BCB alkenyl adamantane derivative, preparation method thereof and hydride

Abstract

The invention relates to the technical field of low-dielectric materials, and particularly discloses a BCB alkenyl adamantane derivative, a preparation method thereof and hydride, and the derivative is specifically shown as follows: at least one BCB alkenyl is contained in substituent groups at 1, 3, 5 and 7 positions of adamantane. According to the present invention, with the strategy of introducing the BCB alkenyl group to the adamantane substituent group, the obtained BCB alkenyl adamantane derivative has characteristics of good thermal property and low dielectric property; meanwhile, the number of substituent groups and the number of BCB alkenyl groups on each substituent group are set as parameters capable of being flexibly adjusted, so that the performance of the derivative can be accurately optimized according to actual requirements. Compared with the prior art, pertinent regulation and control of dielectric constants of existing derivatives can be achieved by adjusting the number of substituent groups, the number of BCB alkenyl groups and other groups on the substituent groups, then directional control over the properties of the derivatives is achieved, and the problem that in the prior art, low-dielectric materials in the fields of high-performance PCBs, electronic packaging and the like are met is solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of low dielectric materials, in particular to a BCB alkene adamantane derivative, a preparation method thereof and a hydride thereof. BACKGROUND

[0002] Under the background of the continuous progress of society and the rapid development of technology, people's requirements for communication network speed and communication frequency are increasingly stringent. This trend has greatly improved the performance standards of printed circuit boards (PCB boards), which is embodied in the pursuit of lower dielectric constant (Dk), lower dielectric loss (Df), higher heat resistance, and lower thermal expansion coefficient. At present, the mass-produced PCBs mostly use thermosetting resins composed of end-vinyl polyphenyl ether and triallyl isocyanurate (TAIC). Although this kind of resin performs excellently in mechanical properties and heat resistance, it cannot meet the increasingly lower Dk and Df requirements due to the presence of polar groups in the molecular structure of TAIC. Therefore, developing new low dielectric materials to further optimize the dielectric properties has become a key problem to be solved in this field.

[0003] Benzocyclobutene (BCB) resin has been proven to be a low dielectric material with excellent performance. It not only has excellent physical properties and chemical stability, but also has excellent high-temperature stability. The unique chemical properties of BCB resin enable it to form both thermoplastic and thermosetting resins. Based on these outstanding characteristics, BCB resin has been widely used in the fields of electronics, microelectronics industry manufacturing, etc. However, BCB monomer is a low-boiling and volatile liquid. In order to improve its stability, it is usually prepared into derivatives to fully exert its performance advantages in practical applications. Adamantane is a class of molecules with special cage-like structure and large volume. It has attracted much attention due to its low polarizability and low dielectric constant. Studies have shown that introducing adamantane skeleton into the main chain or side chain of polyarylate molecules can significantly enhance the thermal stability, chemical stability and optical stability of the polymer, and also has obvious improvement effect on the mechanical properties, dielectric properties and other properties of the polymer.

[0004] In summary, how to prepare derivatives by successfully grafting adamantane into the molecular structure of BCB monomer, and then obtain materials with high thermal stability and low dielectric constant, has become one of the key strategies to improve the performance of PCB boards. SUMMARY

[0005] Therefore, the purpose of the present application is to provide a BCB alkene adamantane derivative, a preparation method thereof and a hydride thereof, to solve the problem of low dielectric materials that meet the requirements of high-performance PCB, electronic packaging and other fields in the prior art.

[0006] To achieve the above technical purposes, the application provides a BCB alkene adamantane derivative, the molecular structure general formula is shown in formula (1):

[0007] Formula (1);

[0008] Among them, the substituents R1, R2, R3, R4 are independently selected from at least one of hydrogen atoms, alkyl groups, alkene groups, aryl groups, and at least one BCB alkene group is included in the substituents R1, R2, R3 and R4.

[0009] Further, in the substituents R1, R2, R3, R4, the number of carbon atoms in the alkyl group is an integer from 1 to 30; the number of carbon atoms in the alkene group is an integer from 2 to 30; the number of carbon atoms in the aryl group is an integer from 6 to 30.

[0010] Further, in the substituents R1, R2, R3, R4, the alkyl group includes at least one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, and their isomers; the alkene group includes at least one of ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, decenyl, styryl, dodecenyl, p-vinylstyryl, biphenylstyryl, BCB alkene group, and their isomers; the aryl group includes at least one of phenyl, biphenyl, naphthyl, phenanthryl, naphthacene, fluorenyl, perylenyl, pyrenyl, anthracenyl, dihydroanthracenyl, pentacenyl, BCB alkene group, and their hydrocarbon-substituted derivatives and isomers.

[0011] Further, the BCB alkene group is selected from one of formula (2) and formula (3):

[0012] Formula (2); Formula (3);

[0013] Among them, R5 includes at least one of a chemical single bond, an alkylene group, an alkenylene group, and an arylene group; R6 includes at least one of hydrogen atoms, alkyl groups, alkene groups, and aryl groups.

[0014] Further, in the linking group R5, the number of carbon atoms in the alkylene group is an integer from 1 to 20; the number of carbon atoms in the alkenylene group is an integer from 2 to 20; the number of carbon atoms in the arylene group is an integer from 6 to 20;

[0015] In the substituent R6, the number of carbon atoms in the alkyl group is an integer from 1 to 30; the number of carbon atoms in the alkene group is an integer from 2 to 30; the number of carbon atoms in the aryl group is an integer from 6 to 30.

[0016] Further, in the linking group R5, the alkylene group includes at least one of methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, decylene, hexadecylene, and isomers thereof; the alkenylene group includes at least one of ethenylene, propenylene, butenylene, pentenylene, hexenylene, heptenylene, octenylene, decenylene, and isomers thereof; and the arylene group includes at least one of phenylene, methylene phenylene, methylene phenylene methyl, styrylene, biphenyl styrylene, and at least one of hydrocarbon-substituted derivatives and isomers thereof.

[0017] Further, in the substituent R6, the alkyl group includes at least one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, and isomers thereof; the alkenyl group includes at least one of ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, decenyl, dodecenyl, styryl, vinyl styryl, biphenyl styryl, and isomers thereof; and the aryl group includes at least one of phenyl, biphenyl, benzocyclobutene, and at least one of hydrocarbon-substituted derivatives and isomers thereof.

[0018] Further, the substituents R1, R2, R3, and R4 each independently include one aromatic ring other than the BCB group.

[0019] The present application provides a preparation method of a BCB alkenyl adamantane derivative, which is prepared by coupling reaction of a halogenated adamantane and an alkenyl BCB derivative, and includes the following steps:

[0020] A halogenated adamantane shown in formula (4) and an alkenyl BCB derivative shown in formula (5) are added to a reaction bottle, an organic solvent, a catalyst, and an acid binding agent are added, and after heating reaction, a post-treatment and purification operation are performed to obtain a BCB alkenyl adamantane derivative;

[0021] Formula (4); Formula (5);

[0022] In the formula, X is halogen; and n is the number of substitutions of halogen at 1, 3, 5, and 7 substitution positions of the halogenated adamantane, and n is an integer of 1 to 4.

[0023] The present application provides a hydride, which is obtained by hydrogenation reduction reaction of the alkenyl bond in the BCB alkenyl adamantane derivative.

[0024] A resin is prepared by using the BCB alkenyl adamantane derivative and / or the hydride provided by the present application.

[0025] A resin composition includes the resin provided by the present application.

[0026] In summary, the present application provides a BCB alkenyl adamantane derivative, which specifically refers to: at least one BCB alkenyl group is contained in the substituents at positions 1, 3, 5 and 7 of adamantane. The present application obtains a low dielectric material with good thermal stability and low dielectric property by introducing BCB alkenyl group into the substituents of adamantane. At the same time, the present application sets the number of substituents and the number of BCB alkenyl groups on each substituent as flexible parameters, so as to accurately optimize the performance of the derivative according to actual needs.

[0027] Compared with the prior art, the present application has the following beneficial effects:

[0028] The BCB alkenyl adamantane derivative provided by the present application can adjust the number of substituents, the number of BCB alkenyl groups and other groups on the substituents to realize the targeted regulation of the dielectric constant of the existing derivative, thereby achieving directional control of the properties of the derivative, and providing a new idea and method for the technical development of the related field. BRIEF DESCRIPTION OF DRAWINGS

[0029] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or the prior art description will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other drawings can also be obtained without creative labor.

[0030] Figure 1 Reaction scheme diagram of the BCB alkenyl adamantane derivative provided for the embodiment 1 of the present application;

[0031] Figure 2 Structural formula of the hydride provided for the embodiment 1 of the present application;

[0032] Figure 3 Reaction scheme diagram of the BCB alkenyl adamantane derivative provided for the embodiment 2 of the present application;

[0033] Figure 4 Structural formula of the hydride provided for the embodiment 2 of the present application;

[0034] Figure 5 Reaction scheme diagram of the BCB alkenyl adamantane derivative provided for the embodiment 3 of the present application;

[0035] Figure 6 Structural formula of the hydride provided for the embodiment 3 of the present application;

[0036] Figure 7Reaction scheme for BCB alkene adamantane derivative provided for Example 4 of the present invention;

[0037] Figure 8 Structure of hydride provided for Example 4 of the present invention;

[0038] Figure 9 Reaction scheme for BCB alkene adamantane derivative provided for Example 5 of the present invention;

[0039] Figure 10 Reaction scheme for BCB alkene adamantane derivative provided for Example 6 of the present invention;

[0040] Figure 11 Reaction scheme for BCB alkene adamantane derivative provided for Example 7 of the present invention;

[0041] Figure 12 Reaction scheme for BCB alkene adamantane derivative provided for Example 8 of the present invention;

[0042] Figure 13 Reaction scheme for BCB alkene adamantane derivative provided for Example 9 of the present invention;

[0043] Figure 14 Reaction scheme for BCB alkene adamantane derivative provided for Example 10 of the present invention;

[0044] Figure 15 Reaction scheme for BCB alkene adamantane derivative provided for Example 11 of the present invention;

[0045] Figure 16 Reaction scheme for BCB alkene adamantane derivative provided for Example 12 of the present invention;

[0046] Figure 17 Reaction scheme for BCB alkene adamantane derivative provided for Example 13 of the present invention;

[0047] Figure 18 Reaction scheme for BCB alkene adamantane derivative provided for Example 14 of the present invention;

[0048] Figure 19 Reaction scheme for BCB alkene adamantane derivative provided for Example 15 of the present invention;

[0049] In the figure, BCB represents a benzocyclobutene group, Ph represents a phenyl group, and BPh represents a biphenyl group. DETAILED DESCRIPTION

[0050] The technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without creative work fall within the scope of the present application.

[0051] In the present application, all the raw materials are not particularly limited in source, and can be purchased on the market or prepared according to the conventional method known to those skilled in the art.

[0052] The present application provides a kind of BCB alkene adamantane derivative, molecular structure general formula is as shown in formula (1):

[0053] Formula (1);

[0054] Wherein, substituent R1, R2, R3, R4 It is independently selected from at least one of hydrogen atom, alkyl, olefin group, aryl, and at least one BCB alkene group is included in substituent R1, R2, R3 and R4. It should be noted that: in the present application, alkyl includes straight-chain or branched alkyl, cycloalkyl;Alkenyl includes straight-chain or branched alkenyl, alkenyl-substituted alkyl;Aryl includes at least one of alkyl-substituted aryl, aryl-substituted alkyl, aryl-substituted aryl, polyaryl group;Polyaryl group includes naphthyl, anthryl, phenanthryl, tetracene, pentacene, fluorenyl, perylene, pyrene, and at least one of their derivatives containing substituents.

[0055] In some embodiments, the number of carbon atoms of alkyl is an integer in 1-30;The number of carbon atoms of alkenyl is an integer in 2-30;The number of carbon atoms of aryl is an integer in 6-30.

[0056] Preferably, in substituent R1, R2, R3, R4, alkyl includes at least one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, and their isomers;Alkenyl includes at least one of ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, styryl, dodecenyl, decenyl, p-vinylstyryl, biphenylstyryl, BCB alkenyl, and their isomers;Aryl includes at least one of phenyl, biphenyl, naphthyl, phenanthryl, tetracene, fluorenyl, perylene, pyrene, anthracene, dihydroanthracene, pentacene, BCB alkenyl, and at least one of their hydrocarbon-substituted derivatives and isomers.

[0057] In some embodiments, BCB alkenyl is selected from one of formula (2), formula (3):

[0058] Formula (2); Formula (3);

[0059] wherein R5 comprises at least one of a chemical single bond, an alkylene group, an alkenylene group, an arylene group; and R6 comprises at least one of a hydrogen atom, an alkyl group, an alkenyl group, an aryl group.

[0060] It is to be noted that the wavy line indicates the position of the adamantane connection; the alkylene group, the alkyl group comprises a straight chain or branched alkyl group, a cycloalkyl group, an alkyl-substituted cycloalkyl group, a cycloalkyl-substituted alkyl group; the alkenylene group, the alkenyl group comprises a straight chain or branched alkenyl group, an alkenyl-substituted alkyl group; the arylene group, the aryl group comprises an alkyl-substituted aryl group, an aryl-substituted alkyl group, an aryl-substituted aryl group, a benzocyclobutene group, a polyaryl group.

[0061] Preferably, in the linking group R5, 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.

[0062] In the substituent R6, the number of carbon atoms of the alkyl group is an integer from 1 to 30; the number of carbon atoms of the alkenyl group is an integer from 2 to 30; the number of carbon atoms of the aryl group is an integer from 6 to 30.

[0063] More preferably, in the linking group R5, the alkylene group comprises at least one of a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a decylene group, a hexadecylene group, and their isomers; the alkenylene group comprises at least one of a vinylene group, a propenylene group, a butenylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, a decenylene group, and their isomers; the arylene group comprises at least one of a phenylene group, a phenylethylene group, a biphenylethylene group, and their hydrocarbon-substituted groups and isomers.

[0064] More preferably, in the substituent R6, the alkyl group comprises at least one of a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, an octadecyl group, and their isomers; the alkenyl group comprises at least one of a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a decenyl group, a dodecalkenyl group, a styryl group, a vinylstyryl group, a biphenylstyryl group, and their isomers; the aryl group comprises at least one of a phenyl group, a biphenyl group, a benzocyclobutene group, and their hydrocarbon-substituted derivatives and isomers.

[0065] In some embodiments, each of the substituents R1, R2, R3, R4 is independently a BCB alkenyl group.

[0066] Preferably, the substituents R1, R2, R3, R4 are the same BCB alkenyl group.

[0067] It should be noted that when the substituents R1 to R4 are all BCB alkenyl groups, the stability and dielectric constant of the BCB alkenyl alkyl derivative can be effectively improved.

[0068] More preferably, under the condition that the substituents R1 to R4 are the same, each of the substituents R1, R2, R3, and R4 independently includes at least one benzene ring other than the BCB ring.

[0069] It should be noted that the substituent R 1~4 Under the same conditions, the stability and dielectric constant of BCB olefin derivatives can be effectively improved by adding at least one benzene ring to each substituent. This strategy of introducing benzene rings can overcome the performance degradation caused by a large number of substituent branches, providing an effective way to optimize the overall performance of BCB olefin derivatives.

[0070] This invention provides a method for preparing BCB alkenyl adamantane derivatives. The BCB alkenyl adamantane derivatives are prepared by a coupling reaction between haloadamantane and alkenyl BCB derivatives, including the following steps:

[0071] Add haloadamantane as shown in formula (4) and alkenyl BCB derivative as shown in formula (5) to the reaction flask, add organic solvent, catalyst and acid-binding agent, and after heating reaction, perform post-treatment purification operation to obtain BCB alkenyl adamantane derivative.

[0072] Equation (4); Equation (5);

[0073] Where X is a halogen; n is the number of halogen substitutions at the 1, 3, 5, and 7 substitution positions of the haloadamantane, and n is an integer from 1 to 4.

[0074] Preferably, the alkenyl BCB derivative is one of formulas (6) to (22):

[0075] Equation (6); Equation (7); Equation (8); Equation (9); Equation (10); Equation (11); Equation (12); Equation (13); Equation (14); Equation (15); Equation (16); Equation (17); Equation (18); Equation (19);

[0076] Formula (20); Formula (21); Formula (22).

[0077] The alkenyl BCB derivative is 4-vinylbenzocyclobutene, and the molar ratio of the halogenated adamantane to the 4-vinylbenzocyclobutene is 1.0: (1.0~5.0).

[0078] The halogen X is at least one of Cl, Br, and I.

[0079] The organic solvent includes at least one of acetonitrile, DMF, NMP, DMA, DMSO, toluene, xylene, and mesitylene, and the volume amount of the organic solvent is 2~20 times of the mass of the halogenated adamantane; preferably, the volume amount of the organic solvent is 5~12 times of the mass of the halogenated adamantane.

[0080] The acid acceptor is at least one of triethylamine, diisopropylethylamine, N-ethyldicyclohexylamine, tetramethylguanidine (TMG), and 1,4-diazabicyclo[2.2.2]octane (DABCO), potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, potassium acetate, sodium acetate, cesium carbonate, and the molar ratio of the acid acceptor to the halogenated adamantane is (1.0~5.0):1.0;

[0081] The catalyst includes a palladium catalyst and a phosphine ligand; the palladium catalyst is at least one of palladium chloride, palladium acetate, diphenylphosphine ferrocene dichloride, tetrakis (triphenylphosphine) palladium, and dichloro bis (triphenylphosphine) palladium, and the molar ratio of the palladium catalyst to the halogenated adamantane is (0.0001~0.05):1; preferably, the molar ratio of the palladium catalyst to the halogenated adamantane is (0.01~0.03):1.0; the phosphine ligand includes at least one of triphenylphosphine, tri (o-methylphenyl) phosphine, tributylphosphine, tricyclohexylphosphine, tri (2-methoxyphenyl) phosphine, and tri (4-trifluoromethylphenyl) phosphine, and the molar ratio of the phosphine ligand to the palladium catalyst is (1.0~5.0):1.0.

[0082] The heating reaction temperature is 80~150℃, and the heating holding reaction time is 5~30h;

[0083] The method for post-treatment is: cooling the reaction liquid to room temperature, filtering insoluble substances, removing the solvent and unreacted raw materials from the filtered solution by reduced pressure distillation;

[0084] The method for purification is column chromatography.

[0085] The present application provides a hydride obtained by hydrogenation reduction of the alkenyl bond in the BCB alkenyl adamantane derivative of the present application; the specific reaction steps are as follows:

[0086] The BCB olefin derivative is added into a hydrogenation reaction autoclave, a hydrogenation solvent and a hydrogenation catalyst are added, and the BCB diamond derivative is hydrogenated under the atmosphere of hydrogen and by pressurizing with hydrogen, stirring, heating and holding, and post-treatment and purification.

[0087] The hydrogenation solvent includes at least one of dioxane, tetrahydrofuran, ethyl acetate, DMF, toluene, xylene, DMSO, NMP and DMAC, and the volume of the hydrogenation solvent is 2-15 times the mass of the BCB olefin derivative;

[0088] The hydrogenation catalyst includes at least one of palladium-carbon, active nickel and platinum-carbon, and the mass of the hydrogenation catalyst is 0.1-10% of the mass of the BCB olefin derivative;

[0089] The pressure of the hydrogen pressurization is 0.2-2.0 Mpa;

[0090] The temperature of the heating reaction is 50-120℃;

[0091] The holding reaction time is 2-10 h;

[0092] The post-treatment method is to remove the hydrogenation catalyst by filtration and remove the solvent by distillation to obtain a crude product;

[0093] The purification method includes crystallization and / or column chromatography of the crude product.

[0094] The resin provided by the embodiment of the present application includes the BCB olefin derivative and / or the hydrogenated product provided by the present application.

[0095] More specifically, the resin can be obtained by ring-opening polymerization of the BCB olefin derivative and / or the hydrogenated product under high-temperature conditions, or by polymerization of the BCB olefin derivative and / or the hydrogenated product with other resins. The obtained resin has low dielectric properties and can be applied in the fields of high-performance PCB boards and packaging.

[0096] The resin composition provided by the embodiment of the present application includes the resin provided by the present application.

[0097] The inventor further provides the following reference examples for describing the present application, and it should be noted that these examples are merely descriptive and do not limit the present application in any way. Due to the limitation of the length, only part of the structures of the hydrogenated product of the present application are listed, and the others can be inferred and omitted.

[0098] Example 1

[0099] The embodiment provides a preparation method of a BCB olefin derivative, and the specific steps are as follows:

[0100] Under the atmosphere of nitrogen, 26.21 g (0.1 mol) of 1-iodoadamantane, 15.62 g (0.12 mol) of 4-vinylbenzocyclobutene, 0.269 g (1.2 mmol) of palladium acetate, 1.1 g (3.6 mmol) of tri (o-methylphenyl) phosphine, 16.8 g of diisopropyl ethylamine and 100 mL of DMF were sequentially added into a 250 mL three-necked flask, and then the mixture was heated to 110°C and reacted for 12 h. After that, the mixture was sequentially subjected to cooling to room temperature, filtration, vacuum distillation, column chromatography separation and purification, and vacuum distillation to obtain the BCB alkenyl adamantane derivative as shown in Figure 1 , with a yield of 22.41 g and a yield of 84.7%.

[0101] The present application provides a hydrogenated product, which is obtained by hydrogenation reduction of the alkenyl bond in the BCB alkenyl adamantane derivative prepared in the embodiment, and the specific steps are as follows:

[0102] The BCB alkenyl adamantane derivative prepared above was added into a hydrogenation reaction autoclave, 25 mL of hydrogenation solvent DMF and 0.05 g of palladium-carbon were added, the atmosphere was replaced with hydrogen, and the hydrogen pressure was 1.0 MPa. The mixture was stirred, heated to 65°C and reacted for 8 h. After that, the mixture was cooled to room temperature, depressurized, and the catalyst was removed by filtration. The filtrate was subjected to vacuum distillation to remove the solvent, and then was subjected to crystallization treatment to obtain 4.5 g of the hydrogenated BCB adamantane derivative (the molecular formula of the hydrogenated product is as shown in Figure 2 ).

[0103] Embodiment 2

[0104] The present embodiment provides a preparation method of a BCB alkenyl adamantane derivative, and the specific steps are as follows:

[0105] Under the atmosphere of nitrogen, 29.40 g (0.1 mol) of 1,3-dibromo adamantane, 32.55 g (0.25 mol) of 4-vinylbenzocyclobutene, 0.538 g (2.4 mmol) of palladium acetate, 2.2 g (7.2 mmol) of tri (o-methylphenyl) phosphine, 33.61 g of diisopropyl ethylamine and 100 mL of DMF were sequentially added into a 250 mL three-necked flask, and then the mixture was heated to 120°C and reacted for 12 h. After that, the mixture was sequentially subjected to cooling to room temperature, filtration, vacuum distillation, column chromatography separation and purification, and vacuum distillation to obtain the BCB alkenyl adamantane derivative as shown in Figure 3 , with a yield of 34.25 g and a yield of 87.24%.

[0106] The present application provides a hydrogenated product, which is obtained by hydrogenation reduction of the alkenyl bond in the BCB alkenyl adamantane derivative prepared in the embodiment, and the specific steps are as follows:

[0107] The BCB olefin diamond derivative prepared above 5.0 g is added into a hydrogenation reaction autoclave, 30 mL of hydrogenation solvent DMF and 0.05 g of palladium-carbon are added, the atmosphere is replaced with hydrogen and pressurized to 1.0 MPa with hydrogen, stirred, heated to 75°C and incubated for 6 h, cooled to room temperature, depressurized, the catalyst is removed by filtration, the filtrate is distilled under reduced pressure to remove the solvent, and then crystallization treatment is performed to obtain the hydrogenated BCB diamond derivative 4.55 g (the molecular formula of the hydrogenated product is as shown in Figure 4 ).

[0108] Example 3

[0109] The present embodiment provides a preparation method of a BCB olefin diamond derivative, and the specific steps are as follows:

[0110] Under a nitrogen atmosphere, 37.29 g (0.1 mol) of 1,3,5-tribromoadamantane, 46.87 g (0.36 mol) of 4-vinylbenzocyclobutene, 0.538 g (2.4 mmol) of palladium acetate, 0.22 g (7.2 mmol) of tri (o-methylphenyl) phosphine, 49.11 g of diisopropyl ethylamine and 120 mL of N,N-dimethylformamide are sequentially added into a 250 mL three-necked flask, heated and stirred to 130°C for 8 h, and then sequentially cooled to room temperature, filtered, distilled under reduced pressure, column chromatography separation and purification, and distilled under reduced pressure to obtain the BCB olefin diamond derivative as shown in Figure 5 , with a yield of 44.25 g and a yield of 85.0%.

[0111] The present embodiment provides a preparation method of a BCB olefin diamond derivative, and the specific steps are as follows:

[0112] The BCB olefin diamond derivative prepared above 5.0 g is added into a hydrogenation reaction autoclave, 30 mL of hydrogenation solvent DMF and 0.05 g of palladium-carbon are added, the atmosphere is replaced with hydrogen and pressurized to 1.0 MPa with hydrogen, stirred, heated to 75°C and incubated for 6 h, cooled to room temperature, depressurized, the catalyst is removed by filtration, the filtrate is distilled under reduced pressure to remove the solvent, and then crystallization treatment is performed to obtain the hydrogenated BCB diamond derivative 4.55 g (the molecular formula of the hydrogenated product is as shown in Figure 6 ).

[0113] Example 4

[0114] The present embodiment provides a preparation method of a BCB olefin diamond derivative, and the specific steps are as follows:

[0115] Under nitrogen atmosphere, 45.18 g (0.1 mol) of 1,3,5,7-tetrabromoadamantane, 65.10 g (0.50 mol) of 4-vinylbenzocyclobutene, 0.21 g of palladium acetate (1.2 mmol), 1.83 g of tri (o-methylphenyl) phosphine (6.0 mmol), 67.21 g of diisopropyl ethylamine and 150 mL of N,N-dimethylformamide were sequentially added into a 250 mL three-necked flask, and then the mixture was heated and stirred to be warmed up to 130°C for 9 h. After that, the mixture was sequentially subjected to cooling to room temperature, filtration, reduced pressure distillation, column chromatography separation and purification, and reduced pressure distillation to obtain the BCB alkenyl adamantane derivative as shown in Figure 7 , with a yield of 55.33 g and a yield of 85.3%.

[0116] The present application provides a hydrogenated product, which is obtained by hydrogenation reduction of the alkenyl bond in the BCB alkenyl adamantane derivative prepared in the present embodiment. The specific steps are as follows:

[0117] The BCB alkenyl adamantane derivative prepared above was added into a hydrogenation reaction autoclave, 40 mL of hydrogenation solvent DMF and 0.15 g of palladium-carbon were added, the atmosphere was replaced with hydrogen and pressurized to 1.0 MPa, and then the mixture was stirred, heated to 75°C and kept for 6 h. After that, the mixture was cooled to room temperature, depressurized, and the catalyst was removed by filtration. The filtrate was subjected to reduced pressure distillation to remove the solvent, and then subjected to crystallization treatment to obtain the hydrogenated BCB adamantane derivative 4.34 g (the molecular formula of the hydrogenated product is as shown in Figure 8 ).

[0118] Example 5

[0119] The present embodiment provides a preparation method of a BCB alkenyl adamantane derivative, and the specific steps are as follows:

[0120] Under nitrogen atmosphere, 9.04 g (0.02 mol) of 1,3,5,7-tetrabromoadamantane, 20.81 g (0.09 mol) of monobenzocyclobutene divinylbenzene, 0.02 g (0.01 mmol) of palladium chloride, 0.15 g (0.05 mmol) of triphenylphosphine, 9.9 g of potassium acetate and 70 mL of NMP were sequentially added into a 250 mL three-necked flask, and then the mixture was heated and stirred to be warmed up to 130°C for 4 h. After that, the mixture was sequentially subjected to cooling to room temperature, filtration, reduced pressure distillation, column chromatography separation and purification, and reduced pressure distillation to obtain the BCB alkenyl adamantane derivative as shown in Figure 9 , with a yield of 17.25 g and a yield of 81.6%.

[0121] The present application provides a hydrogenated product, which is obtained by hydrogenation reduction of the alkenyl bond in the BCB alkenyl adamantane derivative prepared in the present embodiment. The preparation steps are the same as those of Example 4, and the hydrogenated product obtained is as follows:

[0122] Example 6

[0123] The embodiment provides a preparation method of a BCB alkene adamantane derivative, and specific steps are as follows:

[0124] Under a nitrogen atmosphere, 9.04g (0.02mol) of 1,3,5,7-tetrabromoadamantane, 9.71g (0.042mol) of monobenzocyclobutenyl divinylbenzene, 4.37g (0.042mol) of styrene, 0.02g (0.01mmol) of palladium chloride, 0.15g (0.05mmol) of triphenylphosphine, 9.9g of potassium acetate and 70ml of NMP are sequentially added into a 250ml three-necked flask, and then stirring, temperature rising to 130 DEG C and reaction for 8h are carried out; and then temperature lowering to room temperature, filtration, reduced pressure distillation, column chromatography separation and purification, and reduced pressure distillation are sequentially carried out, so that the BCB alkene adamantane derivative shown in the formula (1) is obtained, and the yield is 11.37g, and the yield is 71.0%. Figure 10

[0125] The embodiment provides a preparation method of a BCB alkene adamantane derivative, and specific steps are as follows:

[0126] Embodiment 7

[0127] The embodiment provides a preparation method of a BCB alkene adamantane derivative, and specific steps are as follows:

[0128] Under a nitrogen atmosphere, 9.04g (0.02mol) of 1,3,5,7-tetrabromoadamantane, 9.71g (0.042mol) of monobenzocyclobutenyl divinylbenzene, 4.37g (0.042mol) of styrene, 0.02g (0.01mmol) of palladium chloride, 0.15g (0.05mmol) of triphenylphosphine, 9.9g of potassium acetate and 70ml of NMP are sequentially added into a 250ml three-necked flask, and then stirring, temperature rising to 130 DEG C and reaction for 8h are carried out; and then temperature lowering to room temperature, filtration, reduced pressure distillation, column chromatography separation and purification, and reduced pressure distillation are sequentially carried out, so that the BCB alkene adamantane derivative shown in the formula (1) is obtained, and the yield is 11.37g, and the yield is 71.0%. Figure 11

[0129] The embodiment provides a preparation method of a BCB alkene adamantane derivative, and specific steps are as follows:

[0130] Embodiment 8

[0131] The embodiment provides a preparation method of a BCB alkene adamantane derivative, and specific steps are as follows: ​​

[0132] Under nitrogen atmosphere, 5.88 g (0.02 mol) of 1,3-dibromoadamantane, 8.66 g (0.042 mol) of 4-styrylbenzocyclobutene, 45.8 mg (0.02 mmol) of palladium acetate, 156.6 mg (0.06 mmol) of triphenylphosphine, 13.8 g of potassium carbonate and 30 mL of N,N-dimethylformamide were sequentially added into a 250 mL three-neck flask, which was stirred and heated to 125°C, and then kept for 8 h. After that, the temperature was sequentially decreased to room temperature, filtration, vacuum distillation, column chromatography separation and purification, and vacuum distillation were sequentially performed to obtain the BCB alkenyl adamantane derivative as shown in Figure 12 , with a yield of 8.25 g and a yield of 75.7%.

[0133] The present application provides a hydride, which is obtained by hydrogenation reduction of the alkenyl bond in the BCB alkenyl adamantane derivative prepared in the present example. The difference between the preparation steps of the hydride and those of example 2 is that the hydrogenation catalyst in the preparation step of the hydride is platinum carbon.

[0134] Example 9

[0135] The present example provides a preparation method of a BCB alkenyl adamantane derivative, and the specific steps are as follows:

[0136] Under nitrogen atmosphere, 4.52 g (0.01 mol) of 1,3,5,7-tetrabromoadamantane, 10.22 g (0.044 mol) of bisbenzocyclobutenyl ethylene, 22.4 mg (0.1 mmol) of palladium acetate, 91.2 mg (0.3 mmol) of tri (o-methylphenyl) phosphine, 82.95 g of potassium carbonate and 40 mL of N,N-dimethylformamide were sequentially added into a 100 mL three-neck flask, which was stirred and heated to 120°C, and then kept for 10 h. After that, the temperature was sequentially decreased to room temperature, filtration, vacuum distillation, column chromatography separation and purification, and vacuum distillation were sequentially performed to obtain the BCB alkenyl adamantane derivative as shown in Figure 13 , with a yield of 3.86 g and a yield of 36.5%.

[0137] The present application provides a hydride, which is obtained by hydrogenation reduction of the alkenyl bond in the BCB alkenyl adamantane derivative prepared in the present example. The difference between the preparation steps of the hydride and those of example 4 is that the hydrogenation catalyst in the preparation step of the hydride is platinum carbon.

[0138] Example 10

[0139] The present example provides a preparation method of a BCB alkenyl adamantane derivative, and the specific steps are as follows:

[0140] Under a nitrogen atmosphere, 45.2 g (0.1 mol) of 1,3,5,7-tetrabromoadamantane, 28.6 g (0.22 mol) of 4-vinylbenzocyclobutene, and 28.6 g (0.22 mol) of other compounds were added sequentially to a 250 mL three-necked flask.

[0141] Divinylbenzene, 224 mg (1 mmol) palladium acetate, 912 mg (3 mmol) tris(o-methylphenyl)phosphine, 49.2 g diisopropylethylamine, and 130 mL N,N-dimethylformamide were reacted at 115 °C for 9 h with stirring. The mixture was then cooled to room temperature, filtered, purified by vacuum distillation, column chromatography, and vacuum distillation again to obtain the desired product. Figure 14 The BCB olefin derivative shown has a yield of 21.65 g and a yield of 33.3%.

[0142] This invention provides a hydride obtained by hydrogenation reduction of the olefin bond in the BCB olefin-based alkylene derivative prepared in this embodiment. The difference between this preparation step and that of Example 4 is that the hydrogenation catalyst in the hydride preparation step is platinum-carbon.

[0143] Example 11

[0144] This embodiment provides a method for preparing BCB olefin derivatives, the specific steps of which are as follows:

[0145] Under a nitrogen atmosphere, 4.52 g (0.01 mol) of 1,3,5,7-tetrabromoadamantane, 12.95 g (0.042 mol) of monobenzocyclobutenyldivinylbiphenyl, 44.8 mg (0.2 mmol) of palladium acetate, 182.4 mg (0.6 mmol) of tris(o-methylphenyl)phosphine, 67.21 g of diisopropylethylamine, and 150 mL of N,N-dimethylformamide were added sequentially to a 250 mL three-necked flask. Nitrogen gas was purged, and the mixture was stirred and heated to 125 °C for 8 h. The mixture was then cooled to room temperature, filtered, purified by vacuum distillation, column chromatography, and vacuum distillation again to obtain the desired product. Figure 15 The BCB olefin derivative shown has a yield of 7.73 g and a yield of 52.7%.

[0146] This invention provides a hydride obtained by hydrogenation reduction of the olefin bond in the BCB olefin-based alkylene derivative prepared in this embodiment. The preparation steps are the same as in Example 4.

[0147] Example 12

[0148] This embodiment provides a method for preparing adamantane derivatives containing 4-enhexyl BCB. The difference from Example 4 is that 4-vinylbenzocyclobutene is replaced with an equimolar amount of 4-enhexyl BCB. The resulting adamantane derivative is a four-adamantane derivative containing benzocyclobutenyl groups, and its chemical structure is as follows:Figure 16 As shown.

[0149] 4-Enhexyl BCB is prepared by reacting a Grignard reagent (prepared from 6-bromo-1-hexene) with 4-BrBCB.

[0150] This invention provides a hydride obtained by hydrogenation reduction of the olefin bond in the BCB olefin-based alkylene derivative prepared in this embodiment. The preparation steps are the same as in Example 4.

[0151] Example 13

[0152] This embodiment provides a method for preparing adamantane derivatives of BCB benzo[a]ane. The difference from Example 2 is that 4-vinylbenzo[a]ane is replaced with an equimolar amount of 4-enoctylbenzo[a]ane. The resulting BCB benzo[a]ane derivative is adamantane derivative containing two benzo[a]ane groups substituted with benzo[a]ane groups, and its chemical structural formula is as follows: Figure 17 As shown.

[0153] 4-Enoctyl BCB is prepared by reacting a Grignard reagent (prepared from 8-bromo-1-octene) with 4-BrBCB.

[0154] This invention provides a hydride obtained by hydrogenation reduction of the olefin bond in the BCB olefin-based alkylene derivative prepared in this embodiment. The preparation steps are the same as in Example 4.

[0155] Example 14

[0156] This embodiment provides a method for preparing adamantane derivatives of BCB-based adamantane. The difference from Example 4 is that 4-vinylbenzocyclobutene is replaced with an equimolar amount of butadienylbenzocyclobutene. The resulting BCB-based adamantane derivative is a four-adamantane derivative containing benzocyclobutenyl substituted groups, with the following chemical structural formula: Figure 18 As shown.

[0157] Butadiene-based benzocyclobutene is prepared by reacting butadiene with 4-BrBCB.

[0158] This invention provides a hydride obtained by hydrogenation reduction of the olefin bond in the BCB olefin-based alkylene derivative prepared in this embodiment. The preparation steps are the same as in Example 4.

[0159] Example 15

[0160] This embodiment provides a method for preparing adamantane derivatives of BCB olefins. The difference from Example 4 is that 4-vinylbenzocyclobutene is replaced with an equimolar amount of 1,7-octadienylbenzocyclobutene. The resulting BCB olefins adamantane derivative is a four-adamantane derivative containing benzocyclobutenyl groups, and its chemical structural formula is as follows: Figure 19 As shown.

[0161] wherein 1,7-octadienylbenzocyclobutene is prepared by reacting 1,7-octadiene with 4-BrBCB.

[0162] The present application provides a hydride, which is obtained by hydrogenation reduction of the olefinic bond in the BCB olefinadamantane derivative prepared in the present example. The preparation steps are the same as those in Example 4.

[0163] Application performance test:

[0164] The BCB olefinadamantane derivative prepared in the example and the product after hydrogenation thereof are subjected to performance tests such as dielectric performance and thermal performance, and the results are shown in Table 1.

[0165] Table 1. Test results of application performance of BCB olefinadamantane derivative and product after hydrogenation thereof

[0166]

[0167] Systematic analysis of the data in Table 1 can lead to the following conclusions:

[0168] (1) According to the data of Examples 1-4 and Examples 8-9, it is shown that the more the number of substituents on the 1, 3, 5, and 7 substitution positions of adamantane, the stronger the thermal stability, dielectric performance, and water resistance of the material.

[0169] (2) According to the data of Examples 4-7, it is shown that when the substituents on the 1, 3, 5, and 7 substitution positions of adamantane are the same, the thermal stability and dielectric performance are better.

[0170] (3) As can be seen from the data of Examples 11-15, the shorter the chain length of the substituents, the better the thermal stability and dielectric performance of the BCB olefinadamantane derivative.

[0171] (4) Detailed comparative analysis of the data of Examples 4, 9, and 11 shows that the introduction of a benzene ring has a positive effect on improving the thermal stability and dielectric performance of the derivative. Further comparison of Example 11 and Example 4 shows that by precisely controlling other groups (including benzene rings) in the substituents, the dielectric loss can be optimized without affecting other key properties of the material, which can effectively improve the dielectric performance of the material.

[0172] The above are preferred embodiments of the present application and are not intended to limit the present application. Although the present application has been described in detail with reference to the examples, those skilled in the art can still modify the technical solutions described in the foregoing examples or make equivalent substitutions for some of the technical features, but any modification, equivalent substitution, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A BCB olefinic alkylene derivative, characterized in that, The general molecular structural formula is shown in formula (1): Equation (1); The substituents R1, R2, R3, and R4 are independently selected from at least one of hydrogen atom, alkyl, olefinic, and aryl groups, and the substituents R1, R2, R3, and R4 include at least one BCB olefinic group.

2. The BCB olefin derivative according to claim 1, characterized in that: The number of carbon atoms in the alkyl group is an integer from 1 to 30; The number of carbon atoms in the olefin group is an integer from 2 to 30; The aryl group has an integer number of carbon atoms between 6 and 30.

3. The BCB olefin derivative according to claim 2, characterized in that: The alkyl group includes at least one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, dodecyl, octadecyl, and their isomers; The olefinic group includes at least one of vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, styryl, dodecenyl, decenyl, vinylstyryl, bistyryl, BCB-alkenyl, and their isomers; The aryl group includes at least one of phenyl, biphenyl, naphthyl, phenanthryl, fluorenyl, perylene, pyrene, anthracene, dihydroanthrene, tetraphenyl, pentaphenyl, BCB-alkenyl, and their hydrocarbon-substituted derivatives and isomers.

4. The BCB olefin derivative according to claim 1, characterized in that, The BCB alkenyl group is selected from one of formula (2) and formula (3): Equation (2); Equation (3); Wherein, the linker R5 includes at least one of a single chemical bond, an alkylene group, an alkenyl group, and an aryl group; the substituent R6 includes at least one of a hydrogen atom, an alkyl group, an alkenyl group, and an aryl group.

5. The BCB olefin derivative according to claim 4, characterized in that: In the linker R5, the alkylene group has an integer number of carbon atoms from 1 to 20; the alkenyl group has an integer number of carbon atoms from 2 to 20; and the aryl group has an integer number of carbon atoms from 6 to 20. In substituent R6, the alkyl group has an integer number of carbon atoms from 1 to 30; the olefinic group has an integer number of carbon atoms from 2 to 30; and the aryl group has an integer number of carbon atoms from 6 to 30.

6. The BCB olefin derivative according to claim 5, characterized in that: The alkylene group includes at least one of methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, decylene, hexadecylene, and their isomers; The alkenyl group includes at least one of vinylidene, propenylidene, butenylidene, pentenylidene, hexenylidene, heptenylidene, octenylidene, decenylidene, and their isomers; The arylene group includes at least one of phenylene, methylenephenyl, methylenephenylmethyl, styrene, bistyrene, and their hydrocarbon substituents and isomers; The alkyl group includes at least one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, and their isomers; The olefinic group includes at least one of vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, decenyl, dodecenyl, styryl, vinylstyryl, bistyryl, and their isomers; The aryl group includes at least one of phenyl, biphenyl, benzocyclobutenyl, and their hydrocarbon-substituted derivatives and isomers.

7. A method for preparing a BCB alkenyl adamantane derivative as described in any one of claims 1 to 6, wherein the BCB alkenyl adamantane derivative is prepared by a coupling reaction of a haloadamantane and an alkenyl BCB derivative, characterized in that, Includes the following steps: Add haloadamantane as shown in formula (4) and alkenyl BCB derivative as shown in formula (5) to the reaction flask, add organic solvent, catalyst and acid-binding agent, and after heating reaction, perform post-treatment purification operation to obtain BCB alkenyl adamantane derivative. Equation (4); Equation (5); Where X is a halogen; n is the number of halogen substitutions at the 1, 3, 5, and 7 substitution positions of the haloadamantane, and n is an integer from 1 to 4.

8. A hydride, characterized in that, The olefin bond in the BCB olefin-based alkylene derivative according to any one of claims 1 to 6 is obtained by hydrogenation reduction reaction.

9. A resin, characterized in that, It is prepared from the BCB olefin derivative as described in any one of claims 1 to 6 and / or the hydride as described in claim 8.

10. A resin composition, characterized in that, Includes the resin as described in claim 9.

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