CN104311401B - Containing benzocyclobutene and the thermosetting monomer of Freon C318 unit, preparation method and application thereof - Google Patents

Containing benzocyclobutene and the thermosetting monomer of Freon C318 unit, preparation method and application thereof Download PDF

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CN104311401B
CN104311401B CN201410466607.9A CN201410466607A CN104311401B CN 104311401 B CN104311401 B CN 104311401B CN 201410466607 A CN201410466607 A CN 201410466607A CN 104311401 B CN104311401 B CN 104311401B
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CN104311401A (en
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房强
周俊峰
罗乙杰
王佳佳
金凯凯
王元强
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Shanghai Institute of Organic Chemistry of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
    • C07C43/29—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing halogen
    • 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
    • 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
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/06—One of the condensed rings being a six-membered aromatic ring the other ring being four-membered

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  • Health & Medical Sciences (AREA)
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  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a kind of containing benzocyclobutene with the thermosetting monomer of Freon C318 unit, preparation method and application thereof.Specifically, the invention provides a kind of compound as shown in following formula I.Described compound of formula I can be heating and curing, and forms cured product.Described cured product has good heat resistance and electric property, is suitable as high-temperature-resistant adhesive or electronic devices and components encapsulating material.

Description

Containing benzocyclobutene and the thermosetting monomer of Freon C318 unit, preparation method and application thereof
Technical field
The invention belongs to high-performance polymer and manufacture field, be specifically related to a kind of containing benzocyclobutene with the simple thermosetting resin of trans-1,1,2,2,3,4-Hexafluorocyclobutane. construction unit, preparation method and application.
Background technology
Organic material containing hexafluoro cyclobutyl arylene ether unit has the optical property of excellence because of it, is subject to people's attention in 30 years of past.These materials have higher light transmissioning efficiency and minimum light loss, it is expected to as organic light-guide material (referring to Macromolecules2004,37,5724 and Macromolecules2005,38,8278).On the other hand, owing to C-F key has less polarizable rate, with two or three-functionality-degree containing trifluoro vinyl ether structure for performed polymer, obtain main chain by hot setting and contain the thermosetting resin of hexafluoro cyclobutyl arylene ether functional group, have been developed that and be used as advanced low-k materials (see Mat.Res.Soc.Symp.Proc.1997,443,177).This kind of material not only advantage of lower cost, and there is mechanical property and the low hydroscopicity (see WO9015043) of excellence.But, manufacture hexafluoro cyclobutyl arylene ether polymer by the performed polymer containing trifluoro vinyl ether, often because the reaction of trifluoro vinyl ether is incomplete, the trifluoro vinyl ether of residual can affect the performance of material.Unreacted trifluoro vinyl is subject to nucleopilic reagent attack, simultaneously neither acidproof, also not alkaline-resisting, can affect the resistance to medium (Macromolecules2008,41,7490-7496) of material.
In sum, this area still lack a kind of do not contain or be substantially free of residual trifluoro vinyl ether containing hexafluoro cyclobutyl arylene ether unit organic material.
Summary of the invention
It is an object of the invention to provide a kind of do not contain or be substantially free of residual trifluoro vinyl ether containing hexafluoro cyclobutyl arylene ether unit organic material.
A first aspect of the present invention, it is provided that a kind of compound as shown in following formula I:
A second aspect of the present invention, it is provided that the preparation method of a kind of compound of formula I as described in the first aspect of the invention, described method includes step:
In atent solvent, react with formula III compound with Formula II compound, obtain compound of formula I；
It is preferred that described reaction is carrying out under one or more reagent of lower group: cuprous salt, imidazole ligands, inorganic base, or its combination.
In another preference, the cuprous salt used is Cu-lyt., cuprous bromide or Hydro-Giene (Water Science)., it is preferred to use Cu-lyt..
In another preference, the imidazole ligands used is 1-Methylimidazole., 1,2-methylimidazole, N-1-Butyl-1H-imidazole or N-isopropylimdazole.
In another preference, the inorganic base used is alkali metal；It is preferred that described inorganic base is selected from lower group: hydroxide, carbonate, or its combination；More preferably, described inorganic base is potassium carbonate.
In another preference, in described reaction, described atent solvent is selected from lower group: toluene, dioxane, DMF, N, dinethylformamide, dimethyl sulfoxide, N-Methyl pyrrolidone, hexamethyl phosphoramide, sulfolane, or its combination.
In another preference, in described reaction, described 4-bromine benzocyclobutene (formula III compound) and 4, the mol ratio of 4 '-dihydroxy-diphenyl trans-1,1,2,2,3,4-Hexafluorocyclobutane. ether is 2～5:1.
In another preference, the mol ratio of described 4-bromine benzocyclobutene (formula III compound) and cuprous salt, imidazole ligands and inorganic base is 1～5:0.1～1:0.1～1:1～5.
In another preference, described reaction carries out at 80-160 DEG C.
In another preference, the described response time is 5-30 hour.
In another preference, described Formula II compound is prepared by the following method:
In atent solvent, react with Formula II a compound, obtain Formula II compound；
In another preference, described reaction carries out under the reagent selected from lower group exists: Boron tribromide, pyridine hydrochloride, or aluminium triiodide.
In another preference, described atent solvent is selected from lower group: dichloromethane, chloroform, dichloroethanes, toluene.
In another preference, described reaction carries out at 10 DEG C～40 DEG C, it is preferred that at room temperature carry out.
In another preference, the described response time is 10～20h.
In another preference, described Formula II a compound is prepared by the following method:
In atent solvent, carry out polyreaction with Formula II b compound, obtain Formula II a compound:
In another preference, described solvent is selected from lower group: diphenyl ether, trimethylbenzene, sulfolane, or its combination.
In another preference, described reaction carries out at 120 DEG C～180 DEG C.
In another preference, the described response time is 12～36h.
A third aspect of the present invention, it is provided that a kind of compound as described in the first aspect of the invention is for preparing the purposes of cured product.
A fourth aspect of the present invention, it is provided that a kind of cured product, described cured product is to be undertaken solidifying thus preparing by compound of formula I as described in the first aspect of the invention.
In another preference, described cured product is to carry out individually solidifying thus preparing with compound shown in formula I.
In another preference, described cured product compound of formula I solidifies preparation with other benzocyclobutene monomers or unsaturated double-bond resin alloy；It is preferred that described cured product is to solidify preparation by compound of formula I with the monomer blend selected from lower group: BMI, tolan, stilbene, or its combination.
In another preference, the resin alloy weight ratio of described simple thermosetting resin and other benzocyclobutene monomers or unsaturated double-bond is 1:0.05～8.
In another preference, described cured product has property structure illustrated below:
Wherein, m, n are integer.
In another preference, boundary's electric constant (1-30MHz) of described cured product is 2.3～2.7.
In another preference, in the nitrogen of described cured product, 5% thermogravimetric weight loss temperature is 450～490 DEG C.
In another preference, in the air of described cured product, 5% thermogravimetric weight loss temperature is 380～410 DEG C.
In another preference, in the nitrogen of described cured product, 1000 DEG C of carbon residual rates are >=45%, it is preferred that for >=50%.
In another preference, described being cured as is heating and curing.
In another preference, the described temperature that is heating and curing is 200-300 DEG C.
In another preference, described being heating and curing includes: carry out precuring at 150～200 DEG C, then carries out heat cure at 210～260 DEG C.
In another preference, described pre-cure time is 0.5～4h.
In another preference, described thermal curing time is 1～8h.
A fifth aspect of the present invention, it is provided that a kind of goods, described goods contain compound as described in the first aspect of the invention, or described goods are to prepare with compound as described in the first aspect of the invention.
In another preference, described goods are high temperature resistant ablation resistant material, or electronic devices and components encapsulating material.
A sixth aspect of the present invention, it is provided that a kind of goods, described goods are containing, for example the cured product described in fourth aspect present invention, or described goods are to prepare with the cured product as described in fourth aspect present invention.
A seventh aspect of the present invention, it is provided that the preparation method of the goods described in a kind of present invention the 5th or the 6th, described method includes step:
(1) polymer as described in the first aspect of the invention is provided；
(2) polymer as described in the first aspect of the invention is shaped, obtains pre-shaped articles；
(3) pre-shaped articles obtained in described step (2) is solidified, the goods described in obtaining in the present invention the 5th or the 6th.
In another preference, in described step (2), described molding is to be undertaken by the method selected from lower group: fill mould, solution spin coating, solution drop coating.
In another preference, described cured product compound of formula I solidifies preparation with other benzocyclobutene monomers or unsaturated double-bond resin alloy；It is preferred that described cured product is to solidify preparation by compound of formula I with the monomer blend selected from lower group: BMI, tolan, stilbene, or its combination.
In another preference, described being cured as is heating and curing.
In another preference, the described temperature that is heating and curing is 200-300 DEG C.
In another preference, described being heating and curing includes: carry out precuring at 150～200 DEG C, then carries out heat cure at 210～260 DEG C.
In another preference, described pre-cure time is 0.5～4h.
In another preference, described thermal curing time is 1～8h.
In another preference, described solidification also includes, and after heat cure completes, carries out heat treatment at 260～330 DEG C.
In another preference, described heat treatment time is 1～4h.
In another preference, in described step (2), the described film forming that is shaped to, and described film forming is by selected from the method for lower group: heating and mould pressing, solution spin coating, solution drop coating.
In another preference, described solution spin coating or solution drop coating include: with organic solvent dissolution polymer as described in the first aspect of the invention, then carry out spin coating or drop coating on base material.
In another preference, described organic solvent is selected from lower group: toluene, trimethylbenzene, diphenyl ether, chloroform, acetone, DMF, N,N-dimethylacetamide, dimethyl sulfoxide or N-Methyl pyrrolidone, or its combination.
Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus constituting new or preferred technical scheme.As space is limited, tired no longer one by one state at this.
Detailed description of the invention
The present inventor, through long-term and deep research, is prepared for a kind of thermosetting monomer containing benzocyclobutene and trans-1,1,2,2,3,4-Hexafluorocyclobutane. construction unit and cured product thereof.Described thermosetting monomer has a good processing characteristics, and the cured product after being heating and curing has good thermostability and electric conductivity.Based on above-mentioned discovery, inventor completes the present invention.
Monomer containing benzocyclobutene and trans-1,1,2,2,3,4-Hexafluorocyclobutane. construction unit
The present invention is from molecular design theory, benzocyclobutene unit is introduced in hexafluoro cyclobutyl arylene ether molecular skeleton, obtain thermosetting monomer, as the high-performance coating of a kind of high heat-resisting, low-k and encapsulating material, the fields such as microelectronics industry, Aero-Space and national defence can be applied to.The invention provides a kind of benzocyclobutene and the simple thermosetting resin of trans-1,1,2,2,3,4-Hexafluorocyclobutane. construction unit, and preparation method thereof, the benzocyclobutene resin property obtained is excellent, is suitable to be used as high-performance resin matrix or encapsulating material in the fields such as microelectronics industry, Aero-Space and national defence.
Specifically, the invention provides a kind of compound as shown in following formula I:
The preparation method of described compound of formula I includes step:
In atent solvent, react with formula III compound with Formula II compound, obtain compound of formula I；
In another preference, described reaction is carrying out under one or more reagent of lower group: cuprous salt, imidazole ligands, inorganic base, or its combination.
In another preference, the cuprous salt used is Cu-lyt., cuprous bromide or Hydro-Giene (Water Science)., it is preferred to use Cu-lyt..
In another preference, the imidazole ligands used is 1-Methylimidazole., 1,2-methylimidazole, N-1-Butyl-1H-imidazole or N-isopropylimdazole.
In another preference, the inorganic base used is alkali metal；It is preferred that described inorganic base is selected from lower group: hydroxide, carbonate, or its combination；More preferably, described inorganic base is potassium carbonate.
In another preference, in described reaction, described atent solvent is selected from lower group: toluene, dioxane, DMF, N, dinethylformamide, dimethyl sulfoxide, N-Methyl pyrrolidone, hexamethyl phosphoramide, sulfolane, or its combination.
In another preference, in described reaction, described 4-bromine benzocyclobutene and 4, the mol ratio of 4 '-dihydroxy-diphenyl trans-1,1,2,2,3,4-Hexafluorocyclobutane. ether is 2～5:1.
In another preference, the mol ratio of described 4-bromine benzocyclobutene (formula III compound) and cuprous salt, imidazole ligands and inorganic base is 1～5:0.1～1:0.1～1:1～5.
In another preference, described reaction carries out at 80-160 DEG C.
In another preference, the described response time is 5-30 hour.
In described reaction equation, each raw material can be obtained by conventional route, for instance, in one preferred embodiment of the invention, described Formula II compound is prepared by the following method:
In atent solvent, react with Formula II a compound, obtain Formula II compound；
In another preference, described reaction carries out under the reagent selected from lower group exists: Boron tribromide, pyridine hydrochloride, or aluminium triiodide.
In another preference, described atent solvent is selected from lower group: dichloromethane, chloroform, dichloroethanes, toluene, or its combination.
In another preference, described reaction carries out at 10 DEG C～40 DEG C, it is preferred that at room temperature carry out.
In another preference, the described response time is 10～20h.
In another preference, described Formula II a compound is prepared by the following method:
In atent solvent, carry out polyreaction with Formula II b compound, obtain Formula II a compound:
In another preference, described solvent is selected from lower group: diphenyl ether, trimethylbenzene, sulfolane, or its combination.
In another preference, described reaction carries out at 120 DEG C～180 DEG C.
In another preference, the described response time is 12～36h.
Described compound of formula I may be used for preparing cured product, e.g., by being heating and curing, obtains cured product.It is preferred that be heated under an inert atmosphere solidifying, thus obtaining cured product.
Cured product containing benzocyclobutene and trans-1,1,2,2,3,4-Hexafluorocyclobutane. construction unit
Present invention also offers a kind of cured product, described cured product is to be undertaken solidifying thus preparing by compound of formula I as described in the first aspect of the invention.
The Formulas I thermosetting monomer that described cured product can be described individually carries out solidifying thus preparing, or carries out solidifying with other benzocyclobutene monomers or unsaturated double-bond resin alloy thus preparing.In one preferred embodiment of the invention, the resin alloy weight ratio of described simple thermosetting resin and other benzocyclobutene monomers or unsaturated double-bond is 1:0.05～8.
Described curing mode has no particular limits, it is preferred that for being heating and curing.Preferably, the described temperature that is heating and curing is 200-300 DEG C.
In another preference, described being heating and curing includes: carry out precuring at 150～200 DEG C, then carries out heat cure at 210～260 DEG C.Wherein, described pre-cure time is 0.5～4h, and described thermal curing time is 1～8h.
In another preference, described solidification also includes, and after heat cure completes, carries out heat treatment at 260～330 DEG C.
In another preference, described heat treatment time is 1～4h.
In another preference, described being heating and curing includes: process 0.5～2 hour at 130～170 DEG C, process 0.5～2 hour at 180～220 DEG C, process 0.5～2 hour at 220～260 DEG C, process 0.5～2 hour at 240～280 DEG C, process 4～6 hours at 260～300 DEG C, process 4～6 hours at 280～320 DEG C.
In another preferred embodiment of the present invention, described cured product is the cross-linked structure that the cyclobutane construction unit open loop of compound of formula I is connected to form, for instance following schematic structure:
Wherein, m, n are integer.
Described cyclobutane construction unit can carry out open loop dimerization with other cyclobutane construction units, it is also possible to form chain or netted high polymer with other common open loops of cyclobutane construction unit.
Described cured product has electric property and the heat resistance of excellence, and in another preference, the dielectric constant (1-30MHz) of described cured product is 2.3～2.7.
In another preference, in the nitrogen of described cured product, 5% thermogravimetric weight loss temperature is 450～490 DEG C.
In another preference, in the air of described cured product, 5% thermogravimetric weight loss temperature is 380～410 DEG C.
In another preference, in the nitrogen of described cured product, 1000 DEG C of carbon residual rates are >=45%, it is preferred that for >=50%.
Polymer product containing benzocyclobutene and trans-1,1,2,2,3,4-Hexafluorocyclobutane. construction unit
Present invention also offers a kind of goods, described goods are containing, for example the polymer described in Formulas I, or described goods are to prepare with the polymer as described in Formulas I.
In another preference, described goods carry out solidifying, containing useful compound as described in Formulas I, the cured product obtained, or described goods are to carry out solidifying the cured product obtained with the compound as described in Formulas I to prepare.
In another preference, described goods are high temperature resistant ablation resistant material, or electronic devices and components encapsulating material.
In a preference of the present invention, the preparation method of described goods includes step:
(1) monomer described in Formulas I is provided；
(2) monomer described in Formulas I is shaped, obtains pre-shaped articles；
(3) pre-shaped articles obtained in described step (2) is solidified, obtain described goods.
In another preference, described being cured as is heating and curing.
In another preference, the described temperature that is heating and curing is 200-300 DEG C.
In another preference, described being heating and curing includes: carry out precuring at 150～200 DEG C, then carries out heat cure at 210～260 DEG C.
In another preference, described pre-cure time is 0.5～4h.
In another preference, described thermal curing time is 1～8h.
In another preference, described solidification also includes, and after heat cure completes, carries out heat treatment at 260～330 DEG C.
In another preference, described heat treatment time is 1～4h.
Described forming method has no particular limits, it is possible to select room temperature compacted under method known in the art to be shaped, as by filling mould or being shaped by wiring solution-forming spin coating or drop coating film forming.In a preference of the present invention, in described step (2), the described film forming that is shaped to, and described film forming is by selected from the method for lower group: heating and mould pressing, solution spin coating, solution drop coating.
In another preference, described solution spin coating or solution drop coating include: with the polymer described in organic solvent dissolution such as Formulas I, then carry out spin coating or drop coating on base material.
In another preference, described organic solvent is selected from lower group: toluene, trimethylbenzene, diphenyl ether, chloroform, acetone, DMF, N,N-dimethylacetamide, dimethyl sulfoxide or N-Methyl pyrrolidone, or its combination.
Compared with prior art, the major advantage of the present invention includes:
(1) the invention provides a kind of thermosetting resin prepared containing benzocyclobutene and trans-1,1,2,2,3,4-Hexafluorocyclobutane. construction unit, described resin has good processing characteristics, it is possible to is used for being heating and curing and prepares thermosetting resin.
(2) the invention provides a kind of resin-cured product containing benzocyclobutene and trans-1,1,2,2,3,4-Hexafluorocyclobutane. construction unit, compared with prior art, in cured product of the present invention, rarer unreacted trifluoro vinyl ether end group, therefore has better electric property and heat stability.
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally conventionally condition, or according to manufacturer it is proposed that condition.Unless otherwise indicated, otherwise percentage ratio and number are calculated by weight.
The preparation of embodiment 1 precursor 1 (1-(the bromo-1,1,2,2-tetrafluoro ethyoxyl of 2-) methyl phenyl ethers anisole)
Under argon shield; reaction bulb adds 49.6 grams of p methoxy phenols; 156 gram 1; 2-dibromotetrafluoroethane and 350 milliliters of existing DMSO (dimethyl sulfoxide) steamed; stir 30 minutes under ice-water bath; it is subsequently adding 83 grams of Anhydrous potassium carbonates; remove ice-water bath, room temperature reaction 6 hours, reaction mixture is poured into water; it is stirred vigorously 20 minutes; in batches with chloroform by product extract, extract saturated sodium-chloride water solution wash after rotation be evaporated off dechlorination imitate, residue column chromatography purification (silicagel column; petroleum ether is eluant), yield 77%.1HNMR(300MHz,CDCl3) δ (ppm): 3.81 (s, 3H), 6.89 (d, 2H), 7.15 (d, 2H)；19FNMR(282MHz)δ(ppm):-86.63(t,2F),-68.36(t,2F).
The preparation of embodiment 2 precursor 2 (1-(1,2,2-trifluoro-ethylene oxygen base) methyl phenyl ethers anisole)
Under argon shield, adding 50 grams of 1-(bromo-1,1,2, the 2-tetrafluoro ethyoxyl of 2-) methyl phenyl ethers anisoles, 300 milliliters of new steaming acetonitriles, agitation and dilution, add 25 grams of zinc powders in reaction bulb, temperature rising reflux reacts 24 hours.Being poured into by reactant liquor in 600 milliliters of water, stir more than 15 minutes, extract with chloroform in batches, combined chloroform extract, wash with saturated sodium-chloride water solution, anhydrous sodium sulfate dries more than 12 hours.Rotation is evaporated off dechlorination and imitates, concentrated solution residue column chromatography purification (silicagel column, petroleum ether is eluant) yield 55%.1HNMR(300MHz,CDCl3): δ (ppm): 3.80 (s, 3H), 6.87 (d, 2H), 7.05 (d, 2H)；19FNMR(282MHz,CDCl3):δ(ppm)-133.89(dd,1F),-127.84(dd,1F),-120.79(dd,1F).
The preparation of 3 pairs of (methoxyphenol) hexafluoro cyclobutyl ethers of embodiment 3 precursor (1,1 '-(1,2,2,3,3,4 ,-trans-1,1,2,2,3,4-Hexafluorocyclobutane .-1,2-dioxy base)-two (to methoxybenzenes))
Under argon shield, reaction bulb adds 20 grams of 1-(1,2,2-trifluoro-ethylene oxygen base) methyl phenyl ethers anisoles and 50 milliliters of diphenyl ether, heat to 150 DEG C of reactions 24 hours.It is cooled to rapid column chromatography (petrol ether/ethyl acetate, 10:1) after room temperature, productivity 95%.1HNMR(300MHz,CDCl3): δ (ppm) 3.80 (s, 6H), 6.84 (d, 2H), 7.04-7.10 (m, 4H), 7.44 (d, 2H)；
19FNMR(282MHz,CDCl3):δ(ppm)-132.47,-131.90,-131.65,-131.11,-130.85,-130.58,-130.31,-130.07,-129.90,-129.76,-129.54,-129.11,128.97,-128.75,-128.32,-127.41.
The preparation of embodiment 4 precursor 4 (4,4 '-dihydroxy-diphenyl trans-1,1,2,2,3,4-Hexafluorocyclobutane. ether)
Under argon shield; reaction bulb adds 3 pairs of (methoxyphenol) hexafluoros cyclobutyl ether (10 grams) of presoma; dichloromethane (100 milliliters); mixture is cooled at 0 DEG C; slowly dripping the diethyl ether solution (20 grams) of Boron tribromide, finish, mixture stirs overnight under room temperature; reactant shrend separates organic layer after going out.After removing solvent, crude by column chromatography (petrol ether/ethyl acetate, 10:1) separates, and obtains 4,4 '-dihydroxy-diphenyl trans-1,1,2,2,3,4-Hexafluorocyclobutane. ether, productivity 89%.1HNMR(300MHz,CDCl3):δ(ppm)6.82(d,2H),7.01-7.08(m,4H),7.41(d,2H).19FNMR(282MHz,CDCl3):δ(ppm)-132.44,-131.88,-131.50,-131.00,-130.85,-130.52,-130.30,-130.01,-129.85,-129.79,-129.51,-129.01,128.90,-128.71,-128.30,-127.33.
Embodiment 5 is containing the preparation of benzocyclobutene and the thermosetting monomer of Freon C318 unit
Under argon shield; reaction unit adds 4; 4 '-dihydroxy-diphenyl trans-1,1,2,2,3,4-Hexafluorocyclobutane. ether (19g; 0.05mol) 4-bromine benzocyclobutene (36.6g; 0.2mol); 1.95 grams of Hydro-Giene (Water Science) .s (0.01mol); 6.15 grams of N-1-Butyl-1H-imidazoles (0.05mol); 13.86 gram potassium carbonate (0.1mol); 100 milliliters of toluene, are warming up to 140 DEG C and react 16 hours, be cooled to room temperature; reactant mixture chloroform dilutes, and neutralizes with saturated sodium bicarbonate aqueous solution after the washing of organic layer dilute hydrochloric acid again.Solid crude product is obtained after organic solvent being evaporated off with rotation.White solid product, productivity 66% can be obtained by column chromatography purification (petrol ether/ethyl acetate, 6:1).Proton nmr spectra1H-NMR result (300MHz, CDCl3, ppm) and δ 3.12 (s, 8H), 6.73-7.15 (14H).Mass spectrum (EI/MS) characterizes m/z:584.14 (100.0%).
Embodiment 6 is containing the preparation of benzocyclobutene and the thermosetting monomer of Freon C318 unit
With embodiment 5, but adopting Cu-lyt. is catalyst, products collection efficiency 51%.
Embodiment 7 is containing the preparation of benzocyclobutene and the thermosetting monomer of Freon C318 unit
With embodiment 5, but solvent adopts N-Methyl pyrrolidone, productivity 61%.
The solidification of the thermosetting monomer of embodiment 8 benzocyclobutene and Freon C318 unit
Take 4 grams of embodiment 5 obtained products, it is placed in airtight, to be full of argon glass tubing (diameter 2.5cm, height 8.5cm) in, then glass tubing is placed in oil bath, carries out stage intensification, 150 DEG C × 1 hour, 200 DEG C × 1 hour, 240 DEG C × 1 hour, 260 DEG C × 1 hour, 280 DEG C × 5 hours, 300 DEG C × 5 hours.The resin of light color column crosslinking is obtained after cooling.
The performance of embodiment 9 cured product
Crosslinked resin embodiment 8 obtained, becomes the disk of diameter 2 centimetres, thickness 3 millimeters, tests its dielectric properties with sand papering., this disk is pulverized meanwhile, carry out TGA measurement with the powder of gained.Following table is the dielectric and the heat resistance that solidify resin.
The all documents mentioned in the present invention are incorporated as reference all in this application, are individually recited as reference such just as each section of document.In addition, it is to be understood that after the above-mentioned teachings having read the present invention, the present invention can be made various changes or modifications by those skilled in the art, these equivalent form of values fall within the application appended claims limited range equally.

Claims (11)

1. the compound as shown in following formula I:
2. the preparation method of compound of formula I as claimed in claim 1, it is characterised in that include step:
In atent solvent, react with formula III compound with Formula II compound, obtain compound of formula I；
3. method as claimed in claim 2, it is characterised in that described reaction is carrying out under one or more reagent of lower group: cuprous salt, imidazole ligands, inorganic base, or its combination.
4. method as claimed in claim 2, it is characterised in that described Formula II compound is prepared by the following method:
In atent solvent, react with Formula II a compound, obtain Formula II compound；
5. method as claimed in claim 4, it is characterised in that described Formula II a compound is prepared by the following method:
In atent solvent, carry out polyreaction with Formula II b compound, obtain Formula II a compound:
6. the purposes of compound as claimed in claim 1, it is characterised in that be used for preparing cured product.
7. a cured product, it is characterised in that described cured product is undertaken solidifying thus preparing by compound of formula I as claimed in claim 1.
8. goods, it is characterised in that described goods contain compound as claimed in claim 1, or described goods are prepared with compound as claimed in claim 1.
9. goods, it is characterised in that described goods contain cured product as claimed in claim 7, or described goods are prepared with cured product as claimed in claim 7.
10. the preparation method of goods as claimed in claim 8 or 9, it is characterised in that include step:
(1) compound as claimed in claim 1 is provided；
(2) compound as claimed in claim 1 is shaped, obtains pre-shaped articles；
(3) pre-shaped articles obtained in described step (2) is solidified, obtain goods as claimed in claim 8 or 9.
11. method as claimed in claim 10, it is characterised in that in described step (2), the described film forming that is shaped to, and described film forming are by selected from the method for lower group: heating and mould pressing, solution spin coating, solution drop coating.
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