CN105152881A - Benzocyclobutene monomer containing adamantane and hexafluorocyclobutane structures, and preparation method and application thereof - Google Patents
Benzocyclobutene monomer containing adamantane and hexafluorocyclobutane structures, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a benzocyclobutene monomer containing adamantane and hexafluorocyclobutane structures, and a preparation method thereof. The benzocyclobutene monomer is shown in a formula (IV) which is described in the specification. According to the invention, adamantane with a great rigid structure and hexafluorocyclobutane with a great number of C-F bond structures are introduced into a benzocyclobutene structure, so preparation of a polymer with a low dielectric constant and good thermal stability is made possible. The invention further provides application of the monomer in preparation a polymeric material. A polymer prepared by subjecting the monomer to heating and polymerization has good thermal stability, a low dielectric constant and good film forming performance; a polymer film thereof has excellent surface smoothness and excellent hydrophobicity and is expected to be applied to the field of products of high-performance dielectric layer materials and substrate materials.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of benzocyclobutene monomer, its preparation method containing diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure and preparing the application in polymer materials.
Background technology
Benzocyclobutane olefine resin (BCB) has excellent dielectric properties, mechanical property, high thermal stability and thermo-oxidative stability, solidification value is moderate simultaneously, is therefore used widely as the medium internal layer etc. of the insulation of multilayer wiring interlayer, IC stress buffer/passivation layer, aluminium and GaAs in microelectronics Packaging field.Compared to other organic polymer material, benzocyclobutane olefine resin has lower specific inductivity, can effectively reduce interconnecting signal transport delay, crosstalk and power consumption, therefore, one of selection of high performance dielectric material in super large-scale integration (ULSI) encapsulation is promised to be.But, in order to the development of satisfied ULSI encapsulation technology of new generation, also need the specific inductivity reducing benzocyclobutane olefine resin further, improve its heat-resistant stability simultaneously.
At present, the specific inductivity reducing polymer materials has three kinds of methods usually: (1) introduces the chemical bond of the low polarity such as carbon-fluorine bond in the polymer, and then reduces the polarizability of polymkeric substance; (2) in molecule, introduce the group with the rigidity of larger space volume, thus can reduce the packing density of polymkeric substance, improve the free volume of polymkeric substance, and then reduce specific inductivity; (3) introduce nano-void in the polymer, reduced the density of polymkeric substance by introducing air, and then reduce specific inductivity.If search out a kind of effectively can reduce benzocyclobutane olefine resin specific inductivity and the method for its thermostability can be improved simultaneously, extraordinary actual application prospect will be had.
Summary of the invention
The object of the present invention is to provide a kind of benzocyclobutene monomer containing diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure, this monomer will have the diamantane of larger rigid structure and have in the trans-1,1,2,2,3,4-Hexafluorocyclobutane introducing benzocyclobutene structure of more C-F bond structure, and in order to obtain further, specific inductivity is low, the polymer materials of Heat stability is good provides possibility.
Another object of the present invention is to provide the above-mentioned preparation method containing the benzocyclobutene monomer of diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure.
An also object of the present invention is to provide the above-mentioned benzocyclobutene monomer containing diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure for the preparation of the application in polymer materials.
In order to solve the problems of the technologies described above, the benzocyclobutene monomer containing diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure that embodiments of the present invention provide, its structure is as shown in formula IV:
Wherein, two adamantyls are positioned at ortho position or a position of oxygen-containing functional group simultaneously.
Shown in formula IV containing in the benzocyclobutene monomer structure of diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure, introduce simultaneously and there is larger space volume, compared with the adamantane structure of rigidity of high hydrophobicity and superior heat resistance and the tetra-atomic ring structure of trans-1,1,2,2,3,4-Hexafluorocyclobutane.Wherein, diamantane molecule forms the polycyclic system of body structure by hexanaphthene, the straight symmetry of structure of diamantane, highly stable, molecule subglobular, can be tightly packed in lattice, the structural unit of this rigid molecular structure and diamond structure is similar, has good hydrophobicity and thermotolerance simultaneously; And carbon-fluorine bond (C-F) has lower polarity, the material thus with perfluoroalkyl structure has good hydrophobicity, erosion resistance and dielectric properties usually.The successful acquisition of this kind of benzocyclobutene monomer structure be prepared into Heat stability is good further, polymer materials that specific inductivity is low provides possibility.
Embodiments of the present invention provide this kind to contain the preparation method of the benzocyclobutene monomer of diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure simultaneously, comprise the following steps:
(1) adamantyl p bromophenol is dissolved in solvent, add alkali, react under inert atmosphere protection after 15 ~ 30 minutes, drip 1,2-dibromotetrafluoroethane, react below 50 DEG C, generate the bromo-1-of 4-(2 '-bromo-1 ' containing diamantane side base shown in formula I, 1 ', 2 ', 2 '-tetrafluoro oxyethyl group) benzene;
(2) the bromo-1-of 4-(2 '-bromo-1 ' containing diamantane side base shown in formula I is made, 1 ', 2 ', 2 '-tetrafluoro oxyethyl group) benzene is dissolved in solvent, add back flow reaction after the zinc powder of activation, generate the bromo-1-of 4-(the trifluoro-ethylene oxygen base) benzene containing diamantane side base shown in formula II;
(3) under inert atmosphere protection, make the bromo-1-of 4-(the trifluoro-ethylene oxygen base) benzene containing diamantane side base shown in formula II, at 180 ~ 250 DEG C, dimerization reaction occur, 8 ~ 15 hours reaction times, generate 1,2-bis-(the 4 '-bromine phenoxy group) trans-1,1,2,2,3,4-Hexafluorocyclobutane containing Double diamantane hydrocarbons side base shown in formula III;
(4) by shown in formula III containing Double diamantane hydrocarbons side base 1,2-bis-(4 '-bromine phenoxy group) trans-1,1,2,2,3,4-Hexafluorocyclobutane, 4-benzocyclobutene pinacol borate, alkali and palladium catalyst are dissolved in solvent under inert atmosphere protection, continue inert atmosphere protection next time stream carry out Suzuki reaction, the benzocyclobutene monomer containing diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure shown in obtained formula IV;
Reaction process is as follows:
Wherein, two adamantyls are positioned at ortho position or a position of oxygen-containing functional group simultaneously.
Preferably, what embodiments of the present invention provided contains in the preparation method of the benzocyclobutene monomer of diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure, step (1) and the solvent described in step (2) are the mixture of one or more in dry following solvents: tetrahydrofuran (THF), acetonitrile, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, methylene dichloride, ethyl acetate, dimethyl sulfoxide (DMSO) and Isosorbide-5-Nitrae-dioxane.
Preferably, what embodiments of the present invention provided contains in the preparation method of the benzocyclobutene monomer of diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure, and step (1) and the alkali described in step (4) are mineral alkali or organic bases.Further, above-mentioned mineral alkali is preferably sodium carbonate, salt of wormwood, potassiumphosphate or cesium carbonate; Above-mentioned organic bases is preferably triethylamine or pyridine.
Preferably, what embodiments of the present invention provided contains in the preparation method of the benzocyclobutene monomer of diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure, palladium catalyst described in step (4) can be: bis-triphenylphosphipalladium palladium dichloride, 1,1'-bis-(diphenylphosphine) ferrocene palladium chloride, palladium, palladium chloride, tetrakis triphenylphosphine palladium or two (cyanophenyl) palladium chloride.
Preferably, what embodiments of the present invention provided contains in the preparation method of the benzocyclobutene monomer of diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure, solvent described in step (4) can be: tetrahydrofuran (THF), acetonitrile, N, dinethylformamide, N, one or more mixed solvent in N-N,N-DIMETHYLACETAMIDE, methylene dichloride, ethyl acetate, dimethyl sulfoxide (DMSO) and Isosorbide-5-Nitrae-dioxane; Or be one or more solvents mixed with water in tetrahydrofuran (THF), acetonitrile, DMF, N,N-dimethylacetamide, methylene dichloride, ethyl acetate, dimethyl sulfoxide (DMSO) and Isosorbide-5-Nitrae-dioxane.
In addition, embodiments of the present invention also provide the above-mentioned benzocyclobutene monomer containing diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure preparing the application in polymer materials.
Further, in the above-mentioned application that embodiments of the present invention provide, to prepare the method for polymeric film containing the benzocyclobutene monomer of diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure be:
(1) add in sym-trimethylbenzene by the benzocyclobutene monomer containing diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure shown in formula IV, at 170 ~ 190 DEG C, reflux carries out prepolymerization reaction in 15 ~ 22 hours, obtains water white prepolymer solution;
(2) prepolymer solution is carried out film, drying is carried out to film, is then heating and curing, obtain highly cross-linked polymeric film.
Preferably, above-mentionedly prepare in the method for polymeric film, reflux can be carried out in oil bath, and the mode of film can be such as spin coating; In addition, being heating and curing in step (2) is carried out in Constant Temp. Oven, and preferred elevated cure program is: 190 ~ 210 DEG C/0.5 hour; 230 ~ 250 DEG C/5 hours; 260 DEG C/1 hour.
Aforesaid method provided according to the embodiment of the present invention, by the benzocyclobutene monomer heated polymerizable containing diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure shown in formula IV, prepare a kind of polymkeric substance with good heat-resistant stability, lower specific inductivity; Meanwhile, this polymkeric substance has good film forming properties, and its macromolecule membrane has very excellent profile pattern and excellent hydrophobicity.In the structure of this kind of polymkeric substance, the introducing of diamantane can improve its thermotolerance, meanwhile, due to the rigid structure that diamantane self has, is being introduced into the packing density that can reduce polymkeric substance after in polymkeric substance, increases the free volume of polymkeric substance; And the introducing of trans-1,1,2,2,3,4-Hexafluorocyclobutane, further can reduce the polarizability of polymkeric substance, and then reduce its specific inductivity.Polymeric thin-film material provided by the present invention is expected to be applied to high performance dielectric layer material and baseplate material product scope, has good actual application prospect.
Accompanying drawing explanation
Fig. 1 is the result figure in embodiment 2, polymeric film being carried out to thermogravimetric analysis experiment;
Fig. 2 is the result figure in embodiment 2, polymeric film being carried out to nano-indenter test;
Fig. 3 is the atomic force microscope figure of the polymeric film in embodiment 2;
Fig. 4 is that the specific inductivity of polymeric film in embodiment 2 is with change of frequency figure.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with accompanying drawing, the embodiments of the present invention are explained in detail.But, persons of ordinary skill in the art may appreciate that in each embodiment of the present invention, proposing many ins and outs to make reader understand the application better.But, even without these ins and outs with based on the many variations of following embodiment and amendment, each claim of the application technical scheme required for protection also can be realized.
Embodiment 1 prepares monomer (IV-1)
Monomer prepared by the present embodiment is: 1,2-bis-(4 '-(4 "-benzocyclobutane thiazolinyl)-2 '-(1 "-adamantyl) phenoxy group) trans-1,1,2,2,3,4-Hexafluorocyclobutane (IV-1), namely in logical formula IV, two adamantyls are all positioned at phenyl 2, and structural formula is as follows:
Preparation process is as follows:
(1) by bromo-for starting raw material 4-2-(1 '-adamantyl) phenol (8.0g) (preparation of starting raw material is carried out according to the method provided in document BioorganicChemistry39 (2011) 151 ~ 158), be dissolved in anhydrous dimethyl sulphoxide (50ml) solution, add solid carbonic acid caesium (17.0g), reaction system under nitrogen protection condition after room temperature reaction half an hour, by 1, 2-dibromotetrafluoroethane (19.0g) is added dropwise in above-mentioned reaction solution, after keeping temperature of reaction not react about 24 hours higher than 50 DEG C, reaction solution is poured in the tap water of 100ml, be extracted with ethyl acetate 2 ~ 3 times, merge organic phase, wash with saturated aqueous common salt (50ml*2), then anhydrous sodium sulfate drying is used, concentrated.Thick product, by column chromatography purification, obtains 11.5g colourless oil liquid product 4-bromo-2-(1 '-adamantyl)-1-(2 '-bromo-1 ', 1 ', 2 ', 2 '-tetrafluoro oxyethyl group) benzene (I-1), yield 91%.
The product structure of this step characterizes:
1HNMR(500MHz，CDCl
3)δppm:7.46(d,1H),7.33(dd,1H),7.23(m,1H),2.08(s,3H),2.03(d,6H),1.76(s,6H).
13CNMR(125MHz,CDCl
3)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.
19FNMR(470MHz,CDCl
3)δppm:-67.0(t,2F),-84.7(m,2F).
(2) the first step reaction product (7.0g) is dissolved in the anhydrous acetonitrile of 50ml, add the zinc powder (3.7g) of activation, back flow reaction 60 hours, through column chromatography purification after product filtering and concentrating, obtain the bromo-2-of 4.2g white solid product 4-(1 '-adamantyl)-1-(trifluoro-ethylene oxygen base) benzene (II-1), yield 75.4%.
The product structure of this step characterizes:
1HNMR(500MHz，CDCl
3)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).
19FNMR(470MHz,CDCl
3)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 10 hours are heated under nitrogen protection condition; product is by after column chromatography purification; obtain dimer 1; 2-bis-(4 '-bromo-2 '-(1 "-adamantyl) phenoxy group) trans-1,1,2,2,3,4-Hexafluorocyclobutane (III-1); be white solid (0.76g, yield 76%).
The product structure of this step characterizes:
1HNMR(500MHz,CDCl
3)δppm:7.45(d,2H),7.28-7.26(dd,2H),7.09-7.07(dd,2H),2.09(m,18H),1.78(s,12H).
19FNMR(470MHz,CDCl
3)δppm:-128.4～-128.9(m,6F)
(4) 4-benzocyclobutene pinacol borate first, is prepared:
By 4-bromine benzocyclobutene (2.0g; 10.9mmol), boric acid pinacol ester (3.3g is joined; 11.8mmol), 1; 1'-bis-(diphenylphosphine) ferrocene palladium chloride (70mg; 0.1mmol), Anhydrous potassium carbonate (3.2g; 32.7mmol) join under nitrogen protection in the round-bottomed flask of 100mL with Isosorbide-5-Nitrae-dioxane (40mL), heated overnight at reflux.After question response terminates, in reaction system, add 100mL water, with petroleum ether extraction (30mL*3), merge organic phase, use anhydrous Na
2sO
4drying, after filtering, filtrate concentrates, and concentrated solution uses column chromatography and obtains white solid 4-benzocyclobutene pinacol borate 2.1g (yield 84.0%).
The structural characterization of obtained 4-benzocyclobutene pinacol borate:
1HNMR(500MHz,CDCl
3)δppm:7.68(d,1H),7.49(s,1H),7.07(d,1H),3.18(s,4H),1.33(s,12H).
Then; 3rd step product (2.3g), above-mentioned obtained 4-benzocyclobutene pinacol borate (2.1g), bis-triphenylphosphipalladium palladium dichloride (0.1g), salt of wormwood (1.2g) are joined 100ml two mouthfuls of round-bottomed flasks under nitrogen protection; add tetrahydrofuran (THF) (50ml) and water (10ml), back flow reaction 7 ~ 8 is little under a nitrogen atmosphere terminates up to reaction.50ml tap water is added in reaction system, extract by ethyl acetate (30ml*3), merge organic phase, organic phase saturated aqueous common salt (50ml*1) washs, concentrated after anhydrous sodium sulfate drying, crude product column chromatography purification, obtains 1.8g white solid product 1,2-bis-(4 '-(4 "-benzocyclobutane thiazolinyl)-2 '-(1 "-adamantyl) phenoxy group) trans-1,1,2,2,3,4-Hexafluorocyclobutane (IV-1), yield 73.9%.
Obtained monomer structure characterizes:
1HNMR(500MHz,CDCl
3)δppm:7.51(d,2H),7.37-7.35(dd,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).
19FNMR(470MHz,CDCl
3)δppm:-128.5～-129.0(m,6F)
Embodiment 2 prepares polymeric film with monomer (IV-1)
Weigh the benzocyclobutene monomer (IV-1) containing diamantane group of preparation in 1g embodiment 1, add the sym-trimethylbenzene of 3mL, be heated to 180 DEG C and carry out pre-polymerization, the period was advisable at 20 hours, obtained water white prepolymer solution.Prepolymer solution is carried out film by the mode of spin coating, then film is carried out ramped heating schedule solidification in Constant Temp. Oven, obtain the polymer of BCB film containing perfluorocyclobutane structure that highly cross-linked diamantane is modified; Its program curing is: 190 ~ 210 DEG C/0.5 hour; 230 ~ 250 DEG C/5 hours; 260 DEG C/1 hour.
Carry out thermogravimetric analysis experiment to polymeric film prepared by the present embodiment, its experimental result as shown in Figure 1.As can be seen from Figure 1, polymkeric substance has higher heat decomposition temperature, and decomposition 5% is temperature required is under a nitrogen atmosphere more than 447 DEG C, has good thermostability.
Carry out nano-indenter test experiment to the polymeric film that the present embodiment prepares, its experimental result as shown in Figure 2.As can be seen from Figure 2, this polymeric film has very excellent hardness, and average hardness is 0.769GPa; Young's modulus is large, average out to 10.77GPa.
The atomic force microscope figure of the polymeric film that accompanying drawing 3 is prepared for the present embodiment, as can be seen from accompanying drawing 3, this polymeric film has good film planarization, and its r.m.s. roughness on 1.00 μm of * 1.00 μm of surface-area is 0.6nm.
The specific inductivity of the polymeric film that accompanying drawing 4 is prepared for the present embodiment is with change of frequency figure, and as can be seen from accompanying drawing 4, the specific inductivity of polymeric film is 2.39 (1MHz), has good prospects for commercial application.
Persons of ordinary skill in the art may appreciate that the respective embodiments described above realize specific embodiments of the invention, and in actual applications, various change can be done to it in the form and details, and without departing from the spirit and scope of the present invention.
Claims (10)
1. contain a benzocyclobutene monomer for diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure, its structure is as shown in formula IV:
Wherein, two adamantyls are positioned at ortho position or a position of oxygen-containing functional group simultaneously.
2. the preparation method containing the benzocyclobutene monomer of diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure according to claim 1, is characterized in that, comprise the following steps:
(1) adamantyl p bromophenol is dissolved in solvent, add alkali, react under inert atmosphere protection after 15 ~ 30 minutes, drip 1,2-dibromotetrafluoroethane, react below 50 DEG C, generate the bromo-1-of 4-(2 '-bromo-1 ' containing diamantane side base shown in formula I, 1 ', 2 ', 2 '-tetrafluoro oxyethyl group) benzene;
(2) by the bromo-1-of 4-(2 '-bromo-1 ' containing diamantane side base shown in formula I, 1 ', 2 ', 2 '-tetrafluoro oxyethyl group) benzene is dissolved in solvent, add back flow reaction after the zinc powder of activation, generate the bromo-1-of 4-(the trifluoro-ethylene oxygen base) benzene containing diamantane side base shown in formula II;
(3) under inert atmosphere protection, make the bromo-1-of 4-(the trifluoro-ethylene oxygen base) benzene containing diamantane side base shown in formula II, at 180 ~ 250 DEG C, dimerization reaction occur, 8 ~ 15 hours reaction times, generate 1,2-bis-(the 4 '-bromine phenoxy group) trans-1,1,2,2,3,4-Hexafluorocyclobutane containing Double diamantane hydrocarbons side base shown in formula III;
(4) by shown in formula III containing Double diamantane hydrocarbons side base 1,2-bis-(4 '-bromine phenoxy group) trans-1,1,2,2,3,4-Hexafluorocyclobutane, 4-benzocyclobutene pinacol borate, alkali and palladium catalyst are dissolved in solvent under inert atmosphere protection, continue inert atmosphere protection next time stream carry out Suzuki reaction, the benzocyclobutene monomer containing diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure shown in obtained formula IV;
Reaction process is as follows:
Wherein, two adamantyls are positioned at ortho position or a position of oxygen-containing functional group simultaneously.
3. the preparation method containing the benzocyclobutene monomer of diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure according to claim 2, it is characterized in that, step (1) and the solvent described in step (2) are the mixture of one or more in dry following solvents: tetrahydrofuran (THF), acetonitrile, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, methylene dichloride, ethyl acetate, dimethyl sulfoxide (DMSO) and Isosorbide-5-Nitrae-dioxane.
4. the preparation method containing the benzocyclobutene monomer of diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure according to claim 2, it is characterized in that, step (1) and the alkali described in step (4) are mineral alkali or organic bases.
5. the preparation method containing the benzocyclobutene monomer of diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure according to claim 4, it is characterized in that, described mineral alkali is sodium carbonate, salt of wormwood, potassiumphosphate or cesium carbonate; Described organic bases is triethylamine or pyridine.
6. the preparation method containing the benzocyclobutene monomer of diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure according to claim 2, it is characterized in that, palladium catalyst described in step (4) is: bis-triphenylphosphipalladium palladium dichloride, 1,1'-bis-(diphenylphosphine) ferrocene palladium chloride, palladium, palladium chloride, tetrakis triphenylphosphine palladium or two (cyanophenyl) palladium chloride.
7. the preparation method containing the benzocyclobutene monomer of diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure according to claim 2, it is characterized in that, the solvent described in step (4) is:
The mixed solvent of one or more in tetrahydrofuran (THF), acetonitrile, DMF, N,N-dimethylacetamide, methylene dichloride, ethyl acetate, dimethyl sulfoxide (DMSO) and Isosorbide-5-Nitrae-dioxane;
Or one or more solvents mixed with water in tetrahydrofuran (THF), acetonitrile, DMF, N,N-dimethylacetamide, methylene dichloride, ethyl acetate, dimethyl sulfoxide (DMSO) and Isosorbide-5-Nitrae-dioxane.
8. the benzocyclobutene monomer containing diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure according to claim 1 is preparing the application in polymer materials.
9. application according to claim 8, is characterized in that, with the method that the described benzocyclobutene monomer containing diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure prepares polymeric film is:
(1) add in sym-trimethylbenzene by the benzocyclobutene monomer containing diamantane and trans-1,1,2,2,3,4-Hexafluorocyclobutane structure shown in formula IV, at 170 ~ 190 DEG C, reflux carries out prepolymerization reaction in 15 ~ 22 hours, obtains water white prepolymer solution;
(2) prepolymer solution is carried out film, drying is carried out to film, is then heating and curing, obtain highly cross-linked polymeric film.
10. application according to claim 9, is characterized in that, being heating and curing in described step (2) is carried out in Constant Temp. Oven, and 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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