Dielectric material based on multi-benzocyclobutene as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of dielectric materials, and particularly relates to a dielectric material based on polybenzocyclobutene as well as a preparation method and application of the dielectric material. According to the multi-benzocyclobutene-based dielectric material provided by the invention, different halogenated hydrocarbon, olefin and other raw materials are used, and on the basis of containing more than two benzocyclobutene groups, a specific group can be introduced into a connecting group so as to improve the dielectric property and thermal stability of the material; meanwhile, specific groups can be introduced into R2 and R3 through secondary Heck reaction to further improve the dielectric property and thermal stability of the material, so that the dielectric material with excellent comprehensive properties such as dielectric property and thermal stability is provided, and the technical problem of lack of dielectric materials for high-frequency and high-speed printed circuit boards (PCBs) 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 polybenzocyclobutene and a preparation method and application thereof. BACKGROUND

[0002] The dielectric performance of the material used in the PCB board affects signal transmission. The higher the dielectric constant Dk is, the slower the signal propagation speed in the PCB board will be, resulting in signal delay. The greater the dielectric loss Df is, the more serious the signal attenuation in the signal transmission process will be, reducing the signal transmission distance and quality. Meanwhile, the greater the dielectric loss Df is, the more part of the electric energy will be 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 mass-produced 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 because TAIC contains a polar group. Therefore, it is urgent to develop a new low-dielectric material to meet the demand of the 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 the 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 polybenzocyclobutene and a preparation method and application thereof, to solve the technical problem of the lack of dielectric materials for high-frequency and high-speed PCB in the prior art.

[0006] The first aspect of the application provides a dielectric material based on polybenzocyclobutene, comprising a polybenzocyclobutene derivative and a hydrogenated product thereof. The polybenzocyclobutene derivative has a general structure shown in formula I.

[0007] Formula I;

[0008] In formula I, the linking group Q is selected from at least one of a chemical single bond, an alkylene group, and an arylene group.

[0009] It should be noted that in the present application, the alkylene group, the alkyl group includes straight-chain alkyl group, branched-chain alkyl group, cycloalkyl group, alkyl-substituted cycloalkyl group, cycloalkyl-substituted straight-chain or branched-chain alkyl 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] In formula I, n is an integer not less than 2; preferably, n is 2, 3 or 4; n represents the number of substitutions of the BCB group on the linking group Q.

[0011] In formula I, R1 is selected from at least one of a chemical single bond, alkylene group, alkenylene group, arylene group;

[0012] In formula I, R2 and R3 are selected from at least one of a hydrogen atom, alkyl group and aryl group; when the dielectric material based on polybenzocyclobutene is selected from polybenzocyclobutene derivatives, at most one of R2 and R3 is a hydrogen atom, and when the dielectric material based on polybenzocyclobutene is a hydrogenated product of the polybenzocyclobutene derivative, R2 and R3 are both hydrogen atoms; and R1 can be connected to any position on the ring of the polybenzocyclobutene derivative, i.e. the benzene ring or the cyclobutene moiety.

[0013] In formula I, R' is selected from at least one of a hydrogen atom, alkyl group and aryl group; the substituent R' is at least one substituent other than the linking group R1 on the BCB ring or a substituent forming a ring with the BCB group.

[0014] Preferably, in the linking group Q, 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.

[0015] Preferably, in the linking group Q, the alkylene group is selected from at least one of a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, decylene group, hexadecylene group, cyclopentylene group, cyclohexylene group and isomers thereof.

[0016] The arylene group is selected from at least one of a phenylene group, xylylene group, mesitylene group, tetraphenylene group, diethylphenylene group, triethylphenylene group, biphenylene group, biphenylmethyl group, biphenylethyl group, benzophenone group, triphenylphenyl group and isomers thereof.

[0017] In order to more clearly illustrate the position of the substituent of the alkylene group, the alkylene group is selected from at least one of the following chemical structures, wherein the wavy line represents the position of the benzocyclobutene group and the vinyl group.

[0018] 、 、 、 、 、 、 、 、 、 、 、 、 ;

[0019] For more clarity of the position of substituents, the arylene group is selected from at least one of the following chemical structures, in which the wavy line is the position of the connecting benzocyclobutene vinyl group;

[0020] 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、

[0021] 、 、 、 、 、 .

[0022] Further, in the connecting group R1, the number of carbon atoms of the alkylene group is an integer from 1 to 20; the number of carbon atoms of the alkenylene group is an integer from 2 to 20; the number of carbon atoms of the arylene group is an integer from 6 to 20;

[0023] Preferably, in the connecting group R1, the alkylene group includes at least one of methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, decylene, hexadecylene, and their isomers; the alkenylene group includes at least one of ethenylene, propenylene, butenylene, pentenylene, hexenylene, heptenylene, octenylene, decenylene, and their isomers; the arylene group includes at least one of phenylene, phenystylylene, biphenystylylene, methylenephenyl, methylenephenylmethyl, ethylphenyl, and their hydrocarbon substituent groups and isomers;

[0024] Preferably, in the substituent R', the alkyl group is selected from at least one of alkyl groups having 1 to 30 carbon atoms; the aryl group has an integer number of 6 to 30 carbon atoms, and the aryl group includes at least one of alkyl- and / or aryl-substituted aryl group, aryl-substituted alkyl group, polyaryl group.

[0025] 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 ring formed with the benzene ring in the BCB group.

[0026] The aryl group is selected from at least one of phenyl, o-tolyl, p-tolyl, m-tolyl, o-ethylphenyl, p-ethylphenyl, m-ethylphenyl, o-isopropylphenyl, p-isopropylphenyl, m-isopropylphenyl, biphenyl, naphthyl, phenyl ring formed with the benzene ring in the BCB ring, and benzocyclobutene group formed with the benzene ring in the BCB ring.

[0027] Preferably, in R2 or R3, the alkyl group has 6 to 30 carbon atoms.

[0028] The aryl group has 6 to 30 carbon atoms.

[0029] Preferably, in R2 or R3, the alkyl group is selected from at least one of hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and octadecyl.

[0030] The aryl group is selected from at least one of phenyl, benzyl, methylphenyl, phenylethyl, ethylphenyl, biphenyl, naphthyl, anthryl, dihydroanthryl, tetracenyl, fluorenyl, spirobifluorenyl, pyrenyl, perylenyl, and substituted groups thereof.

[0031] The second aspect of the present application provides a preparation method of a multi-benzocyclobutene-based dielectric material,

[0032] The reaction step includes: performing a Heck reaction on a polyhalogenated hydrocarbon and an alkene-containing benzocyclobutene derivative, or a polyene and a halogenated benzocyclobutene derivative, to obtain a multi-benzocyclobutene-based dielectric material, i.e., a multi-benzocyclobutene derivative.

[0033] Further, after the Heck reaction, the method further includes: performing derivatization on the alkene in the multi-benzocyclobutene derivative to obtain a multi-benzocyclobutene-based dielectric material, i.e., a derivatized multi-benzocyclobutene derivative.

[0034] Preferably, the derivatization method includes: performing a second Heck reaction on the alkene in the multi-benzocyclobutene derivative and a halogenated aromatic hydrocarbon or a halogenated benzocyclobutene.

[0035] Preferably, the Heck reaction is followed by a hydrogenation reaction to obtain the polybenzocyclobutene-based dielectric material, i.e., a hydrogenated polybenzocyclobutene derivative.

[0036] Preferably, the derivatization method comprises halogenation addition to the olefinic bond of the polybenzocyclobutene derivative obtained from the Heck reaction to obtain a halogenated polybenzocyclobutene derivative, followed by Kumada coupling reaction with a halogenated hydrocarbon to obtain the polybenzocyclobutene derivative, i.e., the polybenzocyclobutene-based dielectric material.

[0037] Preferably, the molar ratio of the halogen in the halogenated hydrocarbon or halogenated benzocyclobutene derivative to the double bond in the polyene hydrocarbon or olefinic benzocyclobutene derivative is (0.8-1.2):1.0.

[0038] Preferably, the polyhalogenated hydrocarbon is selected from at least one of at least two halogen-substituted alkanes, arenes.

[0039] Preferably, the polyhalogenated hydrocarbon is selected from at least one of 1,2-dibromobenzene, 1,3-dibromobenzene, 1,4-dibromobenzene, 1,2-dibromomethylbenzene, 1,3-dibromomethylbenzene, 1,4-dibromomethylbenzene, 1,2,3-tribromomethylbenzene, 1,2,4-tribromomethylbenzene, 1,3,5-tribromomethylbenzene, 1,2,3,4-tetrachloromethylbenzene, 1,2,3,5-tetrachloromethylbenzene, 1,2,4,5-tetrachloromethylbenzene, 2,2'-dibromobiphenyl, 4,4'-dibromobiphenyl, 2,2'-dibromobiphenylmethane, 4,4'-dibromostilbene, dichlorobenzene, dichlorobenzene, 1,2-dibromo-1,2-diphenylethane, and isomers thereof.

[0040] The polyene hydrocarbon is selected from at least one of at least two double-bonded olefins, arenes.

[0041] The polyene hydrocarbon is selected from at least one of 1,3-butadiene, 1,4-pentadiene, isoprene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,9-decadiene, cyclopentadiene, trivinylcyclohexane, o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, 1,2,3-trivinylbenzene, 1,2,4-trivinylbenzene, 1,3,5-trivinylbenzene, 1,4-diphenyl-1,3-butadiene, 1,6-diphenyl-1,3,5-hexatriene.

[0042] The halogenated arene includes at least one of chlorinated biphenyl, brominated fluorene, brominated anthracene, brominated pyrene, brominated perylene, and brominated spirobifluorene.

[0043] The chemical structure of the halogenated benzocyclobutene derivative is as follows:

[0044] wherein X is halogen.

[0045] Preferably, the halogen is selected from Cl, Br or I.

[0046] Preferably, the halogenated benzocyclobutene derivative is selected from at least one of 4-bromobenzocyclobutene, 4-chloromethylbenzocyclobutene, 4-bromomethylbenzocyclobutene; and halogenated BCB derivatives further prepared therefrom.

[0047] The chemical structure of the olefin-containing benzocyclobutene derivative is shown in the following formula:

[0048] .

[0049] Preferably, the olefin-containing benzocyclobutene derivative includes at least one of vinylbenzocyclobutene, allylbenzocyclobutene, butenylbenzocyclobutene, pentenylbenzocyclobutene, hexenylbenzocyclobutene, heptenylbenzocyclobutene, octenylbenzocyclobutene, nonenylbenzocyclobutene, decenylbenzocyclobutene, dodecenylbenzocyclobutene, octadecenylbenzocyclobutene;

[0050] Preferably, the olefin-containing benzocyclobutene derivative further includes a compound shown in the following formula:

[0051] 、 、 、

[0052] 、 、

[0053] 、 、 .

[0054] Preferably, the atmosphere used in the Heck reaction is at least one inert gas atmosphere selected from nitrogen, argon, helium;

[0055] The palladium catalyst used is selected from at least one of palladium chloride, palladium acetate, diphenylphosphinyl ferrocene dichloropalladium, tetraphenylphosphine palladium, dichlorodiphenylphosphine palladium, and the amount of the palladium catalyst used is 0.01-5% of the molar amount of the halogenated hydrocarbon or polyolefin;

[0056] The phosphine ligand used is selected from at least one of triphenylphosphine, tri (o-methylphenyl) phosphine, tributylphosphine, tricyclohexylphosphine, tri (2-methoxyphenyl) phosphine, tri (4-trifluoromethylphenyl) phosphine, and the amount of the phosphine ligand used is 0.01-25% of the molar amount of the halogenated hydrocarbon or polyolefin;

[0057] The used acid-binding agent is selected from at least one of triethylamine, diisopropyl ethylamine, N-ethyl dicyclohexylamine, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, potassium acetate, sodium acetate, cesium carbonate, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium tert-butoxide, sodium hydride, and the amount of substance of the acid-binding agent is 100-150% of the molar amount of halogen in the halogenated hydrocarbon or the olefinic bond in the polyene hydrocarbon.

[0058] The used organic solvent is selected from at least one of acetonitrile, dioxane, dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, methyl pyrrolidone, toluene, xylene, and mesitylene, and the volume of the organic solvent is 3-20 times of the mass of the halogenated hydrocarbon or the polyene hydrocarbon.

[0059] Preferably, the temperature of the Heck reaction is 80-150℃, and the time is 5-30h.

[0060] Preferably, the hydrogen gas atmosphere pressure of the hydrogenation reaction is 0.2-2.0Mpa.

[0061] The used catalyst is selected from at least one of palladium-carbon, platinum-carbon, and active nickel, and the mass of the catalyst is 0.1-5.0% of the molar amount of halogen in the halogenated hydrocarbon.

[0062] The used solvent is selected from at least one of acetonitrile, dioxane, dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, methyl pyrrolidone, toluene, xylene, and mesitylene, and the volume of the solvent is 1-30 times of the mass of the halogenated hydrocarbon.

[0063] Preferably, the temperature of the hydrogenation reaction is 50-120℃, and the time is 2-10h.

[0064] Preferably, after the Heck reaction, the hydrogenation reaction further comprises a post-processing step of separation and purification of the Heck reaction, and the post-processing step comprises sequentially cooling, filtering to remove the catalyst, reducing-pressure concentration of the filtrate, passing the concentrated liquid through a neutral alumina column and eluting with n-hexane, and reducing-pressure concentration and drying of the eluent to obtain the solid product, the based-benzocyclobutene dielectric material.

[0065] Preferably, after the hydrogenation reaction, the Heck reaction further comprises a post-processing step of separation and purification of the Heck reaction, and the post-processing step comprises sequentially cooling, filtering to remove the catalyst, reducing-pressure concentration of the filtrate, and crystallization treatment to obtain the solid product, the based-benzocyclobutene dielectric material.

[0066] The third aspect of the present application provides an application of the based-benzocyclobutene dielectric material in the first aspect in preparation of a high-frequency high-speed printed circuit board (PCB) plate.

[0067] Preferably, the application in the preparation of high-frequency high-speed printed circuit board (PCB) is specifically: the application in the preparation of resin sheet, resin composite metal foil, prepreg, laminated board, metal-clad laminated board, potting layer or insulating coating of high-frequency high-speed printed circuit board (PCB).

[0068] The fourth aspect of the present application provides a high-frequency high-speed printed circuit board (PCB), which comprises an insulating substrate made of the dielectric material based on polybenzocyclobutene of the first aspect.

[0069] The fifth aspect of the present application provides a high-frequency high-speed printed circuit board (PCB), which comprises a potting layer made of the dielectric material based on polybenzocyclobutene of the first aspect around the electronic components of the high-frequency high-speed printed circuit board (PCB).

[0070] The sixth aspect of the present application provides a high-frequency high-speed printed circuit board (PCB), which comprises an insulating coating made of the dielectric material based on polybenzocyclobutene of the first aspect on the surface of the electronic components of the high-frequency high-speed printed circuit board (PCB).

[0071] Compared with the prior art, the dielectric material based on polybenzocyclobutene provided by the present application has at least the following beneficial effects:

[0072] 1. The dielectric material based on polybenzocyclobutene provided by the present application contains two or more benzocyclobutene groups in its chemical structure, and by introducing arylene, substituted alkyl, substituted aryl and other groups into the connecting group Q, the dielectric properties and thermal stability of the material are improved.

[0073] 2. The dielectric material based on polybenzocyclobutene provided by the present application contains two or more benzocyclobutene groups in its chemical structure, and by introducing aryl, long-chain alkyl with a carbon atom number of not less than 6 and other groups into R2 and R3 through a secondary Heck reaction, the dielectric properties and thermal stability of the dielectric material can be further improved.

[0074] 3. The dielectric material based on polybenzocyclobutene provided by the present application has excellent comprehensive performance, and can be used to prepare resin sheet, resin composite metal foil, prepreg, laminated board, metal-clad laminated board in high-frequency high-speed printed circuit board (PCB), or to prepare potting layer and insulating coating, and is widely used in high-frequency high-speed printed circuit board (PCB). DETAILED DESCRIPTION

[0075] The present application provides a dielectric material based on polybenzocyclobutene and its preparation method and application, which is used to solve the technical problem of lack of dielectric material for high-frequency high-speed printed circuit board (PCB) in the prior art.

[0076] The technical solutions of the present application will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0077] 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 board (PCB) board, the present application provides a dielectric material based on multiple benzocyclobutene, which has a general structure shown in formula I.

[0078] Formula I;

[0079] In formula I, the linking group Q is selected from at least one of a chemical single bond, an alkylene group, an arylene group, a substituted alkyl group and a substituted aryl group;

[0080] n is an integer not less than 2;

[0081] R1 is selected from at least one of a chemical single bond, an alkylene group, an alkenylene group and an arylene group, R2 and R3 are selected from at least one of a hydrogen atom, an alkyl group and an aryl group, and at most one of R2 and R3 is a hydrogen atom.

[0082] The dielectric material based on the multiple benzocyclobutene provided by the application refers to a dielectric material containing two or more benzocyclobutene groups or alkyl or aryl derivatives and hydrogenated products thereof, and different groups are introduced into the molecular chain to control the spatial structure, electron cloud distribution and polarity, so as to improve the dielectric property and thermal stability; the dielectric material based on the multiple benzocyclobutene can have good low dielectric property and thermal temperature property, and the arylene or substituted aryl group can further improve the dielectric property and thermal property of the dielectric material based on the multiple benzocyclobutene; in addition to the connecting group Q, alkyl and aryl groups can also be introduced into the R2 and R3 positions to improve the dielectric property and thermal stability of the material; compared with the introduction of alkyl groups, when the aryl groups are introduced, the aryl groups have a larger spatial volume and rigidity, the steric hindrance is increased to limit the movement of the molecular chain segments, which is beneficial to improving the dielectric property and thermal stability of the dielectric material based on the multiple benzocyclobutene, but when a long-chain alkyl group with a carbon atom number of not less than 6 is introduced, the performance can also be greatly improved; the introduction of arylene groups into the connecting group Q can also improve the dielectric property and thermal stability of the dielectric material based on the multiple benzocyclobutene; thus, the dielectric material based on the multiple benzocyclobutene provided by the application has excellent dielectric property and thermal stability by introducing aryl groups and other groups into different substitution positions on the basis of using at least two multiple benzocyclobutene groups, and is expected to meet the comprehensive requirements of high-frequency high-speed printed circuit boards (PCB) in dielectric property, thermal property and the like, and overcome the defect that ordinary benzocyclobutene (BCB) cannot be directly used for high-frequency high-speed printed circuit boards (PCB); meanwhile, the application further provides a hydrogenated product of the dielectric material based on the multiple benzocyclobutene; the dielectric material based on the multiple benzocyclobutene and the hydrogenated product thereof have similar chemical structures, and are both used for preparing high-frequency high-speed printed circuit boards (PCB) as dielectric materials with excellent performance; however, the hydrogenated product of the dielectric material based on the multiple benzocyclobutene does not contain unsaturated double bonds, which avoids the large electronic polarizability of the unsaturated double bonds, so as to avoid the large polarization intensity, so that the material has low dielectric property and certain toughness.

[0083] Correspondingly, the application further provides a preparation method of the dielectric material based on the multiple benzocyclobutene; the preparation method adopts a Heck reaction of a halogenated hydrocarbon and an olefin, that is, a coupling reaction of a combination of a polyhalogenated hydrocarbon and a benzocyclobutene-substituted ethylene or a polyolefin and a halogenated benzocyclobutene, so as to obtain the dielectric material based on the multiple benzocyclobutene; in the Heck reaction, different groups can be introduced into the connecting group Q by selecting different polyhalogenated hydrocarbons and polyolefins, for example, aryl groups can be introduced by using a polyhalogenated hydrocarbon such as p-dibromobenzene or a polyolefin such as p-divinylbenzene; by using a reaction substrate containing aryl groups, the performance of the dielectric material based on the multiple benzocyclobutene prepared can be improved.

[0084] In consideration of the fact that the R2 and R3 positions of the dielectric material based on polybenzocyclobutene also affect the performance of the material, and it is difficult to introduce groups such as aryl groups at the R2 and R3 positions by a first Heck reaction, the present application further performs a further derivatization reaction of the double bond, which can be a second Heck reaction, i.e. a reaction by using a halogenated hydrocarbon (halogenated aromatic hydrocarbon) containing an aryl group such as 1-chlorobiphenyl and a first Heck reaction product (containing an unsaturated double bond) to introduce groups such as aryl groups at the R2 / R3 positions to improve the dielectric properties and thermal stability of the dielectric material based on polybenzocyclobutene; or a further halogenation of the double bond, and then a Kumada coupling reaction of the halogen.

[0085] Correspondingly, the present application further performs a hydrogenation reaction to remove the unsaturated double bond in the dielectric material based on polybenzocyclobutene to further improve the dielectric properties.

[0086] Correspondingly, the present application further provides the use of the dielectric material based on polybenzocyclobutene described above. Since the dielectric material based on polybenzocyclobutene provided by the present application has excellent dielectric properties and thermal stability, and good comprehensive performance, it can meet the requirements of high-frequency high-speed printed circuit boards (PCBs), and thus can be used for preparing high-frequency high-speed printed circuit boards (PCBs), such as participating in the preparation of resin sheets, resin composite metal foils, prepregs, laminates, metal-clad laminates and other materials related to insulating substrates of high-frequency high-speed printed circuit boards (PCBs), and can also be used as a potting layer for potting electronic components including chips in high-speed printed circuit boards (PCBs), or as an insulating coating layer coated on the surface of electronic components.

[0087] A dielectric material based on polybenzocyclobutene provided by the present application will be specifically described below in combination with examples and experimental examples.

[0088] Example 1

[0089] The present example provides a preparation method of a dielectric material based on polybenzocyclobutene, which comprises the steps of a Heck reaction, separation and purification.

[0090] The step of the Heck reaction comprises the following steps: under a nitrogen atmosphere, 16.03 g (0.2 mol) of 1,5-hexadiene, 82.37 g (0.45 mol) of 4-BrBCB and 0.45 g (2.0 mmol) of palladium acetate, 1.59 g (6.0 mmol) of triphenylphosphine, 64.6 g of diisopropylethylamine and 250 mL of DMF are sequentially added into a 500 mL high-pressure reaction bottle, and then the reaction bottle is sealed; the reaction bottle is stirred and heated at 85°C for 24 h, and the reaction liquid after the reaction contains a dielectric material based on polybenzocyclobutene (a polybenzocyclobutene derivative);

[0091] The separation and purification step includes: after cooling the reaction solution obtained by the Heck reaction, removing the catalyst and salt by filtration, removing the solvent by distillation under reduced pressure, concentrating, passing the concentrated solution through a neutral alumina chromatographic column and eluting with n-hexane, and concentrating and drying under reduced pressure to obtain 38.95 g of the product, i.e., the dielectric material based on polybenzocyclobutene;

[0092] The hydrogenation reaction step includes: adding 10.0 g of the separated and purified polybenzocyclobutene derivative into a hydrogenation reaction autoclave, adding 60 mL of a solvent DMF and 2% by mass of a catalyst palladium-carbon, replacing the atmosphere with hydrogen, pressurizing to 2.0 MPa with hydrogen, stirring, heating to 60°C and maintaining the temperature for 8 h, and obtaining the hydrogenated product of the dielectric material based on polybenzocyclobutene prepared by the Heck reaction in the reaction solution after the reaction;

[0093] The separation and purification step of the hydrogenated product includes: after cooling the reaction solution obtained by the hydrogenation reaction, removing the catalyst by filtration, removing the solvent by distillation, and purifying the residue by column chromatography to obtain the hydrogenated product of the dielectric material based on benzocyclobutene prepared by the Heck reaction.

[0094] The chemical structure of the dielectric material based on polybenzocyclobutene prepared in this embodiment is shown below:

[0095] .

[0096] Embodiment 2

[0097] This embodiment provides a preparation method of a dielectric material based on polybenzocyclobutene, which includes a Heck reaction step and a separation and purification step.

[0098] The Heck reaction step includes: under a nitrogen atmosphere, sequentially adding 16.03 g (0.2 mol) of 1,5-hexadiene, 164.74 g (0.9 mol) of 4-BrBCB, 0.269 g of palladium acetate (1.2 mmol), 1.738 g of triphenylphosphine (3.6 mmol), 129.15 g of diisopropylethylamine and 500 mL of DMF into a 1000 mL high-pressure reaction bottle, sealing the reaction bottle, stirring, heating to 85°C and maintaining the temperature for 24 h, and obtaining the dielectric material based on polybenzocyclobutene (polybenzocyclobutene derivative) in the reaction solution after the reaction;

[0099] The separation and purification step includes: after cooling the reaction solution obtained by the Heck reaction, removing the catalyst and salt by filtration, removing the solvent by distillation under reduced pressure, concentrating, passing the concentrated solution through a neutral alumina chromatographic column and eluting with n-hexane, and concentrating and drying under reduced pressure to obtain 66.26 g of the product, i.e., the dielectric material based on polybenzocyclobutene;

[0100] The step of hydrogenation reaction includes: adding 10.0 g of the separated and purified polybenzocyclobutene derivative into a hydrogenation reaction autoclave, adding 60 mL of solvent DMF and 2% mass fraction of catalyst palladium-carbon, replacing with hydrogen atmosphere and pressurizing with hydrogen to 2.0 MPa, stirring, heating to 60°C and keeping for 8 h, and the reaction liquid after reaction contains the hydrogenate of the polybenzocyclobutene-based dielectric material prepared by the Heck reaction;

[0101] The step of separation and purification of the hydrogenate includes: after cooling the reaction liquid obtained by the hydrogenation reaction, removing the catalyst by filtration, removing the solvent by distillation and concentrating, and then purifying the residue by column chromatography to obtain the hydrogenate of the benzocyclobutene-based dielectric material prepared by the Heck reaction.

[0102] The chemical structure of the polybenzocyclobutene-based dielectric material prepared in the embodiment is shown as follows:

[0103] .

[0104] Example 3

[0105] The embodiment provides a preparation method of a polybenzocyclobutene-based dielectric material, and the preparation method includes the steps of Heck reaction and separation and purification.

[0106] The step of Heck reaction includes: under nitrogen atmosphere, sequentially adding 18.31 g (0.10 mol) of 4-BrBCB and 0.269 g of palladium acetate (1.2 mmol), 1.738 g of triphenylphosphine (3.6 mmol), 33.6 g / mL of diisopropyl ethylamine and 200 mL of DMF into a 500 mL high-pressure reactor, sealing the high-pressure reactor, replacing with butadiene gas for three times, pressurizing the butadiene gas to 2 MPa, stirring, heating to 85°C and keeping for 24 h, cooling to room temperature, then adding 21.96 g (0.12 mol) of 4-BrBCB, heating to 115°C again under nitrogen atmosphere and keeping for 20 h, and the reaction liquid after reaction contains the polybenzocyclobutene-based dielectric material (polybenzocyclobutene derivative);

[0107] The step of separation and purification includes: after cooling the reaction liquid obtained by the Heck reaction, removing the catalyst by filtration, removing the solvent by distillation and concentrating, purifying the concentrated liquid by passing through a neutral alumina chromatographic column and eluting with n-hexane, and concentrating and drying under reduced pressure to obtain 35.61 g of the product, thereby obtaining the polybenzocyclobutene-based dielectric material;

[0108] The step of hydrogenation reaction includes: 10.0 g of the separated and purified polybenzocyclobutene derivative is added into a hydrogenation reaction autoclave, 60 mL of solvent DMF and 2% mass fraction of catalyst palladium-carbon are added, the atmosphere is replaced by hydrogen and is pressurized to 2.0 MPa by hydrogen, stirring, heating to 60℃ and keeping for 8 h, and the reaction liquid after reaction contains the hydrogenated product of the dielectric material based on polybenzocyclobutene prepared by the Heck reaction;

[0109] The step of separation and purification of the hydrogenated product includes: after the reaction liquid obtained by the hydrogenation reaction is cooled, the catalyst is filtered out, the solvent is distilled off for concentration, and then the residue is purified by column chromatography to obtain the hydrogenated product of the dielectric material based on benzocyclobutene prepared by the Heck reaction.

[0110] The chemical structure of the dielectric material based on polybenzocyclobutene prepared in the embodiment is shown as follows:

[0111] .

[0112] Embodiment 4

[0113] The embodiment provides a preparation method of a dielectric material based on polybenzocyclobutene, and the preparation method includes the steps of Heck reaction and separation and purification.

[0114] The step of Heck reaction includes: under a nitrogen atmosphere, 16.1 g (0.1 mol) of dichlorobenzene, 42.96 g (0.33 mol) of 4-vinyl BCB and 0.269 g of palladium acetate (3.3 mmol), 8.69 g of triphenylphosphine (16.5 mmol), 51.7 g of diisopropyl ethylamine and 220 mL of DMF are sequentially added into a 500 mL reaction bottle, stirring, heating to 115℃ and keeping for 25 h, and the reaction liquid after reaction contains the dielectric material based on polybenzocyclobutene (polybenzocyclobutene derivative);

[0115] The step of separation and purification includes: after the reaction liquid obtained by the Heck reaction is cooled, the catalyst is filtered out, the solvent is distilled off for concentration, the concentrated liquid is chromatographed on a neutral alumina column and is eluted with n-hexane, and the concentrated and dried product is obtained by reduced pressure, so that 28.1 g of the dielectric material based on polybenzocyclobutene is obtained.

[0116] The step of hydrogenation reaction includes: 10.0 g of the separated and purified polybenzocyclobutene derivative is added into a hydrogenation reaction autoclave, 60 mL of solvent DMF and 2% mass fraction of catalyst palladium-carbon are added, the atmosphere is replaced by hydrogen and is pressurized to 2.0 MPa by hydrogen, stirring, heating to 60℃ and keeping for 8 h, and the reaction liquid after reaction contains the hydrogenated product of the dielectric material based on polybenzocyclobutene prepared by the Heck reaction;

[0117] The separation and purification step of the hydride includes: after cooling the reaction solution obtained from the hydrogenation reaction, removing the catalyst by filtration, removing the solvent by distillation and concentrating, and then purifying the residue by column chromatography to obtain the hydride of the dielectric material based on benzocyclobutene prepared by the Heck reaction.

[0118] The chemical structure of the dielectric material based on polybenzocyclobutene prepared in this embodiment is shown below:

[0119] .

[0120] Example 5

[0121] This embodiment provides a preparation method of a dielectric material based on polybenzocyclobutene, which includes a Heck reaction step and a separation and purification step.

[0122] The Heck reaction step includes: under a nitrogen atmosphere, sequentially adding 23.7 g (0.1 mol) of dichlorodiphenylmethane, 29.94 g (0.23 mol) of 4-vinyl BCB, and 0.269 g of palladium acetate (3.3 mmol), 8.69 g of triphenylphosphine (16.5 mmol), 51.7 g of diisopropyl ethylamine, and 220 mL of DMF into a 500 mL reaction bottle, stirring and heating to 115°C, and maintaining the reaction for 25 h, wherein the reaction solution after the reaction contains a dielectric material based on polybenzocyclobutene (a polybenzocyclobutene derivative);

[0123] The separation and purification step includes: after cooling the reaction solution obtained from the Heck reaction, removing the catalyst by filtration, removing the solvent by distillation and concentrating, and then purifying the residue by column chromatography to obtain the hydride of the dielectric material based on benzocyclobutene prepared by the Heck reaction.

[0124] The hydrogenation reaction step includes: adding 10.0 g of the polybenzocyclobutene derivative after separation and purification into a hydrogenation reaction autoclave, adding 80 mL of solvent DMF and 2% by mass of catalyst palladium-carbon, replacing the atmosphere with hydrogen and pressurizing with hydrogen to 1.6 MPa, stirring, heating to 70°C, and maintaining the reaction for 7 h, wherein the reaction solution after the reaction contains a hydride of the dielectric material based on polybenzocyclobutene prepared by the Heck reaction;

[0125] The separation and purification step of the hydride includes: after cooling the reaction solution obtained from the hydrogenation reaction, removing the catalyst by filtration, removing the solvent by distillation and concentrating, and then purifying the residue by column chromatography to obtain the hydride of the dielectric material based on benzocyclobutene prepared by the Heck reaction.

[0126] The chemical structure of the dielectric material based on polybenzocyclobutene prepared in this embodiment is shown below:

[0127] .

[0128] Example 6

[0129] The present example provides a preparation method of a dielectric material based on polybenzocyclobutene, the preparation method comprising: a step of Heck reaction, a step of separation and purification.

[0130] The step of Heck reaction comprises: under nitrogen atmosphere, sequentially adding 13.83 g (0.1 mol) of 1,9-decadiene, 40.27 g (0.22 mol) of 4-BrBCB, and 0.49 g of palladium acetate (2.2 mmol), 2.68 g of tri (o-methylphenyl) phosphine (8.8 mmol), 33.6 g of diisopropyl ethylamine, and 200 mL of DMF into a 500 mL reaction bottle, stirring and heating to 110°C, and keeping the reaction for 20 h, wherein the reaction solution after the reaction contains a dielectric material based on polybenzocyclobutene (a polybenzocyclobutene derivative);

[0131] The step of separation and purification comprises: after cooling the reaction solution obtained by the Heck reaction, removing the catalyst by filtration, removing the solvent by distillation under reduced pressure, and concentrating, subjecting the concentrated solution to a neutral alumina column chromatography and eluting with n-hexane, and spin-drying the solvent, to obtain 26.41 g of the product, thereby obtaining the dielectric material based on polybenzocyclobutene;

[0132] The step of hydrogenation reaction comprises: adding 10.0 g of the polybenzocyclobutene derivative after the separation and purification into a hydrogenation reaction autoclave, adding 70 mL of a solvent DMF and 2% by mass of a catalyst palladium-carbon, replacing the atmosphere with hydrogen, pressurizing with hydrogen to 1.6 MPa, stirring, heating to 70°C, and keeping the reaction for 7 h, wherein the reaction solution after the reaction contains a hydrogenated product of the dielectric material based on polybenzocyclobutene prepared by the Heck reaction;

[0133] The step of separation and purification of the hydrogenated product comprises: after cooling the reaction solution obtained by the hydrogenation reaction, removing the catalyst by filtration, removing the solvent by distillation, and concentrating, and then purifying the residue by column chromatography, to obtain the hydrogenated product of the dielectric material based on polybenzocyclobutene prepared by the Heck reaction.

[0134] The chemical structure of the dielectric material based on polybenzocyclobutene prepared in the present example is shown below:

[0135] .

[0136] Example 7

[0137] The present example provides a preparation method of a dielectric material based on polybenzocyclobutene, the preparation method comprising: a step of Heck reaction, a step of separation and purification, a step of hydrogenation reaction, and a step of separation and purification of a hydrogenated product.

[0138] The step of the Heck reaction includes: under nitrogen atmosphere, sequentially adding 13.83 g (0.1 mol) of 1,9-decadiene, 80.54 g (0.44 mol) of 4-BrBCB, and 0.49 g of palladium acetate (2.2 mmol), 1.01 g of tri (o-methylphenyl) phosphine (3.3 mmol), 64.62 g of diisopropyl ethylamine, and 320 mL of DMF into a 500 mL reaction bottle, stirring, heating to 110°C, and keeping the reaction for 20 h. The reaction liquid after the reaction contains the dielectric material based on polybenzocyclobutene (polybenzocyclobutene derivative);

[0139] The step of separation and purification includes: after cooling the reaction liquid obtained from the Heck reaction, removing the catalyst by filtration, removing the solvent by distillation under reduced pressure, concentrating, passing the concentrated liquid through a neutral alumina chromatographic column, and eluting with n-hexane, and concentrating and drying under reduced pressure to obtain 35.19 g of the product, thereby obtaining the dielectric material based on polybenzocyclobutene;

[0140] The step of the hydrogenation reaction includes: adding the polybenzocyclobutene derivative after separation and purification into a hydrogenation reaction autoclave, adding a solvent DMF with a volume of 10 times the mass of the polybenzocyclobutene derivative and 2% by mass of a catalyst palladium-carbon, replacing the atmosphere with hydrogen, pressurizing with hydrogen to 1.5 MPa, stirring, heating to 80°C, and keeping the reaction for 6 h. The reaction liquid after the reaction contains the hydrogenated product of the dielectric material based on polybenzocyclobutene;

[0141] The step of separation and purification of the hydrogenated product includes: after cooling the reaction liquid obtained from the hydrogenation reaction, removing the catalyst by filtration, removing the solvent by distillation, and then crystallizing the concentrated liquid, thereby obtaining the hydrogenated product of the dielectric material based on benzocyclobutene.

[0142] The chemical structure of the dielectric material based on polybenzocyclobutene prepared in this embodiment is as follows:

[0143] .

[0144] Embodiment 8

[0145] This embodiment provides a preparation method of a dielectric material based on polybenzocyclobutene, which includes the steps of a Heck reaction, separation and purification, a second Heck reaction, separation and purification, a hydrogenation reaction, and separation and purification of a hydrogenated product.

[0146] The steps of the Heck reaction and separation and purification refer to Embodiment 6, and the dielectric material based on polybenzocyclobutene (polybenzocyclobutene derivative) is prepared, and the chemical structure thereof is consistent with that of the product in Embodiment 6;

[0147] The step of the second Heck reaction includes: under nitrogen atmosphere, 4.71 g (0.025 mol) of 1-chlorobiphenyl, 20.02 g (0.055 mol) of the polycyclobutene-based dielectric material prepared in Example 6, 0.49 g of palladium acetate (2.2 mmol), 3.35 g of tri (o-methylphenyl) phosphine (11 mmol), 33.6 g of diisopropyl ethylamine, and 200 mL of DMF are sequentially added into a 500 mL reaction bottle, and the mixture is heated to 110°C under stirring and kept for 20 h. The reaction solution after the reaction contains the polycyclobutene-based dielectric material (polycyclobutene derivative) prepared by the second Heck reaction;

[0148] The step of separation and purification includes: after the reaction solution after the second Heck reaction is cooled, the catalyst is removed by filtration, the solvent is distilled and concentrated under reduced pressure, the concentrated solution is chromatographed on a neutral alumina column and eluted with n-hexane, and the solvent is rotary evaporated to obtain a solid, thereby obtaining the polycyclobutene-based dielectric material prepared by the second Heck reaction;

[0149] The step of hydrogenation reaction includes: the polycyclobutene derivative after the separation and purification is added into a hydrogenation reaction autoclave, 10 times the mass of solvent DMF and 2% by mass of catalyst palladium-carbon are added, the atmosphere is replaced with hydrogen, the hydrogen pressure is increased to 1.5 MPa, the mixture is stirred, heated to 80°C, and kept for 6 h. The reaction solution after the reaction contains the hydrogenated product of the polycyclobutene-based dielectric material prepared by the second Heck reaction;

[0150] The step of separation and purification of the hydrogenated product includes: after the reaction solution after the hydrogenation reaction is cooled, the catalyst is removed by filtration, the solvent is distilled and concentrated, and the concentrated solution is subjected to crystallization treatment, thereby obtaining the hydrogenated product of the polycyclobutene-based dielectric material prepared by the second Heck reaction.

[0151] The chemical structure of the polycyclobutene-based dielectric material prepared by the second Heck reaction in this example is shown below:

[0152] .

[0153] Example 9

[0154] The example provides a preparation method of a polycyclobutene-based dielectric material, and the preparation method includes the steps of Heck reaction, separation and purification, second Heck reaction, separation and purification, hydrogenation reaction, and separation and purification of the hydrogenated product.

[0155] The steps of the second Heck reaction include: under nitrogen atmosphere, 6.128 g (0.025 mol) of 2-bromofluorene, 20.02 g (0.055 mol) of the dielectric material based on polybenzocyclobutene prepared in Example 6, and 0.49 g of palladium acetate (2.2 mmol), 3.35 g of tri (o-methylphenyl) phosphine (11 mmol), 33.6 g of diisopropyl ethylamine, and 200 mL of DMF are sequentially added into a 500 mL reaction bottle, and the reaction is stirred and heated to 110°C and kept for 12 h. The reaction solution after the second Heck reaction contains the dielectric material based on polybenzocyclobutene (polybenzocyclobutene derivative) prepared by the second Heck reaction.

[0156] The steps of the second Heck reaction include: under nitrogen atmosphere, 6.128 g (0.025 mol) of 2-bromofluorene, 20.02 g (0.055 mol) of the dielectric material based on polybenzocyclobutene prepared in Example 6, and 0.49 g of palladium acetate (2.2 mmol), 3.35 g of tri (o-methylphenyl) phosphine (11 mmol), 33.6 g of diisopropyl ethylamine, and 200 mL of DMF are sequentially added into a 500 mL reaction bottle, and the reaction is stirred and heated to 110°C and kept for 12 h. The reaction solution after the second Heck reaction contains the dielectric material based on polybenzocyclobutene (polybenzocyclobutene derivative) prepared by the second Heck reaction.

[0157] The steps of the second Heck reaction include: under nitrogen atmosphere, 6.128 g (0.025 mol) of 2-bromofluorene, 20.02 g (0.055 mol) of the dielectric material based on polybenzocyclobutene prepared in Example 6, and 0.49 g of palladium acetate (2.2 mmol), 3.35 g of tri (o-methylphenyl) phosphine (11 mmol), 33.6 g of diisopropyl ethylamine, and 200 mL of DMF are sequentially added into a 500 mL reaction bottle, and the reaction is stirred and heated to 110°C and kept for 12 h. The reaction solution after the second Heck reaction contains the dielectric material based on polybenzocyclobutene (polybenzocyclobutene derivative) prepared by the second Heck reaction.

[0158] The steps of the second Heck reaction include: under nitrogen atmosphere, 6.128 g (0.025 mol) of 2-bromofluorene, 20.02 g (0.055 mol) of the dielectric material based on polybenzocyclobutene prepared in Example 6, and 0.49 g of palladium acetate (2.2 mmol), 3.35 g of tri (o-methylphenyl) phosphine (11 mmol), 33.6 g of diisopropyl ethylamine, and 200 mL of DMF are sequentially added into a 500 mL reaction bottle, and the reaction is stirred and heated to 110°C and kept for 12 h. The reaction solution after the second Heck reaction contains the dielectric material based on polybenzocyclobutene (polybenzocyclobutene derivative) prepared by the second Heck reaction.

[0159] The steps of the second Heck reaction include: under nitrogen atmosphere, 6.128 g (0.025 mol) of 2-bromofluorene, 20.02 g (0.055 mol) of the dielectric material based on polybenzocyclobutene prepared in Example 6, and 0.49 g of palladium acetate (2.2 mmol), 3.35 g of tri (o-methylphenyl) phosphine (11 mmol), 33.6 g of diisopropyl ethylamine, and 200 mL of DMF are sequentially added into a 500 mL reaction bottle, and the reaction is stirred and heated to 110°C and kept for 12 h. The reaction solution after the second Heck reaction contains the dielectric material based on polybenzocyclobutene (polybenzocyclobutene derivative) prepared by the second Heck reaction.

[0160] The chemical structure of the dielectric material based on polybenzocyclobutene prepared by the second Heck reaction in this example is shown below:

[0161] .

[0162] Example 10

[0163] The embodiment provides a preparation method of a dielectric material based on polybenzocyclobutene, and the preparation method comprises the following steps: a step of Heck reaction, a step of separation and purification, a step of secondary Heck reaction, a step of separation and purification, a step of hydrogenation reaction and a step of separation and purification of a hydride.

[0164] The step of Heck reaction and the step of separation and purification refer to Embodiment 6, and a dielectric material based on polybenzocyclobutene (a polybenzocyclobutene derivative) is prepared, and the chemical structure of the product is consistent with that in Embodiment 6.

[0165] The step of secondary Heck reaction comprises the following steps: under a nitrogen atmosphere, 6.427g (0.025mol) of 1-bromoanthracene, 20.02g (0.055mol) of the dielectric material based on polybenzocyclobutene prepared in Embodiment 6 and 0.49g of palladium acetate (2.2mmol), 3.35g of tri (o-methylphenyl) phosphine (11mmol), 33.6g of diisopropyl ethylamine and 200mL of DMF are sequentially added into a 500mL reaction bottle, the reaction liquid is stirred and heated to 110 DEG C and kept for 12h, and the reaction liquid after reaction contains the dielectric material based on polybenzocyclobutene prepared by the secondary Heck reaction (a polybenzocyclobutene derivative).

[0166] The step of separation and purification comprises the following steps: after the reaction liquid prepared by the secondary Heck reaction is cooled, the catalyst is removed by filtration, the solvent is removed by distillation under reduced pressure, the concentrated liquid is subjected to chromatography on a neutral alumina column and elution with n-hexane, the solvent is spun dry to obtain a solid, and the dielectric material based on polybenzocyclobutene prepared by the secondary Heck reaction is obtained.

[0167] The step of hydrogenation reaction comprises the following steps: the polybenzocyclobutene derivative after the separation and purification is added into a hydrogenation reaction autoclave, 8 times the volume of the mass of the polybenzocyclobutene derivative of solvent DMF and 2% mass fraction of catalyst palladium-carbon are added, the atmosphere is replaced with hydrogen, the hydrogen pressure is 1.5Mpa, the reaction liquid is stirred, heated to 80 DEG C and kept for 6h, and the reaction liquid after reaction contains the hydride of the dielectric material based on polybenzocyclobutene prepared by the secondary Heck reaction.

[0168] The step of separation and purification of the hydride comprises the following steps: after the reaction liquid obtained by the hydrogenation reaction is cooled, the catalyst is removed by filtration, the solvent is removed by distillation, the concentrated liquid is subjected to crystallization treatment, and the hydride of the dielectric material based on polybenzocyclobutene prepared by the secondary Heck reaction is obtained.

[0169] The chemical structure of the dielectric material based on polybenzocyclobutene prepared by the secondary Heck reaction in the embodiment is shown in the following formula:

[0170] .

[0171] Example 11

[0172] The present example provides a preparation method of a dielectric material based on polybenzocyclobutene, which comprises the steps of a Heck reaction, separation and purification, a second Heck reaction, separation and purification, a hydrogenation reaction, and separation and purification of a hydride.

[0173] The steps of the Heck reaction and separation and purification refer to Example 6, and a dielectric material based on polybenzocyclobutene (a polybenzocyclobutene derivative) is prepared, which has the same chemical structure as the product in Example 6;

[0174] The step of the second Heck reaction comprises the steps of a Heck reaction, which comprises adding 7.028 g (0.025 mol) of 1-bromopyrene, 20.02 g (0.055 mol) of the dielectric material based on polybenzocyclobutene prepared in Example 6, and 0.49 g of palladium acetate (2.2 mmol), 3.35 g of tri (o-methylphenyl) phosphine (11 mmol), 33.6 g of diisopropyl ethylamine, and 200 mL of DMF into a 500 mL reaction bottle under a nitrogen atmosphere, stirring, heating to 110°C, and maintaining the reaction for 12 h. The reaction liquid after the reaction contains the dielectric material based on polybenzocyclobutene prepared by the second Heck reaction (a polybenzocyclobutene derivative);

[0175] The step of separation and purification comprises the following steps: after the reaction liquid prepared by the second Heck reaction is cooled, the catalyst is removed by filtration, the solvent is distilled under reduced pressure to concentrate, the concentrated liquid is chromatographed on a neutral alumina column and eluted with n-hexane, the solvent is spun dry to obtain a solid, and the dielectric material based on polybenzocyclobutene prepared by the second Heck reaction is obtained;

[0176] The step of the hydrogenation reaction comprises the following steps: the polybenzocyclobutene derivative after separation and purification is added into a hydrogenation reaction autoclave, a solvent DMF with a volume 10 times the mass of the polybenzocyclobutene derivative and 2% by mass of a catalyst palladium-carbon are added, the atmosphere is replaced with hydrogen and pressurized to 1.5 MPa with hydrogen, stirring, heating to 80°C, and maintaining the reaction for 6 h. The reaction liquid after the reaction contains a hydride of the dielectric material based on polybenzocyclobutene prepared by the second Heck reaction;

[0177] The step of separation and purification of the hydride comprises the following steps: after the reaction liquid obtained by the hydrogenation reaction is cooled, the catalyst is removed by filtration, the solvent is distilled to concentrate, and the concentrated liquid is subjected to crystallization treatment to obtain the hydride of the dielectric material based on polybenzocyclobutene prepared by the second Heck reaction.

[0178] The chemical structure of the dielectric material based on polybenzocyclobutene prepared by the second Heck reaction in the present example is shown below:

[0179] .

[0180] Example 12

[0181] The present embodiment provides a preparation method of a multi-benzocyclobutene-based dielectric material, which comprises the steps of a Heck reaction, separation and purification, a second Heck reaction, separation and purification, a hydrogenation reaction, and separation and purification of a hydride.

[0182] The step of the Heck reaction and the step of separation and purification refer to Example 6, and a multi-benzocyclobutene-based dielectric material (a benzocyclobutene derivative) is prepared, which has the same chemical structure as the product in Example 6.

[0183] The step of the second Heck reaction comprises the following steps: under a nitrogen atmosphere, 7.953 g (0.025 mol) of 3-bromoperylene, 20.02 g (0.055 mol) of the multi-benzocyclobutene-based dielectric material prepared in Example 6, and 0.49 g of palladium acetate (2.2 mmol), 3.35 g of tri (o-methylphenyl) phosphine (11 mmol), 33.6 g of diisopropyl ethylamine, and 200 mL of DMF are sequentially added into a 500 mL reaction bottle, and then the mixture is stirred and heated to 110°C and kept for 12 h. The reaction solution after the reaction contains the multi-benzocyclobutene-based dielectric material prepared by the second Heck reaction (a benzocyclobutene derivative).

[0184] The step of separation and purification comprises the following steps: after the reaction solution prepared by the second Heck reaction is cooled, the catalyst is removed by filtration, the solvent is distilled off under reduced pressure, and the concentrated solution is subjected to chromatography on a neutral alumina column and elution with n-hexane. The solvent is then rotary evaporated to obtain a solid, and the multi-benzocyclobutene-based dielectric material prepared by the second Heck reaction is obtained.

[0185] The step of the hydrogenation reaction comprises the following steps: the multi-benzocyclobutene derivative after separation and purification is added into a hydrogenation reaction autoclave, 10 times the volume of the mass of the multi-benzocyclobutene derivative of solvent DMF and 2% by mass of catalyst palladium-carbon are added, the atmosphere is replaced with hydrogen, and the pressure is increased to 1.5 MPa with hydrogen. The mixture is stirred, heated to 80°C, and kept for 6 h. The reaction solution after the reaction contains the hydride of the multi-benzocyclobutene-based dielectric material prepared by the second Heck reaction.

[0186] The step of separation and purification of the hydride comprises the following steps: after the reaction solution obtained by the hydrogenation reaction is cooled, the catalyst is removed by filtration, the solvent is distilled off, and the concentrated solution is subjected to crystallization treatment to obtain the hydride of the multi-benzocyclobutene-based dielectric material prepared by the second Heck reaction.

[0187] The chemical structure of the dielectric material based on polybenzocyclobutene prepared by the second Heck reaction in this embodiment is shown below:

[0188] .

[0189] Example 13

[0190] This embodiment provides a preparation method of a dielectric material based on polybenzocyclobutene, which comprises the steps of a Heck reaction, separation and purification.

[0191] The step of the Heck reaction comprises the following steps: under a nitrogen atmosphere, 26.40 g (0.1 mol) of p-dibromobenzene, 28.64 g (0.22 mol) of 4-vinyl BCB, 0.39 g of palladium chloride (2.2 mmol), 3.35 g of tri (o-methylphenyl) phosphine (11 mmol), 22.89 g of potassium acetate and 180 mL of NMP are sequentially added into a 500 mL reaction bottle, the reaction liquid is stirred and heated to 125°C, and the reaction is kept for 18 h. The reaction liquid after the reaction contains a dielectric material based on polybenzocyclobutene (a polybenzocyclobutene derivative);

[0192] The step of separation and purification comprises the following steps: after the reaction liquid obtained by the Heck reaction is cooled, the catalyst is removed by filtration, the solvent is removed by distillation under reduced pressure, the concentrated liquid is chromatographed on a neutral alumina column and eluted with n-hexane, and the concentrated and dried liquid is obtained by distillation under reduced pressure. The product is 25.11 g, and the dielectric material based on polybenzocyclobutene is obtained.

[0193] The step of the hydrogenation reaction comprises the following steps: the polybenzocyclobutene derivative after the separation and purification is added into a hydrogenation reaction autoclave, 12 times the volume of the mass of the polybenzocyclobutene derivative of a solvent DMF and 2% by mass of a catalyst palladium-carbon are added, the atmosphere is replaced with hydrogen, the hydrogen pressure is increased to 1.5 MPa, the reaction liquid is stirred and heated to 80°C, and the reaction is kept for 6 h. The reaction liquid after the reaction contains a hydrogenated product of the dielectric material based on polybenzocyclobutene prepared by the Heck reaction;

[0194] The step of separation and purification of the hydrogenated product comprises the following steps: after the reaction liquid obtained by the hydrogenation reaction is cooled, the catalyst is removed by filtration, the solvent is removed by distillation, and the concentrated liquid is obtained by crystallization treatment. The hydrogenated product of the dielectric material based on polybenzocyclobutene prepared by the Heck reaction is obtained.

[0195] The chemical structure of the dielectric material based on polybenzocyclobutene prepared in this embodiment is shown below:

[0196] .

[0197] Example 14

[0198] The embodiment provides a preparation method of a dielectric material based on polybenzocyclobutene, and the preparation method comprises the following steps: a Heck reaction step, a separation and purification step.

[0199] The Heck reaction step comprises the following steps: under a nitrogen atmosphere, 14.70 g (0.1 mol) of p-dichlorobenzene, 28.64 g (0.22 mol) of 4-alkenylhexyl BCB and 0.20 g of palladium chloride (1.1 mmol) are sequentially added into a 500 mL reaction bottle, 0.335 g of tri (o-methylphenyl) phosphine (1.1 mmol), 38.82 g of diethylcyclohexylamine and 90 mL of DMF are added, stirring is performed, heating is performed to 125 DEG C, and reaction is performed for 18 h; and the reaction liquid after reaction contains the dielectric material based on polybenzocyclobutene (polybenzocyclobutene derivative).

[0200] The separation and purification step comprises the following steps: after the reaction liquid obtained through the Heck reaction is cooled, the catalyst is removed through filtration, the solvent is removed through distillation under reduced pressure, the concentrated liquid is subjected to chromatography on a neutral alumina column and is eluted with n-hexane, and the concentrated liquid is dried under reduced pressure to obtain 33.1 g of the product, so as to obtain the dielectric material based on polybenzocyclobutene.

[0201] The hydrogenation reaction step comprises the following steps: the polybenzocyclobutene derivative after the separation and purification is added into a hydrogenation reaction autoclave, 10 times the volume of the polybenzocyclobutene derivative is added into the solvent DMF and 2% mass fraction of the catalyst palladium-carbon, the atmosphere is replaced with hydrogen, the hydrogen pressure is increased to 1.5 MPa, stirring is performed, heating is performed to 80 DEG C, and reaction is performed for 6 h; and the reaction liquid after reaction contains the hydrogenated product of the dielectric material based on polybenzocyclobutene prepared through the Heck reaction.

[0202] The separation and purification step of the hydrogenated product comprises the following steps: after the reaction liquid obtained through the hydrogenation reaction is cooled, the catalyst is removed through filtration, the solvent is removed through distillation, the concentrated liquid is subjected to crystallization treatment, and the hydrogenated product of the dielectric material based on polybenzocyclobutene prepared through the Heck reaction is obtained.

[0203] The chemical structure of the dielectric material based on polybenzocyclobutene prepared in the embodiment is shown in the following formula:

[0204] .

[0205] Embodiment 15

[0206] The present embodiment provides a preparation method of the dielectric material based on polybenzocyclobutene, the polyBCB alkenyl derivative prepared in the embodiment 14 is reacted with 4-BrCH2BCB, the Heck reaction condition and the separation and purification method are the same as those in the embodiment 14, the dielectric material based on polybenzocyclobutene is obtained, and then the hydrogenation reaction condition and the separation and purification method used in the embodiment 14 are used to obtain the hydrogenated product of the dielectric material based on polybenzocyclobutene.

[0207] The chemical structure of the dielectric material based on polybenzocyclobutene prepared in the present embodiment is shown as follows:

[0208] .

[0209] Embodiment 16

[0210] The present embodiment provides a preparation method of the dielectric material based on polybenzocyclobutene, the preparation method comprises the steps of: the Heck reaction, the separation and purification.

[0211] The step of the Heck reaction comprises: under the nitrogen atmosphere, 31.2g (0.1mol) of 4,4'-dibromobiphenyl, 28.64g (0.22mol) of 4-alkenylhexylbenzocyclobutene, 0.49g of palladium acetate (2.2mmol), 1.00g of tricyclohexylphosphine (3.6mmol), 23.55g of potassium acetate and 150mL of NMP are sequentially added into a 500mL reaction bottle, the reaction liquid is stirred and heated to 125°C and kept for 20h, and the reaction liquid after the reaction contains the dielectric material based on polybenzocyclobutene (polybenzocyclobutene derivative);

[0212] The step of the separation and purification comprises: after the reaction liquid obtained by the Heck reaction is cooled, the catalyst is removed by filtration, the solvent is distilled and concentrated under reduced pressure, the concentrated liquid is chromatographed on a neutral alumina column and eluted with n-hexane, and the product is obtained by reducing pressure and drying, 34.11g of the dielectric material based on polybenzocyclobutene is obtained;

[0213] The step of the hydrogenation reaction comprises: the polybenzocyclobutene derivative after the separation and purification is added into a hydrogenation reaction autoclave, 12 times the volume of the mass of the polybenzocyclobutene derivative of the solvent DMF and 2% mass fraction of the catalyst palladium-carbon are added, the atmosphere is replaced with hydrogen, the hydrogen pressure is 1.5Mpa, the reaction liquid after the reaction contains the hydrogenated product of the dielectric material based on polybenzocyclobutene prepared by the Heck reaction;

[0214] The separation and purification step of the hydride includes: after cooling the reaction solution obtained from the hydrogenation reaction, removing the catalyst by filtration, removing the solvent by distillation and concentrating, and then treating the concentrated solution by crystallization to obtain the hydride of the dielectric material based on benzocyclobutene prepared by the Heck reaction.

[0215] The chemical structure of the dielectric material based on polybenzocyclobutene prepared in this embodiment is shown as follows:

[0216] .

[0217] Embodiment 17

[0218] This embodiment provides a preparation method of a dielectric material based on polybenzocyclobutene, which includes a Heck reaction step and a separation and purification step.

[0219] The Heck reaction step includes: under a nitrogen atmosphere, sequentially adding 31.48 g (0.1 mol) of 1,3,5-tribromobenzene, 42.96 g (0.33 mol) of 4-alkenylhexyl BCB, 0.745 g of palladium acetate (3.3 mmol), 0.92 g of tricyclohexylphosphine (3.3 mmol), 34.34 g of potassium acetate, and 220 mL of NMP into a 500 mL reaction bottle, stirring and heating to 115°C, and maintaining the reaction for 22 h, and the reaction solution after the reaction contains a dielectric material based on polybenzocyclobutene (a polybenzocyclobutene derivative);

[0220] The separation and purification step includes: after cooling the reaction solution obtained from the Heck reaction, removing the catalyst by filtration, removing the solvent by distillation and concentrating, and then treating the concentrated solution by neutral alumina chromatography column and elution with n-hexane, and then vacuum concentration and drying to obtain 38.5 g of the product, thereby obtaining the dielectric material based on polybenzocyclobutene;

[0221] The hydrogenation reaction step includes: adding the polybenzocyclobutene derivative after the separation and purification into a hydrogenation reaction autoclave, adding a solvent DMF with a volume 12 times the mass of the polybenzocyclobutene derivative and 2% by mass of a catalyst palladium-carbon, replacing the atmosphere with hydrogen and pressurizing with hydrogen to 1.5 MPa, stirring, heating to 80°C, and maintaining the reaction for 6 h, and the reaction solution after the reaction contains a hydride of the dielectric material based on polybenzocyclobutene prepared by the Heck reaction;

[0222] The separation and purification step of the hydride includes: after cooling the reaction solution obtained from the hydrogenation reaction, removing the catalyst by filtration, removing the solvent by distillation and concentrating, and then treating the concentrated solution by crystallization to obtain the hydride of the dielectric material based on benzocyclobutene prepared by the Heck reaction.

[0223] The chemical structure of the dielectric material based on polybenzocyclobutene prepared in this embodiment is shown as follows:

[0224] .

[0225] The poly-BCB olefin derivatives prepared in Example 1 and Example 3 can be reacted with any at least one halogenated aromatic hydrocarbon in chlorobiphenyl, bromofluorene, bromoanthracene, bromopyrene, bromoperylene according to the method of Example 8-12 to improve the comprehensive performance of the poly-BCB olefin derivatives prepared in Example 1 and Example 3.

[0226] The poly-BCB olefin derivatives prepared in Example 4, 5, 13, 14, 16, 17 can also be modified by modifying the double bond to obtain modified derivatives to improve the comprehensive performance of the compounds. Due to the limitation of the length of the article, specific examples are not listed.

[0227] Experimental Example 1

[0228] The poly-BCB olefin-based dielectric materials prepared in Examples 1-17 are tested for performance in the experimental examples of the present application, and the performance tests include dielectric performance tests and thermal stability (glass transition temperature) tests. The test results of the dielectric performance and thermal stability of the poly-BCB olefin-based dielectric materials prepared in Examples 1-17 before and after hydrogenation are shown in Table 1.

[0229] As can be seen from the dielectric performance and thermal stability of the poly-BCB olefin-based dielectric materials prepared in Examples 1-6 shown in Table 1, the use of a specific structure of a substituted alkyl group at the position of the linking group Q, such as the substituted alkyl group shown in Example 2 or Example 4, and the introduction of three to four benzocyclobutene groups, can improve the dielectric performance and thermal stability of the poly-BCB olefin-based dielectric material. At the same time, comparing the dielectric performance and thermal stability of the poly-BCB olefin-based dielectric materials prepared in Examples 6, 13-17, it can be seen that the use of an aryl group at the position of the linking group Q can also improve the dielectric performance and thermal stability of the poly-BCB olefin-based dielectric material. As can be seen from the dielectric performance and thermal stability of the poly-BCB olefin-based dielectric materials prepared in Examples 8-12, 15, the introduction of an aryl group and a BCB group at the positions of R2 and R3 can also improve the dielectric performance and thermal stability of the poly-BCB olefin-based dielectric material. At the same time, comparing the dielectric performance and thermal stability of the poly-BCB olefin-based dielectric materials prepared in Examples 1-17 provided in Table 1 before and after hydrogenation, it can be seen that hydrogenation can further improve the dielectric performance of the material. The double bond has photosensitive properties and can polymerize with the benzocyclobutene group before and after hydrogenation. The melting point of the product after hydrogenation is reduced, and the alkyl group has better toughness than the olefin bond.

[0230] Table 1: Dielectric performance and thermal stability of poly-BCB olefin-based dielectric materials before and after hydrogenation

[0231]

[0232] The above embodiments are only used to illustrate the technical solutions of the present application, but not limit the present application; although the present application has been described in detail with reference to the above embodiments, those ordinarily skilled in the art should understand that they can still make modifications to the technical solutions recorded in the above embodiments, or make equivalent replacements to some or all of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A dielectric material based on polybenzocyclobutene, characterized in that, Including polybenzocyclobutene derivatives and their hydrogenated products, wherein the polybenzocyclobutene derivatives have the general structural formula shown in Formula I; Formula I; In Formula I, the linker Q is selected from at least one of a single chemical bond, an alkylene group, and an arylene group; n is an integer not less than 2; R1 is selected from at least one of a single chemical bond, alkylene, alkenyl, and aryl; R2 and R3 are selected from at least one of a hydrogen atom, alkyl, and aryl. R' is selected from at least one of hydrogen atom, alkyl, and aryl, and the substituent R' is at least one substituent other than the linker R1 on the BCB ring or a substituent that forms a ring with the BCB group.

2. The dielectric material based on polybenzocyclobutene according to claim 1, characterized in that... In the linker Q, the alkylene group is selected from at least one of methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, decylene, hexadecylene, cyclopentylene, cyclohexylene, and their isomers; The arylene group is selected from at least one of phenylene, xylene, trimethylene, tetramethylene, diethylbenzene, triethylbenzene, biphenylene, biphenylmethylene, biphenylethylene, triphenylbenzene, and their isomers.

3. The dielectric material based on polybenzocyclobutene according to claim 1, characterized in that, In R2 or R3, the alkyl group has 6 to 30 carbon atoms; The aryl group has 6 to 30 carbon atoms.

4. A method for preparing a dielectric material based on polybenzocyclobutene, characterized in that, According to any one of claims 1-3, a dielectric material based on polybenzocyclobutene is provided, the reaction steps comprising: subjecting a polyhalogenated hydrocarbon and a benzocyclobutene derivative containing an alkene bond, or subjecting a polyolefin and a halogenated benzocyclobutene derivative to a Heck reaction, to obtain a dielectric material based on polybenzocyclobutene.

5. The method for preparing a dielectric material based on polybenzocyclobutene according to claim 4, characterized in that, The Heck reaction is followed by derivatization of the olefin bonds in the polybenzocyclobutene derivative, followed by a secondary Heck reaction with a haloaromatic hydrocarbon or a halobenzocyclobutene to obtain a dielectric material based on polybenzocyclobutene.

6. The method for preparing a dielectric material based on polybenzocyclobutene according to claim 4, characterized in that, The Heck reaction is followed by a hydrogenation reaction to obtain a dielectric material based on polybenzocyclobutene.

7. The application of the dielectric material based on polybenzocyclobutene according to any one of claims 1-3 in the preparation of high-frequency and high-speed printed circuit boards (PCBs).

8. A high-frequency, high-speed printed circuit board (PCB), characterized in that, Insulating substrates made of dielectric materials based on polybenzocyclobutene as described in any one of claims 1-3.

9. A high-frequency, high-speed printed circuit board (PCB), characterized in that, Encapsulating electronic components with a potting layer made of a dielectric material based on polybenzocyclobutene as described in any one of claims 1-3.

10. A high-frequency, high-speed printed circuit board (PCB), characterized in that, An insulating coating made of a dielectric material based on polybenzocyclobutene, as described in any one of claims 1-3, is applied to the surface of electronic components.

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