BCB-containing fluorene derivative as well as preparation method and application thereof

Abstract

The invention relates to the field of low dielectric materials, and particularly discloses a BCB-containing fluorene derivative as well as a preparation method and application thereof, and the derivative is specifically shown as follows: in substitution sites 1-10 of fluorene and / or fluorene derivative, substituent groups R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are independently selected from at least one of hydrogen atoms, alkyl groups and aryl groups, and the substituent groups R9 and R10 comprise at least one BCB group. According to the present invention, the BCB group is introduced to the R9 and / or R10 substituent group of the fluorene and / or the fluorene derivative, such that the obtained BCB-containing fluorene derivative has characteristics of good thermal stability and low dielectric property. Meanwhile, the performance of the fluorene derivative containing BCB can be accurately optimized by flexibly regulating and controlling the types of substituent groups, the number of BCB groups on R9 and R10 substituent groups and the structure of the substituent group on the fluorenyl group, so that the problem of meeting low dielectric materials in the fields of high-performance PCBs, electronic packaging and the like in the prior art is solved.

Description

TECHNICAL FIELD

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

[0002] With the continuous progress of society and the rapid development of technology, people's demand for communication network speed is increasing. The continuous improvement of communication frequency puts forward more stringent requirements for printed circuit boards (PCB). These requirements mainly include lower dielectric constant (Dk) and dielectric loss (Df), higher heat resistance, and lower thermal expansion coefficient, etc. At present, the mass-produced PCB mainly uses a thermosetting resin composed of end-vinyl polyphenyl ether and triallyl isocyanurate (TAIC). Although this material has excellent mechanical properties and heat resistance, it is difficult to meet the demand for further reducing Dk and Df due to the presence of polar groups in TAIC.

[0003] As an excellent low dielectric material, benzocyclobutene (BCB) resin has excellent physical properties, chemical stability, and high temperature stability, etc. It can form both thermoplastic resin and thermosetting resin. Based on these outstanding advantages, BCB resin has been widely used in the fields of electronic and microelectronic industry manufacturing, etc. However, BCB monomer is a low-boiling volatile liquid, which usually needs to be prepared into a derivative to achieve more ideal application effect. Fluorene and its derivatives belong to an important class of compounds, which have a rigid planar biphenyl structure and a large conjugated system inside the molecule. This special rigid fused ring structure endows fluorene compounds with many unique photoelectric properties, biological activities, and reactivity, which makes them have potential wide application value in photoelectric materials, medicines and other fields. Most importantly, the reactivity of fluorene compounds makes it easy to modify the structure and introduce fluorene rings into various monomers.

[0004] In recent years, the synthesis of fluorene derivatives and the development of potential new uses of fluorene compounds have become a very active and rapidly developing research field. Fluorene compounds are often used as light emitters in organic light-emitting diodes (OLEDs) due to their excellent photoelectric properties, and can be applied to the preparation of organic thin film transistors and other organic electronic devices. Therefore, how to introduce fluorene and its derivatives into BCB monomers to enhance the stability of BCB monomers and prepare PCB boards with better performance has become an important topic that many researchers are concerned about and in-depth study. SUMMARY

[0005] Therefore, the purpose of the present application is to provide a BCB-containing fluorene derivative and a preparation method and application thereof, which solves the problem of low dielectric materials that meet the needs of high-performance PCB, electronic packaging and other fields in the prior art.

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

[0007] Formula (1);

[0008] Wherein, the substituent groups R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Each is independently selected from at least one of hydrogen atom, alkyl, alkenyl, aryl, and the substituent groups R9 and R 10 including at least one BCB group; the alkyl includes linear or branched alkyl, cycloalkyl; the alkenyl includes linear or branched alkenyl, alkenyl substituted alkyl; the aryl includes alkyl substituted aryl, aryl substituted alkyl, aryl substituted aryl, polyaryl group and its hydrocarbon substituted polyaryl derivative; the alkyl, alkenyl, aryl also includes the group connected with each other and the ring of fluorene.

[0009] Further, the number of carbon atoms of the alkyl is an integer in 1-30; the number of carbon atoms of the alkenyl is an integer in 2-30, and the number of carbon atoms of the aryl is an integer in 6-30.

[0010] Further, the BCB group is shown in formula (2):

[0011] Formula (2);

[0012] Wherein, the linking group R is selected from at least one of chemical single bond, alkylene, alkenylene, arylene; the substituent group R' is selected from at least one of hydrogen atom, alkyl, alkenyl, aryl, and the substituent group R' can also be a substituent group ringed with BCB. The alkylene, alkyl includes linear or branched alkylene, cycloalkylene; the alkenylene, alkenyl includes linear or branched alkenylene, alkenyl substituted alkylene; the arylene, aryl includes alkyl substituted arylene, aryl substituted alkylene, aryl substituted arylene, polyaryl group; the alkyl includes linear or branched alkyl, cycloalkyl; the alkenyl includes linear or branched alkenyl, alkenyl substituted alkyl; the aryl includes alkyl substituted aryl, aryl substituted alkyl, aryl substituted aryl, polyaryl group; the alkyl, alkenyl, aryl also includes the group connected with each other and the ring of BCB.

[0013] Further, the number of carbon atoms of the alkylene is an integer in 1-30; the number of carbon atoms of the alkenylene is an integer in 2-30; the number of carbon atoms of the arylene is an integer in 6-30; the number of carbon atoms of the alkyl is an integer in 1-30; the number of carbon atoms of the alkenyl is an integer in 2-30; the number of carbon atoms of the aryl is an integer in 6-30.

[0014] Further, R9, R 10 Each includes a BCB group.

[0015] Preferably, the substituent R9, R 10 R in the BCB group is a chemical single bond and / or methylene.

[0016] Further, any two adjacent substituents among the substituents R1, R2, R3, R4, R5, R6, R7, R8 are connected to form a benzene ring.

[0017] Further, the linking group R is a chemical single bond and / or methylene; and / or, the substituent R' is a hydrogen atom.

[0018] The present application provides a preparation method of a BCB-containing fluorene derivative, comprising the following reaction steps:

[0019] M1: under a dry atmosphere, a reaction bottle is added with fluorene and / or fluorene derivative, organic solvent, then halogenated BCB derivative, strong base and catalyst, after heating reaction and cooling to room temperature, quenching reaction, extraction, concentration, and then purification treatment are sequentially performed to obtain the BCB-containing fluorene derivative;

[0020] or M2: under a dry atmosphere, a reaction bottle is added with fluorene and / or fluorene derivative, organic solvent, then strong base is added, followed by temperature reduction and addition of halogenated BCB derivative under low temperature, after the addition is completed, the temperature is heated to room temperature for reaction, then quenching reaction, extraction, concentration, and then purification treatment are performed to obtain the BCB-containing fluorene derivative;

[0021] wherein, the structural formula of the fluorene and / or fluorene derivative is shown as formula (3), and the halogenated BCB derivative is shown as formula (4):

[0022] Formula (3); Formula (4);

[0023] In formula (3), the substituents R9', R 10 are each independently selected from at least one of a hydrogen atom, an alkyl group, an alkenyl group, and an aryl group, and at least one of the substituents R9' and R 10 In formula (4), X is halogen; preferably, X includes one of chlorine, bromine, and iodine.

[0024] The present application provides a resin prepared from the BCB-containing fluorene derivative provided by the present application.

[0025] The present application provides a resin composition comprising the resin provided by the present application.

[0026] The present application provides a BCB-containing fluorene derivative, which specifically exhibits that, in the substituents of the fluorene and / or fluorene derivative, the substituents R1, R2, R3, R4, R5, R6, R7, R8, R10 each independently is selected from at least one of a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, and the substituent groups R9and R 10 including at least one BCB group. The present application obtains a low dielectric material with good thermal stability and low dielectric property by introducing a BCB group on R9and / or R 10 substituent of a fluorene and / or a fluorene derivative, to obtain a BCB-containing fluorene derivative.

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

[0028] The BCB-containing fluorene derivative provided by the present application can precisely optimize the performance of the BCB-containing fluorene derivative by flexibly adjusting the types of substituent groups and the BCB group and the number thereof on R9, R 10 substituent, to solve the problem that the low dielectric material in the prior art can meet the requirements of high-performance PCB and electronic packaging fields. 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 prior art description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0030] Figure 1 Reaction scheme diagram of the BCB-containing fluorene derivative provided for Embodiment 1 of the present application;

[0031] Figure 2 Reaction scheme diagram of the BCB-containing fluorene derivative provided for Embodiment 2 of the present application;

[0032] Figure 3 Reaction scheme diagram of the BCB-containing fluorene derivative provided for Embodiment 3 of the present application;

[0033] Figure 4 Reaction scheme diagram of the BCB-containing fluorene derivative provided for Embodiment 4 of the present application;

[0034] Figure 5 Reaction scheme diagram of the BCB-containing fluorene derivative provided for Embodiment 5 of the present application;

[0035] Figure 6 Reaction scheme diagram of the BCB-containing fluorene derivative provided for Embodiment 6 of the present application;

[0036] Figure 7 Reaction scheme diagram of the BCB-containing fluorene derivative provided for Embodiment 7 of the present application;

[0037] Figure 8 Chemical structural formula of the BCB-containing fluorene derivative provided for Example 8 of the present application;

[0038] Figure 9 Reaction scheme of the BCB-containing fluorene derivative provided for Example 9 of the present application;

[0039] Figure 10 Chemical structural formula of the BCB-containing fluorene derivative provided for Example 10 of the present application;

[0040] Figure 11 Chemical structural formula of the BCB-containing fluorene derivative provided for Example 11 of the present application;

[0041] Figure 12 Chemical structural formula of the BCB-containing fluorene derivative provided for Example 12 of the present application;

[0042] Figure 13 Chemical structural formula of the BCB-containing fluorene derivative provided for Example 13 of the present application;

[0043] Figure 14 Chemical structural formula of 2,7-dihexylfluorene provided for Example 14 of the present application;

[0044] Figure 15 Chemical structural formula of the BCB-containing fluorene derivative provided for Example 14 of the present application;

[0045] Figure 16 Chemical structural formula of 2,7-bis(dodecyl)fluorene provided for Example 15 of the present application;

[0046] Figure 17 Chemical structural formula of the BCB-containing fluorene derivative provided for Example 15 of the present application;

[0047] Figure 18 Chemical structural formula of 2,7-bis(octadecyl)fluorene provided for Example 16 of the present application;

[0048] Figure 19 Chemical structural formula of the BCB-containing fluorene derivative provided for Example 16 of the present application;

[0049] Figure 20 HNMR spectrum of the BCB-containing fluorene derivative provided for Example 3 of the present application;

[0050] In the figure, Hex represents n-hexyl, Dode represents n-dodecyl, and Octode represents n-octadecyl. DETAILED DESCRIPTION

[0051] 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.

[0052] 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.

[0053] The present application provides a fluorene derivative containing BCB, and the molecular structure formula is shown in formula (1).

[0054] Formula (1);

[0055] In the formula, the substituents R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 are each independently selected from at least one of a hydrogen atom, an alkyl group, an alkenyl group, and an aryl group, and the substituents R9 and R 10 include at least one BCB group.

[0056] In some embodiments, the alkyl group includes a linear or branched alkyl group, a cyclic alkyl group; the alkenyl group includes a linear or branched alkenyl group, an alkenyl-substituted alkyl group; the aryl group includes an alkyl-substituted aryl group, an aryl-substituted alkyl group, an aryl-substituted aryl group, a polyaryl group; the alkyl group, the alkenyl group, and the aryl group further include groups connected to each other and forming a ring with the fluorene ring.

[0057] In some embodiments, the number of carbon atoms in the alkyl group is an integer from 1 to 30; the number of carbon atoms in the alkenyl group is an integer from 2 to 30; and the number of carbon atoms in the aryl group is an integer from 6 to 30.

[0058] In some specific embodiments, the alkyl group includes 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 dodecyl group, an octadecyl group, and isomers thereof.

[0059] In some specific embodiments, the alkenyl group includes at least one of an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a decenyl group, a dodecenyl group, a styryl group, an ethenylstyryl group, a BCB alkenyl group, and isomers thereof.

[0060] In some specific embodiments, the aryl group includes at least one of a phenyl group, a biphenyl group, a naphthyl group, a fluorenyl group, a perylenyl group, a pyrenyl group, an anthryl group, a dihydroanthryl group, a naphthacene group, a pentacene group, a BCB alkenyl group, and hydrocarbon-substituted derivatives and isomers thereof.

[0061] Substituents R9and R 10 In some embodiments, the BCB group is represented by Formula (2):

[0062] Formula (2);

[0063] In Formula (2), the linking group R is selected from at least one of a chemical single bond, an alkylene group, an alkenylene group, an arylene group; the alkylene group includes a straight chain or branched alkylene group, a cycloalkylene group; the alkenylene group includes a straight chain or branched alkenylene group, an alkenyl-substituted alkylene group; the arylene group includes an alkyl-substituted arylene group, an aryl-substituted alkylene group, an aryl-substituted arylene group, a polyarylene group.

[0064] In Formula (2), the substituent R' is selected from at least one of a hydrogen atom, an alkyl group, an alkenyl group, an aryl group; the substituent R' can also be a cyclic substituent formed by one or more substituents, which are the same or different, and the BCB group. The alkyl group includes a straight chain or branched alkyl group, a cycloalkyl group; the alkenyl group includes a straight chain or branched alkenyl group, an alkenyl-substituted alkyl group; the aryl group includes an alkyl-substituted aryl group, an aryl-substituted alkyl group, an aryl-substituted aryl group, a polyarylene group.

[0065] In some embodiments, the number of carbon atoms in the alkylene group is an integer from 1 to 30; the number of carbon atoms in the alkenylene group is an integer from 2 to 30; the number of carbon atoms in the arylene group is an integer from 6 to 30; the number of carbon atoms in the alkyl group is an integer from 1 to 30; the number of carbon atoms in the alkenyl group is an integer from 2 to 30; the number of carbon atoms in the aryl group is an integer from 6 to 30.

[0066] In some specific embodiments, in the linking group R, the alkylene group includes 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 includes 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 includes at least one of a phenylene group, a methylene phenylene group, a methylene phenylene methyl group, a styrylene group, a biphenylylene group, and their hydrocarbyl-substituted groups and isomers;

[0067] In some specific embodiments, in the substituent R', the alkyl group includes 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 includes 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 dodecyl group, a styryl group, a vinyl styryl group, a biphenylyl styryl group, and their isomers; the aryl group includes at least one of a phenyl group, a biphenyl group, a benzocyclobutene group, and their hydrocarbyl-substituted derivatives and isomers.

[0068] In some specific embodiments, the substituent R' is a substituent that forms a ring with BCB, including one of cyclobutyl, phenyl, benzocyclobutene with the BCB benzene ring.

[0069] In some embodiments, R9, R 10 each independently includes a BCB group.

[0070] Preferably, the substituents R9, R 10 are the same substituent.

[0071] It should be noted that, on the basis that R9, R 10 each independently includes at least one BCB group, if the substituents R9, R 10 are the same substituent and the derivative containing the BCB group exhibits axial symmetry, then the comprehensive performance of the fluorene derivative containing the BCB group can be significantly improved.

[0072] Preferably, at least two of the substituents R1, R2, R3, R4, R5, R6, R7, and R8 are alkyl groups.

[0073] Preferably, the substituents R9, R 10 include R in the BCB group that is a chemical single bond and a methylene group.

[0074] More preferably, any two adjacent substituents of the substituents R1, R2, R3, R4, R5, R6, R7, and R8 are connected to form a benzene ring.

[0075] It should be noted that, on the basis that R9, R 10 each independently includes at least one BCB group and an alkylene group, the comprehensive performance of the derivative can be improved by connecting any two substituents of the substituents R1, R2, R3, R4, R5, R6, R7, and R8 to form a ring. In particular, when the two adjacent substituents R6 and R7 are connected to form a benzene ring, not only the thermal stability and dielectric properties of the derivative are improved, but also the negative effects of the benzene ring in the substituents R9, R 10 are significantly reduced; further, the dielectric constant can be precisely controlled by controlling the number of benzene rings in the substituents R 1~8 and R 9~10 .

[0076] Preferably, the substituents R1, R2, R3, R4, R5, R6, R7, and R8 include at least one alkyl group or aryl group.

[0077] It should be noted that when the substituents R1, R2, R3, R4, R5, R6, R7and R8include at least one alkyl or aryl group, the thermal stability and dielectric properties of the BCB-containing fluorene derivative are far superior to those of the derivative in which the substituents are hydrogen atoms.

[0078] In some embodiments, the linking group R is a chemical single bond and / or a methylene group; in some embodiments, the substituent R' is a hydrogen atom.

[0079] The embodiments of the present application provide a preparation method of a BCB-containing fluorene derivative, comprising the following steps:

[0080] M1: under a dry atmosphere, a reaction bottle is added with fluorene and / or a fluorene derivative, an organic solvent, a halogenated BCB derivative, a strong base and a catalyst, and after heating reaction and cooling to room temperature, a quenching reaction, extraction, concentration, and purification treatment are sequentially performed to obtain the BCB-containing fluorene derivative;

[0081] or M2: under a dry atmosphere, a reaction bottle is added with fluorene and / or a fluorene derivative, an organic solvent, a strong base, and then the temperature is lowered and a halogenated BCB derivative is added under low-temperature conditions, after the addition is completed, the temperature is heated to room temperature for reaction, and then a quenching reaction, extraction, concentration, and purification treatment are sequentially performed to obtain the BCB-containing fluorene derivative;

[0082] wherein the structural formula of the fluorene and / or fluorene derivative is shown in formula (3), and the halogenated BCB derivative is shown in formula (4):

[0083] formula (3); formula (4);

[0084] In formula (3), the substituents R9', R 10 are each independently selected from at least one of a hydrogen atom, an alkyl group, an alkenyl group, and an aryl group, and at least one of the substituents R9' and R 10 is a hydrogen atom;

[0085] In formula (4), X is a halogen; preferably, X includes one of chlorine, bromine, and iodine.

[0086] In some embodiments, when the substituents R9' and R 10 on the fluorene and / or fluorene derivative are both hydrogen atoms, halogen-substituted alkanes and / or halogen-substituted arenes can also be introduced in the process of preparing the BCB-containing fluorene derivative.

[0087] It should be noted that when the substituents R9' and R 10When all are hydrogen atoms, the halogen-substituted alkane and / or halogen-substituted arene can be added before, simultaneously with, or after the halogen-substituted BCB and / or halogen-substituted BCB derivative is added. Because under this condition, there are two chemical reaction modes: (1) M1: the fluorene and / or fluorene derivative first reacts with the halogen-substituted alkane or arene to obtain a substituted fluorene derivative, and the substituted fluorene derivative then reacts with the halogen-substituted BCB and / or halogen-substituted BCB derivative to obtain a fluorene derivative containing a BCB group; or the fluorene and / or fluorene derivative first reacts with the halogen-substituted BCB and / or halogen-substituted BCB derivative, and then reacts with the halogen-substituted alkane or arene; by controlling the ratio of the reaction raw materials, a fluorene derivative containing one BCB group can be obtained; (2) M2: the halogen-substituted alkane or arene is added in the mixture of the fluorene and / or fluorene derivative, the halogen-substituted BCB and / or halogen-substituted BCB derivative, at which time the fluorene and / or fluorene derivative, the halogen-substituted alkane or arene, and the halogen-substituted BCB and / or halogen-substituted BCB derivative will react together to obtain a fluorene derivative containing a BCB group.

[0088] Specifically, the fluorene derivative includes but is not limited to one of the following formulas:

[0089] Formula (5), Formula (6), Formula (7), Formula (8), Formula (9), Formula (10), Formula (11), Formula (12), Formula (13).

[0090] Specifically, the halogenated BCB is selected from one of the following formulas:

[0091] Formula (14), Formula (15), Formula (16).

[0092] In step M1:

[0093] The dry atmosphere includes at least one of a nitrogen atmosphere or an argon atmosphere;

[0094] The molar ratio of the fluorene and / or fluorene derivative to the halogenated BCB derivative is 1.0: (1.0-3.0);

[0095] The organic solvent is selected from at least one of toluene, xylene, trimethylbenzene, acetonitrile, DMF, NMP, DMA, and DMSO, and the volume of the organic solvent is 3-30 times the mass of the fluorene and / or fluorene derivative;

[0096] The strong base is at least one of sodium methoxide, sodium ethoxide, potassium tert-butoxide, and sodium tert-butoxide, and the molar ratio of the strong base to the fluorene and / or fluorene derivative is (1.0-3.5):1;

[0097] The catalyst comprises a palladium catalyst and a phosphine ligand; the palladium catalyst is at least one of palladium acetate, diphenylphosphino ferrocene dichloropalladium, tetrakis-triphenylphosphine palladium, and dichlorobistrimethylphenylphosphine palladium, and the molar ratio of the palladium catalyst to the fluorene and / or fluorene derivative is (0.0001-0.05):1; the phosphine ligand is at least one of triphenylphosphine, tributylphosphine, tricyclohexylphosphine, tris(2-methoxyphenyl)phosphine, and tris(4-trifluoromethylphenyl)phosphine, and the molar ratio of the phosphine ligand to the fluorene and / or fluorene derivative is (0.0001-0.10):1;

[0098] In some embodiments, the heating reaction temperature is 80-150°C, and the reaction time is 5-20h; preferably, the heating reaction temperature is 108-130°C, and the reaction time is 8-12h;

[0099] The method for quenching the reaction and extraction is that cold water is slowly added to the reaction solution, the organic phase is separated, the water phase is extracted with an organic solvent, the organic phases are combined and washed, and then concentrated to obtain a residue;

[0100] The method for treatment is silica gel column chromatography.

[0101] In step M2,

[0102] The drying atmosphere comprises at least one of a nitrogen atmosphere and an argon atmosphere;

[0103] The molar ratio of the fluorene and / or fluorene derivative to the halogenated BCB derivative is 1.0:(1.0-3.0);

[0104] The organic solvent is at least one of diethyl ether, methyl tert-butyl ether, and tetrahydrofuran, and the volume of the organic solvent is 5-40 times the mass of the fluorene and / or fluorene derivative;

[0105] The strong base is n-butyllithium, and the molar ratio of the strong base to the fluorene and / or fluorene derivative is (1.0-3.0):1;

[0106] The low temperature is -78°C to -50°C, and the reaction time at room temperature is 8-20h;

[0107] The method for quenching the reaction and extraction is that water is added to the reaction solution, the organic phase is separated, the water phase is extracted with an organic solvent, the organic phases are combined and washed, and then the organic phase is concentrated to obtain a residue;

[0108] The method for treatment is silica gel column chromatography.

[0109] The resin provided by the present application is prepared from the BCB-containing fluorene derivative provided by the present application. The obtained resin has low dielectric property and can be applied in the fields of high-performance PCB, packaging, etc.

[0110] Specifically, the resin can be obtained by ring-opening polymerization of the BCB-containing fluorene derivative under high-temperature conditions, or by polymerization reaction of the BCB-containing fluorene derivative and other resins.

[0111] The present application provides a resin composition comprising the resin provided by the present application.

[0112] The applicant further provides the following reference specific embodiments for describing the present application. It should be noted that these embodiments are merely descriptive and do not limit the present application in any way.

[0113] Embodiment 1

[0114] The present embodiment provides a preparation method of the BCB-containing fluorene derivative, comprising the following steps:

[0115] Under a nitrogen atmosphere, 16.62 g (0.1 moL) of fluorene was dissolved in 200 mL of toluene solution, 21.97 g (0.12 moL) of 4-BrBCB was added to the above solution, stirred for 10 min, then 16.84 g (0.15 moL) of potassium tert-butoxide, 0.28 g (1 mmol) of tricyclohexyl phosphorus, and 0.11 g (0.5 mmol) of palladium acetate catalyst were added, heated to 108°C and stirred under reflux for 8 h, then cooled to room temperature, quenched with cold water, continued to stir for 0.5 h, extracted with toluene for 2-3 times, purified by silica gel column chromatography to obtain the BCB-containing fluorene derivative. The chemical reaction equation of the present application and the structure of the BCB-containing fluorene derivative can be seen from Figure 1 .

[0116] The HNMR data of the BCB-containing fluorene derivative is: 1H NMR (400 MHz, CDCl3): δ 7.87-7.84 (d, 2H), 7.64-7.60 (d, 2H), 7.41-7.38 (t, 2H), 7.35-7.31 (t, 2H), 7.24-7.05 (m, 3H), 5.09 (s, 1H), 3.19-3.13 (m, 4H). This indicates that the hydrogen atom at the 9th substitution site of the fluorene ring is replaced by a benzocyclobutene ring.

[0117] Embodiment 2

[0118] The present embodiment provides a preparation method of the BCB-containing fluorene derivative, comprising the following steps:

[0119] Under nitrogen atmosphere, 16.62 g (0.1 moL) of fluorene was dissolved in 400 mL of tetrahydrofuran to form an organic solution containing fluorene, the temperature of the reaction system was reduced to -60°C, 68.6 mL (0.11 mmol) of n-butyllithium (1.6 M, n-hexane solution) was slowly injected into the above solution, after the injection was completed, the reaction was stirred at room temperature for 2 hours, the temperature of the reaction system was reduced to -60°C, 16.78 g (0.11 moL) of 4-ClCH2BCB was added, after the addition was completed, the temperature of the reaction system was adjusted to room temperature and stirred for 8 hours, after the stirring was completed, 150 mL of water was slowly added to quench the reaction, the extraction was separated, the organic phase was washed with water, dried, and concentrated to obtain a crude product, the crude product was column chromatographed on silica gel to obtain a BCB-containing fluorene derivative. The chemical reaction equation of the present application and the structure of the BCB-containing fluorene derivative can be seen from Figure 2 .

[0120] The HNMR data of the BCB-containing fluorene derivative prepared in this example is as follows: 1H NMR (400 MHz, CDCl3): δ 7.86-7.83 (d, 2H), 7.62-7.58 (d, 2H), 7.42-7.37 (t, 2H), 7.33-7.30 (t, 2H), 7.26-7.08 (m, 3H), 5.09 (s, 1H), 3.09-3.03 (m, 6H). This indicates that one hydrogen atom on the substituent at the 9th position of the fluorene ring is replaced by a methylbenzocyclobutene.

[0121] Example 3

[0122] The present example provides a method for preparing a BCB-containing fluorene derivative, comprising the following steps:

[0123] Under nitrogen atmosphere, 16.62 g (0.1 moL) of fluorene was dissolved in 400 mL of tetrahydrofuran to form an organic solution containing fluorene, the temperature of the reaction system was reduced to -60°C, 68.6 mL (0.11 mmol) of n-butyllithium (1.6 M, n-hexane solution) was slowly injected into the above solution, after the injection was completed, the reaction was stirred at room temperature for 2 hours, the temperature of the reaction system was reduced to -60°C, 16.78 g (0.11 moL) of 4-ClCH2BCB was added, after the addition was completed, the temperature of the reaction system was adjusted to room temperature and stirred for 8 hours, after the stirring was completed, 150 mL of water was slowly added to quench the reaction, the extraction was separated, the organic phase was washed with water, dried, and concentrated to obtain a crude product, the crude product was column chromatographed on silica gel to obtain a BCB-containing fluorene derivative. The chemical reaction equation of the present application and the structure of the BCB-containing fluorene derivative can be seen from Figure 3 .

[0124] The HNMR spectrum of the BCB-containing fluorene derivative prepared in this example is as follows: Figure 20As shown, the atlas can be seen from the 1H NMR (400 MHz, CDCl3): δ 7.84-7.81 (d, 2H), 7.51-7.49 (d, 2H), 7.42-7.39 (t, 2H), 7.35-7.31 (t, 2H), 7.19-7.17 (d, 2H), 6.98-6.96 (m, 4H), 3.18-3.12 (m, 8H); indicating that the hydrogen atoms at the 9-position of the fluorene ring are all substituted by benzocyclobutene.

[0125] Example 4

[0126] The present embodiment provides a preparation method of a fluorene derivative containing BCB, comprising the following steps:

[0127] Under a nitrogen atmosphere, 8.31 g (0.05 moL) of fluorene was dissolved in 200 mL of tetrahydrofuran to form an organic solution containing fluorene, and the temperature of the reaction system was reduced to -60°C. 68.6 mL (0.11 mmol) of n-butyllithium (1.6 M, n-hexane solution) was slowly injected into the above solution, and after the injection was completed, the reaction was stirred at room temperature for 2 hours. The temperature of the reaction system was reduced to -60°C, and 16.78 g (0.11 moL) of 4-ClCH2BCB was added. After the addition was completed, the temperature of the reaction system was adjusted to room temperature and stirred for 8 h. After the stirring was completed, 80 mL of water was slowly added to quench the reaction, and the extraction was separated. The organic phase was washed with water, dried and concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain a fluorene derivative containing BCB. The chemical reaction equation of the present application and the structural formula of the fluorene derivative containing BCB can be seen from Figure 4 .

[0128] The HNMR data of the fluorene derivative containing BCB prepared in the present embodiment is: 1H NMR (400 MHz, CDCl3): δ 7.88-7.84 (d, 2H), 7.65-7.61 (d, 2H), 7.43-7.39 (t, 2H), 7.34-7.31 (t, 2H), 7.24-7.20 (d, 2H), 7.08-6.98 (m, 4H), 3.13 (s, 4H), 3.10-3.05 (m, 8H); indicating that the hydrogen atoms at the 9-position of the fluorene ring are all substituted by methylbenzocyclobutene.

[0129] Example 5

[0130] The present embodiment provides a preparation method of a fluorene derivative containing BCB, comprising the following steps:

[0131] Step S1, according to the preparation method of Example 1, the phenyl fluorene is prepared from fluorene and iodobenzene, and the specific steps are as follows: 16.62 g (0.1 moL) of fluorene is dissolved in 200 mL of toluene solution under nitrogen atmosphere, 24.48 g (0.12 moL) of iodobenzene is added to the above solution, stirred for 10 min, then 16.84 g (0.15 moL) of potassium tert-butoxide, 0.28 g (1 mmol) of tricyclohexylphosphine, and 0.11 g (0.5 mmol) of palladium acetate catalyst are added, heated to 108℃ and stirred for 8 h, then cooled to room temperature, quenched with cold water, stirred for 0.5 h, extracted with toluene for 2-3 times, purified by silica gel column chromatography to obtain phenyl fluorene.

[0132] Step S2, under nitrogen atmosphere, 12.11 g (0.05 moL) of phenyl fluorene is dissolved in 100 mL of xylene solution, 10.99 g (0.06 moL) of 4-BrBCB is added to the above solution, stirred for 10 min, then 8.42 g (0.075 moL) of potassium tert-butoxide, 0.07 g (0.025 mmol) of tricyclohexylphosphine, and 0.055 g (0.025 mmol) of palladium acetate catalyst are added, heated to 130℃ and stirred for 12 h, then cooled to room temperature, quenched with cold water, stirred for 0.5 h, extracted with toluene for 2-3 times, purified by silica gel column chromatography to obtain BCB-containing fluorene derivative. The chemical reaction equation of the present application and the structure of the BCB-containing fluorene derivative can be seen from Figure 5 .

[0133] Example 6

[0134] The present embodiment provides a preparation method of BCB-containing fluorene derivative, comprising the following steps:

[0135] Step S1, according to the preparation method of Example 2, the benzyl fluorene is prepared from fluorene and benzyl chloride, and the specific steps are as follows: 16.62 g (0.1 moL) of fluorene is dissolved in 400 mL of tetrahydrofuran to form an organic solution containing fluorene, the temperature of the reaction system is reduced to -60℃, 68.6 mL (0.11 mmol) of n-butyllithium (1.6 M, n-hexane solution) is slowly injected into the above solution, after injection, the reaction is stirred at room temperature for 2 hours, the temperature of the reaction system is reduced to -60℃, 13.92 g (0.11 moL) of benzyl chloride is added, after the addition, the temperature of the reaction system is adjusted to room temperature and stirred for 8 h, after stirring, 150 mL of water is slowly added to quench the reaction, extracted and separated, the organic phase is washed with water, dried, concentrated to obtain the crude product, and the crude product is purified by silica gel column chromatography to obtain benzyl fluorene.

[0136] Step S2, 12.80 g (0.05 moL) of benzyl fluorene was dissolved in 200 mL of tetrahydrofuran to form a fluorene-containing organic solution under a nitrogen atmosphere, the temperature of the reaction system was reduced to -60°C, 34.3 mL (0.055 mmol) of n-butyllithium (1.6M, n-hexane solution) was slowly injected into the above solution, after the injection was completed, the reaction was stirred at room temperature for 2 hours, the temperature of the reaction system was reduced to -60°C, 8.02 g (0.053 moL) of benzyl chloride was added, after the addition was completed, the temperature of the reaction system was adjusted to room temperature and stirred for 8 hours, after the stirring was completed, 80 mL of water was slowly added to quench the reaction, the extraction was separated, the organic phase was washed with water, dried, and concentrated to obtain a crude product, the crude product was purified by silica gel column chromatography to obtain a BCB-containing fluorene derivative. The chemical reaction equation of the present application and the structure of the BCB-containing fluorene derivative are shown in Figure 6 .

[0137] Example 7

[0138] The present embodiment provides a preparation method of a BCB-containing fluorene derivative, comprising the following steps:

[0139] Under a nitrogen atmosphere, 21.63 g (0.1 moL) of 3,4-benzofluorene was dissolved in 200 mL of dimethylbenzene solution, 45.76 g (0.25 moL) of 4-BrBCB was added to the above solution, stirred for 10 min, then 16.84 g (0.15 moL) of potassium tert-butoxide, 0.28 g (1 mmol) of tricyclohexylphosphine, and 0.11 g (0.5 mmol) of palladium acetate catalyst were added, heated to 120°C and stirred under reflux for 8 hours, then cooled to room temperature, quenched with cold water, continued to stir for 0.5 hours, extracted with toluene for 2-3 times, purified by silica gel column chromatography to obtain a BCB-containing fluorene derivative. The chemical reaction equation of the present application and the structure of the BCB-containing fluorene derivative are shown in Figure 7 .

[0140] Example 8

[0141] The present embodiment provides a preparation method of a BCB-containing fluorene derivative, comprising the following steps:

[0142] Step S1, 3,4-benzofluorene was used instead of fluorene in an equal molar amount, and the preparation method of Example 1 was used for operation to obtain 9-phenyl 3,4-benzofluorene;

[0143] Step S2, the preparation method of Example 1 was used, and 9-phenyl 3,4-benzofluorene was used instead of fluorene to react with 4-BrBCB to obtain a BCB-containing fluorene derivative as shown in Figure 8 .

[0144] Based on the same reaction principle, 3,4-benzofluorene can be reacted with 4-BrBCB to obtain 9-BCB-3,4-benzofluorene by the preparation method of Example 1, and then 9-BCB-3,4-benzofluorene can be reacted with iodobenzene to obtain the BCB-containing fluorene derivative as shown in Figure 8 .

[0145] Example 9

[0146] The embodiment provides a preparation method of a BCB-containing fluorene derivative, which comprises the following steps:

[0147] In the preparation method of Example 4, 2,3-benzofluorene is used to replace fluorene in an equal molar amount, and the BCB-containing fluorene derivative is obtained. The chemical reaction equation of the embodiment and the structural formula of the BCB-containing fluorene derivative can be referred to Figure 9 .

[0148] Example 10

[0149] The embodiment provides a preparation method of a BCB-containing fluorene derivative, which comprises the following steps:

[0150] In step S1, 2,3-benzofluorene is used to replace fluorene in an equal molar amount, and 4-ClCH2BCB is used to replace 4-ClCH2BCB in an equal molar amount, and the method provided in Example 2 is used to perform experiments, and 9-benzyl-2,3-benzofluorene is obtained.

[0151] In step S2, the preparation method of Example 2 is used, 9-benzyl-2,3-benzofluorene is used to replace fluorene in an equal molar amount, and 4-ClCH2BCB is used to react with 4-ClCH2BCB, and the BCB-containing fluorene derivative as shown in Figure 10 is obtained.

[0152] Based on the same reaction principle, 2,3-benzofluorene can be reacted with 4-ClCH2BCB to obtain 9-BCBCH2-2,3-benzofluorene by the preparation method of Example 2, and then 9-BCBCH2-2,3-benzofluorene can be reacted with chlorobenzene to obtain the BCB-containing fluorene derivative as shown in Figure 10 .

[0153] Example 11

[0154] The embodiment provides a preparation method of a BCB-containing fluorene derivative, which comprises the following steps:

[0155] In the preparation method of Example 3, 1-methylfluorene or 3-methylfluorene or 4-methylfluorene is used to replace fluorene in an equal molar amount, and 4-BrBCB is used to react with 4-BrBCB, and three kinds of fluorene derivatives as shown in Figure 11 are obtained. The structural formula of the BCB-containing fluorene derivative obtained in the embodiment can be referred to Figure 11 (a-c).

[0156] Example 12

[0157] The present example provides a preparation method of a BCB-containing fluorene derivative, comprising the following steps:

[0158] The preparation method of Example 2 is adopted, and 9-ethylfluorene is used to replace fluorene to react with 4-ClCH2BCB in equimolar amount to obtain a BCB-containing fluorene derivative as shown in Figure 12 .

[0159] Example 13

[0160] The present example provides a preparation method of a BCB-containing fluorene derivative, comprising the following steps:

[0161] The preparation method of Example 2 is adopted, and 2,7-di-tert-butylfluorene is used to replace fluorene to react with 4-ClCH2BCB in equimolar amount to obtain a BCB-containing fluorene derivative as shown in Figure 13 .

[0162] Example 14

[0163] The present example provides a preparation method of a BCB-containing fluorene derivative, comprising the following steps:

[0164] Step S1, 1.0 eq of 2,7-dibromofluorene and 0.05 eq of NiCl2(dppp) are dissolved in dry tetrahydrofuran under a nitrogen atmosphere, 2.4 equivalents of n-hexylmagnesium bromide solution are added dropwise at 0-10°C, and the temperature is raised to 50°C for 5h, after the reaction is completed, the temperature is lowered to room temperature, the reaction is quenched with saturated ammonium chloride, then the organic phase is separated, the organic phase is concentrated, and then refined by crystallization to obtain 2,7-dihexylfluorene as shown in Figure 14 .

[0165] Step S2, the preparation method of Example 3 is adopted, and 2,7-dihexylfluorene is used to replace fluorene to react with 4-BrBCB to obtain a BCB-containing fluorene derivative as shown in Figure 15 .

[0166] Example 15

[0167] The present example provides a preparation method of a BCB-containing fluorene derivative, comprising the following steps:

[0168] Step S1, 1.0 eq of 2,7-dibromofluorene and 0.05 eq of NiCl2(dppp) are dissolved in dry tetrahydrofuran under a nitrogen atmosphere, 2.4 equivalents of n-hexylmagnesium bromide solution are added dropwise at 0-10°C, and the temperature is raised to 50°C for 5h, after the reaction is completed, the temperature is lowered to room temperature, the reaction is quenched with saturated ammonium chloride, then the organic phase is separated, the organic phase is concentrated, and then refined by crystallization to obtain 2,7-dihexylfluorene as shown inFigure 16 2,7-dodecylfluorene;

[0169] Step S2, using the preparation method of Example 3, 2,7-dodecylfluorene is used to replace fluorene to react with 4-BrBCB in equal molar, to obtain a BCB-containing fluorene derivative as shown in Figure 17

[0170] Example 16

[0171] The embodiment provides a preparation method of a BCB-containing fluorene derivative, comprising the following steps:

[0172] Step S1, 1.0 eq of 2,7-dibromofluorene and 0.05 eq of NiCl2(dppp) are dissolved in dry tetrahydrofuran under a nitrogen atmosphere, 2.4 eq of octadecylmagnesium bromide is added dropwise at 0-10°C, and the temperature is slowly increased to 50°C for 5h, after the reaction is completed, the temperature is lowered to room temperature, the reaction is quenched with saturated ammonium chloride, then the organic phase is separated, the organic phase is concentrated, and then refined by crystallization, to obtain 2,7-octadecylfluorene as shown in Figure 18

[0173] Step S2, using the preparation method of Example 3, 2,7-dodecylfluorene is used to replace fluorene to react with 4-BrBCB in equal molar, to obtain a BCB-containing fluorene derivative as shown in Figure 19

[0174] Application performance detection:

[0175] The BCB-containing fluorene derivative prepared in the above examples is subjected to performance tests such as dielectric performance and thermal stability, and the results are shown in Table 1.

[0176] Table 1. Application performance test results of BCB-containing fluorene derivatives

[0177]

[0178] Systematic analysis is made on the data in Table 1, and the following conclusions are obtained:

[0179] (1) By comparing the structural formulas of the derivatives obtained from Examples 1 and 2, Examples 3 and 4, and Examples 5 and 6, it can be seen that when the substituent R 1~10 In addition to the BCB group, when other substituents are composed of single atoms, alkanes and / or alkylidene, the change in chain length affected thereby has no significant effect on the thermal stability and dielectric performance of the BCB-containing fluorene derivative prepared in the present application.

[0180] ​​​(2) The data effects of examples 1 and 3, examples 2 and 4, examples 3 and 5, examples 4 and 6 are compared, when the BCB group appears in R 9~10 When the two substitution sites are present, and the structure of the BCB-containing fluorene derivative is axially symmetrical, the performance of the BCB-containing fluorene derivative can be significantly improved.

[0181] (3) From the comparison of the data of examples 7 and 9, examples 8 and 10, it can be seen that when the substitution group R 9~10 Under the condition of containing an alkylene or long-chain alkane, and the substitution group R 1~8 The substitution group R 6~7 form a benzene ring, the thermal stability and dielectric properties of the BCB-containing fluorene derivative can be significantly improved.

[0182] (4) From examples 3 and 5, examples 4 and 6, examples 7 and 8, examples 6 and 10, it can be seen that when the benzene ring is formed at the substitution site R 6~7 The dielectric constant of example 10 is significantly lower than that of example 6, which indicates that the effect of unilaterally adjusting the dielectric constant can be achieved by simultaneously adjusting the benzene ring at the substitution site R 9~10 The dielectric constant of example 10 is significantly lower than that of example 6, which indicates that the effect of unilaterally adjusting the dielectric constant can be achieved by simultaneously adjusting the benzene ring at the substitution site R

[0183] (5) From the data of examples 11, 13-16, it can be seen that when the substitution group R 1~8 is an alkane or a cyclic group or any substitution group is connected to form a ring, the performance of the derivative obtained is much better than that of the substitution group with only hydrogen atoms at the substitution site.

[0184] 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 replacements to some of the technical features, but any modification, equivalent replacement, 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 fluorene derivative containing BCB, characterized in that, The general molecular structural formula is shown in formula (1): Equation (1); Among them, the substituents R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Each is independently selected from at least one of hydrogen atom, alkyl, alkenyl, and aryl, and the substituents R9 and R 10 It includes at least one BCB group.

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

3. The fluorene derivative containing BCB according to claim 1, characterized in that, The BCB group is shown in formula (2): Equation (2); Wherein, the linker R is selected from at least one of a single chemical bond, alkylene, alkenylene, and arylene; and the substituent R' is selected from at least one of a hydrogen atom, alkyl, alkenyl, and aryl.

4. The fluorene derivative containing BCB according to claim 3, characterized in that: The number of carbon atoms in the alkylene group is an integer from 1 to 30; The number of carbon atoms in the subalkenyl group is an integer from 2 to 30; The number of carbon atoms in the arylene group is an integer from 6 to 30; The number of carbon atoms in the alkyl group is an integer from 1 to 30; The alkenyl group has an integer number of carbon atoms between 2 and 30; The aryl group has an integer number of carbon atoms between 6 and 30.

5. The fluorene derivative containing BCB according to claim 1, characterized in that: The R9, R 10 Each of them contains a BCB group.

6. The fluorene derivative containing BCB according to claim 1, characterized in that: Any two adjacent substituents among the substituents R1, R2, R3, R4, R5, R6, R7, and R8 are connected to form a benzene ring.

7. The fluorene derivative containing BCB according to claim 3, characterized in that: The linker R is a chemical single bond and / or a methylene group; and / or the substituent R' is a hydrogen atom.

8. A method for preparing a BCB-containing fluorene derivative as described in any one of claims 1 to 7, characterized in that, The reaction steps include the following: M1: Under a dry atmosphere, fluorene and / or fluorene derivatives, organic solvents, halo-BCB derivatives, strong bases and catalysts are added to a reaction flask. After heating and reacting, the mixture is cooled to room temperature and then subjected to quenching reaction, extraction, concentration and purification in sequence to obtain fluorene derivatives containing BCB. Or M2: Under a dry atmosphere, add fluorene and / or fluorene derivatives, organic solvent, and strong base to the reaction flask, then cool down and add halo-BCB derivatives under low temperature conditions. After the addition is completed, heat the temperature to room temperature to carry out the reaction, then quench the reaction, extract, concentrate, and then purify to obtain fluorene derivatives containing BCB. Wherein, the structural formula of the fluorene and / or fluorene derivative is shown in formula (3), and the halogenated BCB derivative is shown in formula (4): Equation (3); Equation (4); In formula (3), the substituents R9' and R 10 Each of the substituents is independently selected from at least one of hydrogen atom, alkyl, alkenyl, and aryl, and the substituents R9' and R 10 At least one of them is a hydrogen atom; in formula (4), X is a halogen.

9. A resin, characterized in that, It is prepared from the fluorene derivative containing BCB as described in any one of claims 1 to 7.

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

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