CN106498557B - A kind of preparation method of modified nano fiber film - Google Patents
A kind of preparation method of modified nano fiber film Download PDFInfo
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- CN106498557B CN106498557B CN201610831394.4A CN201610831394A CN106498557B CN 106498557 B CN106498557 B CN 106498557B CN 201610831394 A CN201610831394 A CN 201610831394A CN 106498557 B CN106498557 B CN 106498557B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
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Abstract
The present invention provides a kind of preparation methods of modified nano fiber film, include the following steps：Thioether polyimides is mixed with cyanate and polyphenylene oxide with spin solvent, spinning solution is obtained；The spinning solution is subjected to spinning, obtains as-spun fibre film；Heat cure processing is carried out to the as-spun fibre film, obtains modified nano fiber film.Present invention employs the polyphenylene oxide of the cyanate and low-dielectric of low thermal coefficient of expansion and agent of low hygroscopicity energy with itself there is the thioether polyimides of the specific structure of excellent mechanical performance, hot property and excellent electrical properties, dimensional stability to be blended, gained nano-fiber film has inierpeneirating network structure, has excellent low-expansion coefficient.Result according to the embodiment, the thermal linear expansion coefficient for the modified nano fiber film that the present invention obtains is minimum 13.1ppm/ DEG C reachable, and dielectric constant is 1.7~1.9, and hydroscopicity is 0.95~1.10%, Young's modulus is 10.1~10.5GPa, and 5% thermal weight loss temperature is 550~566 DEG C.
Description
Technical field
The present invention relates to electronics cladding and insulating materials technical field more particularly to a kind of systems of modified nano fiber film
Preparation Method.
Background technology
Polyimides is best one of the high-molecular organic material of comprehensive performance, due to high-fire resistance outstanding, excellent
Different dimensional stability, excellent mechanical property and there is low-k, various conjunction within the scope of comparatively wide temperature
At route and processing approach, and microelectronics and aerospace are widely used in as electronics covering material and electrically insulating material
The high-tech areas such as industry.
Currently, the use form of polyimide material is based on thin-film material, Kapton be current heat resistance most
Good organic film can keep its physical property in a short time at 500 DEG C, and temperature is used for a long time and is up to 300 DEG C or more, in automobile and
The fields such as the high temperature resistant parts and printed circuit material of spacecraft are widely applied.
However, although Kapton has above-mentioned excellent performance, with new and high technology industrial expansion, now
Some Kaptons can no longer meet the requirement of lower thermal linear expansion coefficient.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of modified nano fiber film, and what the present invention was prepared changes
Property nano-fiber film have very low thermal linear expansion coefficient.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
The present invention provides a kind of preparation methods of modified nano fiber film, include the following steps：
Thioether polyimides is mixed with cyanate and polyphenylene oxide with spin solvent, spinning solution is obtained；
The spinning solution is subjected to spinning, obtains as-spun fibre film；
Heat cure processing is carried out to the as-spun fibre film, obtains modified nano fiber film.
Preferably, the spin solvent is the mixture of dioxane and n,N-Dimethylformamide；
The volume ratio of the dioxane and N,N-dimethylformamide is (75~90):(10~25).
Preferably, the thioether polyimides and the mass ratio of cyanate and polyphenylene oxide are (60~80):(15~25):(5
~15)；
The thioether polyimides and the mass ratio of the quality sum and spin solvent of cyanate and polyphenylene oxide are 10:(100
~220).
Preferably, the spinning is high-voltage electrostatic spinning；
The positive high voltage of the spinning is 5~14KV；
The negative high voltage of the spinning is 0.1~13KV；
The receiving distance of the spinning is 10~25cm；
It is 0.01~0.6mm/min that the syringe of the spinning, which injects rate,.
Preferably, the temperature of the heat cure processing is 270~300 DEG C；
The time of the heat cure is 45~60 minutes.
Preferably, the preparation method of the thioether polyimides, includes the following steps：
Triphen disulfide dianhydride and diaminodiphenylmethane are subjected to polymerisation in organic solvent, obtain polymerization production
Object；
Imidization processing is carried out to the polymerizate, obtains thioether polyimides.
Preferably, the ratio between amount of substance of the triphen disulfide dianhydride and diaminodiphenylmethane is 1:(1~1.01)；
The mass ratio of the triphen disulfide dianhydride and organic solvent is (65~695):(390~620).
Preferably, the polymerisation carries out in an inert gas atmosphere；
The time of the polymerisation is 8~24 hours.
Preferably, the imidization, which is handled, is：
The polymerizate is mixed with imidizing agent and carries out imidization processing, the imidizing agent includes pyridines
Substance and acetic anhydride；
The ratio between the pyridine substance and the amount of substance of acetic anhydride are (2~8):5；
The mass ratio of the triphen disulfide dianhydride and imidizing agent is 43.44:(39~50).
Preferably, the temperature of the imidization processing is 100~130 DEG C；
The time of the imidization processing is 0.5~8 hour.
The present invention provides a kind of preparation methods of modified nano fiber film, include the following steps：Thioether polyamides is sub-
Amine is mixed with cyanate and polyphenylene oxide with spin solvent, obtains spinning solution；The spinning solution is subjected to spinning, is come into being
Fiber membrane；Heat cure processing is carried out to the as-spun fibre film, obtains modified nano fiber film.Present invention employs low
The cyanate and low-dielectric of coefficient of thermal expansion and agent of low hygroscopicity can polyphenylene oxide with itself with excellent mechanical performance, hot
It can be blended with the thioether polyimides of the specific structure of excellent electrical properties, dimensional stability, gained nano-fiber film has mutual
Network structure is worn, there is excellent low-expansion coefficient.Result according to the embodiment is it is found that the modified nano fiber that the present invention obtains
The thermal linear expansion coefficient of film is minimum up to 13.1ppm/ DEG C.
In addition, the modified nano fiber film that the present invention obtains also has excellent dielectric constant, hydroscopicity, Young's modulus
With the performance parameters such as thermal weight loss temperature, specifically, dielectric constant is 1.7~1.9, hydroscopicity is 0.95~1.10%, Young mould
Amount is 10.1~10.5GPa, and 5% thermal weight loss temperature is 550~566 DEG C.
Description of the drawings
Fig. 1 is the infrared spectrum for the product that the embodiment of the present invention 1 obtains.
Specific implementation mode
The present invention provides a kind of preparation methods of modified nano fiber film, include the following steps：
Thioether polyimides is mixed with cyanate and polyphenylene oxide with spin solvent, spinning solution is obtained；
The spinning solution is subjected to spinning, obtains as-spun fibre film；
Heat cure processing is carried out to the as-spun fibre film, obtains modified nano fiber film.
The present invention is by thioether polyimides and cyanate and polyphenylene oxide and spin solvent.In the present invention, the thioether is poly-
Acid imide can be commercial product or made products.In the present invention, the preparation method of the thioether polyimides, is preferably wrapped
Include following steps：
Triphen disulfide dianhydride and diaminodiphenylmethane are subjected to polymerisation in organic solvent, obtain polymerization production
Object；
Imidization processing is carried out to the polymerizate, obtains thioether polyimides.
Triphen disulfide dianhydride and diaminodiphenylmethane are carried out polymerisation by the present invention in organic solvent, are gathered
Close product.In the present invention, the triphen disulfide dianhydride (PTPSDA) is preferably 3,3 '-triphen disulfide dianhydride (PTPSDA-
3), in 4,4 '-triphen disulfide dianhydrides (PTPSDA-4) and 3,4 '-three kinds of substances of triphen disulfide dianhydride (PTPSDA-34)
Any one or two component mixtures or ternary mixture that are formed in any proportion.
In the present invention, described 3,3 '-triphen disulfide dianhydrides (PTPSDA-3) preferably have structure shown in formula I：
In formula I, R is H or methyl.
In the present invention, described 4,4 '-triphen disulfide dianhydrides (PTPSDA-4) preferably have structure shown in formula II：
In formula II, R is H or methyl.
In the present invention, described 3,4 '-triphen disulfide dianhydrides (PTPSDA-34) preferably have structure shown in formula III：
In formula III, R is H or methyl.
In the present invention, the diaminodiphenylmethane (DADPM) preferably has structure shown in formula IV：
In formula IV, R5、R6、R7And R8It is independently H or methyl, and wherein at least one is methyl.
In the present invention, the diaminodiphenylmethane can be specially
The present invention does not have particular/special requirement to the source of the triphen disulfide dianhydride and diaminodiphenylmethane, using ability
Triphen disulfide dianhydride known to field technique personnel and diaminodiphenylmethane can be specifically triphen disulfide two
The commercial product of acid anhydride and diaminodiphenylmethane.In the present invention, the triphen disulfide dianhydride and diaminodiphenylmethane
The ratio between amount of substance is preferably 1:(1~1.1), more preferably 1:(1~1.05), most preferably 1:(1~1.01).
In the present invention, the organic solvent is preferably dimethylacetylamide.In the present invention, the triphen disulfide two
The mass ratio of acid anhydride and organic solvent is preferably (65~695):(390~620), more preferably (100~600):(400~600),
Most preferably (300~400):(450~550).
In the present invention, the polymerisation preferably carries out in an inert gas atmosphere；The time of the polymerisation is excellent
It is selected as 8~24 hours, more preferably 10~20 hours, most preferably 12~18 hours.In the present invention, the polymerisation is excellent
It is selected in and carries out at room temperature.
The present invention preferably carries out termination process after the polymerisation using end-capping reagent.In the present invention, described
End-capping reagent is preferably phthalic anhydride (PA)；The mass ratio of the triphen disulfide dianhydride and end-capping reagent be preferably (43~
44):(0.1~0.16) is more selected as (43~44):(0.12~0.15), most preferably (43~44):(0.13~0.14).
The present invention does not have particular/special requirement to the condition of the termination process, directly after polymerisation terminates, end-capping reagent is placed in poly-
It closes and is blocked in product system.
After obtaining the polymerizate, the present invention carries out imidization processing to the polymerizate, and it is sub- to obtain thioether polyamides
Amine.In the present invention, the imidization, which is handled, is preferably:The polymerizate is mixed with imidizing agent and is carried out at imidization
Reason, the imidizing agent preferably include pyridine substance and acetic anhydride；The amount of the substance of the pyridine substance and acetic anhydride
The ratio between preferably (2~8):5, more preferably (3~7):5, most preferably (4~6):5.In the present invention, the pyridines object
It is of fine quality to be selected as 2- picolines and/or 3- picolines.
In the present invention, the mass ratio of the triphen disulfide dianhydride and imidizing agent is preferably 43.44:(39~
50), more preferably 43.44:(42~48), most preferably 43.44:(44~46).
In the present invention, the temperature of the imidization processing is preferably 100~130 DEG C, more preferably 105~125 DEG C, most
Preferably 110~120 DEG C；The time of the imidization processing is preferably 0.5~8 hour, more preferably 1~7 hour, most preferably
It is 2~5 hours.
In the present invention, the thioether polyimides (STPI) that the imidization is handled preferably has knot shown in formula V
Structure：
In formula V, R is H or methyl；
R5、R6、R7And R8It is independently H or methyl, and wherein at least one is methyl；
N is 10~10000.
In the present invention, n is preferably 10~10000 in the formula V, more preferably 100~8000, most preferably 1000
~5000.
The spinning solution is carried out spinning by the present invention, obtains as-spun fibre film.In the present invention, the cyanate is excellent
It is selected as the bisphenol-f type cyanate (HF-0) with methyl, the bisphenol-f type cyanate with methyl preferably has knot shown in formula VI
Structure：
In formula VI, R1、R2、R3And R4It is independently H or methyl, and wherein at least one is methyl.
In the present invention, the bisphenol-f type cyanate with methyl can be specially
In the present invention, the polyphenylene oxide preferably has structure shown in formula VII：
In formula VII, n is 10~5000.
In the present invention, n is preferably 10~5000 in the formula VII, more preferably 100~4000, most preferably 1000~
3000。
In the present invention, the spin solvent is preferably dioxane and the mixture of n,N-Dimethylformamide；It is described
The volume ratio of dioxane and N,N-dimethylformamide is preferably (75~90):(10~25), more preferably (78~88):
(12~22), most preferably (80~85):(15~20).
In the present invention, the thioether polyimides and the mass ratio of cyanate and polyphenylene oxide are preferably (60~80):(15
~25):(5~15), more preferably (65~75):(18~22):(8~13), most preferably (68~72):(19~20):(9
~11).
In the present invention, the thioether polyimides and cyanate and the quality sum of polyphenylene oxide and the quality of spin solvent
Than being preferably 10:(100~220), more preferably 10:(120~200), most preferably 10:(150~180).
In the present invention, the spinning is preferably high-voltage electrostatic spinning.In the present invention, the environment temperature of the spinning is excellent
It is selected as 30~60 DEG C, more preferably 35~55 DEG C, most preferably 40~50 DEG C；The ambient humidity of the spinning is preferably 30~
75%, more preferably 35~70%, most preferably 40~60%；The positive high voltage of the spinning is preferably 5~14KV, is more selected as
8~12KV, most preferably 9~11KV；The negative high voltage of the spinning is preferably 0.1~13KV, is more selected as 2~11KV, optimal
It is selected as 5~10KV；Receiving the distance preferably 10~25cm, more preferably 12~22cm, most preferably 15 of the spinning~
20cm；It is preferably 0.01~0.6mm/min that the syringe of the spinning, which injects rate, more preferably 0.05~0.5mm/min, most
Preferably 0.1~0.3mm/min.The present invention does not have particular/special requirement to the specific implementation mode of the spinning, using this field skill
Spinning process known to art personnel carries out.
After obtaining the as-spun fibre film, the present invention carries out heat cure processing to the as-spun fibre film, obtains
Modified nano fiber film.In the present invention, the temperature of the heat cure processing is preferably 270~300 DEG C, more preferably 280
~290 DEG C, most preferably 282~288 DEG C；The time of the heat cure is preferably 45~60 minutes, more preferably 50~58 points
Clock, most preferably 52~54 minutes.
The present invention provides a kind of preparation methods of modified nano fiber film, include the following steps：Thioether polyamides is sub-
Amine is mixed with cyanate and polyphenylene oxide with spin solvent, obtains spinning solution；The spinning solution is subjected to spinning, is come into being
Fiber membrane；Heat cure processing is carried out to the as-spun fibre film, obtains modified nano fiber film.Present invention employs low
The cyanate and low-dielectric of coefficient of thermal expansion and agent of low hygroscopicity can polyphenylene oxide with itself with excellent mechanical performance, hot
It can be blended with the thioether polyimides of the specific structure of excellent electrical properties, dimensional stability, gained nano-fiber film has mutual
Network structure is worn, there is excellent low-expansion coefficient.Result according to the embodiment is it is found that the modified nano fiber that the present invention obtains
The thermal linear expansion coefficient of film is minimum up to 13.1ppm/ DEG C.
In addition, the modified nano fiber film that the present invention obtains also has excellent dielectric constant, hydroscopicity, Young's modulus
With the performance parameters such as thermal weight loss temperature, specifically, dielectric constant is 1.7~1.9, hydroscopicity is 0.95~1.10%, Young mould
Amount is 10.1~10.5GPa, and 5% thermal weight loss temperature is 550~566 DEG C.
The preparation method of modified nano fiber film provided by the invention is described in detail with reference to embodiment,
But they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Triphen disulfide dianhydride (PTPSDA) 43.44g, the diamino hexichol that Shanghai 5-linked chemical plant is sold are weighed at room temperature
Methane (DADPM) 25.44g is that 12 are reacted in room temperature, nitrogen atmosphere is small for solvent with dimethylacetylamide 417ml (390.56g)
When, then blocked with 0.15g phthalic anhydrides (PA).Then chemical imidization reagent is added：Picoline substance and acetic acid
Acid anhydride distinguishes 14.12g and 25.52g, is reacted 60 minutes at 130 DEG C, obtains soluble thioether polyimides (STPI).
The product that the present invention obtains the present invention has carried out infrared detection, and as shown in FIG. 1, FIG. 1 is the present invention for testing result
The infrared spectrum for the product that embodiment 1 obtains.As can be seen from FIG. 1, the product that the embodiment of the present invention 1 obtains is that thioether polyamides is sub-
Amine.
After testing, the thioether polyimides obtained solid content 10%wt dioxane solution, 25 DEG C when power
Viscosity is 6Pas.
Embodiment 2
Triphen disulfide dianhydride (PTPSDA) 43.44g, the diamino hexichol that Shanghai 5-linked chemical plant is sold are weighed at room temperature
Methane (DADPM) 25.44g is that 12 are reacted in room temperature, nitrogen atmosphere is small for solvent with dimethylacetylamide 417ml (390.56g)
When, then blocked with 0.15g phthalic anhydrides (PA).Then chemical imidization reagent is added：Picoline substance and acetic acid
Acid anhydride distinguishes 23.54g and 25.52g, is reacted 40 minutes at 110 DEG C, obtains soluble thioether polyimides (STPI).After testing, it obtains
The thioether polyimides arrived solid content 10%wt dioxane solution, 25 DEG C when dynamic viscosity be 21Pas.
Embodiment 3
Triphen disulfide dianhydride (PTPSDA) 43.44g, the diamino hexichol that Shanghai 5-linked chemical plant is sold are weighed at room temperature
Methane (DADPM) 25.44g is that 12 are reacted in room temperature, nitrogen atmosphere is small for solvent with dimethylacetylamide 417ml (390.56g)
When, then blocked with 0.15g phthalic anhydrides (PA).Then chemical imidization reagent is added：Picoline substance and acetic acid
Acid anhydride distinguishes 37.67g and 25.52g, is reacted 30 minutes at 100 DEG C, obtains soluble thioether polyimides (STPI).After testing, it obtains
The thioether polyimides arrived solid content 10%wt dioxane solution, 25 DEG C when dynamic viscosity be 30Pas.
Embodiment 4
Triphen disulfide dianhydride (PTPSDA) 43.44g, the diamino hexichol that Shanghai 5-linked chemical plant is sold are weighed at room temperature
Methane (DADPM) 25.69g is that 12 are reacted in room temperature, nitrogen atmosphere is small for solvent with dimethylacetylamide 662ml (619.92g)
When, then blocked with 0.16g phthalic anhydrides (PA).Then chemical imidization reagent is added：Picoline substance and acetic acid
Acid anhydride distinguishes 23.75g and 25.52g, is reacted 45 minutes at 110 DEG C, obtains soluble thioether polyimides (STPI).After testing, it obtains
The thioether polyimides arrived solid content 10%wt dioxane solution, 25 DEG C when dynamic viscosity be 19.7Pas.
Embodiment 5
The bisphenol-f type cyanate 1.0g that Yangzhou Jiangdu Wuqiao resin processing plant is sold, the modeling of Shanghai radical innovations are weighed at room temperature
The polyphenylene oxide 0.5g that the sold goods number of material is N300X-701, thioether polyimides STPI 3.5g prepared by embodiment 1 are set
In reaction bulb, it is 7 that dioxane, which is added, with n,N-Dimethylformamide volume ratio:3 mixed solvent 50ml (50.5g), is stirred
It mixes 30 minutes, acquired solution is 30 DEG C through excess temperature, humidity 30%, and positive high voltage 5.0KV, negative high voltage 13.0KV receive
Distance is 10cm, and syringe injects the high-voltage electrostatic spinning that rate is 0.01mm/min, then in 300 DEG C of heat cures 60 minutes, system
A kind of thickness is 8 μm of cyanates/polyphenyl ether modified thioether polyimides high frequency communications nano-fiber film, i.e., of the invention changes
Property nano-fiber film, mechanics, electricity and dimensional stability properties such as table 1.
Embodiment 6
The bisphenol-f type cyanate 1.0g that Yangzhou Jiangdu Wuqiao resin processing plant is sold, the modeling of Shanghai radical innovations are weighed at room temperature
The polyphenylene oxide 0.25g that the sold goods number of material is N300X-701, thioether polyimides STPI 3.75g prepared by embodiment 1
It is placed in a reaction flask, it is 7 that dioxane, which is added, with n,N-Dimethylformamide volume ratio:3 mixed solvent 100ml (101g),
Stirring 30 minutes, acquired solution are 35 DEG C through excess temperature, and humidity 35%, positive high voltage 8.5KV, negative high voltage 1.1KV receive
Distance is 20cm, and syringe injects the high-voltage electrostatic spinning that rate is 0.08mm/min, then in 300 DEG C of heat cures 60 minutes, system
A kind of thickness is 8 μm of cyanates/polyphenyl ether modified thioether polyimides high frequency communications nano-fiber film, i.e., of the invention changes
Property nano-fiber film, mechanics, electricity and dimensional stability properties such as table 1.
Embodiment 7
The bisphenol-f type cyanate 1.25g that Yangzhou Jiangdu Wuqiao resin processing plant is sold, the modeling of Shanghai radical innovations are weighed at room temperature
The polyphenylene oxide 0.75g that the sold goods number of material is N300X-701, thioether polyimides STPI 3.0g prepared by embodiment 1 are set
In reaction bulb, it is 7 that dioxane, which is added, with n,N-Dimethylformamide volume ratio:3 mixed solvent 49.5ml (50.0g),
Stirring 30 minutes, acquired solution are 60 DEG C through excess temperature, and humidity 60%, positive high voltage 14.0KV, negative high voltage 0.1KV connect
It is 25cm by distance, syringe injected the high-voltage electrostatic spinning that rate is 0.06mm/min, then in 300 DEG C of heat cures 45 minutes,
A kind of obtained thickness is 8 μm of cyanates/polyphenyl ether modified thioether polyimides high frequency communications nano-fiber film, i.e., of the invention
Modified nano fiber film, mechanics, electricity and dimensional stability properties such as table 1.
Embodiment 8
The bisphenol-f type cyanate 0.75g that Yangzhou Jiangdu Wuqiao resin processing plant is sold, the modeling of Shanghai radical innovations are weighed at room temperature
The polyphenylene oxide 0.75g that the sold goods number of material is N300X-701, thioether polyimides STPI3.5g prepared by embodiment 1 are set
In reaction bulb, it is 7 that dioxane, which is added, with n,N-Dimethylformamide volume ratio:3 mixed solvent 109ml (110g), is stirred
Mix 30 minutes, acquired solution through excess temperature be 40 DEG C, humidity 50%, positive high voltage 8.5KV, negative high voltage 1.1KV, receive away from
From for 20cm, syringe injects the high-voltage electrostatic spinning that rate is 0.1mm/min, then in 285 DEG C of heat cures 50 minutes, is made one
Kind thickness is 8 μm of cyanates/polyphenyl ether modified thioether polyimides high frequency communications nano-fiber film, i.e. modification of the invention is received
Rice fiber membrane, mechanics, electricity and dimensional stability properties such as table 1.
Embodiment 9
The bisphenol-f type cyanate 1.0g that Yangzhou Jiangdu Wuqiao resin processing plant is sold, the modeling of Shanghai radical innovations are weighed at room temperature
The polyphenylene oxide 0.5g that the sold goods number of material is N300X-701, thioether polyimides STPI 3.5g prepared by embodiment 2 are set
In reaction bulb, it is 3 that dioxane, which is added, with n,N-Dimethylformamide volume ratio:1 mixed solvent 100ml (101g), is stirred
Mix 30 minutes, acquired solution through excess temperature be 35 DEG C, humidity 35%, positive high voltage 8.5KV, negative high voltage 1.1KV, receive away from
From for 20cm, syringe injects the high-voltage electrostatic spinning that rate is 0.08mm/min, then in 300 DEG C of heat cures 50 minutes, is made
A kind of thickness is 8 μm of cyanates/polyphenyl ether modified thioether polyimides high frequency communications nano-fiber film, i.e. modification of the invention
Nano-fiber film, mechanics, electricity and dimensional stability properties such as table 1.
Embodiment 10
The bisphenol-f type cyanate 0.75g that Yangzhou Jiangdu Wuqiao resin processing plant is sold, the modeling of Shanghai radical innovations are weighed at room temperature
The polyphenylene oxide 0.25g that the sold goods number of material is N300X-701, thioether polyimides STPI 4.0g prepared by embodiment 2 are set
In reaction bulb, it is 9 that dioxane, which is added, with n,N-Dimethylformamide volume ratio:1 mixed solvent 100ml (101g), is stirred
Mix 30 minutes, acquired solution through excess temperature be 40 DEG C, humidity 35%, positive high voltage 9.5KV, negative high voltage 1.1KV, receive away from
From for 20cm, syringe injects the high-voltage electrostatic spinning that rate is 0.08mm/min, then in 270 DEG C of heat cures 60 minutes, is made
A kind of thickness is 8 μm of cyanates/polyphenyl ether modified thioether polyimides high frequency communications nano-fiber film, i.e. modification of the invention
Nano-fiber film, mechanics, electricity and dimensional stability properties such as table 1.
Embodiment 11
The bisphenol-f type cyanate 1.0g that Yangzhou Jiangdu Wuqiao resin processing plant is sold, the modeling of Shanghai radical innovations are weighed at room temperature
The polyphenylene oxide 0.25g that the sold goods number of material is N300X-701, thioether polyimides STPI 3.75g prepared by embodiment 2
It is placed in a reaction flask, it is 3 that dioxane, which is added, with n,N-Dimethylformamide volume ratio:1 mixed solvent 60ml (60.5g),
Stirring 30 minutes, acquired solution are 35 DEG C through excess temperature, and humidity 35%, positive high voltage 8.5KV, negative high voltage 2.0KV receive
Distance is 20cm, and syringe injects the high-voltage electrostatic spinning that rate is 0.08mm/min, then in 270 DEG C of heat cures 60 minutes, system
A kind of thickness is 8 μm of cyanates/polyphenyl ether modified thioether polyimides high frequency communications nano-fiber film, i.e., of the invention changes
Property nano-fiber film, mechanics, electricity and dimensional stability properties such as table 1.
Embodiment 12
The bisphenol-f type cyanate 1.25g that Yangzhou Jiangdu Wuqiao resin processing plant is sold, the modeling of Shanghai radical innovations are weighed at room temperature
The polyphenylene oxide 0.75g that the sold goods number of material is N300X-701, thioether polyimides STPI 3.0g prepared by embodiment 2 are set
In reaction bulb, it is 3 that dioxane, which is added, with n,N-Dimethylformamide volume ratio:1 mixed solvent 80ml (81g), stirring
30 minutes, acquired solution was 35 DEG C through excess temperature, and humidity 35%, positive high voltage 8.0KV, negative high voltage 5.5KV receive distance
For 20cm, syringe injects the high-voltage electrostatic spinning that rate is 0.08mm/min, then in 300 DEG C of heat cures 45 minutes, is made one
Kind thickness is 8 μm of cyanates/polyphenyl ether modified thioether polyimides high frequency communications nano-fiber film, i.e. modification of the invention is received
Rice fiber membrane, mechanics, electricity and dimensional stability properties such as table 1.
Embodiment 13
The bisphenol-f type cyanate 0.75g that Yangzhou Jiangdu Wuqiao resin processing plant is sold, the modeling of Shanghai radical innovations are weighed at room temperature
The polyphenylene oxide 0.75g that the sold goods number of material is N300X-701, thioether polyimides STPI 3.5g prepared by embodiment 3 are set
In reaction bulb, it is 3 that dioxane, which is added, with n,N-Dimethylformamide volume ratio:1 mixed solvent 60ml (60.5g), is stirred
It mixes 30 minutes, acquired solution is 30 DEG C through excess temperature, humidity 30%, and positive high voltage 10.0KV, negative high voltage 1.5KV receive
Distance is 20cm, and syringe injects the high-voltage electrostatic spinning that rate is 0.2mm/min, then in 285 DEG C of heat cures 60 minutes, is made
A kind of thickness is 8 μm of cyanates/polyphenyl ether modified thioether polyimides high frequency communications nano-fiber film, i.e. modification of the invention
Nano-fiber film, mechanics, electricity and dimensional stability properties such as table 1.
Embodiment 14
The bisphenol-f type cyanate 1.0g that Yangzhou Jiangdu Wuqiao resin processing plant is sold, the modeling of Shanghai radical innovations are weighed at room temperature
The polyphenylene oxide 0.5g that the sold goods number of material is N300X-701, thioether polyimides STPI 3.5g prepared by embodiment 3 are set
In reaction bulb, it is 7 that dioxane, which is added, with n,N-Dimethylformamide volume ratio:3 mixed solvent 70ml (70.5g), is stirred
Mix 30 minutes, acquired solution through excess temperature be 40 DEG C, humidity 40%, positive high voltage 8.0KV, negative high voltage 1.3KV, receive away from
From for 20cm, syringe injects the high-voltage electrostatic spinning that rate is 0.1mm/min, then in 270 DEG C of heat cures 60 minutes, is made one
Kind thickness is 8 μm of cyanates/polyphenyl ether modified thioether polyimides high frequency communications nano-fiber film, i.e. modification of the invention is received
Rice fiber membrane, mechanics, electricity and dimensional stability properties such as table 1.
Embodiment 15
The bisphenol-f type cyanate 1.0g that Yangzhou Jiangdu Wuqiao resin processing plant is sold, the modeling of Shanghai radical innovations are weighed at room temperature
The polyphenylene oxide 0.5g that the sold goods number of material is N300X-701, thioether polyimides STPI 3.5g prepared by embodiment 4 are set
In reaction bulb, it is 3 that dioxane, which is added, with n,N-Dimethylformamide volume ratio:1 mixed solvent 100ml (101g), is stirred
Mix 30 minutes, acquired solution through excess temperature be 40 DEG C, humidity 40%, positive high voltage 8.0KV, negative high voltage 1.3KV, receive away from
From for 20cm, syringe injects the high-voltage electrostatic spinning that rate is 0.06mm/min, then in 270 DEG C of heat cures 45 minutes, is made
A kind of thickness is 8 μm of cyanates/polyphenyl ether modified thioether polyimides high frequency communications nano-fiber film, i.e. modification of the invention
Nano-fiber film, mechanics, electricity and dimensional stability properties such as table 1.
Embodiment 16
The bisphenol-f type cyanate 1.25g that Yangzhou Jiangdu Wuqiao resin processing plant is sold, the modeling of Shanghai radical innovations are weighed at room temperature
The polyphenylene oxide 0.25g that the sold goods number of material is N300X-701, thioether polyimides STPI 3.5g prepared by embodiment 4 are set
In reaction bulb, it is 3 that dioxane, which is added, with n,N-Dimethylformamide volume ratio:1 mixed solvent 100ml (101g), is stirred
Mix 30 minutes, acquired solution through excess temperature be 40 DEG C, humidity 40%, positive high voltage 8.0KV, negative high voltage 1.3KV, receive away from
From for 20cm, syringe injects the high-voltage electrostatic spinning that rate is 0.06mm/min, then in 300 DEG C of heat cures 60 minutes, is made
A kind of thickness is 8 μm of cyanates/polyphenyl ether modified thioether polyimides high frequency communications nano-fiber film, i.e. modification of the invention
Nano-fiber film, mechanics, electricity and dimensional stability properties such as table 1.
The performance parameter for the modified nano fiber film that 1 embodiment 5~16 of table obtains
As shown in Table 1, the modified nano fiber film that the present invention obtains have very low thermal linear expansion coefficient, it is minimum can
Up to 13.1ppm/ DEG C.In addition, the modified nano fiber film that the present invention obtains also has excellent dielectric constant, hydroscopicity, poplar
The performance parameters such as family name's modulus and thermal weight loss temperature, specifically, dielectric constant is 1.7~1.9, hydroscopicity is 0.95~1.10%,
Young's modulus is 10.1~10.5GPa, and 5% thermal weight loss temperature is 550~566 DEG C.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of modified nano fiber film, includes the following steps：
Thioether polyimides is mixed with cyanate and polyphenylene oxide with spin solvent, spinning solution is obtained；
The spinning solution is subjected to spinning, obtains as-spun fibre film；
Heat cure processing is carried out to the as-spun fibre film, obtains modified nano fiber film.
2. preparation method according to claim 1, which is characterized in that the spin solvent is dioxane and N, N- diformazans
The mixture of base formamide；
The volume ratio of the dioxane and N,N-dimethylformamide is (75~90):(10~25).
3. preparation method according to claim 1 or 2, which is characterized in that the thioether polyimides and cyanate and gather
The mass ratio of phenylate is (60~80):(15~25):(5~15)；
The thioether polyimides and the mass ratio of the quality sum and spin solvent of cyanate and polyphenylene oxide are 10:(100~
220)。
4. preparation method according to claim 1, which is characterized in that the spinning is high-voltage electrostatic spinning；
The positive high voltage of the spinning is 5~14KV；
The negative high voltage of the spinning is 0.1~13KV；
The reception distance of the spinning is 10~25cm；
It is 0.01~0.6mm/min that the syringe of the spinning, which injects rate,.
5. preparation method according to claim 1 or 4, which is characterized in that the temperature of heat cure processing is 270~
300℃；
The time of the heat cure is 45~60 minutes.
6. preparation method according to claim 1, which is characterized in that the preparation method of the thioether polyimides, including
Following steps：
Triphen disulfide dianhydride and diaminodiphenylmethane are subjected to polymerisation in organic solvent, obtain polymerizate；
Imidization processing is carried out to the polymerizate, obtains thioether polyimides.
7. preparation method according to claim 6, which is characterized in that the triphen disulfide dianhydride and diamino hexichol first
The ratio between amount of substance of alkane is 1:(1~1.1)；
The mass ratio of the triphen disulfide dianhydride and organic solvent is (65~695):(390~620).
8. the preparation method described according to claim 6 or 7, which is characterized in that the polymerisation is in an inert gas atmosphere
It carries out；
The time of the polymerisation is 8~24 hours.
9. preparation method according to claim 6, which is characterized in that the imidization, which is handled, is：
The polymerizate is mixed with imidizing agent and carries out imidization processing, the imidizing agent be pyridine substance and
Acetic anhydride；
The ratio between the pyridine substance and the amount of substance of acetic anhydride are (2~8):5；
The mass ratio of the triphen disulfide dianhydride and imidizing agent is 43.44:(39~50).
10. the preparation method according to claim 6 or 9, which is characterized in that the temperature of imidization processing is 100~
130℃；
The time of the imidization processing is 0.5~8 hour.
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| CN111978728A (en) * | 2020-09-01 | 2020-11-24 | 中山职业技术学院 | Preparation method of high-frequency antenna base material resin slurry |
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| CN104109242A (en) * | 2013-04-17 | 2014-10-22 | 中国石油化工股份有限公司 | Processing stock solution of polyimide fiber or film, preparation method and applications thereof |
| CN105131598A (en) * | 2014-06-06 | 2015-12-09 | 台光电子材料股份有限公司 | Low-dielectric resin composition, resin film using same, prepreg and circuit board |
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| CN104109242A (en) * | 2013-04-17 | 2014-10-22 | 中国石油化工股份有限公司 | Processing stock solution of polyimide fiber or film, preparation method and applications thereof |
| CN105131598A (en) * | 2014-06-06 | 2015-12-09 | 台光电子材料股份有限公司 | Low-dielectric resin composition, resin film using same, prepreg and circuit board |
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