CN105152881B - Benzocyclobutene monomer, preparation method and application containing adamantane Yu trans-1,1,2,2,3,4-Hexafluorocyclobutane structure - Google Patents

Benzocyclobutene monomer, preparation method and application containing adamantane Yu trans-1,1,2,2,3,4-Hexafluorocyclobutane structure Download PDF

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CN105152881B
CN105152881B CN201510349759.5A CN201510349759A CN105152881B CN 105152881 B CN105152881 B CN 105152881B CN 201510349759 A CN201510349759 A CN 201510349759A CN 105152881 B CN105152881 B CN 105152881B
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hexafluorocyclobutane
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containing adamantane
adamantane
benzocyclobutene
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CN105152881A (en
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孔令强
肖斐
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Fudan University
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/235—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring and to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C43/247—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring and to a carbon atom of a ring other than a six-membered aromatic ring containing halogen
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/24—Preparation of ethers by reactions not forming ether-oxygen bonds by elimination of halogens, e.g. elimination of HCl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • C08J5/18—Manufacture of films or sheets
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    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers

Abstract

Benzocyclobutene monomer containing adamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure shown in offer formula (IV) of the present invention and preparation method thereof, adamantane with larger rigid structure and the trans-1,1,2,2,3,4-Hexafluorocyclobutane with more C F bond structures are introduced into benzocyclobutene structure by the monomer, and possibility is provided further to prepare the polymer that dielectric constant is low, thermal stability is good.The present invention also further provides for application of the above-mentioned monomer in polymer material is prepared, the polymer being prepared after which is polymerize, not only with preferable heat-resistant stability, relatively low dielectric constant；Also there is preferable filming performance simultaneously, thin polymer film has very excellent profile pattern and excellent hydrophobicity, it is expected to be applied to high performance dielectric layer material and baseplate material product scope.

Description

Benzocyclobutene monomer, preparation method containing adamantane Yu trans-1,1,2,2,3,4-Hexafluorocyclobutane structure And application
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of benzo ring containing adamantane Yu trans-1,1,2,2,3,4-Hexafluorocyclobutane structure Butene monomers, preparation method and the application in polymer material is prepared.
Background technology
There is benzocyclobutane olefine resin (BCB) excellent dielectric properties, mechanical property, high thermal stability and thermal oxide to stablize Property, while solidification temperature is moderate, therefore in microelectronics Packaging field as the insulation of multilayer wiring interlayer, IC stress buffers/passivation Medium internal layer of layer, aluminium and GaAs etc. is used widely.Compared to other organic polymer materials, benzocyclobutane olefine resin With lower dielectric constant, interconnecting signal transmission delay, crosstalk and power consumption can be effectively reduced, therefore, is promised to be One of selection of high performance dielectric material in super large-scale integration (ULSI) encapsulation.But in order to meet ULSI of new generation The development of encapsulation technology, it is also necessary to further reduce the dielectric constant of benzocyclobutane olefine resin, while improve its heat-resistant stability.
At present, the dielectric constant of polymer material is reduced usually there are three types of method：(1) carbon-fluorine bond is introduced in the polymer Etc. the chemical bond of low polarity, and then reduce the polarizability of polymer；(2) rigidity with larger space volume is introduced into molecule Group, thus the packing density of polymer can be reduced, improve the free volume of polymer, and then reduce dielectric constant；(3) Nano-void is introduced in the polymer, and the density of polymer is reduced, and then reduce dielectric constant by introducing air.As can it seeks A kind of dielectric constant that can effectively reduce benzocyclobutane olefine resin and the method that its thermal stability can be improved simultaneously are found, will be had There is extraordinary actual application prospect.
Invention content
The purpose of the present invention is to provide a kind of benzocyclobutene monomer containing adamantane Yu trans-1,1,2,2,3,4-Hexafluorocyclobutane structure, the lists Adamantane with larger rigid structure and the trans-1,1,2,2,3,4-Hexafluorocyclobutane with more C-F bond structures are introduced benzocyclobutene structure by body In, provide possibility further to obtain the polymer material that dielectric constant is low, thermal stability is good.
Another object of the present invention is to provide the above-mentioned benzocyclobutene monomer containing adamantane Yu trans-1,1,2,2,3,4-Hexafluorocyclobutane structure Preparation method.
A further purpose of the present invention is to provide the above-mentioned benzocyclobutene monomer containing adamantane Yu trans-1,1,2,2,3,4-Hexafluorocyclobutane structure The application being used to prepare in polymer material.
In order to solve the above-mentioned technical problem, what embodiments of the present invention were provided contains adamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure Benzocyclobutene monomer, shown in structure such as formula (IV)：
Wherein, two adamantyls are simultaneously positioned at the ortho position of oxygen-containing functional group or meta position.
In the benzocyclobutene monomer structure containing adamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure shown in formula (IV), introduce simultaneously With larger space volume, compared with high hydrophobicity and the rigid adamantane structure of superior heat resistance and the four-membered ring of trans-1,1,2,2,3,4-Hexafluorocyclobutane Structure.Wherein, adamantane molecule is made of the polycyclic system of body structure hexamethylene, and the structure of adamantane is straight symmetrical, high Degree is stablized, and molecule is close to spherical shape, can tightly packed, the structural unit of this rigid molecular structure and Buddha's warrior attendant stone construction in lattice It is similar, while there is good hydrophobicity and heat resistance；And carbon-fluorine bond (C-F) has relatively low polarity, thus with perfluor alkane The material of based structures usually has preferable hydrophobicity, corrosion resistance and dielectric properties.This kind of benzocyclobutene monomer structure It successfully obtains and provides possibility to be further prepared into the polymer material that thermal stability is good, dielectric constant is low.
Embodiments of the present invention provide benzocyclobutene monomer of this kind containing adamantane Yu trans-1,1,2,2,3,4-Hexafluorocyclobutane structure simultaneously Preparation method, include the following steps：
(1) adamantyl p bromophenol is dissolved in solvent, adds in alkali, reacted 15~30 minutes under inert atmosphere protection Afterwards, 1,2- dibromotetrafluoroethanes are added dropwise, are reacted below 50 DEG C, the bromo- 1- of the 4- containing adamantane side group shown in production (I) (2 '-bromo- 1 ', 1 ', 2 ', 2 '-tetrafluoro ethyoxyl) benzene；
(2) the bromo- 1- of the 4- containing adamantane side group shown in formula (I) (2 '-bromo- 1 ', 1 ', 2 ', 2 '-tetrafluoro ethyoxyl) Benzene is dissolved in solvent, adds in back flow reaction after the zinc powder of activation, the bromo- 1- of the 4- containing adamantane side group shown in production (II) (trifluoro-ethylene oxygroup) benzene；
(3) under inert atmosphere protection, bromo- 1- (the trifluoro-ethylene oxygen of the 4- containing adamantane side group shown in formula (II) Base) dimerization reaction occurs at 180~250 DEG C for benzene, and 8~15 hours reaction time contained Double diamantane hydrocarbons shown in production (III) 1,2- bis- (4 '-bromobenzene oxygroup) trans-1,1,2,2,3,4-Hexafluorocyclobutane of side group；
(4) by 1,2- bis- (4 '-bromobenzene oxygroup) trans-1,1,2,2,3,4-Hexafluorocyclobutane, the 4- benzos of the side group containing Double diamantane hydrocarbons shown in formula (III) Cyclobutane pinacol borate, alkali and palladium catalyst are dissolved under inert atmosphere protection in solvent, are continued in inert atmosphere protection Under flow back into row Suzuki reaction, be made formula (IV) shown in the benzocyclobutene list containing adamantane Yu trans-1,1,2,2,3,4-Hexafluorocyclobutane structure Body；
Reaction process is as follows：
Wherein, two adamantyls are simultaneously positioned at the ortho position of oxygen-containing functional group or meta position.
Preferably, the benzocyclobutene list containing adamantane Yu trans-1,1,2,2,3,4-Hexafluorocyclobutane structure that embodiments of the present invention are provided In the preparation method of body, the solvent described in step (1) and step (2) is the mixed of one or more of dry following solvents Close object：Tetrahydrofuran, acetonitrile, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dichloromethane, ethyl acetate, dimethyl Sulfoxide and 1,4- dioxane.
Preferably, the benzocyclobutene list containing adamantane Yu trans-1,1,2,2,3,4-Hexafluorocyclobutane structure that embodiments of the present invention are provided In the preparation method of body, the alkali described in step (1) and step (4) is inorganic base or organic base.Further, above-mentioned inorganic base Preferably sodium carbonate, potassium carbonate, potassium phosphate or cesium carbonate；Above-mentioned organic base is preferably triethylamine or pyridine.
Preferably, the benzocyclobutene list containing adamantane Yu trans-1,1,2,2,3,4-Hexafluorocyclobutane structure that embodiments of the present invention are provided In the preparation method of body, the palladium catalyst described in step (4) can be：Bis-triphenylphosphipalladium palladium dichloride, bis- (hexichol of 1,1'- Base phosphine) ferrocene palladium chloride, palladium, palladium chloride, tetrakis triphenylphosphine palladium or two (cyanophenyl) palladium chlorides.
Preferably, the benzocyclobutene list containing adamantane Yu trans-1,1,2,2,3,4-Hexafluorocyclobutane structure that embodiments of the present invention are provided In the preparation method of body, the solvent described in step (4) can be：Tetrahydrofuran, acetonitrile, N,N-dimethylformamide, N, N- One or more of mixing is molten in dimethylacetylamide, dichloromethane, ethyl acetate, dimethyl sulfoxide (DMSO) and 1,4- dioxane Agent；Or it is tetrahydrofuran, acetonitrile, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dichloromethane, ethyl acetate, diformazan The solvent that one or more of base sulfoxide and 1,4- dioxane are mixed with water.
In addition, embodiments of the present invention also provide the above-mentioned benzocyclobutene list containing adamantane Yu trans-1,1,2,2,3,4-Hexafluorocyclobutane structure Application of the body in polymer material is prepared.
Further, in the above application that embodiments of the present invention are provided, to contain adamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane knot The method that the benzocyclobutene monomer of structure prepares thin polymer film is：
(1) benzocyclobutene monomer containing adamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure shown in formula (IV) is added in into mesitylene In, it is heated to reflux carrying out prepolymerization reaction in 15~22 hours at 170~190 DEG C, obtains the prepolymer solution of water white transparency；
(2) prepolymer solution is subjected to film, film is dried, be then heating and curing, obtain highly cross-linked gather Close object film.
Preferably, it in the above-mentioned method for preparing thin polymer film, is heated to reflux carrying out in oil bath, the mode of film Such as can be spin coating；In addition, being heating and curing in step (2) carries out in Constant Temp. Oven, preferred elevated cure Program is：190~210 DEG C/0.5 hour；230~250 DEG C/5 hours；260 DEG C/1 hour.
The above method provided according to the embodiment of the present invention will contain adamantane and hexafluoro ring fourth shown in formula (IV) The benzocyclobutene monomer heating polymerization of alkyl structure, has been prepared a kind of with preferable heat-resistant stability, relatively low dielectric The polymer of constant；Meanwhile the polymer has preferable filming performance, there is macromolecule membrane very excellent surface to put down Whole property and excellent hydrophobicity.In the structure of this kind of polymer, the introducing of adamantane can improve its heat resistance, simultaneously as The rigid structure that adamantane itself has can reduce the packing density of polymer after being introduced into polymer, increase The free volume of polymer；And the introducing of trans-1,1,2,2,3,4-Hexafluorocyclobutane, the polarizability of polymer can be further reduced, and then reduce it Dielectric constant.Polymeric thin-film material provided by the present invention it is expected to be applied to high performance dielectric layer material and substrate material Expect product scope, there is good actual application prospect.
Description of the drawings
Fig. 1 is the result figure for carrying out thermogravimetric analysis experiment in embodiment 2 to thin polymer film；
Fig. 2 is the result figure for carrying out nano-indenter test in embodiment 2 to thin polymer film；
Fig. 3 is the atomic force microscopy diagram of the thin polymer film in embodiment 2；
Fig. 4 is the dielectric constant of the thin polymer film in embodiment 2 with frequency variation diagram.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to each reality of the present invention The mode of applying is explained in detail.However, it will be understood by those skilled in the art that in each embodiment of the present invention, In order to make the reader understand this application better, many technical details are proposed.But even if without these technical details and base In the various changes and modifications of following embodiment, each claim of the application technical side claimed can also be realized Case.
Embodiment 1 prepares monomer (IV -1)
Monomer manufactured in the present embodiment is：(4 '-(4 "-benzocyclobutane alkenyl) -2 '-(1 "-adamantyl) the benzene oxygen of 1,2- bis- Base) trans-1,1,2,2,3,4-Hexafluorocyclobutane (IV -1), i.e., two adamantyls are respectively positioned on phenyl 2 in general formula (IV), and structural formula is as follows：
Preparation process is as follows：
(1) by starting material 4- bromo- 2- (1 '-adamantyl) phenol (8.0g), (preparation of starting material is according to document The method provided in Bioorganic Chemistry 39 (2011) 151~158 carries out), it is dissolved in anhydrous dimethyl sulphoxide In (50ml) solution, solid carbonic acid caesium (17.0g) is added in, reaction system is under nitrogen protective condition in room temperature reaction half an hour Afterwards, 1,2- dibromotetrafluoroethanes (19.0g) are added dropwise in above-mentioned reaction solution, keep not higher than 50 DEG C reactions about 24 of reaction temperature After hour, reaction solution is poured into the tap water of 100ml, be extracted with ethyl acetate 2~3 times, merged organic phase, use saturated common salt Water (50ml*2) washs, and is then dried with anhydrous sodium sulfate, concentrates.Crude product is purified by column chromatography, obtains 11.5g colorless oils Shape product liquid 4- bromo- 2- (1 '-adamantyl) -1- (2 '-bromo- 1 ', 1 ', 2 ', 2 '-tetrafluoro ethyoxyl) benzene (I-1), yield 91%.
The product structure characterization of this step：
1H NMR (500MHz, CDCl3)δppm:7.46(d,1H),7.33(d d,1H),7.23(m,1H),2.08(s, 3H),2.03(d,6H),1.76(s,6H).
13C NMR(125MHz,CDCl3)δppm:148.1,142.8,131.4,129.8,120.3,119.0,116.3 (m), 113.6 (m), 40.4,37.3,36.6,28.8.
19F NMR(470MHz,CDCl3)δppm:-67.0(t,2F),-84.7(m,2F).
(2) first step reaction product (7.0g) is dissolved in the anhydrous acetonitrile of 50ml, adds in the zinc powder (3.7g) of activation, returned Stream reacts 60 hours, is purified after product filtering and concentrating through column chromatography, obtains bromo- 2- (the 1 '-adamantane of 4.2g white solid products 4- Base) -1- (trifluoro-ethylene oxygroup) benzene (II -1), yield 75.4%.
The product structure characterization of this step：
1H NMR (500MHz, CDCl3)δppm:7.42(d,1H),7.32-7.30(dd,1H),6.89-6.87(dd,1H), 2.09-2.05(m,9H),1.77(s,6H).
19F NMR(470MHz,CDCl3)δppm:-118.7(q,1F),-126.4(q,1F),-134.2(q,1F).
(3) second step product (1.0g) is put into round-bottomed flask, 250 DEG C of reactions is heated under nitrogen protective condition 10 hours, product after purification, obtained dimer 1 by column chromatography, 2- bis- (4 '-bromo- 2 '-(1 "-adamantyl) phenoxy group) six Fluorine cyclobutane (III -1) is white solid (0.76g, yield 76%).
The product structure characterization of this step：
1H NMR(500MHz,CDCl3)δppm:7.45(d,2H),7.28-7.26(d d,2H),7.09-7.07(d d, 2H),2.09(m,18H),1.78(s,12H).
19F NMR(470MHz,CDCl3)δppm:- 128.4~-128.9 (m, 6F)
(4) first, 4- benzocyclobutene pinacol borates are prepared：
By 4- bromines benzocyclobutene (2.0g, 10.9mmol), connection boric acid pinacol ester (3.3g, 11.8mmol), 1,1'- bis- (diphenylphosphine) ferrocene palladium chloride (70mg, 0.1mmol), Anhydrous potassium carbonate (3.2g, 32.7mmol) and 1,4- dioxies six Ring (40mL) is added in the round-bottomed flask of 100mL under nitrogen protection, heated overnight at reflux.It treats after reaction, to reaction 100mL water is added in system, with petroleum ether extraction (30mL*3), merges organic phase, uses anhydrous Na2SO4It is dry, filtrate after filtering Concentration, concentrate use column chromatography to obtain white solid 4- benzocyclobutene pinacol borate 2.1g (yield 84.0%).
The structural characterization of 4- benzocyclobutenes pinacol borate obtained：
1H NMR(500MHz,CDCl3)δppm:7.68(d,1H),7.49(s,1H),7.07(d,1H),3.18(s,4H), 1.33(s,12H).
Then, by third step product (2.3g), 4- benzocyclobutenes pinacol borate (2.1g) obtained above, double three Phenylphosphine palladium chloride (0.1g), potassium carbonate (1.2g) are added to two mouthfuls of round-bottomed flasks of 100ml under nitrogen protection, add in tetrahydrochysene Furans (50ml) and water (10ml), under a nitrogen atmosphere back flow reaction 7~8 hours to reaction terminate.It is added in into reaction system 50ml tap water is extracted with ethyl acetate (30ml*3), merges organic phase, and organic phase is washed with saturated salt solution (50ml*1), It is concentrated after anhydrous sodium sulfate drying, crude product is purified with column chromatography, obtains 1.8g white solid products 1, (4 '-(the 4 "-benzo rings of 2- bis- Cyclobutenyl) -2 '-(1 "-adamantyl) phenoxy groups) trans-1,1,2,2,3,4-Hexafluorocyclobutane (IV -1), yield 73.9%.
Monomer structure characterization obtained：
1H NMR(500MHz,CDCl3)δppm:7.51(d,2H),7.37-7.35(d d,2H),7.30-7.29(m,4H), 7.23(s,2H),7.01(d,2H),3.20(s,8H),2.20(s,12H),2.13(s,6H),1.81(t,12H).
19F NMR(470MHz,CDCl3)δppm:- 128.5~-129.0 (m, 6F)
Embodiment 2 prepares thin polymer film with monomer (IV -1)
The benzocyclobutene monomer (IV -1) containing adamantane group prepared in 1g embodiments 1 is weighed, adds in the equal of 3mL Trimethylbenzene is heated to 180 DEG C of progress pre-polymerizations, and control time was advisable at 20 hours, obtained the prepolymer solution of water white transparency.It will be pre- Oligomer solution carries out film by way of spin coating, and film then is carried out ramped heating schedule in Constant Temp. Oven consolidates Change, obtain the polymer of BCB film of the structure containing Freon C318 of highly cross-linked adamantane modification；Its solidification path Sequence is：190~210 DEG C/0.5 hour；230~250 DEG C/5 hours；260 DEG C/1 hour.
Thermogravimetric analysis experiment is carried out to thin polymer film manufactured in the present embodiment, experimental result is as shown in Figure 1.From figure In 1 as can be seen that polymer have higher heat decomposition temperature, decompose under a nitrogen atmosphere 5% required temperature for 447 DEG C with On, there is preferable thermal stability.
Nano-indenter test experiment, experimental result such as attached drawing 2 are carried out to the thin polymer film that the present embodiment is prepared It is shown.From figure 2 it can be seen that the thin polymer film has very excellent hardness, average hardness 0.769GPa；Young mould Amount is big, average out to 10.77GPa.
Attached drawing 3 is the atomic force microscopy diagram of thin polymer film manufactured in the present embodiment, as can be seen that should from attached drawing 3 Thin polymer film has preferable film planarization, and the r.m.s. roughness on 1.00 μm of * 1.00 μm of surface areas is 0.6nm。
Attached drawing 4 for thin polymer film manufactured in the present embodiment dielectric constant with frequency variation diagram, can from attached drawing 4 Go out, the dielectric constant of thin polymer film is 2.39 (1MHz), has preferable prospects for commercial application.
It will be understood by those skilled in the art that the respective embodiments described above are to realize specific embodiments of the present invention, And in practical applications, can to it, various changes can be made in the form and details, without departing from the spirit and scope of the present invention.

Claims (10)

1. a kind of benzocyclobutene monomer containing adamantane Yu trans-1,1,2,2,3,4-Hexafluorocyclobutane structure, shown in structure such as formula (IV)：
Wherein, two adamantyls are simultaneously positioned at the ortho position of oxygen-containing functional group or meta position.
2. the preparation method described in claim 1 containing adamantane Yu the benzocyclobutene monomer of trans-1,1,2,2,3,4-Hexafluorocyclobutane structure, special Sign is, includes the following steps：
(1) adamantyl p bromophenol is dissolved in solvent, adds in alkali, after being reacted 15~30 minutes under inert atmosphere protection, 1,2- dibromotetrafluoroethanes are added dropwise, are reacted below 50 DEG C, the bromo- 1- of the 4- containing adamantane side group shown in production (I) (2 '-bromo- 1 ', 1 ', 2 ', 2 '-tetrafluoro ethyoxyl) benzene；
(2) it is the bromo- 1- of the 4- containing adamantane side group (2 '-bromo- 1 ', 1 ', 2 ', 2 '-tetrafluoro ethyoxyl) benzene shown in formula (I) is molten In solvent, back flow reaction after the zinc powder of activation is added in, the bromo- 1- (three of the 4- containing adamantane side group shown in production (II) Vinyl fluoride oxygroup) benzene；
(3) under inert atmosphere protection, the bromo- 1- of the 4- containing adamantane side group (trifluoro-ethylene oxygroup) benzene shown in formula (II) Occur dimerization reaction at 180~250 DEG C, 8~15 hours reaction time, the side group containing Double diamantane hydrocarbons shown in production (III) 1,2- bis- (4 '-bromobenzene oxygroup) trans-1,1,2,2,3,4-Hexafluorocyclobutane；
(4) by 1,2- bis- (4 '-bromobenzene oxygroup) trans-1,1,2,2,3,4-Hexafluorocyclobutane, the 4- benzocyclobutanes of the side group containing Double diamantane hydrocarbons shown in formula (III) Alkene pinacol borate, alkali and palladium catalyst are dissolved under inert atmosphere protection in solvent, are continued in inert atmosphere protection next time Stream carries out Suzuki reactions, and the benzocyclobutene monomer containing adamantane Yu trans-1,1,2,2,3,4-Hexafluorocyclobutane structure shown in formula (IV) is made；
Reaction process is as follows：
Wherein, two adamantyls are simultaneously positioned at the ortho position of oxygen-containing functional group or meta position.
3. the preparation method according to claim 2 containing adamantane Yu the benzocyclobutene monomer of trans-1,1,2,2,3,4-Hexafluorocyclobutane structure, It is characterized in that, mixing of the solvent for one or more of dry following solvents described in step (1) and step (2) Object：Tetrahydrofuran, acetonitrile, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dichloromethane, ethyl acetate, dimethyl are sub- Sulfone and 1,4- dioxane.
4. the preparation method according to claim 2 containing adamantane Yu the benzocyclobutene monomer of trans-1,1,2,2,3,4-Hexafluorocyclobutane structure, It is characterized in that, the alkali described in step (1) and step (4) is inorganic base or organic base.
5. the preparation method according to claim 4 containing adamantane Yu the benzocyclobutene monomer of trans-1,1,2,2,3,4-Hexafluorocyclobutane structure, It is characterized in that, the inorganic base is sodium carbonate, potassium carbonate, potassium phosphate or cesium carbonate；The organic base is triethylamine or pyridine.
6. the preparation method according to claim 2 containing adamantane Yu the benzocyclobutene monomer of trans-1,1,2,2,3,4-Hexafluorocyclobutane structure, It is characterized in that, the palladium catalyst described in step (4) is：Bis-triphenylphosphipalladium palladium dichloride, two cyclopentadienyls of 1,1'- bis- (diphenylphosphine) Iron palladium chloride, palladium, palladium chloride, tetrakis triphenylphosphine palladium or two (cyanophenyl) palladium chlorides.
7. the preparation method according to claim 2 containing adamantane Yu the benzocyclobutene monomer of trans-1,1,2,2,3,4-Hexafluorocyclobutane structure, It is characterized in that, the solvent described in step (4) is：
Tetrahydrofuran, acetonitrile, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dichloromethane, ethyl acetate, dimethyl The mixed solvent of one or more of sulfoxide and 1,4- dioxane；
Or tetrahydrofuran, acetonitrile, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dichloromethane, ethyl acetate, diformazan The solvent that one or more of base sulfoxide and 1,4- dioxane are mixed with water.
8. the benzocyclobutene monomer described in claim 1 containing adamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure is preparing polymer material In application.
9. application according to claim 8, which is characterized in that with the benzo containing adamantane Yu trans-1,1,2,2,3,4-Hexafluorocyclobutane structure The method that cyclobutane monomer prepares thin polymer film is：
(1) benzocyclobutene monomer containing adamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure shown in formula (IV) is added in mesitylene, It is heated to reflux carrying out prepolymerization reaction in 15~22 hours at 170~190 DEG C, obtains the prepolymer solution of water white transparency；
(2) prepolymer solution is subjected to film, film is dried, be then heating and curing, obtain crosslinked thin polymer film.
10. application according to claim 9, which is characterized in that being heating and curing in the step (2) is done in electric heating constant temperature It is carried out in dry case, elevated cure program is：190~210 DEG C/0.5 hour；230~250 DEG C/5 hours；260 DEG C/1 hour.
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