CN103755534A - Low-dielectric-constant polymer containing bis(benzenyl fluoride) and dinaphthalene structural units - Google Patents

Low-dielectric-constant polymer containing bis(benzenyl fluoride) and dinaphthalene structural units Download PDF

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CN103755534A
CN103755534A CN201410028010.6A CN201410028010A CN103755534A CN 103755534 A CN103755534 A CN 103755534A CN 201410028010 A CN201410028010 A CN 201410028010A CN 103755534 A CN103755534 A CN 103755534A
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polymkeric substance
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CN103755534B (en
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房强
王佳佳
袁超
贺凤开
金凯凯
陈华
刁屾
田松
童佳伟
孙晶
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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
    • 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
    • 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
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/121—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from organic halides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/316—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain bridged by heteroatoms, e.g. N, P, Si or B
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/59—Stability
    • C08G2261/592—Stability against heat
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/65—Electrical insulator

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Abstract

The invention provides a low-dielectric-constant polymer containing bis(benzenyl fluoride) and dinaphthalene structural units as well as preparation method and application of the low-dielectric-constant polymer containing bis(benzenyl fluoride) and dinaphthalene structural units. Particularly, the invention provides a polymer monomer as shown in the formula I as well as the polymer obtained by polymerization reaction by the monomer. The polymer has favorable electrical performance and film-forming property, and is suitable for serving as packaging materials of insulation coating layers and electronic elements in the electronic and electrical industry.

Description

Containing the low dielectric constant polymer of dual-trifluoromethyl benzene and binaphthyl structure unit
Technical field
The invention belongs to high-performance polymer manufacturing technology field, be specifically related to polymkeric substance and the manufacture method thereof of dual-trifluoromethyl benzene and the dinaphthalene unit of a kind of specific inductivity, mechanical property excellence.
Background technology
Fluorinated poly arylene ether has excellent thermotolerance and photoelectric properties, and for a long time, people just conduct in-depth research it.As high performance thin film, moulding compound and coating, they have been widely used in the fields (referring to Progress in Polymer Science2010,35,1022 – 1077) such as aerospace and electronic apparatus.But in fluorine-containing polyaryl ether, a large amount of polymerization single polymerization monomers that use are expensive perfluor benzene, can cause material cost significantly to improve.
In recent years, trifluoromethyl is introduced in polyarylether structure, utilized the large steric hindrance of trifluoromethyl, and then the research of the free volume of increase polymerization causes this area research personnel's attention.Due to the increase of free volume, the electrical insulation properties of material is significantly improved, and meanwhile, due to the existence of aryl oxide structure, material has excellent resistance toheat and the adhesive property to substrate.
Similarly, there is the problem that cost is higher in the polyarylether containing trifluoromethyl of already having reported, particularly some polymkeric substance is used the route exceeding more than three steps synthetic corresponding containing trifluoromethyl monomer (J.Am.Chem.Soc.2001,123,11071), greatly limited the application of material.
In sum, this area still lacks that a kind of cost is low, and synthetic route is short, has the fluorinated poly arylene ether of excellent thermostability and dielectric properties.
Summary of the invention
The object of this invention is to provide a kind of cost low, synthetic route is short, has the fluorinated poly arylene ether of excellent thermostability and dielectric properties.
A first aspect of the present invention, provides a kind of suc as formula the polymer monomer shown in I:
Figure BDA0000459903240000021
A second aspect of the present invention, provides a kind of preparation method suc as formula the compound shown in I, and described method comprises step:
Figure BDA0000459903240000022
In inert solvent, make the bromo-Isosorbide-5-Nitrae-dual-trifluoromethyl benzene of 2,5-bis-and react with 1-naphthols, obtain formula I compound.
In another preference, described method has the one or more features that are selected from lower group:
Described reaction is carried out under alkali exists, and preferably, described alkali is selected from lower group: potassium hydroxide, Anhydrous potassium carbonate, Carbon Dioxide caesium, or its combination; And/or
Described reaction is carried out in the solvent that is selected from lower group: N-Methyl pyrrolidone, DMSO, or its combination; And/or
Described reaction is carried out at 100～200 ℃; And/or
The described reaction times is 4～20 hours; And/or
The mol ratio of described 1-naphthols and 2,5-, bis-bromo-Isosorbide-5-Nitrae-dual-trifluoromethyl benzenes is 1:1～10.
In another preference, the mol ratio of described 1-naphthols and 2,5-, bis-bromo-Isosorbide-5-Nitrae-dual-trifluoromethyl benzenes is 1:1～10.
In another preference, the mol ratio of described 1-naphthols and 2,5-, bis-bromo-Isosorbide-5-Nitrae-dual-trifluoromethyl benzenes is 1:0.1～1.
A third aspect of the present invention, provides a kind of polymkeric substance, and described polymkeric substance is to prepare by polyreaction with the polymer monomer suc as formula shown in I described in first aspect present invention.
In another preference, described polymkeric substance has suc as formula the structure shown in II:
Figure BDA0000459903240000031
Wherein, n=5～200.
In another preference, the number-average molecular weight of described polymkeric substance is 2490～99000.
In another preference, the number-average molecular weight of described polymkeric substance is 10000～300000.
A fourth aspect of the present invention, provides a kind of preparation method of the formula II compound as described in third aspect present invention, and described method comprises step:
In inert solvent, with the polymer monomer polymerization reaction take place shown in formula I, obtain formula II polymkeric substance.
In another preference, described polyreaction is oxidative polymerization.
In another preference, described reaction is carried out under trivalent iron salt exists; Preferably, described trivalent iron salt is selected from lower group: iron(ic) chloride, iron bromide, ferric sulfate, iron nitrate, or its combination; Be more preferably iron(ic) chloride.
In another preference, described method also has the one or more features that are selected from lower group:
Described solvent is organic solvent, is preferably selected from lower group: oil of mirbane, methylene dichloride, ethylene dichloride, tetrachloroethane, chlorobenzene, dichlorobenzene, or its combination;
Described polymeric reaction temperature is-50～30 ℃;
Described polymerization reaction time is 5～48 hours.
In another preference, described method also comprises aftertreatment; Preferably, described post-treating method is column chromatography.
In another preference, described post-treating method comprises: take neutral alumina (200 to 300 order) as sorbent material, carry out column chromatography take organic solvent as eluent; Preferably, described organic solvent is selected from lower group: toluene, dimethylbenzene, trimethylbenzene, phenyl ether, pimelinketone, trichloromethane, acetone, or its combination.
A fifth aspect of the present invention, provides a kind of goods, it is characterized in that, described goods comprise the polymkeric substance as described in third aspect present invention, or described goods are to use the polymkeric substance as described in third aspect present invention to prepare.
In another preference, described goods are selected from lower group: the insulating material in advanced low-k materials, plain conductor outer cladding insulating material, cable, super large-scale integration.
In another preference, described goods are sheet material or film.
In another preference, described sheet material or film have following characteristics:
Described sheet material or the second-order transition temperature of film are 244 ℃; And/or
Under nitrogen atmosphere, 5% weight loss temperature (T of described sheet material or film d5%) be 519 ℃; And/or
Described sheet material or film carbon yield >=40% at 1000 ℃, is preferably >=50%, is more preferably >=60%; And/or
Described sheet material or the specific inductivity of film (30MHz) are 2.47.
In another preference, described sheet material or film are prepared by the following method: heating and mould pressing, solution spin coating, or molten drop-coated.
In another preference, described sheet material or film are dripped and are coated with preparation by solution spin coating or solution, and described solution spin coating or molten drop-coated comprise: described polymkeric substance is dissolved in organic solvent, by spin coating or drip and be coated with film forming; Preferably, described organic solvent is selected from lower group: toluene, dimethylbenzene, trimethylbenzene, phenyl ether, pimelinketone, trichloromethane, acetone, DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, or its combination.
In should be understood that within the scope of the present invention, above-mentioned each technical characterictic of the present invention and can combining mutually between specifically described each technical characterictic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, at this, tire out and state no longer one by one.
Embodiment
The inventor is through long-term and deep research, unexpectedly prepared a kind of polymkeric substance containing dual-trifluoromethyl benzene and binaphthyl structure unit, described polymkeric substance has low-down specific inductivity and good thermostability, be suitable as there is superior heat-stability, high performance electronic packaging material or the plain conductor coating of low water absorption and low-k, be applied to the fields such as microelectronics processing industry and large electric manufacturing.Based on above-mentioned discovery, contriver has completed the present invention.
Term
As used herein, term " homopolymerization " refers to the polyreaction of being undertaken by a kind of monomer, the polymerization of carrying out as oxalyl hexanediamine monomer.Term " homopolymer " refers to the polymkeric substance being formed by a kind of monomer polymerization, as polyhexamethylene adipamide (nylon 66).Especially, polymerization herein comprises addition polymerization and polycondensation.
As used herein, term " copolymerization " refers to the polyreaction of being undertaken by two or more monomer, the polymerization of carrying out as phenol and formaldehyde monomers.Term " multipolymer " refers to by the polymkeric substance being formed by two or more monomer polymerization, as resol.Especially, polymerization herein comprises addition polymerization and polycondensation.
Bis-naphthol dual-trifluoromethyl benzene ether polymer monomer
Figure BDA0000459903240000051
The invention provides a kind ofly suc as formula the bis-naphthol dual-trifluoromethyl benzene ether polymer monomer shown in I, described monomer can be for carrying out polyreaction, and preparation is containing the polymkeric substance of dual-trifluoromethyl benzene and binaphthyl structure unit.
Described polymer monomer can be prepared by the method for this area routine, for example, in a preference of the present invention, can prepare by the following method:
Figure BDA0000459903240000052
In inert solvent, with 1-naphthols and the reaction of the bromo-Isosorbide-5-Nitrae of 2,5-bis--dual-trifluoromethyl benzene, obtain formula I compound.
Described reaction is preferably carried out under alkali exists, and preferred alkali is selected from lower group: potassium hydroxide, Anhydrous potassium carbonate, Carbon Dioxide caesium, or its combination.
Described inert solvent has no particular limits, can be arbitrarily not with the solvent of reactant reaction, for example (but being not limited to) is selected from the solvent of lower group: N-Methyl pyrrolidone, DMSO, or its combination.
The temperature and time of described reaction is not particularly limited, and can follow the tracks of judgement reaction by TLC complete.In a preferred example, described reaction is carried out 10～20 hours at 100～200 ℃.
The ratio of each raw material has no particular limits, and for example, in a preference of the present invention, the mol ratio of described 1-naphthols and 2,5-, bis-bromo-Isosorbide-5-Nitrae-dual-trifluoromethyl benzenes is 1:0.1～10.
Containing the polymkeric substance of dual-trifluoromethyl benzene and binaphthyl structure unit
The present invention also provides a kind of polymkeric substance, and described polymkeric substance is to use suc as formula the polymer monomer shown in I to prepare by polyreaction.Described polyreaction can be homopolymerization, for example, carries out oxypolymerization between above-mentioned monomer, can be also to carry out copolyreaction with other polymerization single polymerization monomers.
In preferred example, described polymkeric substance has described polymkeric substance and has suc as formula the structure shown in II:
Wherein, n=5～200.
In another preference, the number-average molecular weight of described polymkeric substance is 2490～99000.
In a preferred embodiment of the present invention, described polyreaction comprises step:
In inert solvent, with the polymer monomer polymerization reaction take place shown in formula I, obtain formula II polymkeric substance; Preferably, described polyreaction is oxidative polymerization.
In preference of the present invention, described reaction is carried out under trivalent iron salt exists; Preferably, described trivalent iron salt is selected from lower group: iron(ic) chloride, iron bromide, ferric sulfate, iron nitrate, or its combination; Be more preferably iron(ic) chloride.
Described inert solvent has no particular limits, can be arbitrarily not with the solvent of reactant reaction, be organic solvent, be preferably selected from lower group: oil of mirbane, methylene dichloride, ethylene dichloride, tetrachloroethane, chlorobenzene, dichlorobenzene, or its combination;
Described polymeric reaction temperature is-50～30 ℃;
Described polymerization reaction time is 5～48 hours.
In another preference, described preparation method also comprises step: with the common method aftertreatment in this area, to remove the iron ion that may comprise in polymkeric substance.Polymkeric substance is carried out to purifying necessary.Otherwise the dielectric properties of polymeric film can be subject to very big impact.A kind of preferred post-treating method is column chromatography.
In another preference, described post-treating method comprises: take neutral alumina (200 to 300 order) as sorbent material, carry out column chromatography take organic solvent as eluent; Preferably, described organic solvent is selected from lower group: toluene, dimethylbenzene, trimethylbenzene, phenyl ether, pimelinketone, trichloromethane, acetone, or its combination.
Described polymkeric substance can be used for preparation and comprises the functional article such as (but being not limited to) advanced low-k materials, plain conductor outer cladding insulating material.Because polymkeric substance has good film-forming properties, a kind of preferred described goods are sheet material or film.
Described sheet material or film can be by the common method preparations in this area, as prepared by the following method: heating and mould pressing, solution spin coating, or molten drop-coated.
In a preference of the present invention, described sheet material or film are dripped and are coated with preparation by solution spin coating or solution, and described solution spin coating or molten drop-coated comprise: described polymkeric substance is dissolved in organic solvent, by spin coating or drip and be coated with film forming; Preferably, described organic solvent is selected from lower group: toluene, dimethylbenzene, trimethylbenzene, phenyl ether, pimelinketone, trichloromethane, acetone, DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, or its combination.
Major advantage of the present invention
(1) the invention provides a kind of polymkeric substance containing dual-trifluoromethyl benzene and binaphthyl structure unit, and preparation method thereof, the polymkeric substance obtaining has good film-forming properties and thermostability.
(2) the polymer performance excellence obtaining, in some embodiments of the invention, the glass transition temperature of polymer of preparation is 244 ℃; TGA tests demonstration, polymkeric substance in nitrogen atmosphere, 5% weight loss temperature (T d5%) be 519 ℃, the remaining rates of 1000 ℃ up to 60%.The specific inductivity (30MHz) of film is 2.47.Be applicable to the packaged material of electric industry as insulating coating and electronic devices and components, and for microelectronics processing industry and the application of large electric manufacturing as dielectric materials or plain conductor outer cladding insulating material.
(3) the polymkeric substance cost that the present invention obtains is low, and synthetic method is simple, is applicable to scale operation.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.The experimental technique of unreceipted actual conditions in the following example, conventionally according to normal condition, or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise per-cent and umber calculate by weight.
The raw material 2 using in each embodiment, the bromo-Isosorbide-5-Nitrae-dual-trifluoromethyl benzene of 5-bis-obtains by ordinary method, as, can prepare by currently known methods (referring to Chem.Commun., 2005,372 – 374 and J.Am.Chem.Soc., 2011,133,17839 – 17847).
The preparation of embodiment 1 monomer
Figure BDA0000459903240000071
In the present embodiment, raw materials used 2,5-dibromo bis trifluoromethyl benzene series is by currently known methods preparation (referring to Chem.Commun., 2005,372 – 374 and J.Am.Chem.Soc., 2011,133,17839 – 17847).
Under argon shield, in 100 milliliters of there-necked flasks, add 8.65 grams of 1-naphthols, 7.438 grams 2, 5-dibromo dual-trifluoromethyl benzene and 2.8 grams of potassium hydroxide, inject successively 50 milliliters of DMSO (dimethyl sulfoxide (DMSO)) and 100 milliliters of toluene, stir and be heated to reaction at 150 ℃, after toluene band water is complete, at 150 ℃, react 8 hours again, after being cooled to room temperature, reaction mixture is poured into water, vigorous stirring was extracted with ethyl acetate after 10 minutes, organic phase is used anhydrous sodium sulfate drying 30 minutes after washing three times with saturated sodium-chloride water solution, remove by filter sodium sulfate, filtrate is removed ethyl acetate through decompression, obtain crude product.Crude product obtains 6.67 grams of white crystals through normal hexane column chromatography recrystallization, yield 67%, purity (HPLC) 99.56%.Spectrum Analysis result is as follows: 1h NMR, (400MHz, CDCl 3, ppm): 7.02 (d, 1H), 7.25 (s, 1H), 7.47 (t, 1H), 7.53～7.62 (m, 2H), 7.73 (d, 1H), 7.92 (dd, 1H), 8.15 (d, 1H); 19f NMR (376MHz, CDCl3, ppm) :-62.57 (s, 6F).
The preparation of embodiment 2 monomers
Experimental technique is substantially with embodiment 1, and difference is, replaces potassium hydroxide, product yield 62%, purity (HPLC) 99.33% with Anhydrous potassium carbonate.
The preparation of embodiment 3 monomers
Experimental technique is substantially with embodiment 1, and difference is, by Carbon Dioxide caesium replacement potassium hydroxide, product yield 65%, purity (HPLC) 99.17%.
The preparation of embodiment 4 polymkeric substance
Figure BDA0000459903240000081
Under argon shield, in 25 milliliters of reaction tubess, add 0.747 gram of monomer by embodiment 1 synthesized and 5 milliliters of tetrachloroethane; In 25 milliliters of reaction tubess of another, add 0.608 gram of FERRIC CHLORIDE ANHYDROUS and 2 milliliters of tetrachloroethane, bubbling deoxygenation is after 30 minutes respectively, the tetrachloroethane solution of monomer is injected in iron trichloride in the dry ice bath, be transferred at-5 ℃ and react 24 hours, after reaction finishes, reaction solution is poured in a large amount of methyl alcohol, and add a small amount of concentrated hydrochloric acid acidifying, stir and filter to obtain faint yellow solid after 15 minutes.So adopt methyl alcohol precipitating three times, the light yellow solid obtaining vacuum-drying 12 hours at 80 ℃, obtains 0.4 gram, polymkeric substance.GPC tests (tetrahydrofuran (THF) is eluent, polystyrene standard) and shows, polymkeric substance number-average molecular weight is 96300, and weight-average molecular weight is 264000, and dispersity is 2.74.Spectroscopic characterization result is, 1h NMR (400MHz, CDCl 3, δ in ppm): 7.10～7.20 (d, 1H), 7.41～7.63 (m, 5H), 8.28～8.37 (d, 1H). 19F?NMR(376MHz,CDCl 3,δin?ppm)-62.35(s,6F)。Results of elemental analyses shows, calculated value, C 28h 16f 6o 2: C, 67.47; H, 3.24; F, 22.87; Measured value: C, 67.65; H, 3.45; F, 22.86.
The preparation of embodiment 5 polymkeric substance
Experimental technique is substantially with embodiment 4, and difference is, described polymerization temperature is 0 ℃.0.6 gram of institute's polymer weight that obtains, number-average molecular weight is 49500, and weight-average molecular weight is 152800, and dispersity is 2.86.
The preparation of embodiment 6 polymkeric substance
Experimental technique is substantially with embodiment 4, and difference is, described polymerization temperature is-10 ℃.0.55 gram of institute's polymer weight that obtains, number-average molecular weight is 25800, and weight-average molecular weight is 55800, and dispersity is 2.16.
The preparation of embodiment 7 polymkeric substance
Experimental technique is substantially with embodiment 4, and difference is, described polymerization temperature is-15 ℃.0.7 gram of institute's polymer weight that obtains, number-average molecular weight is 25800, and weight-average molecular weight is 55800, and dispersity is 2.16.
The purifying of embodiment 8 polymkeric substance
Purification step is as follows:
Get 2 grams, above-described embodiment 4 polymkeric substance that obtains, be dissolved in 10 milliliters of toluene, obtained solution is injected to the glass column of 5 centimetres of 40 cm long diameters that is filled with 200 order neutral aluminas, with approximately 1000 milliliters of toluene drip washing, collect leacheate, be concentrated into approximately 10 milliliters of volumes, fall in a large amount of acetone, standing and incline and supernatant liquor, suction filtration is collected solid, vacuum-drying 12 hours at 200 ℃.Obtain white solid.ICP-MASS tests and shows, in polymkeric substance, iron level is lower than 1ppm.
The calorifics of embodiment 9 polymkeric substance and dielectric properties test
Get 0.5 gram and obtained, also with the polymkeric substance that the method for embodiment 8 is purified, be dissolved in 5 milliliters of toluene by embodiment 4, be spun to (resistivity 2 × 10 on heavy doping silicon chip -3Ω × cm), obtaining thickness is the polymeric film of 130 nanometers, then silicon chip is put into quartz tube furnace, under vacuum, 200 ℃ are heated 2 hours, fully except desolventizing.Then in nitrogen atmosphere, be chilled to after room temperature, the aluminium electrode that is 2.4mm in film surface evaporation diameter, and in the metallic aluminium of the back side of silicon chip evaporation 200 nano thickness, so obtain Standard Thin membrane capacitance.By the electric capacity of testing film electrical condenser, calculate specific inductivity and the dielectric loss factor of film.
The polymkeric substance that above-described embodiment 4 is obtained after dry 3 hours, is tested its thermostability by DSC and TGA at 200 ℃ of vacuum drying ovens.Carrier gas used is argon gas, and temperature rise rate is 10 ℃/point.
Concrete data are as shown in the table:
Figure BDA0000459903240000101
All documents of mentioning in the present invention are all quoted as a reference in this application, just as each piece of document, are quoted separately as a reference.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.

Claims (10)

1. one kind suc as formula the polymer monomer shown in I:
Figure FDA0000459903230000011
2. suc as formula the preparation method of the compound shown in I, it is characterized in that, comprise step:
In inert solvent, the bromo-Isosorbide-5-Nitrae-dual-trifluoromethyl benzene of 2,5-bis-is reacted with 1-naphthols, obtain formula I compound.
3. method as claimed in claim 2, is characterized in that, described method has the one or more features that are selected from lower group:
Described reaction is carried out under alkali exists, and preferably, described alkali is selected from lower group: potassium hydroxide, Anhydrous potassium carbonate, Carbon Dioxide caesium, or its combination; And/or
Described reaction is carried out in the solvent that is selected from lower group: N-Methyl pyrrolidone, DMSO, or its combination; And/or
Described reaction is carried out at 100～200 ℃; And/or
The described reaction times is 4～20 hours; And/or
The mol ratio of described 1-naphthols and 2,5-, bis-bromo-Isosorbide-5-Nitrae-dual-trifluoromethyl benzenes is 1:0.1～10.
4. a polymkeric substance, is characterized in that, described polymkeric substance is by polyreaction, to prepare suc as formula the polymer monomer shown in I with claimed in claim 1.
5. polymkeric substance as claimed in claim 4, is characterized in that, described polymkeric substance has suc as formula the structure shown in II:
Figure FDA0000459903230000013
Wherein, n=5～200.
6. the preparation method of formula II compound as claimed in claim 5, is characterized in that, comprises step:
In inert solvent, with the polymer monomer polymerization reaction take place shown in formula I, obtain formula II polymkeric substance.
7. method as claimed in claim 6, is characterized in that, described reaction is carried out under trivalent iron salt exists; Preferably, described trivalent iron salt is selected from lower group: iron(ic) chloride, iron bromide, ferric sulfate, iron nitrate, or its combination; Be more preferably iron(ic) chloride.
8. method as claimed in claim 6, is characterized in that, described method also has the one or more features that are selected from lower group:
Described inert solvent is organic solvent, is preferably selected from lower group: oil of mirbane, methylene dichloride, ethylene dichloride, tetrachloroethane, chlorobenzene, dichlorobenzene, or its combination;
Described polymeric reaction temperature is-50～30 ℃;
Described polymerization reaction time is 5～48 hours.
9. goods, is characterized in that, described goods comprise the polymkeric substance as described in claim 4 or 5, or described goods are to use the polymkeric substance as described in claim 4 or 5 to prepare.
10. goods as claimed in claim 9, is characterized in that, described goods are selected from lower group: the insulating material in advanced low-k materials, plain conductor outer cladding insulating material, cable, super large-scale integration.
CN201410028010.6A 2014-01-21 2014-01-21 Containing dual-trifluoromethyl benzene and the low dielectric constant polymer of binaphthyl structure unit Expired - Fee Related CN103755534B (en)

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