CN108503867A - A kind of porous low dielectric constant diacetylene thin polymer film and preparation method thereof - Google Patents
A kind of porous low dielectric constant diacetylene thin polymer film and preparation method thereof Download PDFInfo
- Publication number
- CN108503867A CN108503867A CN201810159975.7A CN201810159975A CN108503867A CN 108503867 A CN108503867 A CN 108503867A CN 201810159975 A CN201810159975 A CN 201810159975A CN 108503867 A CN108503867 A CN 108503867A
- Authority
- CN
- China
- Prior art keywords
- diacetylene
- polymer
- thin polymer
- dielectric constant
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 C/C1=C\C=C\C(\C(F)(F)F)=C\*=C1 Chemical compound C/C1=C\C=C\C(\C(F)(F)F)=C\*=C1 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F238/00—Copolymers of compounds having one or more carbon-to-carbon triple bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2349/00—Characterised by the use of homopolymers or copolymers of compounds having one or more carbon-to-carbon triple bonds; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention relates to ic manufacturing technology fields, and in particular to a kind of porous low dielectric constant diacetylene thin polymer film and preparation method thereof.The preparation method of the porous low dielectric constant diacetylene thin polymer film of the present invention, including step：Synthesize diacetylene polymer；Diacetylene polymer is placed in organic solvent and is dissolved, is cast in into film container, this is closed into film container, part organic solvent volatilization is waited for, until forming diacetylene thin polymer film；Diacetylene thin polymer film is cured, remaining organic solvent pore is evaporated, obtains porous low dielectric constant diacetylene thin polymer film.The basic material intrinsic dielectric constant is low, and processing performance is excellent, and film forming method is simple, pollution-free generation in forming process, and micropore is evenly distributed and aperture is more uniform, and products therefrom has ultralow dielectric, fine heat-resisting performance.
Description
Technical field
The present invention relates to ic manufacturing technology fields, and in particular to a kind of porous low dielectric constant diacetylene polymerization
Object film and preparation method thereof.
Background technology
With the development of science and technology, the performance of electronic chip rapidly improves, instrument, equipment size constantly reduce.By
Higher and higher in the integrated level of large scale integrated circuit, device feature size is gradually reduced, multilayer wiring and the logic interconnection number of plies
Increase, cause between conductor resistance and conducting wire and layer capacitance increases, RC retardation ratio rises, and which limit the transmission of device speed
Degree, and increase energy consumption, there is a series of problems, such as noise jamming.And it is exactly to reduce to be situated between one of to alleviate the important method of this problem
The dielectric constant of material.
Currently, it is a kind of effective method of reduction material dielectric constant to introduce microcellular structure into material, introduce micro-
Pore structure can increase the free volume of material so that the polar groups number in unit volume reduces, to reduce dielectric constant.
Studying more porous media material at present mainly has：Porous silicon-base material, porous polyimide material, porous fluoropolymer polymer
Material.For porous silicon-base material, nanometer is prepared using CTAB as template using sol-gal process in Wu Zhaofeng et al.
Nanoporous silica silicon thin film, dielectric constant can reach 2.5.But porous silicon-base material fragility is larger, in flexible electronics
Using being restricted.For porous polyimide material, with good mechanical property, heat resistance etc., but due to poly-
Acid imide material intrinsic dielectric constant (2.9-3.6) is higher, therefore passes through the obtained porous polyimide film dielectric of modification
Constant is restricted.14498900 A of patent CN prepare porous polyamides Asia using the technique of gas ions enhancing chemical vapor deposition
Amine film, dielectric constant is between 2.3-2.5.104910409 A of patent CN are prepared using the method for calcium carbonate template etching
Porous polyimide film, dielectric constant 2.60-3.15.For porous fluoropolymer polymer material, introducing fluorine element can be bright
The aobvious dielectric constant for reducing material, but fluorine material has the disadvantages that：1. releasing hydrogen fluoride gas in heating process, base is influenced
Material correlated performance；2. fluoropolymer causes it poor with the adhesive property of electronic device substrate due to its molecule inertia.3. containing
Fluorine material manufacture cost is higher.Therefore the development and application of fluorine-containing porous material is limited.104201149 A of patent CN are with C2F6Make
Fluorine-containing porous polyimide film, dielectric constant 2.37-2.75 are obtained using PEVCD techniques for Fluorine source.
The method and process of presently used most molding porous membrane is all relative complex, and manufacturing cost is higher, and certain works
The by-product that skill generates can cause environmental pollution, and the acid as used by removing pore-forming substance using template etching method is such as
Hydrochloric acid, sulfuric acid etc..Therefore, seek a kind of porous membrane basis material that intrinsic dielectric constant is sufficiently low, prepare resulting materials Jie
The sufficiently low porous membrane of electric constant and preparation process are simple, have important promotion to make the development of electronic information technology
With.
Invention content
The object of the present invention is to provide a kind of porous low dielectric constant diacetylene thin polymer film and preparation method thereof, with
Solve problems of the prior art.
The purpose of the present invention is what is be achieved through the following technical solutions：A kind of porous low dielectric constant diacetylene polymer
The preparation method of film, including step：Synthesize diacetylene polymer；Diacetylene polymer is placed in molten in organic solvent
Solution, is cast in into film container, closes this into film container, part organic solvent volatilization is waited for, until forming diacetylene polymer
Film；Diacetylene thin polymer film is cured, remaining organic solvent pore is evaporated, obtains porous low dielectric constant diacetylene
Thin polymer film.
Further, the diacetylene Polymer Formulation is：
Wherein：R1And R2It is non-polar group；
R4 organic matter expression formulas are：
- O- or-S-；
Wherein：R3 is：
R5 and R6 is also non-polar group.
Further, R1And R2For identical group, R5 and R6 are also identical group.
Further, the reaction monomers of the diacetylene polymer are：
R1 and R2 is non-polar group；
R3 is：
Further, R1And R2For identical group.
Further, monomer reaction polymerization ratio is m:N, wherein 0 ＜ m ＜ 1,0 ＜ n ＜ 1, the sum of m and n are 1, preferably
0.2 ＜ m ＜ 0.8,0.2 ＜ n ＜ 0.8, the sum of m and n are 1, more preferably 0.25 ＜ m ＜ 0.75,0.25 ＜ n ＜ 0.75, m and n
The sum of be 1.
Further, diacetylene polymer is dissolved using organic solvent, organic solvent is selected from dimethyl sulfoxide (DMSO), N, N- bis-
Methylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone, tetrahydrofuran, chloroform, ethyl acetate, dichloromethane, first
It is any in benzene.
Further, volatilize 2h-96h under room temperature, preferably 18h-72h, more preferably for 24 hours -48h.According to solvent
Boiling point is only stored at room temperature a period of time (2h), in favor of fully dissolving when using highly polar high boiling solvent.
Further, molding diacetylene thin polymer film is placed in vacuum drying chamber to dry, drying temperature 30-
70 DEG C, preferably 35-65 DEG C, more preferably 40-60 DEG C；Drying time is 6-72h, preferably 9h-60h, more preferably 12h-
48h。
Further, molding diacetylene thin polymer film is placed in air dry oven and is cured, solidification temperature
It is 110-250 DEG C, preferably 115-200 DEG C, more preferably 110-160 DEG C；Hardening time is 10-120min, preferably 20-
90min, more preferably 30-60min.
The porous low dielectric obtained by the preparation method of the porous low dielectric constant diacetylene thin polymer film is normal
Number diacetylene thin polymer film.
The present invention has the following advantages that compared with prior art：
1. the basic material intrinsic dielectric constant is low, processing performance is excellent, and film forming method simple (solidification and pore-forming
It is be carried out at the same time, simple for process), pollution-free generation in forming process, and micropore is evenly distributed and aperture is more uniform, products therefrom
With ultralow dielectric, fine heat-resisting performance, and since hole is mostly closed pore, so material water absorption rate is relatively low, simultaneously
The mechanical property of material meet demand.
2. the maximum temperature when thermal weight loss 5wt% of diacetylene thin polymer film is 375 DEG C, at room temperature storage modulus E '
4.32GPa is can reach, minimum water absorption rate is only 0.2%.
Specific implementation mode
Technical scheme of the present invention is clearly and completely described below in conjunction with embodiment, it is clear that described reality
It is a part of the embodiment of the present invention to apply example, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
The every other embodiment that art personnel are obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention selects dielectric constant relatively low first, processing performance, the diacetylene of heat resistance and good mechanical performance
Polymer is used as into film base material；Structure design is carried out secondly by diacetylene polymer, introduces large volume alkyl side chain, into
One step reduces dielectric material performance；It is finally heating and curing pore technique using polymer solution, using organic solvent as polymerizeing
Object solvent also serves as pore former, is formed in the cured micropore that is completed at the same time of thin polymer film, porous low dielectric diine third is prepared
Based polymer film.
The preparation method of the porous low dielectric constant diacetylene thin polymer film of the present invention, including step：
(1) synthesis of diacetylene polymer
With dipropargyl ether type monomer by Glaser-Hay oxidative coupling reactions according to reaction monomers copolymerization ratio m:N is aoxidized
Copolymerization obtains diacetylene polymer.
(2) thin polymer film is molded
Diacetylene polymer is dissolved in using ultrasonic oscillation in organic solvent, diacetylene polymer solution is poured
It notes in culture dish, microporous membrane is used in combination to seal, be subsequently placed in level table, volatilize naturally under room temperature, later diacetylene
Based polymer film is molded, and it is organic in thin polymer film to remove that the film after sizing is placed in vacuum drying chamber drying
Solvent.
(3) solidification of thin polymer film and pore-forming
Molding diacetylene thin polymer film is placed in air dry oven and is heating and curing, while vaporized polymer film
In remaining organic solvent pore, finally obtain the diacetylene thin polymer film of porous low dielectric constant.
It is sealed using microporous membrane in order to reduce organic solvent evaporation rate, manufactures vapor liquid equilibrium condition, can be promoted thin
Film uniformity and flatness.
Drying process of the film in vacuum drying chamber does not vapor away all solvents completely, and residual solvent is as subsequent
Pore former pore.
The diacetylene Polymer Formulation is：
R1And R2It is identical or different, and be non-polar group；
R4 organic matter expression formulas are：
- O- or-s-；
Wherein：R3 is：
R5 and R6 is identical or different, and is non-polar group.
The reaction monomers of the diacetylene polymer are：
R1And R2It is identical or different, and be non-polar group；
In the present invention, " non-polar group " refers to not having polar group.Particularly, non-polar group includes alkane
Base, naphthenic base, aryl, aralkyl or alkaryl.The alkyl can be with 1-10 carbon atom, preferably 2-8 carbon atom, especially
It is preferred that 3-8 carbon atom, can be it is straight chain or branch, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl,
Isobutyl group, sec-butyl, tertiary butyl, n-pentyl, isopentyl, tertiary pentyl, hexyl, heptyl, octyl, nonyl, decyl etc..The alkyl
It may include hetero atom, such as F.Including the example of heteroatomic alkyl includes but not limited to-CF3 etc..The naphthenic base is, for example,
Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl etc..The aryl can be C6-C30 aryl, preferably C6-C20
Aryl, more preferable C6-C14 aryl, such as phenyl, naphthalene, anthryl, phenanthryl, xenyl, terphenyl etc..The aralkyl can
For C7-C30 aralkyl, preferably C7-C20 aralkyl, more preferable C7-C15 aralkyl.The alkaryl can be C7-C30 alkane virtues
Base, preferably C7-C20 alkaryls, more preferable C7-C15 alkaryls.
When R1 and R2 is alkyl, aralkyl or alkaryl, the polymer with low-k can be obtained.Therefore, R1
It is preferably alkyl, aralkyl or alkaryl with R2.
R3 is：
Monomer reaction polymerization ratio is m:N, wherein 0 ＜ m ＜ 1,0 ＜ n ＜ 1, the sum of m and n are 1, preferably 0.2 ＜ m ＜
0.8,0.2 ＜ n ＜ 0.8, the sum of m and n are 1, and more preferably 0.25 ＜ m ＜ 0.75,0.25 ＜ n ＜ 0.75, the sum of m and n are 1.
Diacetylene polymer is dissolved using organic solvent, organic solvent is selected from dimethyl sulfoxide (DMSO), N, N- dimethyl formyls
Appoint in amine, n,N-dimethylacetamide, N-Methyl pyrrolidone, tetrahydrofuran, chloroform, ethyl acetate, dichloromethane, toluene
One.
Volatilize 2h-96h, preferably 18h-72h at ambient temperature before the diacetylene thin polymer film molding, more excellent
It is selected as -48h for 24 hours.According to solvent boiling point, when using highly polar high boiling solvent, it is only stored at room temperature a period of time (2h), with profit
In abundant dissolving.
Molding diacetylene thin polymer film is placed in drying in vacuum drying chamber, drying temperature is 30-70 DEG C, preferably
It is 35-65 DEG C, more preferably 40-60 DEG C；Drying time is 6-72h, preferably 9h-60h, more preferably 12h-48h.
Molding diacetylene thin polymer film is placed in air dry oven and is cured, solidification temperature 110-250
DEG C, preferably 115-200 DEG C, more preferably 110-160 DEG C；Hardening time is 10-120min, preferably 20-90min, more excellent
It is selected as 30-60min.
Embodiment 1
(1) synthesis of polymer P EA1-1
It is double with bis- (4- (2- the propargyl alcoholates)) benzene (DBDPE) of 1,1 '-(1,3- dimethylbutylene) and monomer dipropargyl
Phenol A ethers (DPEBA) are according to m:N=0.5:0.5, it is copolymerized to obtain diacetylene polymer by Glaser-Hay oxidative coupling reactions
PEA1-1, product characters are white fibrous solid.
(2) polymer P EA1-1 film formings
It takes 0.3g polymer Ps EA1-1 to be dissolved in 8ml chloroforms, 30min is dissolved using ultrasonic oscillation；Then will
Polymer solution is cast in the culture dish of a diameter of 5cm, and using microporous membrane seal, be placed on level table, in room
Volatilize 48h naturally under the conditions of temperature, and film finalizes the design almost；Film is taken out later, 12h is dried in vacuo at 40 DEG C further to remove
Excessive solvent in polymer P EA1-1 films.
(3) solidification of polymer P EA1-1 films and pore-forming
Molding polymer P EA1-1 films are placed in 120 DEG C of air dry ovens the 60min that is heating and curing, while being evaporated poly-
Close remaining organic solvent chloroform pore in object film；Finally obtain the porous polymer PEA1-1 that thickness is about 0.1mm
Film.
The polymer P EA1-1 films of embodiment 1 have done following performance test：
It is thin that polyalcohol stephanoporate in embodiment 1 is observed using Jeol Ltd. 7800F type scanning electron microscope
Film Cross Section Morphology, and measure pore size size.Micropore is spheroid shape, and major diameter is 4-12 μm, and minor axis is 2-6 μm.
Using Photoshop combination image pro plus photo handling softwares, analyzing processing obtains film sections Electronic Speculum
The holes pixel quantity n of photo Hole and picture whole pixel point quantity n are whole, and then calculate film porosity (%)=n
Hole/n is whole × and 100%.The porosity that polymer porous membrane is calculated is 24.1%.
It is thin to the polyalcohol stephanoporate in embodiment 1 using German NETZSCH companies 449Cjupiter types synchronous solving
Film carries out thermal stability research, and the mass loss temperature for measuring 5% is 331 DEG C.
Dynamic mechanical heat is carried out to thin polymer film using the DMA-1 types dynamic thermomechanical analysis apparatus of Mei Tele companies of Switzerland
Analysis, sample are long 2cm, and the elongate in shape of wide 1cm, temperature range is -300 DEG C of room temperature, heating rate 5k/min.According to obtaining
The storage modulus E ' for (25 DEG C) at room temperature that the Dynamic Viscoelastic linearity curve obtained obtains is 1.35GPa.
Using the Concopt40 model wideband dielectric impedance spectrometers of German Novocontrol companies to more in embodiment 1
Pore polymer film carries out dielectric constant test.The results show that in 100-106Within the scope of Hz, the dielectric constant of thin polymer film
Ranging from 1.16-1.24.Its dielectric constant is 1.16 at 1MHz, has excellent dielectric properties.
Porous low dielectric constant dipropargyl thin polymer film is soaked in 25 DEG C of deionized waters 7 days, polymer is measured
The water absorption rate of film, water absorption rate 0.5%.
Embodiment 2
(1) synthesis of polymer P EA3-1
It is double with bis- (4- (2- the propargyl alcoholates)) benzene (DBDPE) of 1,1 '-(1,3- dimethylbutylene) and monomer dipropargyl
Phenol A ethers (DPEBA) are according to m:N=0.75:0.25, it is copolymerized to obtain diacetylene polymerization by Glaser-Hay oxidative coupling reactions
Object PEA3-1, product characters are white fibrous solid.
(reaction equation such as embodiment 1)
(2) polymer P EA3-1 film formings
It takes 0.3g polymer Ps EA3-1 to be dissolved in 8ml tetrahydrofurans, 30min is dissolved using ultrasonic oscillation；Then will
Polymer solution is cast in the culture dish of a diameter of 5cm, and using microporous membrane seal, be placed on level table, in room
Volatilize 48h naturally under the conditions of temperature, and film finalizes the design almost；Film is taken out later, at 40 DEG C, vacuum drying is for 24 hours further to remove
Excessive solvent in polymer P EA3-1 films.
(3) solidification of polymer P EA3-1 films and pore-forming
Molding polymer P EA3-1 films are placed in 130 DEG C of air dry ovens the 60min that is heating and curing, while being evaporated poly-
Close remaining organic solvent tetrahydrofuran pore in object film；Finally obtain the porous polymer PEA3-1 that thickness is about 0.1mm
Film.
Mode same as Example 1 has carried out correlated performance test to the thin polymer film that embodiment 2 obtains：
Its micropore is spheroid shape, 1.0-3.0 μm of major diameter, 0.5-1.0 μm of minor axis, porosity 6.2%, 5% quality damage
It is 326 DEG C to lose temperature, and it is 3.25GPa that storage modulus, which is E ', at room temperature, in 100-106Within the scope of Hz, the dielectric of thin polymer film
Constant range is 2.13-2.16, its dielectric constant is that 7 days water absorption rates are 0.3% at 2.13,25 DEG C at 1MHz.
Embodiment 3
(1) synthesis of polymer P EA1-1
With monomer dipropargyl Bisphenol A Ether (DPEBA) and 1, bis- (4- (the 2- propine oxygen of 1 '-(1,3- dimethylbutylene)
Base)) benzene (DBDPE) is according to m:N=0.5:0.5, it is copolymerized to obtain diacetylene polymerization by Glaser-Hay oxidative coupling reactions
Object PEA1-1, product characters are white fibrous solid.
(reaction equation such as embodiment 1)
(2) polymer P EA1-1 film formings
It takes 0.3g polymer Ps EA1-1 to be dissolved in 8ml tetrahydrofurans, 30min is dissolved using ultrasonic oscillation；Then will
Polymer solution is cast in the culture dish of a diameter of 5cm, and using microporous membrane seal, be placed on level table, in room
Volatilize 48h naturally under the conditions of temperature, and film finalizes the design almost；Film is taken out later, for 24 hours with further in 40 DEG C of vacuum drying chambers
Remove solvent excessive in polymer P EA1-1 films.
(3) solidification of polymer P EA1-1 films and pore-forming
Molding polymer P EA1-1 films are placed in 140 DEG C of air dry ovens the 30min that is heating and curing, while being evaporated poly-
Close remaining organic solvent tetrahydrofuran pore in object film；Finally obtain the porous polymer PEA1-1 that thickness is about 0.1mm
Film.
Mode same as Example 1 has carried out correlated performance test to the thin polymer film that embodiment 3 obtains：
Its micropore is spheroid shape, 3.0-8.0 μm of major diameter, 1.5-4.0 μm of minor axis, porosity 13.8%, 5% quality damage
It is 331 DEG C to lose temperature, and it is 2.44GPa that storage modulus, which is E ', at room temperature, in 100-106Within the scope of Hz, the dielectric of thin polymer film
Constant range is 1.56-1.61, its dielectric constant is that 7 days water absorption rates are 0.4% at 1.56,25 DEG C at 1MHz.
Embodiment 4
(1) synthesis of polymer P EA1-1
With monomer dipropargyl Bisphenol A Ether (DPEBA) and 1, bis- (4- (the 2- propine oxygen of 1 '-(1,3- dimethylbutylene)
Base)) benzene (DBDPE) is according to m:N=0.5:0.5, it is copolymerized to obtain diacetylene polymerization by Glaser-Hay oxidative coupling reactions
Object PEA1-1, product characters are white fibrous solid.
(reaction equation such as embodiment 1)
(2) polymer P EA1-1 film formings
It takes 0.3g polymer Ps EA1-1 to be dissolved in 8ml chloroforms, 30min is dissolved using ultrasonic oscillation；Then will
Polymer solution is cast in the culture dish of a diameter of 5cm, and using microporous membrane seal, be placed on level table, in room
Volatilize 48h naturally under the conditions of temperature, and film finalizes the design almost；Film is taken out later, 18h is dried in vacuo at 50 DEG C further to remove
Excessive solvent in polymer P EA1-1 films.
(3) solidification of polymer P EA1-1 films and pore-forming
Molding polymer P EA1-1 films are placed in 120 DEG C of air dry ovens the 50min that is heating and curing, while being evaporated poly-
Close remaining organic solvent chloroform pore in object film；Finally obtain the porous polymer PEA1-1 that thickness is about 0.1mm
Film.
Mode same as Example 1 has carried out correlated performance test to the thin polymer film that embodiment 4 obtains：
Its micropore is spheroid shape, 4.0-10.0 μm of major diameter, 1.5-4.5 μm of minor axis, porosity 15.8%, 5% quality
It is 331 DEG C to lose temperature, and it is 1.94GPa that storage modulus, which is E ', at room temperature, in 100-106Within the scope of Hz, Jie of thin polymer film
Electric constant ranging from 1.49-1.53, its dielectric constant is that 7 days water absorption rates are 0.5% at 1.49,25 DEG C at 1MHz.
Embodiment 5
(1) synthesis of polymer P EA1-3
It is double with bis- (4- (2- the propargyl alcoholates)) benzene (DBDPE) of 1,1 '-(1,3- dimethylbutylene) and monomer dipropargyl
Phenol A ethers (DPEBA) are according to m:N=0.25:0.75, it is copolymerized to obtain diacetylene polymerization by Glaser-Hay oxidative coupling reactions
Object PEA1-3, product characters are white fibrous solid.
(reaction equation such as embodiment 1)
(2) polymer P EA1-3 film formings
It takes 0.3g polymer Ps EA1-3 to be dissolved in 8ml tetrahydrofurans, 30min is dissolved using ultrasonic oscillation；Then will
Polymer solution is cast in the culture dish of a diameter of 5cm, and using microporous membrane seal, be placed on level table, in room
Volatilize 48h naturally under the conditions of temperature, and film finalizes the design almost；Film is taken out later, 18h is dried in vacuo at 40 DEG C further to remove
Excessive solvent in polymer P EA1-3 films.
(3) solidification of polymer P EA1-3 films and pore-forming
Molding polymer P EA1-3 films are placed in 150 DEG C of air dry ovens the 30min that is heating and curing, while being evaporated poly-
Close remaining organic solvent tetrahydrofuran pore in object film；Finally obtain the porous polymer PEA1-3 that thickness is about 0.1mm
Film.
Mode same as Example 1 has carried out correlated performance test to the thin polymer film that embodiment 5 obtains：
Its micropore is spheroid shape, major diameter：2.0-7.0 μm, 1.0-3.0 μm of minor axis, porosity 11.7%, 5% quality
It is 341 DEG C to lose temperature, and storage modulus is E '=2.23GPa at room temperature, in 100-106Within the scope of Hz, Jie of thin polymer film
Electric constant ranging from 1.98-2.05., its dielectric constant is that 7 days water absorption rates are 0.3% at 1.98,25 DEG C at 1MHz.
Embodiment 6
(1) synthesis of polymer P EAF1-1
It is double with bis- (4- (2- the propargyl alcoholates)) benzene (DBDPE) of monomer 1,1 '-(1,3- dimethylbutylene) and dipropargyl
Phenol AF ethers (DPEBAF) and according to copolymerization ratio m:N=0.5:0.5, it is copolymerized to obtain diethyl by Glaser-Hay oxidative coupling reactions
Alkynyl polymer P EAF1-1, product characters are white fibrous solid.
(2) polymer P EAF1-1 film formings
It takes 0.3g polymer Ps EAF1-1 to be dissolved in 8ml chloroforms, 30min is dissolved using ultrasonic oscillation；Then will
Polymer solution is cast in the culture dish of a diameter of 5cm, and using microporous membrane seal, be placed on level table, in room
Volatilize 48h naturally under the conditions of temperature, and film finalizes the design almost；Film is taken out later, 18h is dried in vacuo at 40 DEG C further to remove
Excessive solvent in polymer P EAF1-1 films.
(3) solidification of polymer P EAF1-1 films and pore-forming
Molding polymer P EAF1-1 films are placed in 150 DEG C of air dry ovens the 30min that is heating and curing, are evaporated simultaneously
Remaining organic solvent chloroform pore in thin polymer film；Finally obtain the porous polymer that thickness is about 0.1mm
PEAF1-1 films.
Mode same as Example 1 has carried out correlated performance test to the thin polymer film that embodiment 6 obtains：
Its micropore is spheroid shape, 2.5-6.5 μm of major diameter, 2.0-4.0 μm of minor axis, porosity 9.1%, 5% quality damage
It is 350 DEG C to lose temperature, and it is 2.61GPa that storage modulus, which is E ', at room temperature, in 100-106Within the scope of Hz, the dielectric of thin polymer film
Constant range is 1.35-1.38, its dielectric constant is that 7 days water absorption rates are 0.3% at 1.35,25 DEG C at 1MHz.
Embodiment 7
(1) synthesis of polymer P EP3-1
With bis- (4- (2- the propargyl alcoholates)) benzene (DBDPE) of 1,1 '-(1,3- dimethylbutylene) and monomer 4- phenyl -2,6-
Two (4- propargyls-oxygroup-phenyl) pyridines (PPHPP) are according to m:N=0.75:0.25, it is anti-by Glaser-Hay oxidative couplings
It should be copolymerized to obtain diacetylene polymer P EP3-1, product characters are white fibrous solid.
(2) polymer P EP3-1 film formings
It takes 0.3g polymer Ps EP1-1 to be dissolved in 8ml tetrahydrofurans, 30min is dissolved using ultrasonic oscillation；Then will
Polymer solution is cast in the culture dish of a diameter of 5cm, and using microporous membrane seal, be placed on level table, in room
Volatilize 48h naturally under the conditions of temperature, and film finalizes the design almost；Film is taken out later, 18h is with further in 40 DEG C of vacuum drying chambers
Remove solvent excessive in polymer P EP3-1 films.
(3) solidification of polymer P EP3-1 films and pore-forming
Molding polymer P EP3-1 films are placed in 150 DEG C of air dry ovens the 30min that is heating and curing, while being evaporated poly-
Close remaining organic solvent tetrahydrofuran pore in object film；Finally obtain the porous polymer PEP3-1 that thickness is about 0.1mm
Film.
Mode same as Example 1 has carried out correlated performance test to the thin polymer film that embodiment 7 obtains：
Its micropore is spheroid shape, major diameter：1.5-5.0 μm, 0.5-1.5 μm of minor axis, porosity 8.1%, 5% quality damage
It is 360 DEG C to lose temperature, and storage modulus is E '=4.32GPa at room temperature, in 100-106Within the scope of Hz, the dielectric of thin polymer film
Constant range is 1.89-1.93., its dielectric constant is that 7 days water absorption rates are 0.4% at 1.89,25 DEG C at 1MHz.
Embodiment 8
(1) synthesis of polymer P EP3-1
With bis- (4- (2- the propargyl alcoholates)) benzene (DBDPE) of 1,1 '-(1,3- dimethylbutylene) and monomer 4- phenyl -2,6-
Two (4- propargyls-oxygroup-phenyl) pyridines (PPHPP) are according to m:N=0.75:0.25, it is anti-by Glaser-Hay oxidative couplings
It should be copolymerized to obtain diacetylene polymer P EP3-1, product characters are white fibrous solid.
(reaction equation such as embodiment 8)
(2) polymer P EP3-1 film formings
It takes 0.3g polymer Ps EP1-1 to be dissolved in 5ml n,N-Dimethylformamide, is dissolved using ultrasonic oscillation
30min；Then polymer solution is cast in the culture dish of a diameter of 5cm, and using microporous membrane seal, be placed on water
Flat surface stands 2h at ambient temperature, dries 36h in 50 DEG C of vacuum drying chambers later to remove polymer P EP3-1 films
In excessive solvent.
(3) solidification of polymer P EP3-1 films and pore-forming
Molding polymer P EP3-1 films are placed in 160 DEG C of air dry ovens the 60min that is heating and curing, while being evaporated poly-
Close remaining organic solvent n,N-Dimethylformamide pore in object film；Finally obtain the porous polymeric that thickness is about 0.1mm
Object PEP3-1 films.
Mode same as Example 1 has carried out correlated performance test to the thin polymer film that embodiment 8 obtains：
Its micropore is spheroid shape, major diameter：1.5-3.0 μm, 1.0-1.5 μm of minor axis, porosity 12.1%, 5% quality
It is 360 DEG C to lose temperature, and storage modulus is E '=4.12GPa at room temperature, in 100-106Within the scope of Hz, Jie of thin polymer film
Electric constant ranging from 1.84-1.90., its dielectric constant is that 7 days water absorption rates are 0.6% at 1.84,25 DEG C at 1MHz.
Embodiment 9
(1) synthesis of polymer P EF3-1
With bis- (4- (2- the propargyl alcoholates)) benzene (DBDPE) of monomer 1,1 '-(1,3- dimethylbutylene) and 4- (4- fluoroforms
Base) (4- propargyls-oxygroup-phenyl) pyridine (PFPHPP) of phenyl -2,6- bis- and according to copolymerization ratio m:N=0.75:0.25, pass through
Glaser-Hay oxidative coupling reactions are copolymerized to obtain diacetylene polymer P EF3-1, and product characters are white fibrous solid.
(2) polymer P EF3-1 film formings
It takes 0.3g polymer Ps EF3-1 to be dissolved in 4ml tetrahydrofurans, 30min is dissolved using ultrasonic oscillation；Then will
Polymer solution is cast in the culture dish of a diameter of 5cm, and using microporous membrane seal, be placed on level table, in room
Volatilize 48h naturally under the conditions of temperature, and film finalizes the design almost；Film is taken out later, at 40 DEG C, vacuum drying is for 24 hours further to remove
Excessive solvent in polymer P EF3-1 films.
(3) solidification of polymer P EF3-1 films and pore-forming
Molding polymer P EF3-1 films are placed in 150 DEG C of air dry ovens the 50min that is heating and curing, while being evaporated poly-
Close remaining organic solvent tetrahydrofuran pore in object film；Finally obtain the porous polymer PTF3-1 that thickness is about 0.1mm
Film.
Mode same as Example 1 has carried out correlated performance test to the thin polymer film that embodiment 9 obtains：
Its micropore is spheroid shape, 2.5-4.5 μm of major diameter, 1.5-3.0 μm of minor axis, porosity 9.1%, 5% quality damage
It is 375 DEG C to lose temperature, and it is 3.59GPa that storage modulus, which is E ', at room temperature, in 100-106Within the scope of Hz, the dielectric of thin polymer film
Constant range is 1.54-1.57, its dielectric constant is that 7 days water absorption rates are 0.5% at 1.54,25 DEG C at 1MHz.
Embodiment 10
(1) synthesis of polymer P ET1-1
With bis- (4- (2- the propargyl alcoholates)) benzene (DBDPE) and 4 of monomer 1,1 '-(1,3- dimethylbutylene), 4 '-bis- (alkynes
Propyl-oxygroup) diphenyl sulfide (PTBP) and according to copolymerization ratio m:N=0.5:0.5, it is total by Glaser-Hay oxidative coupling reactions
Poly- to obtain diacetylene polymer P ET1-1, product characters are white fibrous solid.
(2) polymer P ET1-1 film formings
It takes 0.3g polymer Ps ET1-1 to be dissolved in 8ml tetrahydrofurans, 30min is dissolved using ultrasonic oscillation；Then will
Polymer solution is cast in the culture dish of a diameter of 5cm, and using microporous membrane seal, be placed on level table, in room
Volatilize 48h naturally under the conditions of temperature, and film finalizes the design almost；Film is taken out later, 18h is dried in vacuo at 40 DEG C further to remove
Excessive solvent in polymer P ET1-1 films.
(3) solidification of polymer P ET1-1 films and pore-forming
Molding polymer P ET1-1 films are placed in 140 DEG C of air dry ovens the 40min that is heating and curing, while being evaporated poly-
Close remaining organic solvent tetrahydrofuran pore in object film；Finally obtain the porous polymer PTE1-1 that thickness is about 0.1mm
Film.
Mode same as Example 1 has carried out correlated performance test to the thin polymer film that embodiment 10 obtains：
Its micropore is spheroid shape, 3.0-5.5 μm of major diameter, 2.0-3.5 μm of minor axis, porosity 11.3%, 5% quality damage
It is 367 DEG C to lose temperature, and it is 3.76GPa that storage modulus, which is E ', at room temperature, in 100-106Within the scope of Hz, the dielectric of thin polymer film
Constant range is 1.72-1.77, its dielectric constant is that 7 days water absorption rates are 0.4% at 1.72,25 DEG C at 1MHz.
Embodiment 11
(1) synthesis of polymer P EO1-1
With bis- (4- (2- the propargyl alcoholates)) benzene (DBDPE) and 4 of monomer 1,1 '-(1,3- dimethylbutylene), 4 '-bis- (alkynes
Propyl-oxygroup) diphenyl ether (P-ODP) and according to copolymerization ratio m:N=0.5:0.5, it is total by Glaser-Hay oxidative coupling reactions
Poly- to obtain diacetylene polymer P EO1-1, product characters are white fibrous solid.
(2) polymer P EO1-1 film formings
0.3g polymer Ps EO1-1 is taken to be dissolved in 8ml tetrahydrofurans, using ultrasonic oscillation dissolving 30mi n；Then will
Polymer solution is cast in the culture dish of a diameter of 5cm, and using microporous membrane seal, be placed on level table, in room
Volatilize 48h naturally under the conditions of temperature, and film finalizes the design almost；Film is taken out later, 18h is dried in vacuo at 40 DEG C further to remove
Excessive solvent in polymer P ET1-1 films.
(3) solidification of polymer P EO1-1 films and pore-forming
Molding polymer P EO1-1 films are placed in 150 DEG C of air dry ovens the 40min that is heating and curing, while being evaporated poly-
Close remaining organic solvent tetrahydrofuran pore in object film；Finally obtain the porous polymer PEO1-1 that thickness is about 0.1mm
Film.
Mode same as Example 1 has carried out correlated performance test to the thin polymer film that embodiment 11 obtains：
Its micropore is spheroid shape, 3.0-5.0 μm of major diameter, 1.5-3.5 μm of minor axis, porosity 10.9%, 5% quality damage
It is 373 DEG C to lose temperature, and it is 3.90GPa that storage modulus, which is E ', at room temperature, in 100-106Within the scope of Hz, the dielectric of thin polymer film
Constant range is 1.88-1.92, its dielectric constant is that 7 days water absorption rates are 0.2% at 1.88,25 DEG C at 1MHz.
Embodiment 12
(1) synthesis of polymer P EO1-1
With bis- (4- (2- the propargyl alcoholates)) benzene (DBDPE) and 4 of monomer 1,1 '-(1,3- dimethylbutylene), 4 '-bis- (alkynes
Propyl-oxygroup) diphenyl ether (P-ODP) and according to copolymerization ratio m:N=0.5:0.5, it is total by Glaser-Hay oxidative coupling reactions
Poly- to obtain diacetylene polymer P EO1-1, product characters are white fibrous solid.
(reaction equation such as embodiment 11)
(2) polymer P EO1-1 film formings
It takes 0.3g polymer Ps EO1-1 to be dissolved in 5ml n,N-dimethylacetamide, is dissolved using ultrasonic oscillation
30min；Then polymer solution is cast in the culture dish of a diameter of 5cm, and using microporous membrane seal, be placed on water
Flat surface stands 2h at ambient temperature, dries 36h in 50 DEG C of vacuum drying chambers later to remove polymer P EO1-1 films
In excessive solvent.
(3) solidification of polymer P EO1-1 films and pore-forming
Molding polymer P EO1-1 films are placed in 160 DEG C of air dry ovens the 60min that is heating and curing, while being evaporated poly-
Close remaining organic solvent n,N-dimethylacetamide pore in object film；Finally obtain the porous polymeric that thickness is about 0.1mm
Object PEO1-1 films.
Mode same as Example 1 has carried out correlated performance test to the thin polymer film that embodiment 12 obtains：
Its micropore is spheroid shape, 2.0-3.0 μm of major diameter, 1.0-2.0 μm of minor axis, porosity 13.1%, 5% quality damage
It is 373 DEG C to lose temperature, and it is 3.64GPa that storage modulus, which is E ', at room temperature, in 100-106Within the scope of Hz, the dielectric of thin polymer film
Constant range is 1.84-1.87, its dielectric constant is that 7 days water absorption rates are 0.4% at 1.84,25 DEG C at 1MHz.
Embodiment 13
(1) synthesis of polymer P EA1-1
With monomer dipropargyl Bisphenol A Ether (DPEBA) and 1, bis- (4- (the 2- propine oxygen of 1 '-(1,3- dimethylbutylene)
Base)) benzene (DBDPE) is according to m:N=0.5:0.5, it is copolymerized to obtain diacetylene polymerization by Glaser-Hay oxidative coupling reactions
Object PEA1-1, product characters are white fibrous solid.
(reaction equation such as embodiment 1)
(2) polymer P EA1-1 film formings
It takes 0.3g polymer Ps EA1-1 to be dissolved in 8ml chloroforms, 30min is dissolved using ultrasonic oscillation；Then will
Polymer solution is cast in the culture dish of a diameter of 5cm, and using microporous membrane seal, be placed on level table, in room
Volatilize 12h naturally under the conditions of temperature, and film finalizes the design almost；Film is taken out later, 72h is with further in 30 DEG C of vacuum drying chambers
Remove solvent excessive in polymer P EA1-1 films.
(3) solidification of polymer P EA1-1 films and pore-forming
Molding polymer P EA1-1 films are placed in 250 DEG C of air dry ovens the 10min that is heating and curing, while being evaporated poly-
Close remaining organic solvent chloroform pore in object film；Finally obtain the porous polymer PEA1-1 that thickness is about 0.1mm
Film.
Mode same as Example 1 has carried out correlated performance test to the thin polymer film that embodiment 3 obtains：
Its micropore is spheroid shape, 4.5-12.0 μm of major diameter, 2.5-6.5 μm of minor axis, porosity 35.3%, 5% quality
It is 331 DEG C to lose temperature, and it is 0.98GPa that storage modulus, which is E ', at room temperature, in 100-106Within the scope of Hz, Jie of thin polymer film
Electric constant ranging from 1.11-1.21, its dielectric constant is that 7 days water absorption rates are 1.0% at 1.11,25 DEG C at 1MHz.
Embodiment 14
(1) synthesis of polymer P EA1-1
With monomer dipropargyl Bisphenol A Ether (DPEBA) and 1, bis- (4- (the 2- propine oxygen of 1 '-(1,3- dimethylbutylene)
Base)) benzene (DBDPE) is according to m:N=0.5:0.5, it is copolymerized to obtain diacetylene polymerization by Glaser-Hay oxidative coupling reactions
Object PEA1-1, product characters are white fibrous solid.
(reaction equation such as embodiment 1)
(2) polymer P EA1-1 film formings
It takes 0.3g polymer Ps EA1-1 to be dissolved in 8ml tetrahydrofurans, 30min is dissolved using ultrasonic oscillation；Then will
Polymer solution is cast in the culture dish of a diameter of 5cm, and using microporous membrane seal, be placed on level table, in room
Volatilize 96h naturally under the conditions of temperature, and film finalizes the design almost；Film is taken out later, 6h is with further in 70 DEG C of vacuum drying chambers
Remove solvent excessive in polymer P EA1-1 films.
(3) solidification of polymer P EA1-1 films and pore-forming
Molding polymer P EA1-1 films are placed in 110 DEG C of air dry ovens the 90min that is heating and curing, while being evaporated poly-
Close remaining organic solvent tetrahydrofuran pore in object film；Finally obtain the porous polymer PEA1-1 that thickness is about 0.1mm
Film.
Mode same as Example 1 has carried out correlated performance test to the thin polymer film that embodiment 3 obtains：
Its micropore is spheroid shape, 3.5-8.0 μm of major diameter, 1.5-4.0 μm of minor axis, porosity 7.3%, 5% quality damage
It is 331 DEG C to lose temperature, and it is 2.58GPa that storage modulus, which is E ', at room temperature, in 100-106Within the scope of Hz, the dielectric of thin polymer film
Constant range is 2.01-2.06, its dielectric constant is that 7 days water absorption rates are 0.5% at 2.01,25 DEG C at 1MHz.
Comparative example 1
(1) synthesis of polymer P EA1-1
With monomer dipropargyl Bisphenol A Ether (DPEBA) and 1, bis- (4- (the 2- propine oxygen of 1 '-(1,3- dimethylbutylene)
Base)) benzene (DBDPE) is according to m:N=0.5:0.5, it is copolymerized to obtain diacetylene polymerization by Glaser-Hay oxidative coupling reactions
Object PEA1-1, product characters are white fibrous solid.
(reaction equation such as embodiment 1)
(2) polymer P EA1-1 film formings
It takes 0.3g polymer Ps EA1-1 to be dissolved in 8ml tetrahydrofurans, 30min is dissolved using ultrasonic oscillation；Then will
Polymer solution is cast in the culture dish of a diameter of 5cm, and using microporous membrane seal, be placed on level table, in room
Volatilize 48h naturally under the conditions of temperature, and film finalizes the design almost；Film is taken out later, 7d is with further in 40 DEG C of vacuum drying chambers
Remove the solvent in polymer P EA1-1 films.
(3) solidification of polymer P EA1-1 films and pore-forming
Molding polymer P EA1-1 films are placed in 140 DEG C of air dry ovens the 30min that is heating and curing, while being evaporated poly-
Close remaining organic solvent tetrahydrofuran pore in object film；Finally obtain the porous polymer PEA1-1 that thickness is about 0.1mm
Film.
Mode same as Example 1 has carried out correlated performance test to the thin polymer film that embodiment 3 obtains：
Institute is dense non-porous film at film, and 5% mass loss temperature is 331 DEG C, and storage modulus is that E ' is at room temperature
4.61GPa, in 100-106Within the scope of Hz, the dielectric constant range of thin polymer film is 2.45-2.51, its dielectric at 1MHz
Constant is 2.45-2.51, and 7 days water absorption rates are 0.1% at 25 DEG C.
Comparative example 2
(1) synthesis of polymer P EA1-1
With monomer dipropargyl Bisphenol A Ether (DPEBA) and 1, bis- (4- (the 2- propine oxygen of 1 '-(1,3- dimethylbutylene)
Base)) benzene (DBDPE) is according to m:N=0.5:0.5, it is copolymerized to obtain diacetylene polymerization by Glaser-Hay oxidative coupling reactions
Object PEA1-1, product characters are white fibrous solid.
(reaction equation such as embodiment 1)
(2) polymer P EA1-1 film formings
It takes 0.3g polymer Ps EA1-1 to be dissolved in 12ml tetrahydrofurans, 30min is dissolved using ultrasonic oscillation；Then will
Polymer solution is cast in the culture dish of a diameter of 5cm, and (no film seal) is placed in level table, natural at ambient temperature
Volatilize 48h, and film finalizes the design almost；Film is taken out later, 6h is further to remove polymer in 40 DEG C of vacuum drying chambers
Solvent in PEA1-1 films.
(3) solidification of polymer P EA1-1 films and pore-forming
Molding polymer P EA1-1 films are placed in 140 DEG C of air dry ovens the 30min that is heating and curing, while being evaporated poly-
Close remaining organic solvent tetrahydrofuran pore in object film；Finally obtain the porous polymer PEA1-1 that thickness is about 0.1mm
Film.
Mode same as Example 1 has carried out correlated performance test to the thin polymer film that embodiment 3 obtains：
Institute is open-pored porous film at film, and film runs through trepanning in the presence of naked eyes are visible, and 5% mass loss temperature is
331 DEG C, it is 0.70GPa that storage modulus, which is E ', at room temperature, and since film runs through trepanning, dielectric constant can not measure.7 days at 25 DEG C
Water absorption rate is 8.2%.
The performance test results of 1 embodiment 1-14 of table
From the foregoing, it will be observed that the diacetylene thin polymer film of the porous low dielectric constant of the present invention has ultralow dielectric normal
Number, can be down to 1.11；With higher heat resisting temperature, demonomerization is copolymerized outside when monomeric species, the related work in embodiment
Skill parameter influences the heat resistance of material little.The storage modulus of porous polymer film can reach 4.32GPa.It is another
Aspect, different technological parameters cause porous polymer film porosity and pore size difference, aperture major diameter exist
Between 1.0-12.0 μm, minor axis is between 0.5-6.0 μm, and porosity is between 6.2%-35.3%.Micropore is distributed in the film
Uniformly, and it is hole-closing structure, therefore the water absorption rate of thin polymer film is influenced less, water absorption rate is relatively low, in 0.2%-
Between 1.0%.Therefore, porous diacetylene thin polymer film of the invention has potential application in integrated circuit fields
And good application prospect.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of porous low dielectric constant diacetylene thin polymer film, which is characterized in that including step：
Synthesize diacetylene polymer；
Diacetylene polymer is placed in organic solvent and is dissolved, is cast in into film container, this is closed into film container, waits for part
Organic solvent volatilizees, until forming diacetylene thin polymer film；
Diacetylene thin polymer film is cured, remaining organic solvent pore is evaporated, obtains porous low dielectric constant diacetylene
Thin polymer film.
2. the preparation method of porous low dielectric constant diacetylene thin polymer film according to claim 1, feature exist
In the diacetylene Polymer Formulation is：
Wherein：R1And R2It is non-polar group；
R4 organic matter expression formulas are：
- O- or-S-；
Wherein：R3 is：
R5 and R6 is also non-polar group.
3. the preparation method of porous low dielectric constant diacetylene thin polymer film according to claim 2, feature exist
In R1And R2For identical group, R5 and R6 are also identical group.
4. the preparation method of porous low dielectric constant diacetylene thin polymer film according to claim 2, feature exist
In the reaction monomers of the diacetylene polymer are：
R1 and R2 is non-polar group；
R3 is：
5. the preparation method of porous low dielectric constant diacetylene thin polymer film according to claim 4, feature exist
In monomer reaction polymerization ratio is m:N, wherein 0 ＜ m ＜ 1,0 ＜ n ＜ 1, the sum of m and n are 1.
6. the preparation method of porous low dielectric constant diacetylene thin polymer film according to claim 1, feature exist
In organic solvent is selected from dimethyl sulfoxide (DMSO), n,N-Dimethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone, four
It is any in hydrogen furans, chloroform, ethyl acetate, dichloromethane, toluene.
7. the preparation method of porous low dielectric constant diacetylene thin polymer film according to claim 1, feature exist
In volatilize 2-96h under room temperature.
8. the preparation method of porous low dielectric constant diacetylene thin polymer film according to claim 1, feature exist
In, molding diacetylene thin polymer film is placed in drying in the drying box that vacuum degree is -0.08- (- 0.1) MPa, it is dry warm
Degree is 30-70 DEG C, drying time 6h-72h.
9. the preparation method of porous low dielectric constant diacetylene thin polymer film according to claim 1, feature exist
In, molding diacetylene thin polymer film is placed in air dry oven and is cured, solidification temperature is 110-250 DEG C, Gu
The change time is 10-90min.
10. passing through the preparation method of claim 1-9 any one of them porous low dielectric constant diacetylene thin polymer films
The porous low dielectric constant diacetylene thin polymer film of acquisition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810159975.7A CN108503867B (en) | 2018-02-26 | 2018-02-26 | Porous low-dielectric-constant diacetylene polymer film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810159975.7A CN108503867B (en) | 2018-02-26 | 2018-02-26 | Porous low-dielectric-constant diacetylene polymer film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108503867A true CN108503867A (en) | 2018-09-07 |
| CN108503867B CN108503867B (en) | 2020-11-06 |
Family
ID=63375662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810159975.7A Active CN108503867B (en) | 2018-02-26 | 2018-02-26 | Porous low-dielectric-constant diacetylene polymer film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108503867B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120315481A1 (en) * | 2011-06-07 | 2012-12-13 | Korea University Research And Business Foundation | Porous diacetylene particles, synthesis method thereof |
| CN106496529A (en) * | 2016-11-17 | 2017-03-15 | 北京航空航天大学 | A kind of low-k diacetylene polymer, Its Preparation Method And Use |
-
2018
- 2018-02-26 CN CN201810159975.7A patent/CN108503867B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120315481A1 (en) * | 2011-06-07 | 2012-12-13 | Korea University Research And Business Foundation | Porous diacetylene particles, synthesis method thereof |
| CN106496529A (en) * | 2016-11-17 | 2017-03-15 | 北京航空航天大学 | A kind of low-k diacetylene polymer, Its Preparation Method And Use |
Non-Patent Citations (1)
| Title |
|---|
| HINKO CACKOVIC,: "MATERIAL TRANSPORT AND ORGANIZING PHENOMENA OF LANGMUIR-BLODGETT MEMBRANES FROM POLYMERIZABLE BUILT UP DIACETYLENE AMPHIPHILES ON HYDROPHOBIC SUPPORTS", 《JOURNAL OF MEMBRANE SCIENCE》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108503867B (en) | 2020-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110105570B (en) | Polyimide material with high heat resistance and low thermal expansion coefficient and preparation method thereof | |
| JP5805826B2 (en) | Method for producing polyamic acid, polyimide, and graphite sheet | |
| JP2007111645A5 (en) | ||
| CN109293957B (en) | COFs film material with ultra-low dielectric constant | |
| CN109575285B (en) | Method for preparing polyimide film by using PI matrix resin | |
| Li et al. | Gel polymer electrolyte prepared by in situ polymerization of MMA monomers in room temperature ionic liquid | |
| CN115612165B (en) | Flame-retardant benzoxazine aerogel and preparation method thereof | |
| CN102911595B (en) | Benzimidazole-type humidity-sensitive high-molecular coating material and preparation method and application thereof | |
| Wang et al. | Facile preparation of multifunctional poly (amide‐imide)/polyaniline films: Combining self‐cleaning, self‐extinguishing, and conductive | |
| CN105111439A (en) | Humidity-sensitive biphenyl polyimide capacitor and making method thereof | |
| CN108503867A (en) | A kind of porous low dielectric constant diacetylene thin polymer film and preparation method thereof | |
| CN105001778A (en) | Fluorine-containing polyimide humidity-sensitive capacitor and preparation method therefor | |
| CN109627440B (en) | Soluble polyimide-based resin polymer material and application thereof | |
| CN111072964B (en) | Polyimide precursor composition and preparation method and application thereof | |
| KR102116834B1 (en) | A coating composition comprising bis-type silane compound | |
| CN102816517B (en) | Light cured polyimide coating for optical fiber, and preparation method thereof | |
| CN105006364A (en) | BAHPP type polyimide humidity-sensitive capacitor and preparing method thereof | |
| CN105176379B (en) | A kind of humicap and preparation method thereof | |
| CN110616036B (en) | Polyimide varnish composition and polyimide film containing same | |
| CN113248534A (en) | Organic small-molecule thermoelectric material and preparation method thereof | |
| CN109535422B (en) | Diamine compound, polyimide film, and flexible display device | |
| JP2017188378A (en) | Organic conductive film and manufacturing method therefor | |
| CN115785505B (en) | Low dielectric poly (m-phenylene isophthalamide) film and preparation method thereof | |
| CN108485514A (en) | A kind of polymer matrix composite and preparation method thereof for capacitor | |
| Mo et al. | Siloxane‐containing polyimide films with high heat resistance and low dielectric constant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210302 Address after: 100083 No. 37, Haidian District, Beijing, Xueyuan Road Patentee after: Beijing northern sky long hawk UAV Technology Co.,Ltd. Address before: 100191 Beihang University, Haidian District, Xueyuan Road, 37, Beijing Patentee before: BEIHANG University |
|
| TR01 | Transfer of patent right |