CN109082119A - A kind of cellulose modified polyimides corona-resistant film and preparation method thereof - Google Patents
A kind of cellulose modified polyimides corona-resistant film and preparation method thereof Download PDFInfo
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- 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
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- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention relates to a kind of cellulose modified polyimides corona-resistant films and preparation method thereof, include following preparation step: aluminium isopropoxide, KH550 silane coupling agent, emulsifier is added in pretreated cellulose, and high-pressure emulsification machine high speed disperses to form uniform lotion；4,4'- diaminodiphenyl ether and dimethyl acetamide are dissolved into containing amine aqueous solution, are stirred by lotion and containing amine aqueous solution, then pyromellitic acid anhydride is added to described step by step and is passed through in mixed solution to be fabricated to polyamic acid resin；Obtained polyamic acid resin forms film by casting technique, and heating obtains cellulose modified polyester-imide film.In film of the invention, aluminium oxide particles are uniformly distributed into Kapton；Cellulose forms reticular structure inside film, improves film strength；The introducing of cellulose can also improve the dielectric properties and corona-resistance property of film.
Description
Technical field
The present invention relates to the field of material preparation of chemical industry and chemistry, and in particular, to a kind of Kapton, more specifically
Ground is related to a kind of cellulose modified polyimides corona-resistant film and preparation method thereof.
Background technique
Polyimides (PI) film has good heat resistance, mechanical performance, electric property and radiation resistance, in electricity
The fields such as sub- industrial circle and aerospace play highly important effect.However the corona-resistance property of common PI film compared with
Difference is no longer satisfied the requirement on the special electrical equipment such as high-voltage generator, high-pressure engine, variable-frequency motor.
In order to solve the deficiency in terms of PI film corona-resistance property, DuPont Corporation released one after another at 1994 or so by
Inverter fed motor PI series thin film Kapton CR and the Kapton FCR of nano aluminium oxide filling.Kapton CR 50Hz alternating current,
Under the electric field strength of 20MV/m, the service life can be more than 100,000 hours, and the service life of traditional Kapton 100HN film only has
200h or so.But due to expensive, and for the strategic concerns of high-end devices.It is necessary to grasp mature Inverter fed motor for the country
PI film preparing technology.
In recent decades, China expands detailed research to Inverter fed motor PI film, has obtained certain achievement and conclusion,
Wherein think to influence many because being known as of material property for polyimides Inverter fed motor nanocomposite.Preparation process, nanometer
The type of filler, content, surface chemical modification are to influence the key factor of composite property.Polyimides corona-resistant film
Preparation process mainly has In-situ reaction and sol-gel method, both techniques respectively have advantage and disadvantage.In-situ reaction generally requires pair
Nanofiller carries out surface chemical modification, but the surface chemical modification effect of inorganic nano-filler is poor, it is difficult to improve nanometer and fill out
Expect the dispersibility in polyimide matrix.However, its process is simple, technical maturity is very suitable to industrial production.Colloidal sol-is solidifying
Glue method can allow nanoparticle it is evenly dispersed with matrix among, but there is also many disadvantages.Such as need to be added a certain amount of water and
Catalyst, this can have a significant impact the performance of polymer；Followed by during gel drying, solvent, small molecule, water are waved
Hair may cause material internal and generate shrinkage stress, influence the mechanics and mechanical performance of material；In addition, this method cannot achieve pair
The control of inorganic particle crystal form.There is also problems in industrialization production for sol-gel method craft.Related nanofiller
Type, other than the nano-scale alumina that E.I.Du Pont Company uses, nanosized SiO_2, nano TiO 2, nano-ZnO, nano-aluminum nitride, montmorillonite
(MMT) corona-resistance property of Kapton can be improved in various degree.Different nanofiller collaboration additions, can also be into one
Step improves the corona-resistance property (Applied Surface Science 2012,263:30) of film.
Chinese patent CN101812183A discloses a kind of system of polyimide multilayer complex films containing inorganic nanometer powder
Preparation Method, including following steps: (1) pretreatment of inorganic nanometer powder；(2) with 4,4 '-diaminodiphenyl ethers, equal benzene four
Formic acid dianhydride is that starting monomer is dissolved in solvent, and polymerization generates polyamic acid solution；(3) by pretreated inorganic nanometer powder
It through ultrasonic disperse in solvent, is added in polyamic acid solution, prepares the polyamic acid solution containing inorganic nanometer powder；
(4) by containing inorganic nanometer powder polyamic acid solution and pure polyamic acid solution carry out plastic film mulch in order respectively；(5) by film
It is put into baking oven and handles to obtain the polyimide hybrid MULTILAYER COMPOSITE containing inorganic nanometer powder in 50-400 DEG C of progress hot imidization
Film.Obtaining the composite polyimide material containing inorganic nanometer powder often reduces the mechanical property of film, especially works as nano powder
It is more significant for the reduction of film performance when body dispersion is uneven.
Chinese patent CN101805517A discloses a kind of manufacturing method of inorganic particle filled Kapton, will
Abrading-ball of the diameter no more than 6mm is added in the grinding barrel of medium motion grinding machine, and part organic solvent, inorganic particle and surface is added
Modifying agent carries out ball milling, evenly spreads to inorganic particle in organic solvent, obtains inorganic particle/organic solvent suspension.It will
Above-mentioned inorganic particle/organic solvent suspension, remaining organic solvent, equimolar diamines and dianhydride be added in reaction kettle by
The method of more solito prepares inorganic particle/polyamic acid solution suspended substance, obtains according to conventional the tape casting production technology inorganic
Particles filled Kapton.Thin-film transparent is good, good mechanical performance.
However the Kapton that above-mentioned addition inorganic particulate is compound, in the limitation for improving corona-resistance property, and
And the deficiencies of uneven there are inorganic particulate dispersion.Therefore needing to develop a kind of can be obviously improved Kapton Inverter fed motor
Performance can preferably control inorganic particulate being uniformly distributed in the film, and film can reach the requirement of industrialization.
Summary of the invention
For present inventor in the compound Kapton of current inorganic particulate, inorganic particulate dispersion is uneven,
Bond strength is inadequate, and corona-resistance property improves the deficiencies of limited, a kind of cellulose modified Kapton is developed, with solution
One of certainly above-mentioned insufficient problem is a variety of.
According to the first aspect of the invention, a kind of Kapton is provided, concrete scheme is as follows:
A kind of cellulose modified Kapton, the composition of product include the component of following parts by weight composition:
About 150-200 parts of polyimides, about 1-5 parts of nano alumina particles, about 0.01-1 parts of cellulose, silane coupling agent
About 1-5 parts, which is characterized in that cellulose is supported on nano alumina particles, the nano aluminium oxide being evenly distributed in the film.
Preferably, the partial size of the nano alumina particles is about 2-50nm.
Preferably, the cellulose is 15-20% relative to the weight fraction of nano aluminium oxide.
The present invention also provides a kind of preparation methods of cellulose modified Kapton comprising following steps:
(1) cellulose pre-processes: cellulose being carried out after suitably crushing, alkali leaching processing, washing is dried；Steam is carried out again
Explosion treatment；
(2) it prepares lotion: the pretreated cellulose of step (1) being added in deionized water, magnetic agitation adds
Aluminium isopropoxide, KH550 silane coupling agent, emulsifier, high-pressure emulsification machine high speed disperse to form uniform lotion；
(3) it prepares polyamide: 4,4'- diaminodiphenyl ether and dimethyl acetamide being dissolved into amine-containing molten
Liquid stirs the lotion of step (2) and being added in reaction kettle simultaneously according to mass ratio for 1:1.1~20 containing amine aqueous solution for step (3)
Mixing is mixed, then according to pyromellitic acid anhydride and 4, the mass ratio of 4'- diaminodiphenyl ether is that the ratio of 1:1~1.2 will be equal
Pyromellitic dianhydride, which is added step by step to described, passes through in mixed solution to obtain polyamic acid resin；
(4) polyamic acid resin that step (3) obtains casting film-forming: is formed into film by casting technique；
(5) film imidization: the film that step (4) obtains is heated, and it is sub- to obtain Inverter fed motor porous aluminas/polyamides
Amine film.
Preferably, in the step (1), the cellulose is lignocellulosic.
Preferably, in the step (1), the steam blasting technique is about 1.0-3.0Mpa using pressure, and the time is about
300-600s。
Preferably, in the step (2), the cellulose, aluminium isopropoxide, KH550, emulsifier mass ratio be 0.1-1:
1:0.001-0.02:0.005-0.01；More preferably, cellulose, aluminium isopropoxide, KH550, emulsifier mass ratio be 0.8-1:
1:0.001-0.005:0.008-0.01 most preferably, being 1:1:0.002:0.01.
Preferably, the emulsifier is alkyl phenol polyoxyethylene ether.
Preferably, in the step (3), amine-containing solution ratio is that mass ratio is 4,4'- diaminodiphenyl ether 20-25%
It is mixed with dimethyl acetamide 75-80%.
Preferably, the casting technique in the step (4) is to heat polyamic acid resin on slobbering machine to carry out salivation shape
At film, the film by salivation is stretched on longitudinal stretching machine according to required size.
Preferably, the heating temperature in the step (5) is 350-450 DEG C.
Herein, it should be noted that the description of above-mentioned technical proposal is exemplary, and this specification can be in different forms
It embodies, and should not be construed as limited to technical solution set forth herein.It will be so that the disclosure will on the contrary, providing these explanations
It is thorough and complete, and will sufficiently conveys range disclosed in this specification to those skilled in the art.In addition, of the invention
Technical solution be limited solely by the scope of the following claims.
For describing shape, size disclosed in the various aspects of specification and claims, ratio, angle and number only
It is example, therefore, specification and claims are not limited to shown details.In the following description, when relevant known
It is detailed by omitting when function or the detailed description of configuration are confirmed as unnecessarily obscuring the emphasis of specification and claims
Description.
Using " comprising " described in this specification, " having " and "comprising", unless " only~" is used, it is no
Can also then have another part or other parts, term used usually can be odd number but can also indicate plural form.
It is noted that although being likely to occur herein and describing various composition using term " first ", " second " etc.
And part, but these ingredients and part should not be limited by these terms.These terms are only used to distinguish an ingredient and portion
Divide and another ingredient and part.For example, the first component can be referred to as in the case where not departing from the range of this specification
Two components, and similarly, the second component can be referred to as the first component.
According to the technique and scheme of the present invention, by the pretreatment of early period, emulsification procedure, cellulose is equably supported on oxygen
Change aluminium presoma, acted on using the dispersion winding in lotion of cellulose, can by alumina dispersion be distributed to polyamides Asia
In amine film；Applicant is not intended to be subject to any theory research, but cellulose may form reticular structure inside film,
Also having on the tensile strength and elasticity modulus that improve film energetically influences.Meanwhile the introducing and the structure of cellulose,
The dielectric properties and corona-resistance property of film are also improved, service life of the film in strong-electromagnetic field is extended.
Detailed description of the invention
Fig. 1 a is the SEM figure on the surface layer of the cellulose modified Kapton of embodiment 1；
Fig. 1 b is the SEM figure of the cross section of the cellulose modified Kapton of embodiment 1；
Specific embodiment
It makes an explanation below with reference to embodiment to specific technical solution of the present invention.
Embodiment one
A kind of preparation method of cellulose modified polyester-imide film, it includes following steps:
10g lignocellulosic is crushed, alkali soaks 30min, washes, and it is dry, it is quick-fried in the steam that pressure 1.6MPa carries out 300s
Broken, obtained pretreated cellulose is added in deionized water, and magnetic agitation adds 10g aluminium isopropoxide, 0.02gKH550
Silane coupling agent, 0.1g emulsifier disperse to form uniform lotion in high-pressure emulsification machine high speed；By 4,4'- diamino hexichol
Ether 25% and dimethyl acetamide 75% (mass percent) are dissolved into containing amine aqueous solution, by lotion and containing amine aqueous solution according to matter
Amount is stirred than being 1:4 while being added in reaction kettle；Then according to pyromellitic acid anhydride and 4,4'- diaminodiphenyl ether
Mass ratio is that the ratio of 1:1~1.2 passes through the addition of pyromellitic acid anhydride substep in mixed solution to be fabricated to described
Polyamic acid resin；Obtained polyamic acid resin forms film by casting technique；Film is heated at 400 DEG C, obtains fiber
The modified polyester-imide film of element.
The SEM figure for wherein obtaining the surface layer that embodiment 1 obtains cellulose modified Kapton is as shown in Figure 1a, horizontal
The SEM figure in section is as shown in Figure 1 b.It can also be seen that film surface and inside are evenly distributed with cellulose and inorganic from SEM
Particle, cellulose tend to be formed the structure of intertexture, and this similar reticular structure is able to ascend the inner tensions of film, to change
The elasticity and tensile mechanical properties of kind film.
Embodiment two
A kind of preparation method of cellulose modified polyester-imide film, it includes following steps:
2.5g lignocellulosic is crushed, alkali soaks 30min, washes, and it is dry, it is quick-fried in the steam that pressure 1.5MPa carries out 400s
Broken, obtained pretreated cellulose is added in deionized water, and magnetic agitation adds 10g aluminium isopropoxide, 0.01gKH550
Silane coupling agent, 0.1g emulsifier disperse to form uniform lotion in high-pressure emulsification machine high speed；By 4,4'- diamino hexichol
Ether 20% and dimethyl acetamide 80% are dissolved into containing amine aqueous solution, according to mass ratio are that 1:4 is same by lotion and containing amine aqueous solution
When be added in reaction kettle and be stirred, then according to pyromellitic acid anhydride and 4, the mass ratio of 4'- diaminodiphenyl ether is 1:1
~1.2 ratio pyromellitic acid anhydride is added step by step to described passes through in mixed solution to be fabricated to polyamic acid tree
Rouge；Obtained polyamic acid resin forms film by casting technique；Film is heated at 400 DEG C, obtains cellulose modified gather
Ester imines film.
Embodiment three
A kind of preparation method of cellulose modified polyester-imide film, it includes following steps:
10g lignocellulosic is crushed, alkali soaks 30min, washes, and it is dry, it is quick-fried in the steam that pressure 1.6MPa carries out 300s
Broken, obtained pretreated cellulose is added in deionized water, and magnetic agitation adds 10 aluminium isopropoxides, 0.02gKH550
Silane coupling agent, 0.1g emulsifier disperse to form uniform lotion in high-pressure emulsification machine high speed；By 4,4'- diamino hexichol
Ether 25% and dimethyl acetamide 75% are dissolved into containing amine aqueous solution, according to mass ratio are that 1:4 is same by lotion and containing amine aqueous solution
When be added in reaction kettle and be stirred, then according to pyromellitic acid anhydride and 4, the mass ratio of 4'- diaminodiphenyl ether is 1:1
Pyromellitic acid anhydride substep is added to described~1.2 ratio passes through in mixed solution to be fabricated to polyamic acid tree
Rouge；Obtained polyamic acid resin forms film by casting technique；Film is heated at 370 DEG C, obtains cellulose modified gather
Ester imines film.
Example IV
A kind of preparation method of cellulose modified polyester-imide film, it includes following steps:
5g lignocellulosic is crushed, alkali soaks 30min, washes, and it is dry, it is quick-fried in the steam that pressure 2.0MPa carries out 300s
Broken, obtained pretreated cellulose is added in deionized water, and magnetic agitation adds 10g aluminium isopropoxide, 0.1gKH550
Silane coupling agent, 0.1g emulsifier disperse to form uniform lotion in high-pressure emulsification machine high speed；By 4,4'- diamino hexichol
Ether 25% and dimethyl acetamide 75% are dissolved into containing amine aqueous solution, according to mass ratio are that 1:10 is same by lotion and containing amine aqueous solution
When be added in reaction kettle and be stirred, then according to pyromellitic acid anhydride and 4, the mass ratio of 4'- diaminodiphenyl ether is 1:1
Pyromellitic acid anhydride substep is added to described~1.2 ratio passes through in mixed solution to be fabricated to polyamic acid tree
Rouge；Obtained polyamic acid resin forms film by casting technique；Film is heated at 430 DEG C, obtains cellulose modified gather
Ester imines film.
Embodiment five
A kind of preparation method of cellulose modified polyester-imide film, it includes following steps:
5g lignocellulosic is crushed, alkali soaks 30min, washes, and it is dry, it is quick-fried in the steam that pressure 2.0MPa carries out 600s
Broken, obtained pretreated cellulose is added in deionized water, and magnetic agitation adds 10g aluminium isopropoxide, 0.2gKH550
Silane coupling agent, 0.1g emulsifier disperse to form uniform lotion in high-pressure emulsification machine high speed；By 4,4'- diamino hexichol
Ether 25% and dimethyl acetamide 75% are dissolved into containing amine aqueous solution, according to mass ratio are that 1:10 is same by lotion and containing amine aqueous solution
When be added in reaction kettle and be stirred, then according to pyromellitic acid anhydride and 4, the mass ratio of 4'- diaminodiphenyl ether is 1:1
Pyromellitic acid anhydride substep is added to described~1.2 ratio passes through in mixed solution to be fabricated to polyamic acid tree
Rouge；Obtained polyamic acid resin forms film by casting technique；Film is heated at 360 DEG C, obtains cellulose modified gather
Ester imines film.
Embodiment six
A kind of preparation method of cellulose modified polyester-imide film, it includes following steps:
1g lignocellulosic is crushed, alkali soaks 30min, washes, and it is dry, it is quick-fried in the steam that pressure 1.6MPa carries out 300s
Broken, obtained pretreated cellulose is added in deionized water, and magnetic agitation adds 10g aluminium isopropoxide, 0.05gKH550
Silane coupling agent, 0.1g emulsifier disperse to form uniform lotion in high-pressure emulsification machine high speed；By 4,4'- diamino hexichol
Ether 25% and dimethyl acetamide 75% are dissolved into containing amine aqueous solution, according to mass ratio are that 1:8 is same by lotion and containing amine aqueous solution
When be added in reaction kettle and be stirred, then according to pyromellitic acid anhydride and 4, the mass ratio of 4'- diaminodiphenyl ether is 1:1
Pyromellitic acid anhydride substep is added to described~1.2 ratio passes through in mixed solution to be fabricated to polyamic acid tree
Rouge；Obtained polyamic acid resin forms film by casting technique；Film is heated at 400 DEG C, obtains cellulose modified gather
Ester imines film.
Cellulose modified polyester-imide film is obtained to embodiment 1-6 to perform the following performance tests.
(1), corona-resistance property is tested
The Kapton is prepared using technique according to embodiments of the present invention, preparing thickness is about 10 μm poly-
Acid imide laminated film.Laminated film is cut into the sample of several 50mm × 50mm, and carries out Inverter fed motor test.Inverter fed motor test
Using IEC-60343 standard, i.e. corona bar electrode diameter 6mm (electrode end surface diameter 4mm, radius of corner R1mm), plate electrode is straight
Diameter 50mm, test condition are room temperature, 40% or less ambient humidity, frequency 50Hz, field strength 20kV/mm.
(2), relative dielectric constant is tested
This serial experiment is designed according to international standard ASTMD150 method, is adopted using three outstanding dielectric temperature spectrometers, test fixture
With parallel-plate electrode principle, tests electrode and be made of upper/lower electrode+guard electrode.In order to ensure the accuracy of measurement result, sample
Product are prepared into the following size: 1, sample size: diameter 5-40mm, and thickness is less than 1mm；2, sample shape is prepared as circular membrane sample
Top electrode is plated on product, two sides；3, sample surfaces are flat and smooth, and guarantee contacts well with parallel pole.
(3), volume resistivity is tested
Laminated film is cut into the sample of several 50mm × 50mm, and carries out resistivity measurement.Using national standard
The method of GBT1410-2006 tests film volumetric resistivity.Instrument is the test of Air China's epoch ZST-121 volume resistance
Instrument.
(4), tensile strength and elongation at break test
Stretcher is the advanced servo-system electronic tensile machine of TSL (thin film electronic puller system).Sample preparation: polyimides
10 μm of film thickness, width 30mm.Test speed: 100 ± 30mm/min.Test load range is that 50-1000N is adjustable.Examination
Sample clamping: sample is placed in two fixture of testing machine, makes the sample longitudinal axis and upper and lower clamp central line coincident, and fixture is elastic to be suitable for.
The calculation formula of tensile strength:
Tensile strength calculation formula:
σ=F/b
σ: tensile strength (kN/m)
F: force value (N)
B: width (mm).
Elongation at break calculation formula:
Elongation at break=△ L/L*100%
Former long L, deformed breaking length are L', then extension at break △ L=L'-L.
(5), elasticity modulus is tested
Using " nano-hardness tester and Laser Ultrasonic Technique detect thin flexible film modulus " (Chinese measuring technology, 2007 years the
The phase of volume 33 the 1st) test method recorded carries out elasticity modulus test to the film of invention, and film thickness selects 100 μm.Impression examination
Instrument is tested using microhardness test instrument Fischerscopo H100.Pressure head used in test is triangular pyramid pressure head, indentation test
It is carried out according to iso standard 14577-1.Test setting three maximum loads 5,10,15mN.Loading procedure in 30s points 60 times it is complete
Creep time when at, maximum load is set as 30s.Uninstall process is identical as load.Maximum load, loading velocity are being set,
Behind selected sample position to be measured, the load-displacement relationship during test macro automatically and continuously recording loading and unloading.Obtain two
The different curve of item is because the elastic-plastic of sample generating material in the load of power deforms, and in the unloading of power, elasticity is extensive
It is multiple.Then elasticity modulus is calculated by formula.
Electrical property and Mechanics Performance Testing are carried out to the sample of embodiment, as a result such as table 1.
Table 1
It can be seen that from table compared with prior art, cellulose modified Kapton of the invention, including resistance to
Every electrical property including corona performance is improved, and the high voltage electric field lower service life extends significant.Simultaneously as cellulose is equably
It is even introduced with reticular structure, so that mechanical property of the film in terms of tensile strength and elasticity modulus is also improved.
The above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be to the present invention
Embodiment restriction.For those of ordinary skill in the art, it can also make on the basis of the above description
Other various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all of the invention
Made any modifications, equivalent replacements, and improvements etc., should be included in the protection of the claims in the present invention within spirit and principle
Within the scope of.
The present invention at least provides following scheme:
A kind of cellulose modified Kapton of scheme 1., including constituent component as follows in parts by weight:
About 150-200 parts of polyimides, about 1-5 parts of nano alumina particles, about 0.01-1 parts of cellulose, silane coupling agent
About 1-5 parts, which is characterized in that cellulose can be supported on nano alumina particles, and what is be evenly distributed in the film is nano oxidized
Aluminium.
The cellulose modified polyester-imide film of the one kind of scheme 2. as described in scheme 1 or 2, which is characterized in that described to receive
The average grain diameter of rice aluminium oxide particles is about 2-50nm.
The cellulose modified polyester-imide film of the one kind of scheme 3. as described in any one of scheme 1 to 3, feature exist
In the cellulose is 15-20% relative to the weight fraction of the nano alumina particles.
A kind of preparation method of the cellulose modified Kapton as described in any one of scheme 1-3 of scheme 4.,
It includes the following steps:
Step (1): cellulose pretreatment: cellulose is crushed, and is then carried out alkali leaching processing, is washed, dries；Again into
Row Steam explosion treatment；
Step (2): preparation lotion: the pretreated cellulose of step (1) being added in deionized water, magnetic agitation,
Aluminium isopropoxide, KH550 silane coupling agent, emulsifier are added, high-pressure emulsification machine high speed disperses to form uniform lotion；
Step (3): it prepares polyamide: 4,4'- diaminodiphenyl ether and dimethyl acetamide being dissolved into and contained
Amine aqueous solution stirs the lotion of step (2) and described be added in reaction kettle simultaneously according to mass ratio for 1:1.1~20 containing amine aqueous solution
Mixing, then according to pyromellitic acid anhydride and 4, the mass ratio of 4'- diaminodiphenyl ether for 1:1~1.2 ratio by equal benzene
Tetracarboxylic acid dianhydride be added step by step to it is above-mentioned through in mixed solution to obtain polyamic acid resin；
Step (4): the polyamic acid resin that step (3) obtains casting film-forming: is formed into film by casting technique；
Step (5): film imidization: the film that step (4) obtains is heated, and is obtained special with improved Inverter fed motor
The cellulose modified Kapton of property.
The preparation method as described in scheme 4 of scheme 5., which is characterized in that in the step (1), the cellulose is wooden
Cellulose.
The preparation method as described in scheme 4 of scheme 6., which is characterized in that in the step (1), the steam blasting technique
It is about 1.0-3.0Mpa using pressure, the time is about 300-600s.
The preparation method as described in scheme 4 of scheme 7., which is characterized in that in the step (2), the pretreated fibre
Tie up element, aluminium isopropoxide, KH550, emulsifier mass ratio be 0.1-1:1:0.001-0.02:0.005-0.01.
Preparation method of the scheme 8. as described in any one of scheme 4 to 7, which is characterized in that the emulsifier is alkyl phenol
Polyoxyethylene ether.
Preparation method of the scheme 9. as described in any one of scheme 4 to 8, which is characterized in that amine-containing in the step (3)
Solution ratio is that mass ratio is that 4,4'- diaminodiphenyl ether 20-25% and dimethyl acetamide 75-80% mix.
Preparation method of the scheme 10. as described in any one of scheme 4 to 9, which is characterized in that adding in the step (5)
Hot temperature is 350-450 DEG C.
The preparation method of one or more cellulose modified Kaptons can be also provided independently in the present invention.Example
Such as:
The preparation method of the cellulose modified Kapton of scheme 11., described method includes following steps:
Step (1): cellulose pretreatment: cellulose is crushed, and is then carried out alkali leaching processing, is washed, dries；Again into
Row Steam explosion treatment；
Step (2): preparation lotion: the pretreated cellulose of step (1) being added in deionized water, magnetic agitation,
Aluminium isopropoxide, KH550 silane coupling agent, emulsifier are added, high-pressure emulsification machine high speed disperses to form uniform lotion；
Step (3): it prepares polyamide: 4,4'- diaminodiphenyl ether and dimethyl acetamide being dissolved into and contained
Amine aqueous solution stirs the lotion of step (2) and described be added in reaction kettle simultaneously according to mass ratio for 1:1.1~20 containing amine aqueous solution
Mixing, then according to pyromellitic acid anhydride and 4, the mass ratio of 4'- diaminodiphenyl ether for 1:1~1.2 ratio by equal benzene
Tetracarboxylic acid dianhydride be added step by step to it is above-mentioned through in mixed solution to obtain polyamic acid resin；
Step (4): the polyamic acid resin that step (3) obtains casting film-forming: is formed into film by casting technique；
Step (5): film imidization: the film that step (4) obtains is heated, and is obtained special with improved Inverter fed motor
The cellulose modified Kapton of property.
Preparation method of the scheme 12. as described in scheme 11, which is characterized in that in the step (1), the cellulose is wood
Matter cellulose.
Preparation method of the scheme 13. as described in scheme 11, which is characterized in that in the step (1), the steam blasting work
Skill is about 1.0-3.0Mpa using pressure, and the time is about 300-600s.
Preparation method of the scheme 14. as described in scheme 11, which is characterized in that described pretreated in the step (2)
Cellulose, aluminium isopropoxide, KH550, emulsifier mass ratio be 0.1-1:1:0.005-0.02:0.005-0.01.
Preparation method of the scheme 15. as described in any one of scheme 11 to 14, which is characterized in that the emulsifier is alkyl
Phenol polyethenoxy ether.
Preparation method of the scheme 16. as described in any one of scheme 11 to 15, which is characterized in that in the step (3), contain
Amine aqueous solution proportion is that mass ratio is that 4,4'- diaminodiphenyl ether 20-25% and dimethyl acetamide 75-80% mix.
Preparation method of the scheme 17. as described in any one of scheme 11 to 16, which is characterized in that in the step (5)
Heating temperature is 350-450 DEG C.
Claims (10)
1. a kind of cellulose modified Kapton, including constituent component as follows in parts by weight:
About 150-200 parts of polyimides, about 1-5 parts of nano alumina particles, about 0.01-1 parts of cellulose, silane coupling agent about 1-
5 parts, which is characterized in that cellulose is supported on nano alumina particles, the nano aluminium oxide being evenly distributed in the film.
2. a kind of cellulose modified polyester-imide film as described in claim 1, which is characterized in that the nano aluminium oxide
The average grain diameter of particle is about 2-50nm.
3. a kind of cellulose modified polyester-imide film as described in any one of claims 1 to 2, which is characterized in that institute
It is 15-20% that cellulose, which is stated, relative to the weight fraction of the nano alumina particles.
4. a kind of preparation method of cellulose modified Kapton as claimed any one in claims 1 to 3, packet
Include following steps:
Step (1): cellulose pretreatment: cellulose is crushed, and is then carried out alkali leaching processing, is washed, dries；It is steamed again
Vapour explosion treatment；
Step (2): preparation lotion: the pretreated cellulose of step (1) being added in deionized water, magnetic agitation, then plus
Enter aluminium isopropoxide, KH550 silane coupling agent, emulsifier, high-pressure emulsification machine high speed disperses to form uniform lotion；
Step (3): it prepares polyamide: 4,4'- diaminodiphenyl ether and dimethyl acetamide being dissolved into amine-containing molten
Liquid, by the lotion of step (2) and it is described containing amine aqueous solution according to mass ratio be 1:1.1~20 be added in reaction kettle simultaneously stir it is mixed
Close, then according to pyromellitic acid anhydride and 4, the mass ratio of 4'- diaminodiphenyl ether for 1:1~1.2 ratio by equal benzene four
Formic acid dianhydride be added step by step to it is above-mentioned through in mixed solution to obtain polyamic acid resin；
Step (4): the polyamic acid resin that step (3) obtains casting film-forming: is formed into film by casting technique；
Step (5): film imidization: the film that step (4) obtains is heated, and is obtained with improved corona resisting characteristics
Cellulose modified Kapton.
5. preparation method as claimed in claim 4, which is characterized in that in the step (1), the cellulose is wood fibre
Element.
6. preparation method as claimed in claim 4, which is characterized in that in the step (1), the steam blasting technique is used
Pressure is about 1.0-3.0Mpa, and the time is about 300-600s.
7. preparation method as claimed in claim 4, which is characterized in that in the step (2), the pretreated fiber
Element, aluminium isopropoxide, KH550, emulsifier mass ratio be 0.1-1:1:0.001-0.02:0.005-0.01.
8. the preparation method as described in any one of claim 4 to 7, which is characterized in that the emulsifier is alkyl phenol polyoxy
Vinethene.
9. the preparation method as described in any one of claim 4 to 8, which is characterized in that in the step (3), contain amine aqueous solution
Proportion is that mass ratio is that 4,4'- diaminodiphenyl ether 20-25% and dimethyl acetamide 75-80% mix.
10. the preparation method as described in any one of claim 4 to 9, which is characterized in that the heating temperature in the step (5)
Degree is 350-450 DEG C.
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| CN115109285A (en) * | 2022-06-21 | 2022-09-27 | 太湖方舟新材料科技有限公司 | Wear-resistant polyimide insulating film and preparation method thereof |
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