CN104829837B - A kind of method using magnetic particle sensing to add hot preparation soluble polyimide - Google Patents
A kind of method using magnetic particle sensing to add hot preparation soluble polyimide Download PDFInfo
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Abstract
A kind of method using magnetic particle sensing to add hot preparation soluble polyimide, the present invention relates to the preparation method of soluble polyimide.The invention solves the problems that existing when preparing soluble polyimide, the resin property that soluble polyimide presoma polyamic acid is brought by external heat source heating inequality during acid imide is cyclized is unstable, and heating ramp rate is slow, the problem of imidization cycle length.Preparation method: first prepare high magnetic response polyimides/Fe3O4Composite magnetic nanoparticle, then by soluble polyamide acid solution, water entrainer and high magnetic response polyimides/Fe3O4Composite magnetic nanoparticle is placed in reacting by heating in HF induction heating apparatus, last precipitating, filters, precipitation washing, dries.Present invention is mainly used for a kind of method using magnetic particle sensing to add hot preparation soluble polyimide.
Description
Technical field
The present invention relates to the preparation method of soluble polyimide.
Background technology
Polyimides is the aromatic heterocyclic polymer in constitutional repeating unit containing imide ring, and it is up to now in industry
One of the highest polymeric material of temperature classification of field application, the combination property of its excellence in addition, with thin film, resin, fiber,
Separate the form such as film and be widely used in Aero-Space, the field such as electric.Traditional polyimides is generally by aromatic series
Tetracarboxylic acid anhydride and aromatic diamine be raw material by being initially formed polyamic acid, then imidization dehydration formed polyimides, common
Imidization method has hot imidization method and chemical imidization method, has good application foundation.But existing hot imidization reaction week
Phase is long, and energy resource consumption can be significantly greatly increased, such as the hot imidization reaction experience 170-190 of polyimides in patent CN101985498B
DEG C 10-12h back flow reaction, temperature reaction slowly and long heated at constant temperature process too increase equipment loss.Chemistry
Imidization is in addition to forming imide ring, it is also possible to forming different acid imide, the molecular weight of product that the most thoroughly can cause of imidization divides
Cloth broadens, it is difficult to directly obtain high-performance polyimide, combines heat after using chemical imidization in patent CN1175031C
Imidization reaction just can overcome problem above, but its follow-up hot imidization response time is also at 2h-20h.Document
(Macromol.Rapid Comm.2011,32:254-288) and patent (CN101735457B) report employing microwave radiation method
Prepare the production method of soft polyimide foam, hence it is evident that improve the production cycle of polyimide foam, but the side used
Method pertains only to polyimide foam, can not be generalized to polyimides field；Use thermal source that external container is heated simultaneously, can lead
Cause system heating inequality, because the performance of polyimides is directly related with imidization degree, locally the difference of heats is to poly-
Acid imide product stability brings problem.
Along with developing rapidly of microelectronics and aerospace field, owing to polyimides is easily prepared and stable performance,
High-performance polyimide demand sharply increases: composite wood mentioned by document (Thin Solid Film 2011,519:2339-2343)
Polyimides prepreg used by material, the imidization excessive cycle that its solidification process occurs, it is difficult to improving production efficiency；Document
(Adv.Funct.Mater.2015,25:78-84) mentions for polyimides used for electronic packaging equally, faces imidization equally
The difficult problem that speed is slow, imidization degree is unstable.Conventionally used composite and adhesive polyimides are required for experience
The hot imidization process that 5-15h does not waits.It can be seen that the Long Time Thermal imines of polyimides conventional manufacturing process seriously limits
The energy efficiency when production cycle of material, application and mould consumption.
Common sensing heating is a kind of to be easily achieved the method that magnetic mold quickly heats.It is that alternating current is attached by being positioned at
Near conductive coil produces magnetic field, and externally-applied magnetic field causes vortex flow within the workpiece, and vortex flow produces heat due to electricresistance effect
Amount.Conventional sensing heating is to use heating source outside equipment, but for larger volume (such as glass container) external heat, equally
The problems such as inequality of being heated in bringing container and the rate of heat addition are slow.
Utilizing the distinctive hysteresis effect of nanoparticle, relaxation effect etc. can be heat energy by alternating magnetic field energy conversion, and subtracts
Few power consumption.But high-curie temperature magnetic nano-particle is (such as Fe3O4、Fe2O3) in resin and solution system, it is easy to group
Combinate form becomes cluster, while impact dispersibility in system, directly uses magnetic nano-particle to be heated to higher in system
Temperature can cause significantly being heated inequality and very difficult maintenance system temperature a stationary value.And use the magnetic Nano of cladding
Particle have not been reported as thermal source, and can cladding be used to promote preparation effect be unknown.
Summary of the invention
The invention solves the problems that existing when preparing soluble polyimide, soluble polyimide presoma-polyamic acid exists
The resin property instability brought by external heat source heating inequality during acid imide cyclisation, and heating ramp rate is slow, sub-
The problem of amination cycle length, and provide a kind of and use magnetic particle to sense the method adding hot preparation soluble polyimide.
A kind of method using magnetic particle sensing to add hot preparation soluble polyimide of the present invention is to enter according to the following steps
OK:
One, 1., under nitrogen atmosphere, room temperature and stirring condition, in three-necked bottle, high bp polar solvent and fragrance are added
Diamidogen, reacts 0.5h～1h, then adds aromatic dianhydride in three-necked bottle, reacts 1h～5h, then adds tertiary amine in three-necked bottle,
Reaction 2h～3h, stops stirring, obtains reactant liquor, under agitation, is instilled with the speed of 2mL/s～10mL/s by reactant liquor
In acetone, after being added dropwise to complete, continue stirring 1h～6h, then stand 3 days～10 days, obtain the standing liquid containing filament, will contain
In the standing liquid of filament, filament is taken out, and is dried by filament, gathered in the vacuum drying oven that temperature is 20 DEG C～30 DEG C
Amic acid amine salt；
Described aromatic diamines is 1:(0.90～0.95 with the mol ratio of aromatic diamines acid anhydride)；Described aromatic diamines and uncle
The mol ratio of amine is 1:(1.90～2.10)；Described aromatic dianhydride and the gross mass of aromatic diamines and high bp polar solvent
Mass ratio is 1:5；
Described aromatic diamines is 4,4 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, two (3-amino-benzene oxygens)
Benzophenone or 2-(3-aminophenyl)-5-amino benzothiazole；
Described aromatic dianhydride be 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3,4 ', 4 '-diphenyl ether tetracarboxylic dianhydride or
3,3,4 ', 4 '-two sulfuryl tetracarboxylic dianhydrides；
Described tertiary amine is a kind of or the most several in triethylamine, trialkyl tertiary amine and Dodecyl Dimethyl Amine
Mixture；
Described high bp polar solvent is DMAC N,N' dimethyl acetamide, N,N-dimethylformamide and N-crassitude
A kind of or the most several mixture in ketone；
2., under agitation, polyamic acid amine salt is placed in hydrothermal reaction kettle, and add iron salt, Polyethylene Glycol and
Ethylene glycol solvent, reacts 5h～10h, and then hydrothermal reaction kettle is warming up to temperature is 190 DEG C～210 DEG C, and is 190 in temperature
DEG C～210 DEG C at be incubated 3h～7h, then hydrothermal reaction kettle is naturally cooled to room temperature, obtains crude product, uses outer strong magnet general
Crude product separates washing 3 times～5 times, and dries at temperature is 80 DEG C～120 DEG C, obtains high magnetic response polyimides/Fe3O4
Composite magnetic nanoparticle；
Described polyamic acid amine salt is 10:(1～50 with the mass ratio of iron salt)；Described polyamic acid amine salt and poly-second
The mass ratio of glycol is 10:(0.1～3.0)；Described polyamic acid amine salt is 10:(80～300 with the mass ratio of ethylene glycol)；
Described iron salt be the one in Iron(III) chloride hexahydrate, Iron dichloride tetrahydrate and four ferrous sulfate hydrates or its
In several mixture；
Described high magnetic response polyimides/Fe3O4In composite magnetic nanoparticle, the general structure of polyimides is:Described n is 9～49；
Described R1For-O-orDescribed R2For
Or described high magnetic response polyimides/Fe3O4The structure of polyimides in composite magnetic nanoparticle
Formula is:Described n is 9～49；Described R2For
Two, the three-necked bottle that asbestos cloth wraps up is placed in the heating loop coil of HF induction heating apparatus, then to three
Logical nitrogen atmosphere in neck bottle, then add in three-necked bottle soluble polyamide acid solution, water entrainer and high magnetic response polyimides/
Fe3O4Composite magnetic nanoparticle, low whipping speed is 25rpm～100rpm, stirs 1h～5h, obtains mixed solution；
Described soluble polyamide acid solution and the mass ratio of water entrainer are 10:(2～4.8)；Described high magnetic response
Polyimides/Fe3O4Composite magnetic nanoparticle is (0.1～0.5) with the mass ratio of soluble polyamide acid solution: 1；
Three, under conditions of the frequency at alternating magnetic field is 80kHz～200kHz, the output of regulation HF induction heating apparatus
Power makes mixed solution be warming up to 120 DEG C～145 DEG C, and at temperature is 120 DEG C～145 DEG C back flow reaction 0.5h～
1.5h, discharge water entrainer and water, then the output regulating HF induction heating apparatus make mixed solution be warming up to 146 DEG C～
164 DEG C, stopped reaction after being warming up to 146 DEG C～164 DEG C, obtain reacted solution；
Four, close HF induction heating apparatus, reacted solution is down to room temperature, utilize permanent magnet by high in three-necked bottle
Magnetic response polyimides/Fe3O4Composite magnetic nanoparticle removes, and obtains the solution after removing magnetic nano-particle, then will remove
Solution after magnetic nano-particle is added drop-wise in distilled water, precipitating 1h～4h, filters, and precipitation washing, is finally 130 DEG C in temperature
～dry at 140 DEG C, obtain soluble polyimide；
Described soluble polyimide general structure is:
Described n is 3～49；
Described R1For:
Described R2For:
The invention has the beneficial effects as follows: the present invention uses high magnetic response polyimides/Fe3O4Composite magnetic nanoparticle exists
Magnetothermal effect sensing under alternation external magnetic field adds hot preparation polyimides.By polyimides bag built-in in polyamic acid solution
Cover magnetic nano-particle, it is achieved the inside rapid thermal response effect that external heat source does not possesses.Additionally, whole process relates to rise
The multistep process, only regulation output such as temperature heating-zone of constant temperature water-intensification heating can only improve the existing temperature of solution, but folded
Add the high magnetic response polyimides/Fe of dependence3O4Composite magnetic nanoparticle, the most quickly meets with a response consistent, stable holding also
And higher ectonexine temperature.
The present invention uses high magnetic response polyimides/Fe3O4Composite magnetic nanoparticle is as corresponding thermal source, it is to avoid magnetic
Property the high surface energy of nanoparticle and even magnetic moment intermolecular forces, the magnetic-particle agglomeration in the polyamic acid solution caused,
It is difficult in system form mono-dispersed nano particle, the problem that simultaneously can hinder again the dehydration condensation of polyamic acid.Adopt
With the magnetic nano-particle of Coated with Organic Matter, rely on the balance of the repulsive force between polymer and interparticle captivation, it is achieved super
The single dispersing of paramagnetic magnetic nano-particle, further with phase between the polyamic acid in the polyimides of particle surface and solution
As the backbone structure intermolecular force that brings, reach thermal source dispersion homogeneity in polyamic acid solution, it is to avoid not
The temperature being dispersed in high-temperature hot imidization is unstable, improves the stability of heats, simultaneously compared to other Organic substances
Coated magnetic particles, preparation has the best magnetic response effect in situ, thus quickly improves reaction temperature.
The present invention is applicable in hot imidization process, the polymerization knot that the polyimides formed does not separates out in polar solvent
Structure type, it is ensured that with permanent magnet, magnetic nano-particle in solution can be pipetted after prepared by polymer, thus not affect matrix
Resin property.The method can be greatly improved imidization efficiency, shortens the response time (from conventional hot imidization 5-15 hour
Shorten to 0.5～1.5 hour), obtain stable performance simultaneously and good soluble polyimide is (strong from hot strength and bending
Degree, glass transition temperature, heat decomposition temperature data), thus meet the field such as Aero-Space and microelectronics to easily prepared and
Stable performance polyimides demand.
The present invention uses magnetic particle to sense the method adding hot preparation soluble polyimide for a kind of.
Accompanying drawing explanation
Fig. 1 is the high magnetic response polyimides/Fe of embodiment one preparation3O4The scanning electron of composite magnetic nanoparticle shows
Micro mirror figure；
Fig. 2 is the high magnetic response polyimides/Fe of embodiment one preparation3O4The X-ray diffraction of composite magnetic nanoparticle is bent
Line chart；
Fig. 3 is the high magnetic response polyimides/Fe of embodiment one preparation3O4The infrared curve chart of composite magnetic nanoparticle；
Fig. 4 is the high magnetic response polyimides/Fe of embodiment one preparation3O4The vibrating example magnetic of composite magnetic nanoparticle
Strong index contour figure；
Fig. 5 is that the present invention uses magnetic particle sensing to add the heating arrangement schematic diagram of hot preparation soluble polyimide；1 is
Condensing tube, 2 is water-taker, and 3 is thermometer, and 4 is stirring paddle, and 5 is nitrogen port, and 6 is loop coil, and 7 is high magnetic response polyamides
Imines/Fe3O4Composite magnetic nanoparticle, 8 is polyamic acid solution, and 9 is HF induction heating apparatus；
Fig. 6 is infrared curve chart；1 is the soluble polyimide of embodiment one preparation；2 is the solvable of embodiment two preparation
Property polyimides；3 is the soluble polyimide of embodiment three preparation；4 is the soluble polyimide of embodiment four preparation；5
Soluble polyimide for embodiment five preparation；6 is the soluble polyimide of contrast experiment one preparation；7 is contrast experiment
The soluble polyimide of two preparations.
Detailed description of the invention
Detailed description of the invention one: combine Fig. 5 and illustrate present embodiment, a kind of employing magnetic described in present embodiment
It is to sequentially include the following steps: that particle sensing adds the method for hot preparation soluble polyimide
One, 1., under nitrogen atmosphere, room temperature and stirring condition, in three-necked bottle, high bp polar solvent and fragrance are added
Diamidogen, reacts 0.5h～1h, then adds aromatic dianhydride in three-necked bottle, reacts 1h～5h, then adds tertiary amine in three-necked bottle,
Reaction 2h～3h, stops stirring, obtains reactant liquor, under agitation, is instilled with the speed of 2mL/s～10mL/s by reactant liquor
In acetone, after being added dropwise to complete, continue stirring 1h～6h, then stand 3 days～10 days, obtain the standing liquid containing filament, will contain
In the standing liquid of filament, filament is taken out, and is dried by filament, gathered in the vacuum drying oven that temperature is 20 DEG C～30 DEG C
Amic acid amine salt；
Described aromatic diamines is 1:(0.90～0.95 with the mol ratio of aromatic diamines acid anhydride)；Described aromatic diamines and uncle
The mol ratio of amine is 1:(1.90～2.10)；Described aromatic dianhydride and the gross mass of aromatic diamines and high bp polar solvent
Mass ratio is 1:5；
Described aromatic diamines is 4,4 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, two (3-amino-benzene oxygens)
Benzophenone or 2-(3-aminophenyl)-5-amino benzothiazole；
Described aromatic dianhydride be 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3,4 ', 4 '-diphenyl ether tetracarboxylic dianhydride or
3,3,4 ', 4 '-two sulfuryl tetracarboxylic dianhydrides；
Described tertiary amine is a kind of or the most several in triethylamine, trialkyl tertiary amine and Dodecyl Dimethyl Amine
Mixture；
Described high bp polar solvent is DMAC N,N' dimethyl acetamide, N,N-dimethylformamide and N-crassitude
A kind of or the most several mixture in ketone；
2., under agitation, polyamic acid amine salt is placed in hydrothermal reaction kettle, and add iron salt, Polyethylene Glycol and
Ethylene glycol solvent, reacts 5h～10h, and then hydrothermal reaction kettle is warming up to temperature is 190 DEG C～210 DEG C, and is 190 in temperature
DEG C～210 DEG C at be incubated 3h～7h, then hydrothermal reaction kettle is naturally cooled to room temperature, obtains crude product, uses outer strong magnet general
Crude product separates washing 3 times～5 times, and dries at temperature is 80 DEG C～120 DEG C, obtains high magnetic response polyimides/Fe3O4
Composite magnetic nanoparticle；
Described polyamic acid amine salt is 10:(1～50 with the mass ratio of iron salt)；Described polyamic acid amine salt and poly-second
The mass ratio of glycol is 10:(0.1～3.0)；Described polyamic acid amine salt is 10:(80～300 with the mass ratio of ethylene glycol)；
Described iron salt be the one in Iron(III) chloride hexahydrate, Iron dichloride tetrahydrate and four ferrous sulfate hydrates or its
In several mixture；
Described high magnetic response polyimides/Fe3O4In composite magnetic nanoparticle, the general structure of polyimides is:Described n is 9～49；
Described R1For-O-orDescribed R2For
Or described high magnetic response polyimides/Fe3O4The knot of polyimides in composite magnetic nanoparticle
Structure formula is:Described n is 9～49；Described R2For
Two, the three-necked bottle that asbestos cloth wraps up is placed in the heating loop coil of HF induction heating apparatus, then to three
Logical nitrogen atmosphere in neck bottle, then add in three-necked bottle soluble polyamide acid solution, water entrainer and high magnetic response polyimides/
Fe3O4Composite magnetic nanoparticle, low whipping speed is 25rpm～100rpm, stirs 1h～5h, obtains mixed solution；
Described soluble polyamide acid solution and the mass ratio of water entrainer are 10:(2～4.8)；Described high magnetic response
Polyimides/Fe3O4Composite magnetic nanoparticle is (0.1～0.5) with the mass ratio of soluble polyamide acid solution: 1；
Three, under conditions of the frequency at alternating magnetic field is 80kHz～200kHz, the output of regulation HF induction heating apparatus
Power makes mixed solution be warming up to 120 DEG C～145 DEG C, and at temperature is 120 DEG C～145 DEG C back flow reaction 0.5h～
1.5h, discharge water entrainer and water, then the output regulating HF induction heating apparatus make mixed solution be warming up to 146 DEG C～
164 DEG C, stopped reaction after being warming up to 146 DEG C～164 DEG C, obtain reacted solution；
Four, close HF induction heating apparatus, reacted solution is down to room temperature, utilize permanent magnet by high in three-necked bottle
Magnetic response polyimides/Fe3O4Composite magnetic nanoparticle removes, and obtains the solution after removing magnetic nano-particle, then will remove
Solution after magnetic nano-particle is added drop-wise in distilled water, precipitating 1h～4h, filters, and precipitation washing, is finally 130 DEG C in temperature
～dry at 140 DEG C, obtain soluble polyimide；
Described soluble polyimide general structure is:
Described n is 3～49；
Described R1For:
Described R2For:
Fig. 5 is that the present invention uses magnetic particle sensing to add the heating arrangement schematic diagram of hot preparation soluble polyimide；1 is
Condensing tube, 2 is water-taker, and 3 is thermometer, and 4 is stirring paddle, and 5 is nitrogen port, and 6 is loop coil, and 7 is high magnetic response polyamides
Imines/Fe3O4Composite magnetic nanoparticle, 8 is polyamic acid solution, and 9 is HF induction heating apparatus.
Present embodiment provides the benefit that: the present invention uses high magnetic response polyimides/Fe3O4Composite magnetic nanoparticle
Son magnetothermal effect sensing under alternation external magnetic field adds hot preparation polyimides.Sub-by built-in polyamides in polyamic acid solution
Amine coated magnetic nanoparticle, it is achieved the inside rapid thermal response effect that external heat source does not possesses.Additionally, whole process relates to
To the multistep process such as heating-zone of constant temperature water-intensification heating that heat up, only regulation output can only improve the existing temperature of solution, but
It is that superposition relies on high magnetic response polyimides/Fe3O4Composite magnetic nanoparticle, the most quickly meet with a response consistent, stable guarantor
Hold and higher ectonexine temperature.
The present invention uses high magnetic response polyimides/Fe3O4Composite magnetic nanoparticle is as corresponding thermal source, it is to avoid magnetic
Property the high surface energy of nanoparticle and even magnetic moment intermolecular forces, the magnetic-particle agglomeration in the polyamic acid solution caused,
It is difficult in system form mono-dispersed nano particle, the problem that simultaneously can hinder again the dehydration condensation of polyamic acid.Adopt
With the magnetic nano-particle of Coated with Organic Matter, rely on the balance of the repulsive force between polymer and interparticle captivation, it is achieved super
The single dispersing of paramagnetic magnetic nano-particle, further with phase between the polyamic acid in the polyimides of particle surface and solution
As the backbone structure intermolecular force that brings, reach thermal source dispersion homogeneity in polyamic acid solution, it is to avoid not
The temperature being dispersed in high-temperature hot imidization is unstable, improves the stability of heats, simultaneously compared to other Organic substances
Coated magnetic particles, preparation has the best magnetic response effect in situ, thus quickly improves reaction temperature.
The present invention is applicable in hot imidization process, the polymerization knot that the polyimides formed does not separates out in polar solvent
Structure type, it is ensured that with permanent magnet, magnetic nano-particle in solution can be pipetted after prepared by polymer, thus not affect matrix
Resin property.The method can be greatly improved imidization efficiency, shortens the response time (from conventional hot imidization 5-15 hour
Shorten to 0.5～1.5 hour), obtain stable performance simultaneously and good soluble polyimide is (strong from hot strength and bending
Degree, glass transition temperature, heat decomposition temperature data), thus meet the field such as Aero-Space and microelectronics to easily prepared and
Stable performance polyimides demand.
Detailed description of the invention two: present embodiment is unlike detailed description of the invention one: the permanent magnetism described in step 4
Ferrum be magnetic induction be 0.1 tesla～1.5 teslas.Other is identical with detailed description of the invention two.
Detailed description of the invention three: present embodiment is unlike one of detailed description of the invention one or two: institute in step 2
The water entrainer stated is the mixture of a kind of or two of which in toluene and dimethylbenzene.Other is with detailed description of the invention one or two-phase
With.
Detailed description of the invention four: present embodiment is unlike one of detailed description of the invention one to three: institute in step one
The high magnetic response polyimides/Fe stated3O4The particle diameter of composite magnetic nanoparticle is 50nm～3um.Other and detailed description of the invention
One to three is identical.
Detailed description of the invention five: present embodiment is unlike one of detailed description of the invention one to four: institute in step 2
In the soluble polyamide acid solution stated, the general structure of soluble polyamide acid is:
Described n is 3～49；
Described R1For:
Described R2For:
Other is identical with detailed description of the invention one to four.
Detailed description of the invention six: present embodiment is unlike one of detailed description of the invention one to five: institute in step 2
The soluble polyamide acid solution stated is prepared the most according to the following steps:
In a nitrogen atmosphere, under room temperature, aromatic diamines and intensive polar solvent are placed in three-necked bottle, stirring and dissolving 1h～3h,
Then in three-necked bottle, add aromatic series tetracarboxylic dianhydride with the rate of addition of 1mg/s～10mg/s, obtain reaction system, will reaction
System continues stirring and dissolves 1h～5h, obtains soluble polyamide acid solution；
Described aromatic diamines is 1:(0.75～0.98 with the mol ratio of aromatic series tetracarboxylic dianhydride)；Described aromatic diamines
The 10%～15% of reaction system quality is accounted for the quality summation of aromatic series tetracarboxylic dianhydride；
Described intensive polar solvent is the mixed of one or both in N,N-dimethylformamide and DMAC N,N' dimethyl acetamide
Compound；
Described aromatic diamines is double (the trifluoromethyl)-4,4-benzidine of 2,2'-, 1,3-pair (3-amino-benzene oxygen)
Double (4-amino-benzene oxygen) benzene of benzene, 1,3-, 3,3'-diaminodiphenyl ether or 3,3'-diaminobenzophenone；
Described aromatic series tetracarboxylic dianhydride is 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3,4 ', 4 '-diphenyl ether tetrabasic carboxylic acid
Dianhydride, Bisphenol A Type Diether Dianhydride or 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids.Other is identical with detailed description of the invention one to five.
Use following example checking beneficial effects of the present invention: combine Fig. 5 specific illustrative embodiment one to five.
Embodiment one:
The present embodiment is a kind of uses magnetic particle to sense the method adding hot preparation soluble polyimide, specifically by following
Step is carried out:
One, 1., under nitrogen atmosphere, room temperature and stirring condition, in three-necked bottle, 101.8g N, N-dimethylacetamide are added
Amine and 10.00g (0.05mol) 3,4 '-diaminodiphenyl ether, reacts 1h, then adds 10.36g (0.0475mol) in three-necked bottle
3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, reacts 3h, then adds 10.10g triethylamine in three-necked bottle, react 3h, stop
Stirring, obtains reactant liquor, under agitation, instills in acetone by reactant liquor with the speed of 5mL/s, after being added dropwise to complete, continues
Stirring 2h, then stands 10 days, obtains the standing containing filament, taken out by filament in the standing containing filament, in temperature be
Filament is dried by the vacuum drying oven of 25 DEG C, obtains polyamic acid amine salt；
2., under agitation, 2g polyamic acid amine salt is placed in 100mL hydrothermal reaction kettle, and adds 10g six hydration
Ferric chloride, 0.5g Polyethylene Glycol and 40g ethylene glycol solvent, react 10h, and then hydrothermal reaction kettle is warming up to temperature is 205
DEG C, and be 205 times insulation 6h in temperature, then hydrothermal reaction kettle is naturally cooled to room temperature, obtain crude product, use outer strong magnet
Crude product is separated washing 3 times, and dries at temperature is 120 DEG C, obtain high magnetic response polyimides/Fe3O4Composite magnetic is received
Rice corpuscles；
Two, the three-necked bottle that asbestos cloth wraps up is placed in the heating loop coil of HF induction heating apparatus, then to three
Logical nitrogen atmosphere in neck bottle, then it is poly-to add 50g soluble polyamide acid solution, 15g toluene and 5g height magnetic response in three-necked bottle
Acid imide/Fe3O4Composite magnetic nanoparticle, low whipping speed is 100rpm, stirs 1h, obtains mixed solution；
Three, under conditions of the frequency at alternating magnetic field is 100kHz, the output of regulation HF induction heating apparatus makes
Obtain mixed solution and be warming up to 125 DEG C, and back flow reaction 0.5h at temperature is 125 DEG C, discharge toluene and water, then regulate high frequency sense
The output answering firing equipment makes mixed solution be warming up to 149 DEG C, and stopped reaction after being warming up to 149 DEG C, after being reacted
Solution；
Four, close HF induction heating apparatus, reacted solution is down to room temperature, utilize permanent magnet by high in three-necked bottle
Magnetic response polyimides/Fe3O4Composite magnetic nanoparticle removes, and obtains the solution after removing magnetic nano-particle, then will remove
Solution after magnetic nano-particle is added drop-wise in distilled water, precipitating 1h, filters, precipitation washing, finally dries at temperature is 130 DEG C
Dry, obtain soluble polyimide.
The structural formula of soluble polyimide prepared by the present embodiment is:
Permanent magnet described in step 4 is that magnetic induction is in 0.3 tesla；
High magnetic response polyimides/Fe described in step one3O4The particle diameter of composite magnetic nanoparticle is 1um.
High magnetic response polyimides/Fe described in step one3O4The structural formula of polyimides in composite magnetic nanoparticle
For:
In soluble polyamide acid solution described in described step 2, the structural formula of soluble polyamide acid is:
Described soluble polyamide acid solution is prepared the most according to the following steps:
In a nitrogen atmosphere, by 2.45g (8.38mmol) 1 under room temperature, double (3-amino-benzene oxygen) benzene of 3-and 45g N, N-
Dimethylformamide is placed in three-necked bottle, stirring and dissolving 3h, then adds 2.55g in three-necked bottle with the rate of addition of 10mg/s
(8.22mmol) 3,3,4 ', 4 '-diphenyl ether tetracarboxylic dianhydride, obtain reaction system, reaction system is continued stirring and dissolves 1h
～5h, obtain soluble polyamide acid solution.
Embodiment two:
The present embodiment is a kind of uses magnetic particle to sense the method adding hot preparation soluble polyimide, specifically by following
Step is carried out:
One, 1., under nitrogen atmosphere, room temperature and stirring condition, in three-necked bottle, 101.8g N, N-dimethylacetamide are added
Amine and 10.00g (0.05mol) 3,4 '-diaminodiphenyl ether, reacts 1h, then adds 10.36g (0.0475mol) in three-necked bottle
3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, reacts 3h, then adds 10.10g triethylamine in three-necked bottle, react 3h, stop
Stirring, obtains reactant liquor, under agitation, instills in acetone by reactant liquor with the speed of 5mL/s, after being added dropwise to complete, continues
Stirring 2h, then stands 10 days, obtains the standing containing filament, taken out by filament in the standing containing filament, in temperature be
Filament is dried by the vacuum drying oven of 25 DEG C, obtains polyamic acid amine salt；
2., under agitation, 2g polyamic acid amine salt is placed in 100mL hydrothermal reaction kettle, and adds 10g six hydration
Ferric chloride, 0.5g Polyethylene Glycol and 40g ethylene glycol solvent, react 10h, and then hydrothermal reaction kettle is warming up to temperature is 205
DEG C, and at temperature is 205 DEG C, it is incubated 6h, then hydrothermal reaction kettle is naturally cooled to room temperature, obtain crude product, use outer strong magnetic
Crude product is separated washing 3 times by ferrum, and dries at temperature is 120 DEG C, obtains high magnetic response polyimides/Fe3O4Composite magnetic
Nanoparticle；
Two, the three-necked bottle that asbestos cloth wraps up is placed in the heating loop coil of HF induction heating apparatus, then to three
Logical nitrogen atmosphere in neck bottle, then it is poly-to add 50g soluble polyamide acid solution, 15g toluene and 15g height magnetic response in three-necked bottle
Acid imide/Fe3O4Composite magnetic nanoparticle, low whipping speed is 100rpm, stirs 1h, obtains mixed solution；
Three, under conditions of the frequency at alternating magnetic field is 100kHz, the output of regulation HF induction heating apparatus makes
Obtain mixed solution and be warming up to 130 DEG C, and back flow reaction 0.5h at temperature is 130 DEG C, discharge toluene and water, then regulate high frequency sense
The output answering firing equipment makes mixed solution be warming up to 164 DEG C, and stopped reaction after being warming up to 164 DEG C, after being reacted
Solution；
Four, close HF induction heating apparatus, reacted solution is down to room temperature, utilize permanent magnet by high in three-necked bottle
Magnetic response polyimides/Fe3O4Composite magnetic nanoparticle removes, and obtains the solution after removing magnetic nano-particle, then will remove
Solution after magnetic nano-particle is added drop-wise in distilled water, precipitating 1h, filters, precipitation washing, finally dries at temperature is 130 DEG C
Dry, obtain soluble polyimide.
The structural formula of soluble polyimide prepared by the present embodiment is:
Permanent magnet described in step 4 be magnetic induction be 0.3 tesla；
High magnetic response polyimides/Fe described in step one3O4The particle diameter of composite magnetic nanoparticle is 1um.
High magnetic response polyimides/Fe described in step one3O4The structural formula of polyimides in composite magnetic nanoparticle
For:
In soluble polyamide acid solution described in described step one, the structural formula of soluble polyamide acid is:
Described soluble polyamide acid solution is prepared the most according to the following steps:
In a nitrogen atmosphere, by 2.45g (8.38mmol) 1 under room temperature, double (3-amino-benzene oxygen) benzene of 3-and 45g N, N-
Dimethyl acetylamide is placed in three-necked bottle, stirring and dissolving 3h, then adds 2.55g in three-necked bottle with the rate of addition of 10mg/s
(8.22mmol) 3,3,4 ', 4 '-diphenyl ether tetracarboxylic dianhydride, obtain reaction system, reaction system is continued stirring and dissolves 2h,
Obtain soluble polyamide acid solution.
Embodiment three:
The present embodiment is a kind of uses magnetic particle to sense the method adding hot preparation soluble polyimide, specifically by following
Step is carried out:
One, 1., under nitrogen atmosphere, room temperature and stirring condition, in three-necked bottle, 101.8g N, N-dimethylacetamide are added
Amine and 10.00g (0.05mol) 3,4 '-diaminodiphenyl ether, reacts 1h, then adds 10.36g (0.0475mol) in three-necked bottle
3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, reacts 3h, then adds 10.10g triethylamine in three-necked bottle, react 3h, stop
Stirring, obtains reactant liquor, under agitation, instills in acetone by reactant liquor with the speed of 5mL/s, after being added dropwise to complete, continues
Stirring 2h, then stands 10 days, obtains the standing containing filament, taken out by filament in the standing containing filament, in temperature be
Filament is dried by the vacuum drying oven of 25 DEG C, obtains polyamic acid amine salt；
2., under agitation, 2g polyamic acid amine salt is placed in hydrothermal reaction kettle, and adds 10g six and be hydrated trichlorine
Changing ferrum, 0.5g Polyethylene Glycol and 40g ethylene glycol solvent, react 10h, then hydrothermal reaction kettle is warming up to temperature is 205 DEG C, and
At temperature is 205 DEG C, it is incubated 6h, then hydrothermal reaction kettle is naturally cooled to room temperature, obtain crude product, use outer strong magnet to incite somebody to action
Crude product separates washing 3 times, and dries at temperature is 120 DEG C, obtains high magnetic response polyimides/Fe3O4Composite magnetic nanometer
Particle；
Two, the three-necked bottle that asbestos cloth wraps up is placed in the heating loop coil of HF induction heating apparatus, then to three
Logical nitrogen atmosphere in neck bottle, then in three-necked bottle, add 50g soluble polyamide acid solution, 15g dimethylbenzene and 5g height magnetic response
Polyimides/Fe3O4Composite magnetic nanoparticle, low whipping speed is 100rpm, stirs 1h, obtains mixed solution；
Three, under conditions of the frequency at alternating magnetic field is 100kHz, the output of regulation HF induction heating apparatus makes
Obtain mixed solution and be warming up to 125 DEG C, and back flow reaction 0.5h at temperature is 125 DEG C, discharge dimethylbenzene and water, then regulate high frequency
The output of induction heating equipment makes mixed solution be warming up to 149 DEG C, and stopped reaction after being warming up to 149 DEG C is reacted
After solution；
Four, close HF induction heating apparatus, reacted solution is down to room temperature, utilize permanent magnet by high in three-necked bottle
Magnetic response polyimides/Fe3O4Composite magnetic nanoparticle removes, and obtains the solution after removing magnetic nano-particle, then will remove
Solution after magnetic nano-particle is added drop-wise in distilled water, precipitating 1h, filters, precipitation washing, finally dries at temperature is 130 DEG C
Dry, obtain soluble polyimide.
The structural formula of soluble polyimide prepared by the present embodiment is:
Permanent magnet described in step 4 be magnetic induction be 0.3 tesla；
High magnetic response polyimides/Fe described in step one3O4The particle diameter of composite magnetic nanoparticle is 1um.
High magnetic response polyimides/Fe described in step one3O4The structural formula of polyimides in composite magnetic nanoparticle
For:
In soluble polyamide acid solution described in described step one, the structural formula of soluble polyamide acid is:
Described soluble polyamide acid solution is prepared the most according to the following steps:
In a nitrogen atmosphere, by 1.60g (8.04mmol) 1 under room temperature, double (3-amino-benzene oxygen) benzene of 3-and 45g N, N-
Dimethylformamide is placed in three-necked bottle, stirring and dissolving 3h, then adds 3.39g in three-necked bottle with the rate of addition of 10mg/s
(7.638mmol) 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids, obtain reaction system, reaction system is continued stirring and dissolves 1h
～5h, obtain soluble polyamide acid solution.
Embodiment four:
The present embodiment is a kind of uses magnetic particle to sense the method adding hot preparation soluble polyimide, specifically by following
Step is carried out:
One, 1., under nitrogen atmosphere, room temperature and stirring condition, in three-necked bottle, 101.8g N, N-dimethylacetamide are added
Amine and 10.00g (0.05mol) 3,4 '-diaminodiphenyl ether, reacts 1h, then adds 10.36g (0.0475mol) in three-necked bottle
3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, reacts 3h, then adds 10.10g triethylamine in three-necked bottle, react 3h, stop
Stirring, obtains reactant liquor, under agitation, instills in acetone by reactant liquor with the speed of 5mL/s, after being added dropwise to complete, continues
Stirring 2h, then stands 10 days, obtains the standing containing filament, taken out by filament in the standing containing filament, in temperature be
Filament is dried by the vacuum drying oven of 25 DEG C, obtains polyamic acid amine salt；
2., under agitation, 2g polyamic acid amine salt is placed in 100mL hydrothermal reaction kettle, and adds 10g six hydration
Ferric chloride, 0.5g Polyethylene Glycol and 40g ethylene glycol solvent, react 10h, and then hydrothermal reaction kettle is warming up to temperature is 205
DEG C, and at temperature is 205 DEG C, it is incubated 6h, then hydrothermal reaction kettle is naturally cooled to room temperature, obtain crude product, use outer strong magnetic
Crude product is separated washing 3 times by ferrum, and dries at temperature is 120 DEG C, obtains high magnetic response polyimides/Fe3O4Composite magnetic
Nanoparticle；
Two, the three-necked bottle that asbestos cloth wraps up is placed in the heating loop coil of HF induction heating apparatus, then to three
Logical nitrogen atmosphere in neck bottle, then in three-necked bottle, add 50g soluble polyamide acid solution, 15g dimethylbenzene and 5g height magnetic response
Polyimides/Fe3O4Composite magnetic nanoparticle, low whipping speed is 100rpm, stirs 1h, obtains mixed solution；
Three, under conditions of the frequency at alternating magnetic field is 100kHz, the output of regulation HF induction heating apparatus makes
Obtain mixed solution and be warming up to 145 DEG C, and back flow reaction 1h at temperature is 145 DEG C, discharge dimethylbenzene and water, then regulate high frequency sense
The output answering firing equipment makes mixed solution be warming up to 164 DEG C, and stopped reaction after being warming up to 164 DEG C, after being reacted
Solution；
Four, close HF induction heating apparatus, reacted solution is down to room temperature, utilize permanent magnet by high in three-necked bottle
Magnetic response polyimides/Fe3O4Composite magnetic nanoparticle removes, and obtains the solution after removing magnetic nano-particle, then will remove
Solution after magnetic nano-particle is added drop-wise in distilled water, precipitating 1h, filters, precipitation washing, finally dries at temperature is 130 DEG C
Dry, obtain soluble polyimide.
The structural formula of soluble polyimide prepared by the present embodiment is:
Permanent magnet described in step 4 be magnetic induction be 0.3 tesla；
High magnetic response polyimides/Fe described in step one3O4The particle diameter of composite magnetic nanoparticle is 1um.
High magnetic response polyimides/Fe described in step one3O4The structural formula of polyimides in composite magnetic nanoparticle
For:
In soluble polyamide acid solution described in described step one, the structural formula of soluble polyamide acid is:
Described soluble polyamide acid solution is prepared the most according to the following steps:
In a nitrogen atmosphere, by 1.99g (9.93mmol) 3,3'-diaminodiphenyl ether and 45g N, N-dimethyl under room temperature
Acetamide is placed in three-necked bottle, stirring and dissolving 3h, then adds 3.02g in three-necked bottle with the rate of addition of 10mg/s
(9.74mmol) 3,3,4 ', 4 '-diphenyl ether tetracarboxylic dianhydride, obtain reaction system, reaction system is continued stirring and dissolves 2h,
Obtain soluble polyamide acid solution.
Embodiment five:
The present embodiment is a kind of uses magnetic particle to sense the method adding hot preparation soluble polyimide, specifically by following
Step is carried out:
One, 1., under nitrogen atmosphere, room temperature and stirring condition, in three-necked bottle, 101.8g N, N-dimethylacetamide are added
Amine and 10.00g (0.05mol) 3,4 '-diaminodiphenyl ether, reacts 1h, then adds 10.36g (0.0475mol) in three-necked bottle
3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, reacts 3h, then adds 10.10g triethylamine in three-necked bottle, react 3h, stop
Stirring, obtains reactant liquor, under agitation, instills in acetone by reactant liquor with the speed of 5mL/s, after being added dropwise to complete, continues
Stirring 2h, then stands 10 days, obtains the standing containing filament, taken out by filament in the standing containing filament, in temperature be
Filament is dried by the vacuum drying oven of 25 DEG C, obtains polyamic acid amine salt；
2., under agitation, 2g polyamic acid amine salt is placed in 100mL hydrothermal reaction kettle, and adds 10g six hydration
Ferric chloride iron salt, 0.5g Polyethylene Glycol and 40g ethylene glycol solvent, react 10h, and then hydrothermal reaction kettle is warming up to temperature is
205 DEG C, and at temperature is 205 DEG C, it is incubated 6h, then hydrothermal reaction kettle is naturally cooled to room temperature, obtain crude product, outside employing
Crude product is separated washing 3 times by strong magnet, and dries at temperature is 120 DEG C, obtains high magnetic response polyimides/Fe3O4Compound
Magnetic nano-particle；
Two, the three-necked bottle that asbestos cloth wraps up is placed in the heating loop coil of HF induction heating apparatus, then to three
Logical nitrogen atmosphere in neck bottle, then in three-necked bottle, add 50g soluble polyamide acid solution, 15g dimethylbenzene and 5g height magnetic response
Polyimides/Fe3O4Composite magnetic nanoparticle, low whipping speed is 100rpm, stirs 1h, obtains mixed solution；
Three, under conditions of the frequency at alternating magnetic field is 100kHz, the output of regulation HF induction heating apparatus makes
Obtain mixed solution and be warming up to 145 DEG C, and back flow reaction 1h at temperature is 145 DEG C, discharge dimethylbenzene and water, then regulate high frequency sense
The output answering firing equipment makes mixed solution be warming up to 164 DEG C, and stopped reaction after being warming up to 164 DEG C, after being reacted
Solution；
Four, close HF induction heating apparatus, reacted solution is down to room temperature, utilize permanent magnet by high in three-necked bottle
Magnetic response polyimides/Fe3O4Composite magnetic nanoparticle removes, and obtains the solution after removing magnetic nano-particle, then will remove
Solution after magnetic nano-particle is added drop-wise in distilled water, precipitating 1h, filters, precipitation washing, finally dries at temperature is 130 DEG C
Dry, obtain soluble polyimide.
The structural formula of soluble polyimide prepared by the present embodiment is:
Permanent magnet described in step 4 be magnetic induction be 0.3 tesla；
High magnetic response polyimides/Fe described in step one3O4The particle diameter of composite magnetic nanoparticle is 1um.
High magnetic response polyimides/Fe described in step one3O4The structural formula of polyimides in composite magnetic nanoparticle
For:
In soluble polyamide acid solution described in described step one, the structural formula of soluble polyamide acid is:
Described soluble polyamide acid solution is prepared the most according to the following steps:
In a nitrogen atmosphere, by 2.45g (8.38mmol) 1 under room temperature, double (3-amino-benzene oxygen) benzene of 3-and 45g N, N-
Dimethyl acetylamide is placed in three-necked bottle, stirring and dissolving 3h, then adds 2.55g in three-necked bottle with the rate of addition of 10mg/s
(8.22mmol) 3,3,4 ', 4 '-diphenyl ether tetracarboxylic dianhydride, obtain reaction system, reaction system is continued stirring and dissolves 1h
～5h, obtain soluble polyamide acid solution.
Contrast experiment one:
It is to sequentially include the following steps: that this contrast experiment prepares the preparation method of soluble polyimide
One, the three-necked bottle that asbestos cloth wraps up is placed in the heating loop coil of HF induction heating apparatus, then to three
Logical nitrogen atmosphere in neck bottle, then in three-necked bottle, add 50g soluble polyamide acid solution and 15g toluene, low whipping speed is
100rpm, stirs 1h, obtains mixed solution；
Two, regulation heating mantle power makes mixed solution be warming up to 125 DEG C, and back flow reaction 1h at temperature is 125 DEG C,
Discharge toluene and water, then the output regulating HF induction heating apparatus makes mixed solution be warming up to 149 DEG C, is warming up to
Stopped reaction after 149 DEG C, obtains reacted solution；
Three, reacted solution is down to room temperature, the solution after being lowered the temperature, then the solution after cooling is added drop-wise to distillation
In water, precipitating 1h, filters, precipitation washing, finally dries at temperature is 130 DEG C, obtain soluble polyimide.
The structural formula of the soluble polyimide of this contrast experiment one preparation is:
In soluble polyamide acid solution described in step one, the structural formula of soluble polyamide acid is:
Soluble polyamide acid solution described in step one is prepared the most according to the following steps:
In a nitrogen atmosphere, by 2.45g (8.38mmol) 1 under room temperature, double (3-amino-benzene oxygen) benzene of 3-and 45g N, N-
Dimethylformamide is placed in three-necked bottle, stirring and dissolving 3h, then adds 2.55g in three-necked bottle with the rate of addition of 10mg/s
(8.22mmol) 3,3,4 ', 4 '-diphenyl ether tetracarboxylic dianhydride, obtain reaction system, reaction system is continued stirring and dissolves 2h,
Obtain soluble polyamide acid solution.
Contrast experiment two:
The preparation method of the soluble polyimide described in this contrast experiment is to sequentially include the following steps:
One, the three-necked bottle that asbestos cloth wraps up is placed in the heating loop coil of HF induction heating apparatus, then to three
Logical nitrogen atmosphere in neck bottle, then in three-necked bottle, add 50g soluble polyamide acid solution and 15g dimethylbenzene, low whipping speed
For 100rpm, stir 1h, obtain mixed solution；
Two, regulation heating mantle power makes mixed solution be warming up to 145 DEG C, and back flow reaction at temperature is 145 DEG C
10h, discharges dimethylbenzene and water, then the output regulating HF induction heating apparatus makes mixed solution be warming up to 164 DEG C, rises
Stopped reaction after warm to 164 DEG C, obtains reacted solution；
Three, reacted solution is down to room temperature, the solution after being lowered the temperature, then the solution after cooling is added drop-wise to distillation
In water, precipitating 1h, filters, precipitation washing, finally dries at temperature is 130 DEG C, obtain soluble polyimide.
The structural formula of soluble polyimide prepared by this contrast experiment is:
In soluble polyamide acid solution described in step one, the structural formula of soluble polyamide acid is:
Soluble polyamide acid solution described in step one is prepared the most according to the following steps:
In a nitrogen atmosphere, by 2.45g (8.38mmol) 1 under room temperature, double (3-amino-benzene oxygen) benzene of 3-and 45g N, N-
Dimethyl acetylamide is placed in three-necked bottle, stirring and dissolving 1h～3h, then adds in three-necked bottle with the rate of addition of 10mg/s
2.55g (8.22mmol) 3,3,4 ', 4 '-diphenyl ether tetracarboxylic dianhydride, obtain reaction system, continue to stir and molten by reaction system
Solve 2h, obtain soluble polyamide acid solution.
Fig. 1 is the high magnetic response polyimides/Fe of embodiment one preparation3O4The scanning electron of composite magnetic nanoparticle shows
Micro mirror figure.As seen from the figure, microsphere is high magnetic response polyimides/Fe3O4Composite magnetic microsphere, rough surface and bigger microsphere
A size of polyimides covered effect.
Fig. 2 is the high magnetic response polyimides/Fe of embodiment one preparation3O4The X-ray diffraction of composite magnetic nanoparticle is bent
Line chart, as seen from the figure, in figure, 15deg～20deg fills the air peak is unformed polyimides, and indicating peak in figure is Fe3O4The spy of lattice
Levy peak.
Fig. 3 is the high magnetic response polyimides/Fe of embodiment one preparation3O4The infrared curve chart of composite magnetic nanoparticle.
As seen from the figure, 1779cm-1And 1720cm-1For carbonyl symmetric vibration peak, 570cm-1For Fe3O4The infrared signature of Fe-O key in crystal
Absworption peak.
Fig. 4 is the high magnetic response polyimides/Fe of embodiment one preparation3O4The vibrating example magnetic of composite magnetic nanoparticle
Strong index contour figure.As seen from the figure, high magnetic response polyimides/Fe3O4The saturation magnetization of composite magnetic nanoparticle still reaches
To 70emu/g, there is the corresponding effect of good magnetic.
Fig. 6 is infrared curve chart；1 is the soluble polyimide of embodiment one preparation；2 is the solvable of embodiment two preparation
Property polyimides；3 is the soluble polyimide of embodiment three preparation；4 is the soluble polyimide of embodiment four preparation；5
Soluble polyimide for embodiment five preparation；6 is the soluble polyimide of contrast experiment one preparation；7 is contrast experiment
The soluble polyimide of two preparations.Utilize the soluble polyimide that embodiment one to five is prepared by Fourier infrared spectrograph
And contrast experiment one to two preparation soluble polyimide test, FT-IR (KBr, cm-1): 1780cm-1and
1718cm-1(C=O), 1591cm-1Imines symmetric vibration peak；At 1591cm-1For C=C stretching vibration peak；At 1370cm-1It is C-N
Symmetrical (C=C), 1370cm-1(C-N).It follows that from the point of view of structure, 1780cm-1And 1718cm-1For acyl stretching vibration peak,
At 1231cm-1And 1031cm-1It is symmetry and the asymmetrical stretching vibration peak of ehter bond, therefore, provable embodiment one to five respectively
The soluble type polyimides of preparation meets structural formula.But the infrared curve of contrast experiment one, at 1660cm-1There is acyl Asia asymmetric
Absorb vibration peak, it was demonstrated that under the conditions of Gai, polyimides imidization degree be not exclusively, do not send out in other embodiment and comparative example
Existing, illustrate that imidization is complete.
Table 1 glass transition temperature test data
Table 1 tests data for glass transition temperature.Soluble type polyimides to embodiment one to embodiment five preparation
And the polyimides of contrast experiment one to two preparation carries out DSC and tests data, utilize differential scanning calorimeter, heating rate 10
DEG C/min, N2Atmosphere, tests the glass transition temperature difference of the same many sub-samplings of batch resin；Embodiment is compared to contrast
Example, has the best numerical stability, and glass transition temperature is all within ± 2 DEG C, and except the glass of embodiment three
Glass transition temperature is beyond 212 DEG C, and remaining is all at 213 DEG C～214 DEG C, it is shown that imidization is complete, polyimides master
Chain structure is stable.But contrast test one shows that the polyreaction glass transition temperature under the identical time only has 195 DEG C～203
DEG C, imidization is incomplete, the less stable of resin simultaneously.
Table 2 thermal weight loss test data
Table 2 tests data for thermal weight loss, and soluble type polyimides and contrast to embodiment one to embodiment five preparation are real
The soluble type polyimides testing one to two preparation carries out thermal weight loss test；Thermal weight loss: test uses thermal gravimetric analyzer (TGA),
Heating rate: 10 DEG C/min, N2Atmosphere, tests thermal weight loss performance in its nitrogen；As seen from table, embodiment one to five is far above right
Ratio experiment one, 600 DEG C of carbon yields under its nitrogen bring up to more than 70%, 5% thermal weight loss temperature more than 500 DEG C, equivalent or
Higher than standard manufacturing method, i.e. contrast experiment two, it is possible to reach the hot property of polyimides, meet temperature resistant grade and thermally-stabilised
The demand of property.
The performance of table 3 polyimide material plate
The polyamides of soluble type polyimides embodiment one to embodiment five prepared and contrast experiment one to two preparation is sub-
Amine, as in mould, is put into hot press at room temperature, is gradually heated up by grinding tool.When mould is warming up to 300 DEG C, pressurize 2MPa,
Then temperature is warming up to 370 DEG C, and the 15MPa that presses from 300 DEG C, solid under conditions of temperature is 370 DEG C and pressure is 15MPa
Change 1h, then be down to pressure relief taking-up mould after room temperature, obtain polyimide material plate.By GB/T 2567-2008 resin cast
Body method for testing performance is tested, and the results are shown in Table 3.
Table 3 is the performance of polyimide material plate, the plate being made up of the soluble type polyimides of embodiment one to five preparation
Material, its mechanical property (hot strength and bending strength) is all significantly larger than identical preparation time and uses the synthesis of simple hot imidization method
Polyimides sheet material, and be equal to or higher than the polyimides sheet material using conventional preparation time to obtain.
Claims (6)
1. one kind uses magnetic particle to sense the method adding hot preparation soluble polyimide, it is characterised in that a kind of employing magnetic
It is to sequentially include the following steps: that particle sensing adds the method for hot preparation soluble polyimide
One, 1., under nitrogen atmosphere, room temperature and stirring condition, in three-necked bottle, high bp polar solvent and aromatic diamines are added,
Reaction 0.5h～1h, then in three-necked bottle, add aromatic dianhydride, react 1h～5h, in three-necked bottle, then add tertiary amine, reaction
2h～3h, stops stirring, obtains reactant liquor, under agitation, with the speed of 2mL/s～10mL/s, reactant liquor is instilled acetone
In, after being added dropwise to complete, continue stirring 1h～6h, then stand 3 days～10 days, obtain the standing liquid containing filament, will contain thread
In the standing liquid of thing, filament is taken out, and is dried by filament, obtain polyamide in the vacuum drying oven that temperature is 20 DEG C～30 DEG C
Amine acid salt；
Described aromatic diamines is 1:(0.90～0.95 with the mol ratio of aromatic dianhydride)；Described aromatic diamines rubs with tertiary amine
That ratio is 1:(1.90～2.10)；The mass ratio of described aromatic dianhydride and the gross mass of aromatic diamines and high bp polar solvent
For 1:5；
Described aromatic diamines is 4,4 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, two (3-amino-benzene oxygen) hexichol
Ketone or 2-(3-aminophenyl)-5-amino benzothiazole；
Described aromatic dianhydride is 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride or 3,
3 ', 4,4 '-two sulfuryl tetracarboxylic dianhydrides；
Described tertiary amine is trialkyl tertiary amine；
Described high bp polar solvent is in DMAC N,N' dimethyl acetamide, N,N-dimethylformamide and N-Methyl pyrrolidone
A kind of or the most several mixture；
2., under agitation, polyamic acid amine salt is placed in hydrothermal reaction kettle, and adds iron salt, Polyethylene Glycol and second two
Alcoholic solvent, react 5h～10h, then hydrothermal reaction kettle is warming up to temperature is 190 DEG C～210 DEG C, and temperature be 190 DEG C～
It is incubated 3h～7h at 210 DEG C, then hydrothermal reaction kettle is naturally cooled to room temperature, obtain crude product, use outer strong magnet slightly to produce
Thing separates washing 3 times～5 times, and dries at temperature is 80 DEG C～120 DEG C, obtains high magnetic response polyimides/Fe3O4Compound
Magnetic nano-particle；
Described polyamic acid amine salt is 10:(1～50 with the mass ratio of iron salt)；Described polyamic acid amine salt and Polyethylene Glycol
Mass ratio be 10:(0.1～3.0)；Described polyamic acid amine salt is 10:(80～300 with the mass ratio of ethylene glycol)；
Described iron salt is a kind of or the most several in Iron(III) chloride hexahydrate, Iron dichloride tetrahydrate and four ferrous sulfate hydrates
The mixture planted；
Described high magnetic response polyimides/Fe3O4In composite magnetic nanoparticle, the general structure of polyimides is:Described n is 9～49；
Described R1For-O-orDescribed R2For
Or described high magnetic response polyimides/Fe3O4In composite magnetic nanoparticle, the general structure of polyimides is:Described n is 9～49；Described R2For
Two, the three-necked bottle that asbestos cloth wraps up is placed in the heating loop coil of HF induction heating apparatus, then to three-necked bottle
Interior logical nitrogen atmosphere, then in three-necked bottle, add soluble polyamide acid solution, water entrainer and high magnetic response polyimides/Fe3O4
Composite magnetic nanoparticle, low whipping speed is 25rpm～100rpm, stirs 1h～5h, obtains mixed solution；
Described soluble polyamide acid solution and the mass ratio of water entrainer are 10:(2～4.8)；Described high magnetic response polyamides
Imines/Fe3O4Composite magnetic nanoparticle is (0.1～0.5) with the mass ratio of soluble polyamide acid solution: 1；
Three, under conditions of the frequency at alternating magnetic field is 80kHz～200kHz, the output of regulation HF induction heating apparatus
Mixed solution is made to be warming up to 120 DEG C～145 DEG C, and back flow reaction 0.5h～1.5h at temperature is 120 DEG C～145 DEG C, row
Go out water entrainer and water, then the output regulating HF induction heating apparatus make mixed solution be warming up to 146 DEG C～164 DEG C,
Stopped reaction after being warming up to 146 DEG C～164 DEG C, obtains reacted solution；
Four, close HF induction heating apparatus, reacted solution is down to room temperature, utilize permanent magnet to be rung by high magnetic in three-necked bottle
Answer polyimides/Fe3O4Composite magnetic nanoparticle removes, and obtains the solution after removing magnetic nano-particle, then will remove magnetic
Solution after nanoparticle is added drop-wise in distilled water, precipitating 1h～4h, filter, precipitation washing, finally temperature be 130 DEG C～
Dry at 140 DEG C, obtain soluble polyimide；
Described soluble polyimide general structure is:
Described n is 3～49；
Described R1For:-O-、
Described R2For:
A kind of method using magnetic particle sensing to add hot preparation soluble polyimide the most according to claim 1, its
The magnetic induction being characterised by the permanent magnet described in step 4 is 0.1 tesla～1.5 teslas.
A kind of method using magnetic particle sensing to add hot preparation soluble polyimide the most according to claim 1, its
It is characterised by the mixture that the water entrainer described in step 2 is a kind of or two of which in toluene and dimethylbenzene.
A kind of method using magnetic particle sensing to add hot preparation soluble polyimide the most according to claim 1, its
It is characterised by the high magnetic response polyimides/Fe described in step one3O4The particle diameter of composite magnetic nanoparticle is 50nm～3 μm.
A kind of method using magnetic particle sensing to add hot preparation soluble polyimide the most according to claim 1, its
It is characterised by the soluble polyamide acid solution described in step 2 that the general structure of soluble polyamide acid is:
Described n is 3～49；
Described R1For:-O-、
Described R2For:
A kind of method using magnetic particle sensing to add hot preparation soluble polyimide the most according to claim 1, its
It is characterised by what the soluble polyamide acid solution described in step 2 was prepared the most according to the following steps:
In a nitrogen atmosphere, under room temperature, aromatic diamines and intensive polar solvent are placed in three-necked bottle, stirring and dissolving 1h～3h, then
In three-necked bottle, add aromatic series tetracarboxylic dianhydride with the rate of addition of 1mg/s～10mg/s, obtain reaction system, by reaction system
Continue stirring and dissolve 1h～5h, obtaining soluble polyamide acid solution；
Described aromatic diamines is 1:(0.75～0.98 with the mol ratio of aromatic series tetracarboxylic dianhydride)；Described aromatic diamines and virtue
The quality summation of fragrant race tetracarboxylic dianhydride accounts for the 10%～15% of reaction system quality；
Described intensive polar solvent is one or both the mixture in N,N-dimethylformamide and DMAC N,N' dimethyl acetamide；
Described aromatic diamines be double (the trifluoromethyl)-4,4-benzidine of 2,2'-, double (3-amino-benzene oxygen) benzene of 1,3-,
Double (4-amino-benzene oxygen) benzene of 1,3-, 3,3'-diaminodiphenyl ether or 3,3'-diaminobenzophenone；
Described aromatic series tetracarboxylic dianhydride is 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl ether tetrabasic carboxylic acid two
Acid anhydride, Bisphenol A Type Diether Dianhydride or 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids.
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