Benzocyclobutene-based dielectric material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of dielectric materials, and particularly relates to a benzocyclobutene-based dielectric material as well as a preparation method and application thereof. The benzocyclobutene-based dielectric material provided by the invention is obtained by carrying out a Heck reaction on a halogenated benzocyclobutene derivative, dicyclopentadiene and / or a dicyclopentadiene derivative, has excellent comprehensive properties such as dielectric properties and thermal stability, and can be used in a high-frequency and high-speed printed circuit board (PCB); meanwhile, by introducing different substituent groups, hydrogenation is performed to remove unsaturated double bonds, so that the dielectric property of the benzocyclobutene-based dielectric material is further improved, and the technical problem that a dielectric material for a high-frequency and high-speed printed circuit board (PCB) is lacked in the prior art can be solved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of dielectric materials, and particularly relates to a dielectric material based on benzocyclobutene and a preparation method and application thereof. BACKGROUND

[0002] The dielectric performance of the material used in the PCB board will affect signal transmission. The higher the dielectric constant Dk, the slower the signal propagation speed in the PCB board, resulting in signal delay. The greater the dielectric loss Df, the more serious the signal attenuation in the signal transmission process, reducing the signal transmission distance and quality. Meanwhile, the greater the dielectric loss Df, the more part of the electric energy is converted into heat energy, affecting the reliability of the PCB board.

[0003] In recent years, with the development of the technical fields of 5G communication, automotive intelligent driving, and computing chip, the demand for high-frequency and high-speed printed circuit boards (PCB) is promoted. The high-frequency and high-speed PCB requires more excellent dielectric constant Dk and dielectric loss Df. Meanwhile, the miniaturization and refinement of the high-frequency and high-speed PCB also put forward higher requirements on the heat resistance and thermal expansion coefficient of the used material. At present, the PCB mainly uses the composite thermosetting resin of end-vinyl polyphenyl ether and triallyl isocyanurate (TAIC). Although the composite thermosetting resin has excellent mechanical properties and heat resistance, it cannot meet the lower Dk and Df due to the presence of polar groups in TAIC. Therefore, it is urgent to develop new low-dielectric materials to meet the demand of high-frequency and high-speed PCB.

[0004] Benzocyclobutene (BCB) is an excellent low-dielectric material. However, benzocyclobutene (BCB) is a low-boiling-point volatile liquid and cannot be directly used in high-frequency and high-speed PCB. It needs to be made into a derivative to make it more widely used. SUMMARY

[0005] Therefore, the application provides a dielectric material based on benzocyclobutene and a preparation method and application thereof, to solve the technical problem of lack of dielectric material for high-frequency and high-speed PCB in the prior art.

[0006] The first aspect of the application provides a dielectric material based on benzocyclobutene, which comprises a BCB-containing dicyclopentadiene derivative and a hydrogenated product thereof. The BCB-containing dicyclopentadiene derivative has a general structure shown in formula I.

[0007] Formula I;

[0008] In formula I, the substituents R1, R2, R3, R4, R5, and R6 are at least one of a hydrogen atom, an alkyl group, and an aryl group, and at least one BCB group is included in the substituents R1, R2, R3, and R4.

[0009] It should be noted that in the present application, the alkyl group includes linear or branched alkyl group, cycloalkyl group; the aryl group includes alkyl-substituted aryl group, aryl-substituted alkyl group, aryl-substituted aryl group, polyaryl group and hydrocarbyl-substituted polyaryl group.

[0010] The hydrogenate is a hydrogenation product of reducing the double bond in the BCB-containing dicyclopentadiene derivative, including at least one double bond reduction; preferably, the hydrogenate is a hydrogenate in which all the double bonds are reduced.

[0011] The molecular structure of the BCB group is shown in Formula II:

[0012] Formula II;

[0013] In Formula II, the linking group R is selected from at least one of a chemical single bond, alkylene group and arylene group; one end of the linking group R is connected to any one carbon atom of the BCB ring, and the other end is represented by a wavy line to be connected to any one carbon atom of the double bond in dicyclopentadiene;

[0014] In Formula II, the substituent group R' is selected from at least one of hydrogen atom, alkyl group and aryl group; the substituent group R' is at least one substituent group other than the linking group R of the BCB ring or a substituent group forming a ring with the BCB.

[0015] Preferably, in the linking group R, the chemical single bond is represented as a single bond directly connecting the BCB benzene ring; the number of carbon atoms in the alkylene group is an integer from 1 to 30, and the number of carbon atoms in the arylene group is an integer from 6 to 30.

[0016] Preferably, in the linking group R, the alkylene group is selected from at least one of methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, nonylene group, decylene group, dodecylene group, hexadecylene group, octadecylene group and their isomers.

[0017] The arylene group is selected from at least one of phenylene group, benzylidene group, phenylethylene group, biphenylene group, methylene phenylethyl group, biphenylene methyl group, biphenylmethyl group, biphenylethyl group and their isomers.

[0018] Preferably, in the substituent group R', the alkyl group is selected from at least one of alkyl groups with a carbon atom number of 1 to 30; the number of carbon atoms in the aryl group is an integer from 6 to 30, and the aryl group includes at least one of alkyl- and / or aryl-substituted aryl group, aryl-substituted alkyl group and polyaryl group.

[0019] Preferably, in the substituent R', the alkyl group is selected from at least one of methyl, ethyl, propyl, butyl, pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, dodecyl, eicosyl, and isomers thereof, and cyclobutyl ringed with the benzene ring in the BCB group.

[0020] Preferably, in the substituent R', the aryl group is selected from at least one of phenyl, o-tolyl, p-tolyl, m-tolyl, o-ethylphenyl, p-ethylphenyl, m-ethylphenyl, o-iso-propylphenyl, p-iso-propylphenyl, m-iso-propylphenyl, biphenyl, naphthyl, phenyl ringed with the benzene ring in the BCB ring, and benzocyclobutene group ringed with the benzene ring in the BCB ring.

[0021] The second aspect of the present application provides a preparation method of a dielectric material based on benzocyclobutene, which can prepare the dielectric material based on benzocyclobutene according to the first aspect of the present application. The reaction steps of the preparation method include: carrying out a Heck reaction on a halogenated benzocyclobutene derivative, dicyclopentadiene and / or a dicyclopentadiene derivative to obtain a dielectric material based on benzocyclobutene, i.e., a dicyclopentadiene derivative containing BCB.

[0022] Preferably, after the Heck reaction, a hydrogenation reaction is further included to obtain a hydrogenated product of the dielectric material based on benzocyclobutene, i.e., a dicyclopentadiene derivative containing BCB.

[0023] Preferably, the chemical structure of the halogenated benzocyclobutene derivative is as shown in any one of the following chemical structures:

[0024] wherein X is a halogen.

[0025] Preferably, the halogen is selected from Cl, Br or I.

[0026] Preferably, the chemical structure of the dicyclopentadiene and the dicyclopentadiene derivative thereof is as shown below:

[0027] wherein substituents R1', R2', R3', R4', R5 and R6 are selected from at least one of a hydrogen atom, an alkyl group and an aryl group, and at least one of the substituents R1', R2', R3' and R4' is a hydrogen atom.

[0028] Preferably, the ratio of the molar amount of the halogenated benzocyclobutene derivative to the molar amount of the dicyclopentadiene and / or the dicyclopentadiene derivative is (1.0-5.5):1.0.

[0029] Preferably, the ratio of the molar amount of the halogenated benzocyclobutene derivative to the molar amount of the dicyclopentadiene and / or the dicyclopentadiene derivative is (1.0-5.0):1.0.

[0030] Preferably, the atmosphere used in the Heck reaction is at least one of nitrogen, argon, and helium;

[0031] The palladium catalyst used in the Heck reaction is selected from at least one of palladium chloride, palladium acetate, diphenylphosphinyl ferrocene dichloride, triphenylphosphine palladium, and dichlorobistrimethylphenylphosphine palladium, and the amount of palladium catalyst is 0.01-5% of the molar amount of the halogenated BCB derivative;

[0032] The phosphine ligand used in the Heck reaction is selected from at least one of triphenylphosphine, tri(o-methylphenyl)phosphine, tributylphosphine, tricyclohexylphosphine, tri(2-methoxyphenyl)phosphine, and tri(4-trifluoromethylphenyl)phosphine, and the amount of phosphine ligand is 0.01-15% of the molar amount of the halogenated BCB derivative;

[0033] The acid binding agent used in the Heck reaction is selected from at least one of triethylamine, diisopropylethylamine, N-ethyldicyclohexylamine, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, potassium acetate, sodium acetate, and cesium carbonate, and the amount of acid binding agent is 100-150% of the molar amount of the halogenated BCB derivative;

[0034] The organic solvent used in the Heck reaction is selected from at least one of acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, toluene, xylene, and mesitylene, and the volume of the organic solvent is 1-30 times the mass of the dicyclopentadiene and / or dicyclopentadiene derivative.

[0035] Preferably, the temperature of the Heck reaction is 80-150°C, and the time is 5-20 h.

[0036] Preferably, the hydrogen gas atmosphere pressure of the hydrogenation reaction is 0.2-2.0 Mpa;

[0037] The catalyst used in the hydrogenation reaction is selected from at least one of palladium-carbon, platinum-carbon, and active nickel, and the amount of catalyst is 0.1-10.0% of the mass of the BCB-containing dicyclopentadiene derivative;

[0038] The solvent used in the hydrogenation reaction is selected from at least one of acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, toluene, xylene, and mesitylene, and the volume of the solvent is 3-15 times the mass of the BCB-containing dicyclopentadiene derivative.

[0039] Preferably, the temperature of the hydrogenation reaction is 50-120°C, and the time is 2-10 h.

[0040] Preferably, after the Heck reaction, the process further comprises a post-treatment step of separation and purification of the Heck reaction before the hydrogenation reaction: sequentially cooling to room temperature, removing the catalyst by filtration, concentrating the filtrate under reduced pressure, passing the concentrated residue through a neutral alumina column and eluting with n-hexane, and spinning to dry the solvent in the eluate to obtain the product, the dielectric material based on benzocyclobutene.

[0041] Preferably, after the hydrogenation reaction, the process further comprises a post-treatment step of separation and purification of the hydrogenation reaction: sequentially cooling to room temperature, removing the catalyst by filtration, concentrating the filtrate under reduced pressure, passing the crude product through a crystallization process or a silica gel column chromatography, and spinning to dry the solvent in the eluate to obtain the product, the dielectric material based on benzocyclobutene.

[0042] The third aspect of the present application provides an application of the dielectric material based on benzocyclobutene in the first aspect in the preparation of a high-frequency high-speed printed circuit board (PCB).

[0043] Preferably, the application in the preparation of a high-frequency high-speed printed circuit board (PCB) is specifically an application in the preparation of a resin sheet, a resin composite metal foil, a prepreg, a laminate, a metal-clad laminate, a potting layer, or an insulating coating layer of a high-frequency high-speed printed circuit board (PCB).

[0044] The fourth aspect of the present application provides a high-frequency high-speed printed circuit board (PCB) comprising an insulating substrate made of the dielectric material based on benzocyclobutene in the first aspect.

[0045] The fifth aspect of the present application provides a high-frequency high-speed printed circuit board (PCB), wherein a potting layer made of the dielectric material based on benzocyclobutene in the first aspect is filled around electronic components of the high-frequency high-speed printed circuit board (PCB).

[0046] The sixth aspect of the present application provides a high-frequency high-speed printed circuit board (PCB), wherein an insulating coating layer made of the dielectric material based on benzocyclobutene in the first aspect is coated on the surface of electronic components of the high-frequency high-speed printed circuit board (PCB).

[0047] Compared with the prior art, the dielectric material based on benzocyclobutene provided by the present application has at least the following beneficial effects:

[0048] 1. The dielectric material based on benzocyclobutene provided by the present application contains benzocyclobutene and a dicyclopentadiene group, has excellent dielectric properties and thermal stability, and can meet the comprehensive requirements of high-frequency high-speed printed circuit boards (PCBs) in terms of dielectric properties and thermal properties.

[0049] 2、The dielectric material based on benzocyclobutene provided by the application can further improve the dielectric property / thermal stability of the dielectric material based on benzocyclobutene by introducing different substituents or removing unsaturated double bonds through hydrogenation in the structure.

[0050] 3、The dielectric material based on benzocyclobutene provided by the application is obtained by carrying out Heck reaction on halogen-substituted benzocyclobutene and / or benzocyclobutene derivatives and dicyclopentadiene and / or dicyclopentadiene derivatives, and almost no by-products are generated in the process of the Heck reaction, and the yield is high.

[0051] 4、The dielectric material based on benzocyclobutene provided by the application has excellent comprehensive performance, and can be used for preparing resin sheets, resin composite metal foils, prepregs, laminates and metal-clad laminates in high-frequency high-speed printed circuit boards (PCB), or preparing potting layers and insulating coating layers, and is widely applied in high-frequency high-speed printed circuit boards (PCB). DETAILED DESCRIPTION

[0052] The application provides a dielectric material based on benzocyclobutene and a preparation method and application thereof, and aims to solve the technical problem of lack of dielectric materials for high-frequency high-speed printed circuit boards (PCB) in the prior art.

[0053] The technical solutions of the application will be clearly and completely described below. Obviously, the described embodiments are some of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative efforts belong to the protection scope of the application.

[0054] In view of the defects that the current low-dielectric material benzocyclobutene (BCB) is a low-boiling-point volatile liquid and cannot be directly used for high-frequency high-speed printed circuit boards (PCB), the application provides a dielectric material based on benzocyclobutene, the dielectric material based on benzocyclobutene is selected from BCB-containing dicyclopentadiene derivatives and hydrogenated products thereof, and the BCB-containing dicyclopentadiene derivatives have the structure general formula shown in formula I.

[0055] Formula I;

[0056] In formula I, the substituents R1, R2, R3, R4, R5 and R6 are at least one of a hydrogen atom, an alkyl group and an aryl group, and at least one of the substituents R1, R2, R3 and R4 contains a BCB group.

[0057] It is to be understood that alkyl includes straight-chain or branched-chain alkyl, cycloalkyl, substituted cycloalkyl, cycloalkyl-substituted alkyl; aryl includes alkyl-substituted aryl, aryl-substituted alkyl, aryl-substituted aryl, polyaryl group; polyaryl group includes naphthalene, anthracene, phenanthrene, naphthacene, pentacene, fluorene, perylene, pyrene, and derivatives thereof containing substituents.

[0058] The dielectric material based on benzocyclobutene provided by the present application introduces dicyclopentadiene and derivatives thereof, the double bond on the dicyclopentadiene (DCPD) has the property of unsaturated olefin, and the chemical property is very active. The dicyclopentadiene is introduced into resin synthesis, and through continuous research and development, a series of products of unsaturated polyester resin have been developed so far, which are widely used in the fields of corrosion resistance, high temperature resistance, ship use, surface coating, SMC / BMC, etc., and are not used for preparing printed circuit board (PCB). In the present application, halogen-substituted benzocyclobutene (BCB) and / or benzocyclobutene (BCB) derivatives, dicyclopentadiene and / or dicyclopentadiene derivatives are reacted through Heck reaction. On the one hand, the defect that benzocyclobutene (BCB) is a low-boiling-point volatile liquid is avoided, and the low dielectric property of benzocyclobutene (BCB) can be utilized. On the other hand, the high-temperature resistance property of dicyclopentadiene and derivatives thereof is also utilized. The dielectric material based on benzocyclobutene prepared by the present application not only has good dielectric property as a full carbon-hydrogen structure, but also has good thermal stability, and is expected to meet the comprehensive requirements of high-frequency high-speed printed circuit board (PCB) in dielectric property, thermal property, etc., and overcome the defect that ordinary benzocyclobutene (BCB) cannot be directly used for high-frequency high-speed printed circuit board (PCB). Meanwhile, the present application further provides a hydride of the dielectric material based on benzocyclobutene. The dielectric material based on benzocyclobutene and the hydride thereof have similar chemical structures, and are both used for preparing high-frequency high-speed printed circuit board (PCB) as dielectric materials with excellent properties. However, the hydride of the dielectric material based on benzocyclobutene removes the unsaturated double bond, avoids the defect that the large electronic polarizability of the unsaturated double bond easily leads to large polarization intensity, and increases the dielectric constant of the material, so that the dielectric loss is easily avoided. The dielectric property of the dielectric material based on benzocyclobutene is further improved.

[0059] As preferred, the present application further provides a group of dielectric materials based on benzocyclobutene with the following chemical structures (wherein BCB represents a benzocyclobutene group, Ph represents a phenyl group, and Bn represents a benzyl group), as shown in A~L:

[0060] A, B;

[0061] C, D;

[0062] E、 F;

[0063] G、 H;

[0064] I、 J;

[0065] K、 L。

[0066] As can be seen from the chemical structures A~D, I, J, in the dielectric material based on benzocyclobutene shown in formula I, in addition to the BCB group, the substituents R1, R2, R3, R4may also be hydrogen or aryl such as phenyl, benzyl, and of course alkyl; as can be seen from the chemical structures E~H, K, L, in the dielectric material based on benzocyclobutene shown in formula I, in addition to the chemical single bond, the linking group R may also be alkylene such as methylene, or arylene; by using different substituents on the structure of the dielectric material based on benzocyclobutene, the performance of the dielectric material based on benzocyclobutene can be improved, for example, by using more BCB groups for substitution, as the number of BCB groups on R1, R2, R3, R4increases, the thermal stability and dielectric properties of the dielectric material based on benzocyclobutene also show an increasing trend, or by using phenyl substitution, the thermal stability of the dielectric material based on benzocyclobutene can be improved, by using aryl substitution, compared with alkyl substitution, the dielectric constant and dielectric loss can be further reduced on the basis of improving the thermal stability, so that the dielectric properties are further improved; further, the present application can also use alkyl, aryl and the like to substitute hydrogen atoms on any at least one carbon atom other than the linking group bond R of the BCB group, so as to further affect the space structure, electron cloud distribution, polarity of the dielectric material based on benzocyclobutene and improve the dielectric properties, for example, compared with alkyl, introducing aryl and the like substituents on any at least one carbon atom other than the linking group bond of the BCB group can further improve the dielectric properties and thermal stability of the dielectric material based on benzocyclobutene.

[0067] Correspondingly, the present application also provides a preparation method of the dielectric material based on benzocyclobutene, which is a Heck reaction, that is, carrying out a Heck reaction on halogenated benzocyclobutene derivatives, dicyclopentadiene and / or dicyclopentadiene derivatives, and then a dielectric material based on benzocyclobutene is obtained, of course, in order to further improve the dielectric properties, hydrogenation is required after the Heck reaction to remove the unsaturated double bond.

[0068] As preferred, in the Heck reaction of the halogenated benzocyclobutene derivative, the dicyclopentadiene and / or the dicyclopentadiene derivative, since the number of the BCB groups in the chemical structure of the product will affect the performance, more BCB groups will make the dielectric performance and thermal stability of the product improved; therefore, the present application needs to control the molar amount of the halogenated benzocyclobutene derivative, the dicyclopentadiene and / or the dicyclopentadiene derivative to be (1.0~5.5):1.0, and further considering that the halogen-substituted benzocyclobutene and its derivative needs to be slightly excessive, so it is controlled to be (1.0~5.0):1.0.

[0069] Correspondingly, the present application also provides the application of the above-mentioned dielectric material based on benzocyclobutene. Since the dielectric material based on benzocyclobutene provided by the present application has excellent dielectric performance and thermal stability, and good comprehensive performance, it can meet the requirements of high-frequency high-speed printed circuit board PCB, so it can be used for preparing high-frequency high-speed printed circuit board PCB, such as participating in the preparation of resin sheets, resin composite metal foils, prepregs, laminates, metal-clad laminates and other materials related to the insulating substrate of high-frequency high-speed printed circuit board PCB, and can also be used as a potting layer for potting electronic components including chips in high-speed printed circuit board PCB, or as an insulating coating layer coated on the surface of electronic components.

[0070] The dielectric material based on benzocyclobutene provided by the present application will be specifically described below in combination with examples and experimental examples.

[0071] Example 1

[0072] The present embodiment provides a preparation method of a dielectric material based on benzocyclobutene, which comprises the steps of Heck reaction, separation and purification, hydrogenation reaction, and separation and purification of hydride.

[0073] The step of Heck reaction comprises: sequentially adding 13.22g of dicyclopentadiene (0.1mol), 22.00g of 4-bromobenzocyclobutene (0.12mol) and 0.269g of palladium acetate (1.2mmol) into a 250mL three-necked flask, adding 1.10g of tri (o-methylphenyl) phosphine (3.6mmol), 14.16g of triethylamine and 110mL of acetonitrile, passing nitrogen, stirring and heating to reflux for 16h, and obtaining a reaction solution containing the dielectric material based on benzocyclobutene (BCB-containing dicyclopentadiene derivative) after the reaction;

[0074] The separation and purification step includes: after the reaction solution from the Heck reaction is cooled to room temperature, the salt and catalyst are removed by filtration, the unreacted raw material and solvent are removed by distillation under reduced pressure, the concentrated residue is passed through a neutral alumina column and washed with n-hexane, and the solvent is spin-dried to obtain 21.1 g of the product, a dielectric material based on benzocyclobutene (BCB-containing dicyclopentadiene derivative);

[0075] The hydrogenation reaction step includes: the BCB-containing dicyclopentadiene derivative after separation and purification is added to a hydrogenation reaction autoclave, 10 times the mass of solvent and 2% by mass of catalyst are added, the atmosphere is replaced with hydrogen, the pressure is increased to 1.5 MPa with hydrogen, stirring is performed, heating is performed to 80°C and the reaction is maintained for 6 h, and the reaction solution after the reaction contains a hydrogenated product of the dielectric material based on benzocyclobutene (hydrogenated product of the BCB-containing dicyclopentadiene derivative);

[0076] The separation and purification step of the hydrogenated product includes: after the reaction solution from the hydrogenation reaction is cooled to room temperature, the catalyst is removed by filtration, the solvent is removed by distillation, the concentrated residue is passed through a silica gel column and washed with n-hexane, and the solvent is spin-dried to obtain the hydrogenated product of the dielectric material based on benzocyclobutene (hydrogenated product of the BCB-containing dicyclopentadiene derivative).

[0077] The Heck reaction formula and the product molecular structure formula in this embodiment are as follows:

[0078] ;

[0079] The hydrogenated product molecular structure formula is as follows:

[0080] .

[0081] Example 2

[0082] The embodiment provides a preparation method of a dielectric material based on benzocyclobutene, and the preparation method includes a Heck reaction step, a separation and purification step, a hydrogenation reaction step, and a hydrogenated product separation and purification step.

[0083] The Heck reaction step includes: 13.22 g of dicyclopentadiene (0.1 mol), 45.76 g of 4-bromobenzocyclobutene (0.25 mol), and 0.538 g of palladium acetate (2.4 mmol), 2.19 g of tri (o-methylphenyl) phosphine (7.2 mmol), 30.36 g of triethylamine, and 220 mL of acetonitrile are sequentially added to a 500 mL three-necked bottle, nitrogen is passed, stirring is performed, the temperature is increased to reflux, and reaction is performed for 22 h, and the reaction solution after the reaction contains the dielectric material based on benzocyclobutene (BCB-containing dicyclopentadiene derivative);

[0084] The separation and purification step includes: after the reaction solution obtained from the Heck reaction is cooled to room temperature, the salt and catalyst are removed by filtration, the unreacted raw material and solvent are removed by distillation under reduced pressure, the concentrated residue is passed through a neutral alumina column and eluted with n-hexane, and the solvent is spin-dried to obtain 30.12 g of the product, a dielectric material based on benzocyclobutene (BCB-containing dicyclopentadiene derivative);

[0085] The hydrogenation reaction step includes: the BCB-containing dicyclopentadiene derivative after separation and purification is added to a hydrogenation reaction autoclave, 10 times the mass of solvent and 2% by mass of catalyst are added, the atmosphere is replaced with hydrogen and pressurized to 1.5 MPa with hydrogen, stirred, heated to 80°C and incubated for 6 h, and the reaction solution after the reaction contains a hydrogenated product of the dielectric material based on benzocyclobutene (hydrogenated product of the BCB-containing dicyclopentadiene derivative);

[0086] The separation and purification step of the hydrogenated product includes: after the reaction solution obtained from the hydrogenation reaction is cooled to room temperature, the catalyst is removed by filtration, the solvent is removed by distillation and concentrated, the concentrated residue is passed through a silica gel column and eluted with n-hexane, and the solvent is spin-dried to obtain the hydrogenated product of the dielectric material based on benzocyclobutene (hydrogenated product of the BCB-containing dicyclopentadiene derivative).

[0087] The Heck reaction formula and product molecular structure formula in this embodiment are as follows:

[0088] ;

[0089] The hydrogenated product molecular structure formula is as follows:

[0090] .

[0091] Example 3

[0092] The embodiment provides a preparation method of a dielectric material based on benzocyclobutene, and the preparation method includes a Heck reaction step, a separation and purification step, a hydrogenation reaction step, and a hydrogenated product separation and purification step.

[0093] The Heck reaction step includes: 13.22 g of dicyclopentadiene (0.1 mol), 65.90 g of 4-bromobenzocyclobutene (0.36 mol), 0.538 g of palladium acetate (2.4 mmol), 2.19 g of tris (o-methylphenyl) phosphine (7.2 mmol), 55.3 g of potassium carbonate and 100 mL of N,N-dimethylformamide are sequentially added to a 250 mL three-necked bottle, nitrogen is passed, stirred, heated to 110°C for 19 h, and the reaction solution after the reaction contains a dielectric material based on benzocyclobutene (BCB-containing dicyclopentadiene derivative);

[0094] The separation and purification step includes: after the reaction solution obtained from the Heck reaction is cooled to room temperature, the salt and catalyst are removed by filtration, the unreacted raw material and solvent are removed by distillation under reduced pressure, the concentrated residue is passed through a neutral alumina column and eluted with n-hexane, and the solvent is spin-dried to obtain 39.85 g of the product, a dielectric material based on benzocyclobutene (BCB-containing dicyclopentadiene derivative);

[0095] The hydrogenation reaction step includes: the BCB-containing dicyclopentadiene derivative after separation and purification is added to a hydrogenation reaction autoclave, 10 times the mass of solvent and 2% by mass of catalyst are added, the atmosphere is replaced with hydrogen and pressurized to 1.5 MPa with hydrogen, stirred, heated to 80°C and incubated for 6 h, and the reaction solution after the reaction contains a hydrogenated product of the dielectric material based on benzocyclobutene (hydrogenated product of the BCB-containing dicyclopentadiene derivative);

[0096] The separation and purification step of the hydrogenated product includes: after the reaction solution obtained from the hydrogenation reaction is cooled to room temperature, the catalyst is removed by filtration, the solvent is removed by distillation and concentrated, the concentrated residue is passed through a silica gel column and eluted with n-hexane, and the solvent is spin-dried to obtain the hydrogenated product of the dielectric material based on benzocyclobutene (hydrogenated product of the BCB-containing dicyclopentadiene derivative).

[0097] The Heck reaction formula and product molecular structure formula in this embodiment are as follows:

[0098] ;

[0099] The molecular structure formula of the hydrogenated product is as follows:

[0100] .

[0101] Example 4

[0102] The embodiment provides a preparation method of a dielectric material based on benzocyclobutene, and the preparation method comprises a Heck reaction step, a separation and purification step, a hydrogenation reaction step, and a hydrogenated product separation and purification step.

[0103] The Heck reaction step includes: 13.22 g of dicyclopentadiene (0.1 mol), 91.52 g of 4-bromobenzocyclobutene (0.50 mol), 0.807 g of palladium acetate (3.6 mmol), 3.29 g of tris (o-methylphenyl) phosphine (10.8 mmol), 82.95 g of potassium carbonate, and 380 mL of N,N-dimethylformamide are sequentially added to a 1000 mL three-necked bottle, nitrogen is introduced, stirring is performed, the temperature is raised to 130°C, and reaction is performed for 18 h, and the reaction solution after the reaction contains a dielectric material based on benzocyclobutene (BCB-containing dicyclopentadiene derivative);

[0104] The separation and purification step includes: after the reaction solution obtained from the Heck reaction is cooled to room temperature, the salt and catalyst are removed by filtration, the unreacted raw material and solvent are removed by distillation under reduced pressure, the concentrated residue is passed through a neutral alumina column and eluted with n-hexane, and the solvent is spin-dried to obtain 49.55 g of the product, a dielectric material based on benzocyclobutene (BCB-containing dicyclopentadiene derivative);

[0105] The hydrogenation reaction step includes: the BCB-containing dicyclopentadiene derivative after separation and purification is added to a hydrogenation reaction autoclave, 10 times the mass of solvent and 2% by mass of catalyst are added, the atmosphere is replaced with hydrogen and pressurized to 1.5 MPa with hydrogen, stirred, heated to 80°C and incubated for 6 h, and the reaction solution after the reaction contains a hydrogenated product of the dielectric material based on benzocyclobutene (hydrogenated product of the BCB-containing dicyclopentadiene derivative);

[0106] The separation and purification step of the hydrogenated product includes: after the reaction solution obtained from the hydrogenation reaction is cooled to room temperature, the catalyst is removed by filtration, the solvent is removed by distillation and concentrated, the concentrated residue is passed through a silica gel column and eluted with n-hexane, and the solvent is spin-dried to obtain the hydrogenated product of the dielectric material based on benzocyclobutene (hydrogenated product of the BCB-containing dicyclopentadiene derivative).

[0107] The Heck reaction formula and product molecular structure formula in this embodiment are as follows:

[0108] ;

[0109] The molecular structure formula of the hydrogenated product is as follows:

[0110] .

[0111] Example 5

[0112] The present embodiment provides a preparation method of a dielectric material based on benzocyclobutene, which includes a Heck reaction step, a separation and purification step, a hydrogenation reaction step, and a hydrogenated product separation and purification step.

[0113] The Heck reaction step includes: 13.22 g of dicyclopentadiene (0.1 mol), 18.31 g of 4-chloromethylbenzocyclobutene (0.12 mol), 0.213 g of palladium chloride (1.2 mmol), 0.944 g of triphenylphosphine (3.6 mmol), 82.95 g of potassium carbonate, and 90 mL of N,N-dimethylformamide are sequentially added to a 250 mL three-necked flask, nitrogen is passed, stirred, heated to 130°C for 15 h, and the reaction solution after the reaction contains a dielectric material based on benzocyclobutene (BCB-containing dicyclopentadiene derivative);

[0114] The separation and purification step includes: after the reaction solution from the Heck reaction is cooled to room temperature, the salt and catalyst are removed by filtration, the unreacted raw material and solvent are removed by distillation under reduced pressure, the concentrated residue is passed through a neutral alumina column and eluted with n-hexane, and the solvent is spin-dried to obtain 23.09 g of the product, a dielectric material based on benzocyclobutene (BCB-containing dicyclopentadiene derivative);

[0115] The hydrogenation reaction step includes: the BCB-containing dicyclopentadiene derivative after separation and purification is added to a hydrogenation reaction autoclave, 10 times the mass of solvent and 2% by mass of catalyst are added, the atmosphere is replaced with hydrogen and pressurized to 1.5 MPa with hydrogen, stirred, heated to 80°C and incubated for 6 h, and the reaction solution after the reaction contains a hydrogenated product of the dielectric material based on benzocyclobutene (hydrogenated product of the BCB-containing dicyclopentadiene derivative);

[0116] The separation and purification step of the hydrogenated product includes: after the reaction solution from the hydrogenation reaction is cooled to room temperature, the catalyst is removed by filtration, the solvent is removed by distillation and concentrated, and the concentrated residue is then purified by silica gel column chromatography to obtain the hydrogenated product of the dielectric material based on benzocyclobutene (hydrogenated product of the BCB-containing dicyclopentadiene derivative).

[0117] The Heck reaction formula and product molecular structure formula in this embodiment are as follows:

[0118] .

[0119] Example 6

[0120] The embodiment provides a preparation method of a dielectric material based on benzocyclobutene, and the preparation method includes a Heck reaction step, a separation and purification step, a hydrogenation reaction step, and a hydrogenated product separation and purification step.

[0121] The Heck reaction step includes: 13.22 g of dicyclopentadiene (0.1 mol), 36.63 g of 4-chloromethylbenzocyclobutene (0.24 mol), 0.426 g of palladium chloride (2.4 mmol), 1.26 g of triphenylphosphine (4.8 mmol), 82.95 g of potassium carbonate and 300 mL of N,N-dimethylformamide are sequentially added to a 500 mL three-necked bottle, nitrogen is passed, stirred, heated to 130°C and reacted for 20 h, and the reaction solution after the reaction contains a dielectric material based on benzocyclobutene (BCB-containing dicyclopentadiene derivative);

[0122] The separation and purification step includes: after the reaction solution obtained from the Heck reaction is cooled to room temperature, the catalyst is removed by filtration, the unreacted raw materials and solvent are removed by distillation under reduced pressure, the concentrated residue is passed through a neutral alumina column and eluted with n-hexane, and the solvent is spin-dried to obtain 33.25 g of the product, a dielectric material based on benzocyclobutene (BCB-containing dicyclopentadiene derivative);

[0123] The hydrogenation reaction step includes: the BCB-containing dicyclopentadiene derivative after separation and purification is added to a hydrogenation reaction autoclave, 10 times the mass of solvent and 2% by mass of catalyst are added, the atmosphere is replaced with hydrogen and pressurized to 1.5 MPa with hydrogen, stirred, heated to 80°C and incubated for 6 h, and the reaction solution after the reaction contains a hydrogenated product of the dielectric material based on benzocyclobutene (hydrogenated product of the BCB-containing dicyclopentadiene derivative);

[0124] The separation and purification step of the hydrogenated product includes: after the reaction solution obtained from the hydrogenation reaction is cooled to room temperature, the catalyst is removed by filtration, the solvent is removed by distillation and concentrated, and the concentrated residue is then purified by silica gel column chromatography to obtain the hydrogenated product of the dielectric material based on benzocyclobutene (hydrogenated product of the BCB-containing dicyclopentadiene derivative).

[0125] The Heck reaction formula and product molecular structure formula in this embodiment are as follows:

[0126] .

[0127] Example 7

[0128] The embodiment provides a preparation method of a dielectric material based on benzocyclobutene, and the preparation method includes a Heck reaction step, a separation and purification step, a hydrogenation reaction step, and a hydrogenated product separation and purification step.

[0129] The Heck reaction step includes: 13.22 g of dicyclopentadiene (0.1 mol), 54.94 g of 4-chloromethylbenzocyclobutene (0.36 mol), 0.639 g of palladium chloride (3.6 mmol), 1.89 g of triphenylphosphine (7.2 mmol), 82.95 g of potassium carbonate, and 300 mL of N,N-dimethylformamide are sequentially added to a 500 mL three-necked bottle, nitrogen is passed, stirred, heated to 130°C, and reacted for 24 h, and the reaction solution after the reaction contains a dielectric material based on benzocyclobutene (BCB-containing dicyclopentadiene derivative);

[0130] The separation and purification step includes: after the reaction solution obtained from the Heck reaction is cooled to room temperature, the catalyst is removed by filtration, the unreacted raw materials and solvent are removed by distillation under reduced pressure, the concentrated residue is passed through a neutral alumina column and eluted with n-hexane, and the solvent is spin-dried to obtain 44.05 g of the product, a dielectric material based on benzocyclobutene (BCB-containing dicyclopentadiene derivative);

[0131] The hydrogenation reaction step includes: the BCB-containing dicyclopentadiene derivative after separation and purification is added to a hydrogenation reaction autoclave, 10 times the mass of solvent and 2% by mass of catalyst are added, the atmosphere is replaced with hydrogen and pressurized to 1.5 MPa with hydrogen, stirred, heated to 80°C and incubated for 6 h, and the reaction solution after the reaction contains a hydrogenated product of the dielectric material based on benzocyclobutene (hydrogenated product of the BCB-containing dicyclopentadiene derivative);

[0132] The hydrogenated product separation and purification step includes: after the reaction solution obtained from the hydrogenation reaction is cooled to room temperature, the catalyst is removed by filtration, the solvent is removed by distillation and concentrated, and the concentrated residue is then purified by silica gel column chromatography to obtain the hydrogenated product of the dielectric material based on benzocyclobutene (hydrogenated product of the BCB-containing dicyclopentadiene derivative).

[0133] The Heck reaction formula and product molecular structure formula in this embodiment are as follows:

[0134] .

[0135] Embodiment 8

[0136] The embodiment provides a preparation method of a dielectric material based on benzocyclobutene, and the preparation method includes a Heck reaction step, a separation and purification step, a hydrogenation reaction step, and a hydrogenated product separation and purification step.

[0137] The Heck reaction step includes: 13.22 g of dicyclopentadiene (0.1 mol), 76.31 g of 4-chloromethylbenzocyclobutene (0.5 mol), and 0.887 g of palladium chloride (5.0 mmol) are sequentially added to a 1000 mL three-necked bottle, 2.62 g of triphenylphosphine (10.0 mmol), 82.95 g of potassium carbonate, and 380 mL of N,N-dimethylformamide are added, nitrogen is introduced, stirring is performed, the temperature is raised to 130°C, and reaction is performed for 26 h, and the reaction solution after the reaction contains a dielectric material based on benzocyclobutene (BCB-containing dicyclopentadiene derivative);

[0138] The separation and purification step includes: after the reaction solution obtained from the Heck reaction is cooled to room temperature, the catalyst is removed by filtration, and unreacted raw materials and solvents are removed by distillation under reduced pressure; the concentrated residue is passed through a neutral alumina column and eluted with n-hexane; and the solvent is spin-dried to obtain 51.65 g of the product, i.e., a dielectric material based on benzocyclobutene (BCB-containing dicyclopentadiene derivative);

[0139] The hydrogenation reaction step includes: the BCB-containing dicyclopentadiene derivative obtained after the separation and purification is added to a hydrogenation reaction autoclave, 10 times the mass of a solvent and 2% by mass of a catalyst are added, the atmosphere is replaced with hydrogen, the hydrogen pressure is increased to 1.5 MPa, stirring is performed, heating is performed to 80°C and the reaction is maintained for 6 h; and the reaction solution obtained after the reaction contains a hydrogenated product of the dielectric material based on benzocyclobutene (hydrogenated product of the BCB-containing dicyclopentadiene derivative).

[0140] The separation and purification step of the hydrogenated product includes: after the reaction solution obtained from the hydrogenation reaction is cooled to room temperature, the catalyst is removed by filtration, the solvent is removed by distillation and concentrated, and the concentrated residue is subjected to a crystallization treatment to obtain the hydrogenated product of the dielectric material based on benzocyclobutene (hydrogenated product of the BCB-containing dicyclopentadiene derivative).

[0141] In this embodiment, the Heck reaction formula and the product molecular structure formula are as shown in the following formula:

[0142] .

[0143] Example 9

[0144] The embodiment provides a preparation method of a dielectric material based on benzocyclobutene, and the preparation method includes a step of preparing phenyl dicyclopentadiene, a step of Heck reaction, a separation and purification step, a hydrogenation reaction step, and a separation and purification step of a hydrogenated product.

[0145] The step of preparing phenyl dicyclopentadiene includes: 26.44 g of dicyclopentadiene (0.2 mol), 49 g of iodobenzene (0.24 mol), 0.54 g of palladium acetate (2.4 mmol), 2.2 g of tris (o-methylphenyl) phosphine (7.2 mmol), 28.32 g of triethylamine, and 220 mL of acetonitrile are sequentially added to a 500 mL three-necked bottle, nitrogen is passed, stirring is performed to increase the temperature to reflux, and the reaction is maintained for 18 h; after the reaction solution obtained after the reaction is cooled to room temperature, the salt and catalyst are removed by filtration, the solvent is concentrated by distillation under reduced pressure, the concentrated residue is passed through a neutral alumina column and eluted with n-hexane, and the solvent is spin-dried to obtain phenyl dicyclopentadiene.

[0146] The step of the Heck reaction includes: sequentially adding 20.83 g of the prepared phenyl dicyclopentadiene (0.1 mol), 45.76 g of 4-bromobenzocyclobutene (0.25 mol), 0.807 g of palladium acetate (3.6 mmol), 3.29 g of tri (o-methylphenyl) phosphine (10.8 mmol), 82.95 g of potassium carbonate, and 350 mL of N,N-dimethylformamide into a 1000 mL three-necked flask, stirring, heating to reflux, and reacting for 16 h under nitrogen. The reaction solution after the reaction contains a benzocyclobutene-based dielectric material (BCB-containing dicyclopentadiene derivative);

[0147] The step of separation and purification includes: after the reaction solution after the Heck reaction is cooled to room temperature, filtering to remove the salt and catalyst, distilling off the unreacted raw material and solvent under reduced pressure, passing the concentrated residue through a neutral alumina column and eluting with n-hexane, and spinning to dry the solvent. 37.52 g of the product is obtained, and a benzocyclobutene-based dielectric material (BCB-containing dicyclopentadiene derivative) is obtained.

[0148] The step of the hydrogenation reaction includes: adding the BCB-containing dicyclopentadiene derivative after separation and purification into a hydrogenation reaction autoclave, adding 10 times the mass of a solvent and 2% by mass of a catalyst, replacing the atmosphere with hydrogen, pressurizing to 1.5 MPa with hydrogen, stirring, heating to 80°C and maintaining the temperature for 6 h. The reaction solution after the reaction contains a hydrogenated product of the benzocyclobutene-based dielectric material (hydrogenated product of the BCB-containing dicyclopentadiene derivative).

[0149] The step of separation and purification of the hydrogenated product includes: after the reaction solution after the hydrogenation reaction is cooled to room temperature, filtering to remove the catalyst, distilling off the solvent to concentrate, and then passing the concentrated residue through a silica gel column for purification. A hydrogenated product of the benzocyclobutene-based dielectric material (hydrogenated product of the BCB-containing dicyclopentadiene derivative) is obtained.

[0150] The formula of the Heck reaction and the molecular structure of the product in this embodiment are as follows:

[0151] .

[0152] Example 10

[0153] The embodiment provides a preparation method of a benzocyclobutene-based dielectric material, and the preparation method includes the steps of preparing dicyclopentadiene, a Heck reaction, separation and purification, a hydrogenation reaction, and separation and purification of a hydrogenated product.

[0154] The step of preparing diphenyl dicyclopentadiene includes: sequentially adding 26.44 g of dicyclopentadiene (0.2 mol), 98 g of iodobenzene (0.48 mol), 0.54 g of palladium acetate (2.4 mmol), 2.2 g of tri (o-methylphenyl) phosphine (7.2 mmol), 28.32 g of triethylamine and 220 mL of acetonitrile into a 1000 mL three-necked flask, passing nitrogen, stirring, heating to reflux, reacting for 24 h, cooling the reaction solution to room temperature, filtering to remove salt and catalyst, distilling off unreacted raw materials and solvent under reduced pressure, passing the concentrated residue through a neutral alumina column and washing with n-hexane, and spinning to dry the solvent to obtain diphenyl dicyclopentadiene.

[0155] The step of the Heck reaction includes: sequentially adding 28.44 g of diphenyl dicyclopentadiene (0.1 mol), 45.76 g of 4-bromobenzocyclobutene (0.25 mol) and 0.807 g of palladium acetate (3.6 mmol) into a 1000 mL three-necked flask, 3.29 g of tri (o-methylphenyl) phosphine (10.8 mmol), 82.95 g of potassium carbonate and 300 mL of N, N-dimethylformamide, passing nitrogen, stirring, heating to 130 °C, reacting for 14 h, and cooling the reaction solution to room temperature to obtain a dielectric material based on benzocyclobutene (a dicyclopentadiene derivative containing BCB);

[0156] The step of separation and purification includes: cooling the reaction solution obtained in the Heck reaction to room temperature, filtering to remove salt and catalyst, distilling off unreacted raw materials and solvent under reduced pressure, passing the concentrated residue through a neutral alumina column and washing with n-hexane, spinning to dry the solvent, and obtaining 45.20 g of product to obtain a dielectric material based on benzocyclobutene (a dicyclopentadiene derivative containing BCB);

[0157] The step of the hydrogenation reaction includes: adding the dicyclopentadiene derivative containing BCB after separation and purification into a hydrogenation reaction autoclave, adding 10 times the mass of solvent and 2% by mass of catalyst, replacing the atmosphere with hydrogen and pressurizing to 1.5 MPa with hydrogen, stirring, heating to 80 °C and reacting for 6 h, and cooling the reaction solution to room temperature to obtain a hydrogenated product of the dielectric material based on benzocyclobutene (a hydrogenated product of the dicyclopentadiene derivative containing BCB);

[0158] The step of separation and purification of the hydrogenated product includes: cooling the reaction solution obtained in the hydrogenation reaction to room temperature, filtering to remove catalyst, distilling off solvent and concentrating, and then passing the concentrated residue through a crystallization treatment to obtain a hydrogenated product of the dielectric material based on benzocyclobutene (a hydrogenated product of the dicyclopentadiene derivative containing BCB).

[0159] The formula of the Heck reaction and the molecular structure of the product in the embodiment are as follows:

[0160] .

[0161] Example 11

[0162] The present embodiment provides a preparation method of a dielectric material based on benzocyclobutene, which comprises the steps of preparing benzyl dicyclopentadiene, Heck reaction, separation and purification, hydrogenation reaction, and separation and purification of hydride.

[0163] The step of preparing benzyl dicyclopentadiene comprises: sequentially adding 26.44 g of dicyclopentadiene (0.2 mol), 30.38 g of benzyl chloride (0.24 mol), and 0.54 g of palladium acetate (2.4 mmol), 2.2 g of tri (o-methylphenyl) phosphine (7.2 mmol), 28.32 g of triethylamine, and 220 mL of acetonitrile into a 500 mL three-necked flask, passing nitrogen, stirring, and heating to reflux for 24 h; after the reaction, the reaction solution is cooled to room temperature, and then the salt and catalyst are removed by filtration, and the unreacted raw materials and solvents are removed by distillation under reduced pressure; the concentrated residue is passed through a neutral alumina column and eluted with n-hexane, and the solvent is rotary evaporated to obtain benzyl dicyclopentadiene.

[0164] The step of Heck reaction comprises: sequentially adding 22.23 g of benzyl dicyclopentadiene (0.1 mol), 36.63 g of 4-chloromethyl benzocyclobutene (0.24 mol), and 0.807 g of palladium acetate (3.6 mmol), 3.29 g of tri (o-methylphenyl) phosphine (10.8 mmol), 82.95 g of potassium carbonate, and 300 mL of N,N-dimethylformamide into a 500 mL three-necked flask, passing nitrogen, stirring, and heating to 130°C for 16 h; after the reaction, the reaction solution contains a dielectric material based on benzocyclobutene (BCB-containing dicyclopentadiene derivative).

[0165] The step of separation and purification comprises: after the reaction solution obtained by the Heck reaction is cooled to room temperature, the salt and catalyst are removed by filtration, and the unreacted raw materials and solvents are removed by distillation under reduced pressure; the concentrated residue is passed through a neutral alumina column and eluted with n-hexane, and the solvent is rotary evaporated to obtain 42.06 g of the product, and a dielectric material based on benzocyclobutene (BCB-containing dicyclopentadiene derivative).

[0166] The step of hydrogenation reaction comprises: adding the BCB-containing dicyclopentadiene derivative after separation and purification into a hydrogenation reaction autoclave, adding 10 times the mass of a solvent and 2% by mass of a catalyst, replacing the atmosphere with hydrogen, and pressurizing with hydrogen to 1.5 MPa; stirring, heating to 80°C, and maintaining the temperature for 6 h; and after the reaction, the reaction solution contains a hydride of the dielectric material based on benzocyclobutene (BCB-containing dicyclopentadiene derivative hydride).

[0167] The step of separation and purification of the hydride includes: after the reaction solution obtained from the hydrogenation reaction is cooled to room temperature, the catalyst is removed by filtration, the solvent is removed by distillation for concentration, and then the concentrated residue is purified by silica gel column chromatography to obtain the hydride of the dicyclopentadiene derivative containing BCB (the hydride of the dicyclopentadiene derivative containing BCB).

[0168] In this embodiment, the Heck reaction formula and the product molecular structure formula are as shown in the following formula:

[0169] .

[0170] Embodiment 12

[0171] The embodiment provides a preparation method of a dielectric material based on benzocyclobutene, and the preparation method comprises the steps of preparing dicyclopentadiene dibenzyl, a Heck reaction, separation and purification, a hydrogenation reaction, and separation and purification of a hydride.

[0172] The step of preparing dicyclopentadiene dibenzyl includes: sequentially adding 26.44 g of dicyclopentadiene (0.2 mol), 60.76 g of benzyl chloride (0.48 mol), 0.54 g of palladium acetate (2.4 mmol), 2.2 g of tri (o-methylphenyl) phosphine (7.2 mmol), 28.32 g of triethylamine and 220 mL of acetonitrile into a 500 mL three-necked bottle, passing nitrogen, stirring and heating to reflux for 24 h, after the reaction, cooling the reaction solution to room temperature, removing the salt and catalyst by filtration, removing the unreacted raw materials and the solvent by distillation under reduced pressure, passing the concentrated residue through a neutral alumina column and washing with n-hexane, and spinning to dry the solvent, to obtain dicyclopentadiene dibenzyl.

[0173] The step of the Heck reaction includes: sequentially adding 27.04 g of dicyclopentadiene dibenzyl (0.1 mol), 36.63 g of 4-chloromethyl benzocyclobutene (0.24 mol) and 0.538 g of palladium acetate (2.4 mmol) into a 500 mL three-necked bottle, 2.19 g of tri (o-methylphenyl) phosphine (7.2 mmol), 55.3 g of potassium carbonate and 300 mL of N,N-dimethylformamide, passing nitrogen, stirring and heating to 130 DEG C for 16 h, and after the reaction, the reaction solution contains the dielectric material based on benzocyclobutene (the dicyclopentadiene derivative containing BCB);

[0174] The step of separation and purification includes: after the reaction solution obtained from the Heck reaction is cooled to room temperature, the salt and the catalyst are removed by filtration, the unreacted raw materials and the solvent are removed by distillation under reduced pressure, the concentrated residue is passed through a neutral alumina column and washed with n-hexane, and the solvent is spun to dry, to obtain 50.18 g of the product, and the dielectric material based on benzocyclobutene (the dicyclopentadiene derivative containing BCB);

[0175] The step of hydrogenation reaction includes: adding the separated and purified BCB-containing dicyclopentadiene derivative into a hydrogenation reaction autoclave, adding 10 times mass of solvent and 2% mass fraction of catalyst, replacing with hydrogen atmosphere and pressurizing with hydrogen to 1.5 MPa, stirring, heating to 80°C and keeping for 6 h, and the reaction liquid after reaction contains the hydrogenate of the benzocyclobutene-based dielectric material (hydrogenate of the BCB-containing dicyclopentadiene derivative);

[0176] The step of separation and purification of the hydrogenate includes: after the reaction liquid obtained by hydrogenation reaction is cooled to room temperature, the catalyst is removed by filtration, the solvent is removed by distillation for concentration, and then the concentrated residue is subjected to crystallization treatment to obtain the hydrogenate of the BCB-containing dicyclopentadiene derivative (hydrogenate of the BCB-containing dicyclopentadiene derivative).

[0177] The Heck reaction formula and the product molecular structure formula in the embodiment are as shown in the following formula:

[0178] .

[0179] Example 13

[0180] The embodiment provides a preparation method of a benzocyclobutene-based dielectric material, and the preparation method includes the steps of Heck reaction, separation and purification, secondary Heck reaction and post-treatment.

[0181] The step of Heck reaction includes: sequentially adding 13.22 g of dicyclopentadiene (0.1 mol), 45.76 g of 4-bromobenzocyclobutene (0.25 mol) and 0.538 g of palladium acetate (2.4 mmol) into a 500 mL three-necked bottle, adding 2.19 g of tri (o-methylphenyl) phosphine (7.2 mmol), 30.36 g of triethylamine and 220 mL of acetonitrile, passing nitrogen, stirring, heating to reflux for 24 h, and the reaction liquid after reaction contains the diphenylpropylcyclobutene-based dicyclopentadiene;

[0182] The step of separation and purification includes: after the reaction liquid obtained by Heck reaction is cooled to room temperature, the salt and catalyst are removed by filtration, the unreacted raw material and solvent are removed by distillation under reduced pressure, the concentrated residue is passed through a neutral alumina column and washed with n-hexane, and the solvent is spun dry to obtain about 30.02 g of product, and the diphenylpropylcyclobutene-based dicyclopentadiene obtained is consistent in chemical structure with the benzocyclobutene-based dielectric material prepared in Example 2.

[0183] The second Heck reaction and post-treatment step includes: adding 29.64 g of diphenylpropenylbicyclopentadiene (0.1 mol), 24.48 g of iodobenzene (0.12 mol), 0.269 g of palladium acetate (1.2 mmol), 1.10 g of tris (o-methylphenyl) phosphine (3.6 mmol), 14.16 g of triethylamine and 110 mL of acetonitrile into a 500 mL three-neck flask in sequence, passing nitrogen, stirring and heating to reflux for 24 h, cooling the reaction solution to room temperature after the reaction, removing the salt and catalyst by filtration, removing the unreacted raw materials and solvent by distillation under reduced pressure, passing the concentrated residue through a neutral alumina column and washing with n-hexane, and spinning to dry the solvent to obtain the benzocyclobutene-based dielectric material, which has the same chemical structure as the benzocyclobutene-based dielectric material prepared in Example 10.

[0184] Example 14

[0185] The embodiment provides a preparation method of a benzocyclobutene-based dielectric material, which includes a Heck reaction step, a separation and purification step, and a second Heck reaction and post-treatment step.

[0186] The Heck reaction step includes: adding 13.22 g of bicyclopentadiene (0.1 mol), 36.63 g of 4-chloromethylbenzocyclobutene (0.24 mol) and 0.426 g of palladium chloride (2.4 mmol), 1.26 g of triphenylphosphine (4.8 mmol), 82.95 g of potassium carbonate and 300 mL of N,N-dimethylformamide into a 500 mL three-neck flask in sequence, passing nitrogen, stirring and heating to 130°C for 18 h, and cooling the reaction solution to room temperature after the reaction to obtain diphenylpropenylbicyclopentadiene, which contains benzocyclobutene.

[0187] The separation and purification step includes: cooling the reaction solution obtained by the Heck reaction to room temperature, removing the salt and catalyst by filtration, removing the unreacted raw materials and solvent by distillation under reduced pressure, passing the concentrated residue through a neutral alumina column and washing with n-hexane, spinning to dry the solvent, and obtaining about 30.02 g of the product, i.e., diphenylpropenylbicyclopentadiene, which has the same chemical structure as the benzocyclobutene-based dielectric material prepared in Example 6.

[0188] The secondary Heck reaction and post-treatment steps include: sequentially adding 29.64 g of diphenylpropylcyclobutenylbicyclopentadiene (0.1 mol), 31.64 g of benzyl chloride (0.25 mol), 0.538 g of palladium acetate (2.4 mmol), 2.19 g of tri (o-methylphenyl) phosphine (7.2 mmol), 30.36 g of triethylamine, and 220 mL of acetonitrile into a 500 mL three-necked flask, passing nitrogen, stirring to raise the temperature to reflux, and reacting for 24 h. After the reaction, the reaction solution is cooled to room temperature, and the salt and catalyst are removed by filtration. The unreacted raw materials and solvent are removed by distillation under reduced pressure. The concentrated residue is passed through a neutral alumina column and eluted with n-hexane. The solvent is spin-dried to obtain a benzocyclobutene-based dielectric material having a chemical structure consistent with the benzocyclobutene-based dielectric material prepared in Example 12.

[0189] Experimental Example 1

[0190] The hydrogenated product of the benzocyclobutene-based dielectric material prepared in Examples 1-14 and the benzocyclobutene-based dielectric material prepared in Examples 1-12 is tested for performance in Experimental Example 1 of the present application. The performance tests include dielectric performance tests and thermal stability tests. The test results of the dielectric performance and thermal stability of the benzocyclobutene-based dielectric material prepared in Examples 1-14 are shown in Table 1, and the test results of the dielectric performance and thermal stability of the hydrogenated product of the benzocyclobutene-based dielectric material prepared in Examples 1-12 are shown in Table 2.

[0191] Table 1: Dielectric performance and thermal stability of the benzocyclobutene-based dielectric material

[0192]

[0193] Table 2: Dielectric performance and thermal stability of the hydrogenated product of the benzocyclobutene-based dielectric material

[0194]

[0195] As can be seen from the dielectric properties and thermal stability of the benzocyclobutene-based dielectric materials prepared from Examples 1-4 or Examples 1-8 shown in Table 1, with the increase of the number of BCB substituents, the dielectric constant of the benzocyclobutene-based dielectric material decreases, the dielectric loss decreases, and the glass transition temperature shows an upward trend, indicating that the dielectric properties and thermal stability are improved; as can be seen from the dielectric properties and thermal stability of the benzocyclobutene-based dielectric materials prepared from Examples 2, 9-10, with the increase of the number of aryl substituents (Ph), the glass transition temperature of the benzocyclobutene-based dielectric material increases, and the benzocyclobutene-based dielectric material can still maintain good comprehensive dielectric properties; and as can be seen from the dielectric properties and thermal stability of the benzocyclobutene-based dielectric materials prepared from Examples 6, 11-12, with the increase of the number of benzyl substituents (Bn), the glass transition temperature of the benzocyclobutene-based dielectric material increases, and the benzocyclobutene-based dielectric material can still make the dielectric constant decrease and the dielectric loss decrease, indicating that the technical solution provided in the embodiments of the present application obtains an ideal dielectric material with excellent dielectric properties and thermal properties by using benzyl modification.

[0196] As can be seen from the properties of the benzocyclobutene-based dielectric materials and their hydrogenated products provided in Examples 1-2 shown in Table 1 and Table 2, the present application can further improve the dielectric properties of the benzocyclobutene-based dielectric material by removing the unsaturated double bond through hydrogenation.

[0197] The above embodiments are only used to illustrate the technical solutions of the present application, rather than limit them; although the present application has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions recorded in the above embodiments, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solution deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A benzocyclobutene-based dielectric material, characterized by, The BCB-containing dicyclopentadiene derivative and its hydrogenated product have a general structure shown in Formula I. Formula I; In Formula I, the substituents R1, R2, R3, R4, R5, and R6 are at least one of a hydrogen atom, an alkyl group, and an aryl group, and at least one of the substituents R1, R2, R3, and R4 is a BCB group.

2. The benzocyclobutene-based dielectric material of claim 1, wherein, The molecular structure of the BCB group is shown in Formula II. Formula II; In Formula II, the linking group R is connected to any position on the BCB ring, and the substituent R' is at least one substituent on the BCB ring other than the linking group R or a substituent forming a ring with the BCB benzene ring.

3. A method for producing a dielectric material based on benzocyclobutene, characterized in that, The reaction steps for preparing the benzocyclobutene-based dielectric material of claim 1 or 2 include: performing a Heck reaction on a halogenated benzocyclobutene derivative, dicyclopentadiene, and / or a dicyclopentadiene derivative to obtain the benzocyclobutene-based dielectric material.

4. The method for preparing a dielectric material based on benzocyclobutene according to claim 3, characterized in that, The reaction steps further include a hydrogenation reaction after the Heck reaction to obtain the benzocyclobutene-based dielectric material.

5. The method for preparing a dielectric material based on benzocyclobutene according to claim 3, characterized in that, The ratio of the molar amount of the halogenated benzocyclobutene derivative to the molar amount of the dicyclopentadiene and / or the dicyclopentadiene derivative is (1.0-5.5):1.

0.

6. Use of the benzocyclobutene-based dielectric material of any one of claims 1-2 in the preparation of a high-frequency high-speed printed circuit board (PCB).

7. Use according to claim 6, characterized in that, Use in the preparation of a resin sheet, a resin composite metal foil, a prepreg, a laminate, a metal-clad laminate, a potting layer, or an insulating coating for a high-frequency high-speed printed circuit board (PCB).

8. A high frequency high speed printed circuit board (PCB) board, characterized by, An insulating substrate made of the benzocyclobutene-based dielectric material of any one of claims 1-2.

9. A high frequency high speed printed circuit board (PCB) board, characterized by, A potting layer made of the benzocyclobutene-based dielectric material of any one of claims 1-2 around an electronic component.

10. A high frequency high speed printed circuit board (PCB) board, characterized by, An insulating coating made of the benzocyclobutene-based dielectric material of any one of claims 1-2 on the surface of an electronic component.

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