, 0.0035, and 0.0037 can be synthesized, which can meet the requirements of high-frequency and high-speed copper clad laminates.

[0059] An application of a low dielectric hydrocarbon resin in the preparation of a high-frequency copper clad laminate, using the above-mentioned low dielectric hydrocarbon resin.

[0060] It should be noted that the hydrocarbon resin synthesized by this technical solution has a low dielectric constant and a dielectric loss ≤ 0.0045, enabling the hydrocarbon resin of this technical solution to meet the requirements of the high-speed and high-frequency copper clad laminate field and be used in the field of high-speed and high-frequency copper clad laminate materials. This technical solution has developed a new application field for divinylbenzene polymers.

[0061] The technical solution of the present invention will be further elaborated below in conjunction with specific embodiments.

[0062] Example 1

[0063] The synthesis method of the low-dielectric hydrocarbon resin in this example includes the following steps:

[0064] (1) Add 100 g of divinylbenzene and 100 g of solvent (methyl ethyl ketone) to a 1000 ml flask, start stirring, heat to 40 °C, and keep warm for 30 min to obtain a first mixture;

[0065] (2) Add 1 g of catalyst (methanesulfonic acid) to the first mixture and stir for 60 min to obtain a second mixture;

[0066] (3) Add 3 g of chain transfer agent (2,4-diphenyl-4-methyl-1-pentene) to the second mixture, keep the temperature at 40 °C, and react for 20 h; after the reaction is completed, add an aqueous sodium bicarbonate solution for phase separation, and collect the organic phase;

[0067] (4) Wash the organic phase 3 times with deionized water, and then remove the solvent under reduced pressure to obtain a white viscous substance, which is the low-dielectric hydrocarbon resin.

[0068] Specifically, through testing, it is obtained that the weight-average molecular weight of the low-dielectric hydrocarbon resin in this example is 28,000. After the low-dielectric hydrocarbon resin is made into a cured sheet by a conventional method in the art, the dielectric loss test is carried out under the condition of a frequency of 5G, and the dielectric loss of the cured sheet is measured to be 0.0032. It can be seen that the low-dielectric hydrocarbon resin prepared in this example has a low dielectric loss. Due to the low dielectric loss, the communication signal delay is low and the signal loss is small, so it can meet the requirements of current high-speed and high-frequency communications. At the same time, the glass transition temperature DMA test of the cured sheet prepared in this example reaches 228 °C. Thus, it can be seen that the low-dielectric hydrocarbon resin in this example has a high glass transition temperature.

[0069] Example 2

[0070] The synthesis method of the low-dielectric hydrocarbon resin in this example includes the following steps:

[0071] (1) Add 100 g of divinylbenzene and 150 g of solvent (100 g of butyl acetate + 50 g of toluene) to a 1000 ml flask. Start stirring and heat to 60 °C. Keep the temperature for 30 min to obtain the first mixture;

[0072] (2) Add 4.5 g of catalyst (p-toluenesulfonic acid) to the first mixture and stir for 60 min to obtain the second mixture;

[0073] (3) Add 0.5 g of chain transfer agent (dodecyl mercaptan) to the second mixture. Keep the temperature at 60 °C and react for 40 h. After the reaction is completed, add an aqueous sodium bicarbonate solution for phase separation and collect the organic phase;

[0074] (4) Wash the organic phase 4 times with deionized water, and then remove the solvent under reduced pressure to obtain a white viscous substance, which is the low dielectric hydrocarbon resin.

[0075] Specifically, through testing, it is obtained that the weight average molecular weight of the low dielectric hydrocarbon resin in this example is 9500. After the low dielectric hydrocarbon resin is made into a cured film by a conventional method in the art, the dielectric loss test is carried out under the condition of a frequency of 5 G. The dielectric loss of the cured film is measured to be 0.0035. It can be seen that the low dielectric hydrocarbon resin prepared in this example has a low dielectric loss. At the same time, the glass transition temperature DMA test is carried out on the cured film prepared in this example, and it reaches 210 °C. Thus, it can be seen that the low dielectric hydrocarbon resin in this example has a high glass transition temperature.

[0076] Example 3

[0077] The synthesis method of the low dielectric hydrocarbon resin in this example includes the following steps:

[0078] (1) Add 200 g of divinylbenzene and 100 g of solvent (methyl acetate) to a 1000 ml flask. Start stirring and heat to 35 °C. Keep the temperature for 30 min to obtain the first mixture;

[0079] (2) Add 1.8 g of catalyst (methanesulfonic acid) to the first mixture and stir for 60 min to obtain the second mixture;

[0080] (3) Add 1 g of chain transfer agent (dodecyl mercaptan) to the second mixture. Keep the temperature at 35 °C and react for 50 h. After the reaction is completed, add an aqueous sodium bicarbonate solution for phase separation and collect the organic phase;

[0081] (4) Wash the organic phase 4 times with deionized water, and then remove the solvent under reduced pressure to obtain a white viscous substance, which is the low dielectric hydrocarbon resin.

[0082] Specifically, the test shows that the weight average molecular weight of the low dielectric hydrocarbon resin of this embodiment is 15500; after the low dielectric hydrocarbon resin is made into a cured sheet according to the conventional method in the art, a dielectric loss test is performed under a frequency of 5G, and the dielectric loss of the cured sheet is 0.0037. It can be seen that the low dielectric hydrocarbon resin prepared in this embodiment has a low dielectric loss. At the same time, the cured sheet prepared in this embodiment is subjected to a glass transition temperature DMA test, which reaches 230°C. It can be seen that the low dielectric hydrocarbon resin of this embodiment has a high glass transition temperature.

[0083] The technical principle of the present invention is described above in conjunction with specific embodiments. These descriptions are only for explaining the principle of the present invention and cannot be interpreted as limiting the scope of protection of the present invention in any way. Based on the explanations herein, those skilled in the art can associate other specific implementations of the present invention without paying creative labor, and these methods will fall within the scope of protection of the present invention.

Claims

1. A synthesis method of a low-dielectric hydrocarbon resin, the weight-average molecular weight of the low-dielectric hydrocarbon resin being 9,500 and the dielectric loss Df being 0.0035, characterized in that, The synthesis method of the low-dielectric hydrocarbon resin is as follows: (1) Add 100 g of divinylbenzene and 150 g of solvent to a 1000 ml flask, start stirring, heat to 60 °C, and keep warm for 30 min to obtain a first mixture; wherein, the solvent composition is: 100 g of butyl acetate and 50 g of toluene; (2) Add 4.5 g of the catalyst p-toluenesulfonic acid to the first mixture and stir for 60 min to obtain a second mixture; (3) Add 0.5 g of the chain transfer agent dodecyl mercaptan to the second mixture, keep the temperature at 60 °C, and react for 40 h; after the reaction is completed, add an aqueous sodium bicarbonate solution for phase separation, and collect the organic phase; (4) Wash the organic phase 4 times with deionized water, and then remove the solvent under reduced pressure to obtain a white viscous substance, which is the low-dielectric hydrocarbon resin.

2. A low-dielectric hydrocarbon resin synthesized by the synthesis method according to claim 1.

3. An application of the low-dielectric hydrocarbon resin according to claim 2 in the preparation of high-frequency copper clad laminates.

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