CN104829837A - Method for preparing soluble polyimide by adopting magnetic particle induction heating - Google Patents
Method for preparing soluble polyimide by adopting magnetic particle induction heating Download PDFInfo
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- 0 C*c1cc(Oc2cc(N(C(c(c3c4)ccc4Oc(cc4)cc(C(N5*C)=O)c4C5=O)=O)C3=O)ccc2)ccc1 Chemical compound C*c1cc(Oc2cc(N(C(c(c3c4)ccc4Oc(cc4)cc(C(N5*C)=O)c4C5=O)=O)C3=O)ccc2)ccc1 0.000 description 2
Abstract
The invention discloses a method for preparing soluble polyimide by adopting magnetic particle induction heating and relates to a method for preparing the soluble polyimide. The invention solves the problems of unstable resin performance, slow heating speed and long imidization period caused by the heating differences of the outer heat source in the imide cyclization process of the soluble polyimide precursor-polyamide acid when preparing the soluble polyimide. The preparation method comprises the following steps: firstly preparing a high magnetic response polyimide/Fe3O4 compound magnetic nano-particle, heating the soluble polyamide acid solution, a water-carrying agent and the high magnetic response polyimide/Fe3O4 compound magnetic nano-particle in a high frequency induction heating device, precipitating, filtering, depositing, rinsing and baking. The method is used for preparing the soluble polyimide by adopting a magnetic particle induction heating device.
Description
Technical field
The present invention relates to the preparation method of soluble polyimide.
Background technology
Polyimide is the aromatic heterocyclic polymer containing imide ring in repeated structural unit, it is up to now at one of the highest polymer materials of temperature classification of industrial circle application, in addition the over-all properties of its excellence, is widely used in aerospace, the field such as electric with forms such as film, resin, fiber, separatory membranes.Traditional polyimide is that raw material passes through first to form polyamic acid by aromatic tetracarboxylic acid anhydride and aromatic diamine usually, then imidization dehydration forms polyimide, and common imidization method has hot imidization method and chemical imidization method, has good application foundation.But existing hot imidization is long for reaction time, greatly can increase energy consumption, as the 10-12h back flow reaction of hot imidization reaction experience 170-190 DEG C of polyimide in patent CN101985498B, temperature reaction slowly and long thermostatically heating process too increase equipment loss.Chemical imidization is except formation imide ring, also may form different imide, the molecular weight of product distribution that thoroughly can not cause of imidization broadens, be difficult to directly obtain high-performance polyimide, after adopting chemical imidization in patent CN1175031C, just can overcome above problem in conjunction with hot imide reaction, but its follow-up hot imidization reaction times is also at 2h-20h.Document (Macromol.Rapid Comm.2011, the production method adopting microwave radiation method to prepare soft polyimide foam 32:254-288) is reported with patent (CN101735457B), significantly improve the production cycle of polyimide foam, but the method adopted only relates to polyimide foam, polyimide field can not be generalized to; Adopt thermal source to heat external container, system can be caused to heat uneven, because the performance of polyimide is directly related with imidization degree, the difference of local heating effect brings problem to polyimide stability simultaneously.
Along with the develop rapidly of microelectronics and aerospace field, because polyimide is easy to preparation and stable performance, high-performance polyimide demand sharply increases: document (Thin Solid Film 2011,519:2339-2343) mention matrix material polyimide prepreg, the imidization excessive cycle that its solidification process occurs, is difficult to improving production efficiency; Document (Adv.Funct.Mater.2015,25:78-84) is mentioned for polyimide used for electronic packaging equally, faces that imidization speed is slow, a difficult problem for imidization degree instability equally.Usually matrix material used and tackiness agent polyimide all need to experience 5-15h hot imidization process not etc.Can find out, the Energy efficiency when Long Time Thermal imines of polyimide conventional manufacturing process seriously limits the production cycle of material, application and mould consumption.
Common induction heating is a kind of method being easy to realize magnetic mold rapid heating.Be that exchange current produces magnetic field by being positioned at neighbouring electrically-conductive coil, externally-applied magnetic field causes eddy current within the workpiece, and eddy current produces heat due to electricresistance effect.Conventional induction heating adopts heating source outward at equipment, but for comparatively large vol (as Glass Containers) indirect heating, can bring in container be heated inequality and the problem such as heating rate is slow equally.
Utilize the distinctive hysteresis effect of nanoparticle, relaxation effect etc. can be heat energy by alternating magnetic field energy conversion, and reduce power consumption.But high-curie temperature magnetic nano-particle is (as Fe
3o
4, Fe
2o
3) being easy to reunite in resin and solution system forms cluster, while the dispersiveness of impact in system, directly adopt magnetic nano-particle in system, be heated to comparatively high temps and can cause significantly being heated inequality and being difficult to maintenance system temperature a stationary value.And adopt coated magnetic nano-particle to have not been reported as thermal source, adopt coated can promote preparation effect be unknown.
Summary of the invention
The present invention will solve existing when preparing soluble polyimide, soluble polyimide presoma-polyamic acid is unstable by the uneven resin property brought of external heat source heating in imide cyclization process, and heating ramp rate is slow, the problem that the imidization cycle is long, and a kind of method adopting magnetic particle induction heating to prepare soluble polyimide is provided.
A kind of method adopting magnetic particle induction heating to prepare soluble polyimide of the present invention is carried out according to the following steps:
One, 1., at nitrogen atmosphere, under room temperature and agitation condition, high bp polar solvent and aromatic diamines is added in three-necked bottle, reaction 0.5h ~ 1h, aromatic dianhydride is added again in three-necked bottle, reaction 1h ~ 5h, then in three-necked bottle, tertiary amine is added, reaction 2h ~ 3h, stop stirring, obtain reaction solution, under agitation, by reaction solution with in the speed of 2mL/s ~ 10mL/s instillation acetone, after being added dropwise to complete, continue to stir 1h ~ 6h, then 3 days ~ 10 days are left standstill, obtain the standing liquid containing filament, take out containing filament in the standing liquid of filament, be in the vacuum drying oven of 20 DEG C ~ 30 DEG C, filament is dried in temperature, obtain polyamic acid amine salt,
The mol ratio of described aromatic diamines and aromatic diamines acid anhydride is 1:(0.90 ~ 0.95); Described aromatic diamines and the mol ratio of tertiary amine are 1:(1.90 ~ 2.10); The mass ratio of described aromatic dianhydride and the total mass of aromatic diamines and high bp polar solvent is 1:5;
Described aromatic diamines is 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, two (3-amino-benzene oxygen) benzophenone or 2-(3-aminophenyl)-5-An base benzoxazole;
Described aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3,4 ', 4 '-phenyl ether tetracarboxylic dianhydride or 3,3,4 ', 4 '-two sulfuryl tetracarboxylic dianhydride;
Described tertiary amine is a kind of or wherein several mixture in triethylamine, trialkyl tertiary amine and Dodecyl Dimethyl Amine;
Described high bp polar solvent is a kind of or wherein several mixture in N,N-dimethylacetamide, DMF and N-Methyl pyrrolidone;
2., under agitation, polyamic acid amine salt is placed in hydrothermal reaction kettle, and add molysite, polyoxyethylene glycol and ethylene glycol solvent, reaction 5h ~ 10h, then hydrothermal reaction kettle being warming up to temperature is 190 DEG C ~ 210 DEG C, and 3h ~ 7h is incubated at temperature is 190 DEG C ~ 210 DEG C, again hydrothermal reaction kettle is naturally cooled to room temperature, obtain crude product, adopt outer strong magnet crude product to be separated washing 3 times ~ 5 times, and dry at temperature is 80 DEG C ~ 120 DEG C, obtain high magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle;
Described polyamic acid amine salt and the mass ratio of molysite are 10:(1 ~ 50); Described polyamic acid amine salt and the mass ratio of polyoxyethylene glycol are 10:(0.1 ~ 3.0); Described polyamic acid amine salt and the mass ratio of ethylene glycol are 10:(80 ~ 300);
Described molysite is a kind of or wherein several mixture in Iron(III) chloride hexahydrate, Iron dichloride tetrahydrate and four ferrous sulfate hydrates;
Described high magnetic response polyimide/Fe
3o
4in composite magnetic nanoparticle, the general structure of polyimide is:
described n is 9 ~ 49;
Described R
1for-O-or
described R
2for
Or described high magnetic response polyimide/Fe
3o
4in composite magnetic nanoparticle, the general structure of polyimide is:
described n is 9 ~ 49; Described R
2for
Two, the three-necked bottle that woven asbesto wraps up is placed in the heating toroidal coil of HF induction heating apparatus, then logical nitrogen atmosphere in three-necked bottle, then in three-necked bottle, adds soluble polyamide acid solution, water entrainer and high magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle, low whipping speed is 25rpm ~ 100rpm, stirs 1h ~ 5h, obtains mixing solutions;
Described soluble polyamide acid solution and the mass ratio of water entrainer are 10:(2 ~ 4.8); Described high magnetic response polyimide/Fe
3o
4the mass ratio of composite magnetic nanoparticle and soluble polyamide acid solution is (0.1 ~ 0.5): 1;
Three, under the frequency of alternating magnetic field is the condition of 80kHz ~ 200kHz, the output rating of HF induction heating apparatus is regulated to make mixing solutions 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, the output rating of HF induction heating apparatus is regulated to make mixing solutions be warming up to 146 DEG C ~ 164 DEG C again, 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, utilizes permanent magnet by magnetic response polyimide/Fe high in three-necked bottle
3o
4composite magnetic nanoparticle shifts out, and obtains the solution after removing magnetic nano-particle, then is added drop-wise in distilled water by removing the solution after magnetic nano-particle, precipitating 1h ~ 4h, filters, precipitation washing, last oven dry at temperature is 130 DEG C ~ 140 DEG C, obtains soluble polyimide;
Described soluble polyimide general structure is:
described n is 3 ~ 49;
Described R
1for:
Described R
2for:
The invention has the beneficial effects as follows: the present invention adopts high magnetic response polyimide/Fe
3o
4the magnetothermal effect induction heating of composite magnetic nanoparticle under alternation foreign field prepares polyimide.By polyimide coated magnetic nanoparticle built-in in polyamic acid solution, realize the inside rapid thermal response effect that indirect heating source does not possess.In addition, whole process relates to the multistep process such as heating-zone of constant temperature water-intensification heating that heat up, and only regulation output power can only improve the existing temperature of solution, but superposition relies on high magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle, meets with a response consistent, stable maintenance and higher ectonexine temperature unexpectedly fast.
The present invention adopts high magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle is as corresponding thermal source, avoid the high surface energy of magnetic nano-particle and even magnetic moment intermolecular forces, magnetic-particle agglomeration in the polyamic acid solution caused, be difficult in system, form mono-dispersed nano particle, the problem of the dehydration condensation of polyamic acid can be hindered again simultaneously.Adopt the magnetic nano-particle of Coated with Organic Matter, repulsive force between dependence polymkeric substance and the balance of interparticle magnetism, realize the single dispersing of superparamagnetic magnetic nano-particle, utilize the Intermolecular Forces that backbone structure similar between the polyamic acid in the polyimide of particle surface and solution brings further, reach the dispersion homogeneity of thermal source in polyamic acid solution, avoid the uneven temperature instability being dispersed in high-temperature hot imidization, improve the stability of heats, simultaneously compared to other Coated with Organic Matter magnetic particles, original position preparation has more good magnetic response effect, thus Quick high reaction temperature.
The present invention is applicable in hot imidization process, the paradigmatic structure type that the polyimide formed is not separated out in polar solvent, guarantees to be pipetted by magnetic nano-particle in solution with permanent magnet after polymkeric substance preparation, thus does not affect matrix resin performance.This method can greatly improve imidization efficiency, Reaction time shorten (shortening to 0.5 ~ 1.5 hour from conventional hot imidization 5-15 hour), obtain stable performance and good soluble polyimide (from tensile strength and flexural strength, second-order transition temperature, heat decomposition temperature data) simultaneously, thus meet the field such as aerospace and microelectronics to being easy to preparation and stable performance polyimide demand.
The present invention is used for a kind of method adopting magnetic particle induction heating to prepare soluble polyimide.
Accompanying drawing explanation
Fig. 1 is high magnetic response polyimide/Fe prepared by embodiment one
3o
4the scanning electron microscope diagram of composite magnetic nanoparticle;
Fig. 2 is high magnetic response polyimide/Fe prepared by embodiment one
3o
4the X-ray diffraction graphic representation of composite magnetic nanoparticle;
Fig. 3 is high magnetic response polyimide/Fe prepared by embodiment one
3o
4the infrared graphic representation of composite magnetic nanoparticle;
Fig. 4 is high magnetic response polyimide/Fe prepared by embodiment one
3o
4the vibrating sample magnetometer graphic representation of composite magnetic nanoparticle;
Fig. 5 is that the present invention adopts magnetic particle induction heating to prepare the heating arrangement schematic diagram of soluble polyimide; 1 is prolong, and 2 is water-taker, and 3 is thermometer, and 4 is stirring rake, and 5 is nitrogen port, and 6 is toroidal coil, and 7 is high magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle, 8 is polyamic acid solution, and 9 is HF induction heating apparatus;
Fig. 6 is infrared graphic representation; 1 is soluble polyimide prepared by embodiment one; 2 is soluble polyimide prepared by embodiment two; 3 is soluble polyimide prepared by embodiment three; 4 is soluble polyimide prepared by embodiment four; 5 is soluble polyimide prepared by embodiment five; 6 is soluble polyimide prepared by contrast experiment one; 7 is soluble polyimide prepared by contrast experiment two.
Embodiment
Embodiment one: composition graphs 5 illustrates present embodiment, a kind of method adopting magnetic particle induction heating to prepare soluble polyimide described in present embodiment is carried out according to the following steps:
One, 1., at nitrogen atmosphere, under room temperature and agitation condition, high bp polar solvent and aromatic diamines is added in three-necked bottle, reaction 0.5h ~ 1h, aromatic dianhydride is added again in three-necked bottle, reaction 1h ~ 5h, then in three-necked bottle, tertiary amine is added, reaction 2h ~ 3h, stop stirring, obtain reaction solution, under agitation, by reaction solution with in the speed of 2mL/s ~ 10mL/s instillation acetone, after being added dropwise to complete, continue to stir 1h ~ 6h, then 3 days ~ 10 days are left standstill, obtain the standing liquid containing filament, take out containing filament in the standing liquid of filament, be in the vacuum drying oven of 20 DEG C ~ 30 DEG C, filament is dried in temperature, obtain polyamic acid amine salt,
The mol ratio of described aromatic diamines and aromatic diamines acid anhydride is 1:(0.90 ~ 0.95); Described aromatic diamines and the mol ratio of tertiary amine are 1:(1.90 ~ 2.10); The mass ratio of described aromatic dianhydride and the total mass of aromatic diamines and high bp polar solvent is 1:5;
Described aromatic diamines is 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, two (3-amino-benzene oxygen) benzophenone or 2-(3-aminophenyl)-5-An base benzoxazole;
Described aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3,4 ', 4 '-phenyl ether tetracarboxylic dianhydride or 3,3,4 ', 4 '-two sulfuryl tetracarboxylic dianhydride;
Described tertiary amine is a kind of or wherein several mixture in triethylamine, trialkyl tertiary amine and Dodecyl Dimethyl Amine;
Described high bp polar solvent is a kind of or wherein several mixture in N,N-dimethylacetamide, DMF and N-Methyl pyrrolidone;
2., under agitation, polyamic acid amine salt is placed in hydrothermal reaction kettle, and add molysite, polyoxyethylene glycol and ethylene glycol solvent, reaction 5h ~ 10h, then hydrothermal reaction kettle being warming up to temperature is 190 DEG C ~ 210 DEG C, and 3h ~ 7h is incubated at temperature is 190 DEG C ~ 210 DEG C, again hydrothermal reaction kettle is naturally cooled to room temperature, obtain crude product, adopt outer strong magnet crude product to be separated washing 3 times ~ 5 times, and dry at temperature is 80 DEG C ~ 120 DEG C, obtain high magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle;
Described polyamic acid amine salt and the mass ratio of molysite are 10:(1 ~ 50); Described polyamic acid amine salt and the mass ratio of polyoxyethylene glycol are 10:(0.1 ~ 3.0); Described polyamic acid amine salt and the mass ratio of ethylene glycol are 10:(80 ~ 300);
Described molysite is a kind of or wherein several mixture in Iron(III) chloride hexahydrate, Iron dichloride tetrahydrate and four ferrous sulfate hydrates;
Described high magnetic response polyimide/Fe
3o
4in composite magnetic nanoparticle, the general structure of polyimide is:
described n is 9 ~ 49;
Described R
1for-O-or
described R
2for
Or described high magnetic response polyimide/Fe
3o
4in composite magnetic nanoparticle, the general structure of polyimide is:
described n is 9 ~ 49; Described R
2for
Two, the three-necked bottle that woven asbesto wraps up is placed in the heating toroidal coil of HF induction heating apparatus, then logical nitrogen atmosphere in three-necked bottle, then in three-necked bottle, adds soluble polyamide acid solution, water entrainer and high magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle, low whipping speed is 25rpm ~ 100rpm, stirs 1h ~ 5h, obtains mixing solutions;
Described soluble polyamide acid solution and the mass ratio of water entrainer are 10:(2 ~ 4.8); Described high magnetic response polyimide/Fe
3o
4the mass ratio of composite magnetic nanoparticle and soluble polyamide acid solution is (0.1 ~ 0.5): 1;
Three, under the frequency of alternating magnetic field is the condition of 80kHz ~ 200kHz, the output rating of HF induction heating apparatus is regulated to make mixing solutions 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, the output rating of HF induction heating apparatus is regulated to make mixing solutions be warming up to 146 DEG C ~ 164 DEG C again, 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, utilizes permanent magnet by magnetic response polyimide/Fe high in three-necked bottle
3o
4composite magnetic nanoparticle shifts out, and obtains the solution after removing magnetic nano-particle, then is added drop-wise in distilled water by removing the solution after magnetic nano-particle, precipitating 1h ~ 4h, filters, precipitation washing, last oven dry at temperature is 130 DEG C ~ 140 DEG C, obtains soluble polyimide;
Described soluble polyimide general structure is:
described n is 3 ~ 49;
Described R
1for:
Described R
2for:
Fig. 5 is that the present invention adopts magnetic particle induction heating to prepare the heating arrangement schematic diagram of soluble polyimide; 1 is prolong, and 2 is water-taker, and 3 is thermometer, and 4 is stirring rake, and 5 is nitrogen port, and 6 is toroidal coil, and 7 is high magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle, 8 is polyamic acid solution, and 9 is HF induction heating apparatus.
The beneficial effect of present embodiment is: the present invention adopts high magnetic response polyimide/Fe
3o
4the magnetothermal effect induction heating of composite magnetic nanoparticle under alternation foreign field prepares polyimide.By polyimide coated magnetic nanoparticle built-in in polyamic acid solution, realize the inside rapid thermal response effect that indirect heating source does not possess.In addition, whole process relates to the multistep process such as heating-zone of constant temperature water-intensification heating that heat up, and only regulation output power can only improve the existing temperature of solution, but superposition relies on high magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle, meets with a response consistent, stable maintenance and higher ectonexine temperature unexpectedly fast.
The present invention adopts high magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle is as corresponding thermal source, avoid the high surface energy of magnetic nano-particle and even magnetic moment intermolecular forces, magnetic-particle agglomeration in the polyamic acid solution caused, be difficult in system, form mono-dispersed nano particle, the problem of the dehydration condensation of polyamic acid can be hindered again simultaneously.Adopt the magnetic nano-particle of Coated with Organic Matter, repulsive force between dependence polymkeric substance and the balance of interparticle magnetism, realize the single dispersing of superparamagnetic magnetic nano-particle, utilize the Intermolecular Forces that backbone structure similar between the polyamic acid in the polyimide of particle surface and solution brings further, reach the dispersion homogeneity of thermal source in polyamic acid solution, avoid the uneven temperature instability being dispersed in high-temperature hot imidization, improve the stability of heats, simultaneously compared to other Coated with Organic Matter magnetic particles, original position preparation has more good magnetic response effect, thus Quick high reaction temperature.
The present invention is applicable in hot imidization process, the paradigmatic structure type that the polyimide formed is not separated out in polar solvent, guarantees to be pipetted by magnetic nano-particle in solution with permanent magnet after polymkeric substance preparation, thus does not affect matrix resin performance.This method can greatly improve imidization efficiency, Reaction time shorten (shortening to 0.5 ~ 1.5 hour from conventional hot imidization 5-15 hour), obtain stable performance and good soluble polyimide (from tensile strength and flexural strength, second-order transition temperature, heat decomposition temperature data) simultaneously, thus meet the field such as aerospace and microelectronics to being easy to preparation and stable performance polyimide demand.
Embodiment two: present embodiment and embodiment one unlike: the permanent magnet described in step 4 is magnetic induction density is 0.1 tesla ~ 1.5 tesla.Other is identical with embodiment two.
Embodiment three: one of present embodiment and embodiment one or two are a kind of in toluene and dimethylbenzene or the wherein mixture of two kinds unlike: the water entrainer described in step 2.Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three are unlike high magnetic response polyimide/Fe described in step one
3o
4the particle diameter of composite magnetic nanoparticle is 50nm ~ 3um.Other is identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: in the soluble polyamide acid solution described in step 2, the general structure of soluble polyamide acid is:
described n is 3 ~ 49;
Described R
1for:
Described R
2for:
other is identical with embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: the soluble polyamide acid solution described in step 2 is specifically prepared 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, aromatic series tetracarboxylic dianhydride is added with the rate of addition of 1mg/s ~ 10mg/s, obtain reaction system, reaction system is continued stir and dissolve 1h ~ 5h, obtains soluble polyamide acid solution;
The mol ratio of described aromatic diamines and aromatic series tetracarboxylic dianhydride is 1:(0.75 ~ 0.98); The quality summation of described aromatic diamines and aromatic series tetracarboxylic dianhydride accounts for 10% ~ 15% of reaction system quality;
Described intensive polar solvent is one or both the mixture in DMF and N,N-dimethylacetamide;
Described aromatic diamines is 2,2'-two (trifluoromethyl)-4,4-benzidine, 1, two (3-amino-benzene oxygen) benzene, 1 of 3-, 3-two (4-amino-benzene oxygen) benzene, 3,3'-diaminodiphenyl oxides or 3,3'-diaminobenzophenone;
Described aromatic series tetracarboxylic dianhydride is 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3,4 ', 4 '-phenyl ether tetracarboxylic dianhydride, Bisphenol A Type Diether Dianhydride or 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids.Other is identical with embodiment one to five.
Following examples are adopted to verify beneficial effect of the present invention: composition graphs 5 illustrates embodiment one to five.
Embodiment one:
A kind of method adopting magnetic particle induction heating to prepare soluble polyimide of the present embodiment, specifically carry out according to the following steps:
One, 1., at nitrogen atmosphere, under room temperature and agitation condition, 101.8g N is added in three-necked bottle, N-N,N-DIMETHYLACETAMIDE and 10.00g (0.05mol) 3, 4 '-diaminodiphenyl oxide, reaction 1h, 10.36g (0.0475mol) 3 is added again in three-necked bottle, 3, 4 ', 4 '-biphenyl tetracarboxylic dianhydride, reaction 3h, then in three-necked bottle, 10.10g triethylamine is added, reaction 3h, stop stirring, obtain reaction solution, under agitation, by reaction solution with in the speed of 5mL/s instillation acetone, after being added dropwise to complete, continue to stir 2h, then 10 days are left standstill, obtain leaving standstill containing filament, the middle filament that leaves standstill containing filament is taken out, be in the vacuum drying oven of 25 DEG C, filament is dried in temperature, obtain polyamic acid amine salt,
2., under agitation, 2g polyamic acid amine salt is placed in 100mL hydrothermal reaction kettle, and add 10g Iron(III) chloride hexahydrate, 0.5g polyoxyethylene glycol and 40g ethylene glycol solvent, reaction 10h, then hydrothermal reaction kettle being warming up to temperature is 205 DEG C, and be 205 times insulation 6h in temperature, again hydrothermal reaction kettle is naturally cooled to room temperature, obtain crude product, adopt outer strong magnet crude product to be separated washing 3 times, and dry at temperature is 120 DEG C, obtain high magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle;
Two, the three-necked bottle that woven asbesto wraps up is placed in the heating toroidal coil of HF induction heating apparatus, then logical nitrogen atmosphere in three-necked bottle, then in three-necked bottle, adds 50g soluble polyamide acid solution, 15g toluene and 5g height magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle, low whipping speed is 100rpm, stirs 1h, obtains mixing solutions;
Three, under the frequency of alternating magnetic field is the condition of 100kHz, the output rating of HF induction heating apparatus is regulated to make mixing solutions be warming up to 125 DEG C, and at temperature is 125 DEG C back flow reaction 0.5h, discharge toluene and water, the output rating of HF induction heating apparatus is regulated to make mixing solutions be warming up to 149 DEG C again, stopped reaction after being warming up to 149 DEG C, obtains reacted solution;
Four, close HF induction heating apparatus, reacted solution is down to room temperature, utilizes permanent magnet by magnetic response polyimide/Fe high in three-necked bottle
3o
4composite magnetic nanoparticle shifts out, and obtains the solution after removing magnetic nano-particle, then is added drop-wise in distilled water by removing the solution after magnetic nano-particle, precipitating 1h, filters, and precipitation washing, finally dries, obtain soluble polyimide at temperature is 130 DEG C.
The structural formula of soluble polyimide prepared by the present embodiment is:
Permanent magnet described in step 4 is that magnetic induction density is in 0.3 tesla;
High magnetic response polyimide/Fe described in step one
3o
4the particle diameter of composite magnetic nanoparticle is 1um.
High magnetic response polyimide/Fe described in step one
3o
4in composite magnetic nanoparticle, the structural formula of polyimide is:
In soluble polyamide acid solution described in described step 2, the structural formula of soluble polyamide acid is:
Described soluble polyamide acid solution is specifically prepared according to the following steps:
In a nitrogen atmosphere, under room temperature, two for 2.45g (8.38mmol) 1,3-(3-amino-benzene oxygen) benzene and 45g DMF are placed in three-necked bottle, stirring and dissolving 3h, then in three-necked bottle, 2.55g (8.22mmol) 3,3,4 ' is added with the rate of addition of 10mg/s, 4 '-phenyl ether tetracarboxylic dianhydride, obtain reaction system, reaction system is continued stir and dissolve 1h ~ 5h, obtains soluble polyamide acid solution.
Embodiment two:
A kind of method adopting magnetic particle induction heating to prepare soluble polyimide of the present embodiment, specifically carry out according to the following steps:
One, 1., at nitrogen atmosphere, under room temperature and agitation condition, 101.8g N is added in three-necked bottle, N-N,N-DIMETHYLACETAMIDE and 10.00g (0.05mol) 3, 4 '-diaminodiphenyl oxide, reaction 1h, 10.36g (0.0475mol) 3 is added again in three-necked bottle, 3, 4 ', 4 '-biphenyl tetracarboxylic dianhydride, reaction 3h, then in three-necked bottle, 10.10g triethylamine is added, reaction 3h, stop stirring, obtain reaction solution, under agitation, by reaction solution with in the speed of 5mL/s instillation acetone, after being added dropwise to complete, continue to stir 2h, then 10 days are left standstill, obtain leaving standstill containing filament, the middle filament that leaves standstill containing filament is taken out, be in the vacuum drying oven of 25 DEG C, filament is dried in temperature, obtain polyamic acid amine salt,
2., under agitation, 2g polyamic acid amine salt is placed in 100mL hydrothermal reaction kettle, and add 10g Iron(III) chloride hexahydrate, 0.5g polyoxyethylene glycol and 40g ethylene glycol solvent, reaction 10h, then hydrothermal reaction kettle being warming up to temperature is 205 DEG C, and 6h is incubated at temperature is 205 DEG C, again hydrothermal reaction kettle is naturally cooled to room temperature, obtain crude product, adopt outer strong magnet crude product to be separated washing 3 times, and dry at temperature is 120 DEG C, obtain high magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle;
Two, the three-necked bottle that woven asbesto wraps up is placed in the heating toroidal coil of HF induction heating apparatus, then logical nitrogen atmosphere in three-necked bottle, then in three-necked bottle, adds 50g soluble polyamide acid solution, 15g toluene and 15g height magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle, low whipping speed is 100rpm, stirs 1h, obtains mixing solutions;
Three, under the frequency of alternating magnetic field is the condition of 100kHz, the output rating of HF induction heating apparatus is regulated to make mixing solutions be warming up to 130 DEG C, and at temperature is 130 DEG C back flow reaction 0.5h, discharge toluene and water, the output rating of HF induction heating apparatus is regulated to make mixing solutions be warming up to 164 DEG C again, stopped reaction after being warming up to 164 DEG C, obtains reacted solution;
Four, close HF induction heating apparatus, reacted solution is down to room temperature, utilizes permanent magnet by magnetic response polyimide/Fe high in three-necked bottle
3o
4composite magnetic nanoparticle shifts out, and obtains the solution after removing magnetic nano-particle, then is added drop-wise in distilled water by removing the solution after magnetic nano-particle, precipitating 1h, filters, and precipitation washing, finally dries, obtain soluble polyimide at temperature is 130 DEG C.
The structural formula of soluble polyimide prepared by the present embodiment is:
Permanent magnet described in step 4 is magnetic induction density is 0.3 tesla;
High magnetic response polyimide/Fe described in step one
3o
4the particle diameter of composite magnetic nanoparticle is 1um.
High magnetic response polyimide/Fe described in step one
3o
4in composite magnetic nanoparticle, the structural formula of polyimide is:
In soluble polyamide acid solution described in described step one, the structural formula of soluble polyamide acid is:
described soluble polyamide acid solution is specifically prepared according to the following steps:
In a nitrogen atmosphere, under room temperature, two for 2.45g (8.38mmol) 1,3-(3-amino-benzene oxygen) benzene and 45g N,N-dimethylacetamide are placed in three-necked bottle, stirring and dissolving 3h, then in three-necked bottle, 2.55g (8.22mmol) 3,3,4 ' is added with the rate of addition of 10mg/s, 4 '-phenyl ether tetracarboxylic dianhydride, obtain reaction system, reaction system is continued stir and dissolve 2h, obtains soluble polyamide acid solution.
Embodiment three:
A kind of method adopting magnetic particle induction heating to prepare soluble polyimide of the present embodiment, specifically carry out according to the following steps:
One, 1., at nitrogen atmosphere, under room temperature and agitation condition, 101.8g N is added in three-necked bottle, N-N,N-DIMETHYLACETAMIDE and 10.00g (0.05mol) 3, 4 '-diaminodiphenyl oxide, reaction 1h, 10.36g (0.0475mol) 3 is added again in three-necked bottle, 3, 4 ', 4 '-biphenyl tetracarboxylic dianhydride, reaction 3h, then in three-necked bottle, 10.10g triethylamine is added, reaction 3h, stop stirring, obtain reaction solution, under agitation, by reaction solution with in the speed of 5mL/s instillation acetone, after being added dropwise to complete, continue to stir 2h, then 10 days are left standstill, obtain leaving standstill containing filament, the middle filament that leaves standstill containing filament is taken out, be in the vacuum drying oven of 25 DEG C, filament is dried in temperature, obtain polyamic acid amine salt,
2., under agitation, 2g polyamic acid amine salt is placed in hydrothermal reaction kettle, and add 10g Iron(III) chloride hexahydrate, 0.5g polyoxyethylene glycol and 40g ethylene glycol solvent, reaction 10h, then hydrothermal reaction kettle being warming up to temperature is 205 DEG C, and 6h is incubated at temperature is 205 DEG C, again hydrothermal reaction kettle is naturally cooled to room temperature, obtain crude product, adopt outer strong magnet crude product to be separated washing 3 times, and dry at temperature is 120 DEG C, obtain high magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle;
Two, the three-necked bottle that woven asbesto wraps up is placed in the heating toroidal coil of HF induction heating apparatus, then logical nitrogen atmosphere in three-necked bottle, then in three-necked bottle, adds 50g soluble polyamide acid solution, 15g dimethylbenzene and 5g height magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle, low whipping speed is 100rpm, stirs 1h, obtains mixing solutions;
Three, under the frequency of alternating magnetic field is the condition of 100kHz, the output rating of HF induction heating apparatus is regulated to make mixing solutions be warming up to 125 DEG C, and at temperature is 125 DEG C back flow reaction 0.5h, discharge dimethylbenzene and water, the output rating of HF induction heating apparatus is regulated to make mixing solutions be warming up to 149 DEG C again, stopped reaction after being warming up to 149 DEG C, obtains reacted solution;
Four, close HF induction heating apparatus, reacted solution is down to room temperature, utilizes permanent magnet by magnetic response polyimide/Fe high in three-necked bottle
3o
4composite magnetic nanoparticle shifts out, and obtains the solution after removing magnetic nano-particle, then is added drop-wise in distilled water by removing the solution after magnetic nano-particle, precipitating 1h, filters, and precipitation washing, finally dries, obtain soluble polyimide at temperature is 130 DEG C.
The structural formula of soluble polyimide prepared by the present embodiment is:
Permanent magnet described in step 4 is magnetic induction density is 0.3 tesla;
High magnetic response polyimide/Fe described in step one
3o
4the particle diameter of composite magnetic nanoparticle is 1um.
High magnetic response polyimide/Fe described in step one
3o
4in composite magnetic nanoparticle, the structural formula of polyimide is:
In soluble polyamide acid solution described in described step one, the structural formula of soluble polyamide acid is:
Described soluble polyamide acid solution is specifically prepared according to the following steps:
In a nitrogen atmosphere, by 1.60g (8.04mmol) 1 under room temperature, two (3-amino-benzene oxygen) benzene of 3-and 45g N, dinethylformamide is placed in three-necked bottle, stirring and dissolving 3h, then in three-necked bottle, adds 3.39g (7.638mmol) 4 with the rate of addition of 10mg/s, 4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids, obtain reaction system, reaction system is continued stir and dissolve 1h ~ 5h, obtains soluble polyamide acid solution.
Embodiment four:
A kind of method adopting magnetic particle induction heating to prepare soluble polyimide of the present embodiment, specifically carry out according to the following steps:
One, 1., at nitrogen atmosphere, under room temperature and agitation condition, 101.8g N is added in three-necked bottle, N-N,N-DIMETHYLACETAMIDE and 10.00g (0.05mol) 3, 4 '-diaminodiphenyl oxide, reaction 1h, 10.36g (0.0475mol) 3 is added again in three-necked bottle, 3, 4 ', 4 '-biphenyl tetracarboxylic dianhydride, reaction 3h, then in three-necked bottle, 10.10g triethylamine is added, reaction 3h, stop stirring, obtain reaction solution, under agitation, by reaction solution with in the speed of 5mL/s instillation acetone, after being added dropwise to complete, continue to stir 2h, then 10 days are left standstill, obtain leaving standstill containing filament, the middle filament that leaves standstill containing filament is taken out, be in the vacuum drying oven of 25 DEG C, filament is dried in temperature, obtain polyamic acid amine salt,
2., under agitation, 2g polyamic acid amine salt is placed in 100mL hydrothermal reaction kettle, and add 10g Iron(III) chloride hexahydrate, 0.5g polyoxyethylene glycol and 40g ethylene glycol solvent, reaction 10h, then hydrothermal reaction kettle being warming up to temperature is 205 DEG C, and 6h is incubated at temperature is 205 DEG C, again hydrothermal reaction kettle is naturally cooled to room temperature, obtain crude product, adopt outer strong magnet crude product to be separated washing 3 times, and dry at temperature is 120 DEG C, obtain high magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle;
Two, the three-necked bottle that woven asbesto wraps up is placed in the heating toroidal coil of HF induction heating apparatus, then logical nitrogen atmosphere in three-necked bottle, then in three-necked bottle, adds 50g soluble polyamide acid solution, 15g dimethylbenzene and 5g height magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle, low whipping speed is 100rpm, stirs 1h, obtains mixing solutions;
Three, under the frequency of alternating magnetic field is the condition of 100kHz, the output rating of HF induction heating apparatus is regulated to make mixing solutions be warming up to 145 DEG C, and at temperature is 145 DEG C back flow reaction 1h, discharge dimethylbenzene and water, the output rating of HF induction heating apparatus is regulated to make mixing solutions be warming up to 164 DEG C again, stopped reaction after being warming up to 164 DEG C, obtains reacted solution;
Four, close HF induction heating apparatus, reacted solution is down to room temperature, utilizes permanent magnet by magnetic response polyimide/Fe high in three-necked bottle
3o
4composite magnetic nanoparticle shifts out, and obtains the solution after removing magnetic nano-particle, then is added drop-wise in distilled water by removing the solution after magnetic nano-particle, precipitating 1h, filters, and precipitation washing, finally dries, obtain soluble polyimide at temperature is 130 DEG C.
The structural formula of soluble polyimide prepared by the present embodiment is:
Permanent magnet described in step 4 is magnetic induction density is 0.3 tesla;
High magnetic response polyimide/Fe described in step one
3o
4the particle diameter of composite magnetic nanoparticle is 1um.
High magnetic response polyimide/Fe described in step one
3o
4in composite magnetic nanoparticle, the structural formula of polyimide is:
In soluble polyamide acid solution described in described step one, the structural formula of soluble polyamide acid is:
Described soluble polyamide acid solution is specifically prepared according to the following steps:
In a nitrogen atmosphere, under room temperature, 1.99g (9.93mmol) 3,3'-diaminodiphenyl oxide and 45g N,N-dimethylacetamide are placed in three-necked bottle, stirring and dissolving 3h, then in three-necked bottle, 3.02g (9.74mmol) 3,3,4 ' is added with the rate of addition of 10mg/s, 4 '-phenyl ether tetracarboxylic dianhydride, obtain reaction system, reaction system is continued stir and dissolve 2h, obtains soluble polyamide acid solution.
Embodiment five:
A kind of method adopting magnetic particle induction heating to prepare soluble polyimide of the present embodiment, specifically carry out according to the following steps:
One, 1., at nitrogen atmosphere, under room temperature and agitation condition, 101.8g N is added in three-necked bottle, N-N,N-DIMETHYLACETAMIDE and 10.00g (0.05mol) 3, 4 '-diaminodiphenyl oxide, reaction 1h, 10.36g (0.0475mol) 3 is added again in three-necked bottle, 3, 4 ', 4 '-biphenyl tetracarboxylic dianhydride, reaction 3h, then in three-necked bottle, 10.10g triethylamine is added, reaction 3h, stop stirring, obtain reaction solution, under agitation, by reaction solution with in the speed of 5mL/s instillation acetone, after being added dropwise to complete, continue to stir 2h, then 10 days are left standstill, obtain leaving standstill containing filament, the middle filament that leaves standstill containing filament is taken out, be in the vacuum drying oven of 25 DEG C, filament is dried in temperature, obtain polyamic acid amine salt,
2., under agitation, 2g polyamic acid amine salt is placed in 100mL hydrothermal reaction kettle, and add 10g Iron(III) chloride hexahydrate molysite, 0.5g polyoxyethylene glycol and 40g ethylene glycol solvent, reaction 10h, then hydrothermal reaction kettle being warming up to temperature is 205 DEG C, and 6h is incubated at temperature is 205 DEG C, again hydrothermal reaction kettle is naturally cooled to room temperature, obtain crude product, adopt outer strong magnet crude product to be separated washing 3 times, and dry at temperature is 120 DEG C, obtain high magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle;
Two, the three-necked bottle that woven asbesto wraps up is placed in the heating toroidal coil of HF induction heating apparatus, then logical nitrogen atmosphere in three-necked bottle, then in three-necked bottle, adds 50g soluble polyamide acid solution, 15g dimethylbenzene and 5g height magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle, low whipping speed is 100rpm, stirs 1h, obtains mixing solutions;
Three, under the frequency of alternating magnetic field is the condition of 100kHz, the output rating of HF induction heating apparatus is regulated to make mixing solutions be warming up to 145 DEG C, and at temperature is 145 DEG C back flow reaction 1h, discharge dimethylbenzene and water, the output rating of HF induction heating apparatus is regulated to make mixing solutions be warming up to 164 DEG C again, stopped reaction after being warming up to 164 DEG C, obtains reacted solution;
Four, close HF induction heating apparatus, reacted solution is down to room temperature, utilizes permanent magnet by magnetic response polyimide/Fe high in three-necked bottle
3o
4composite magnetic nanoparticle shifts out, and obtains the solution after removing magnetic nano-particle, then is added drop-wise in distilled water by removing the solution after magnetic nano-particle, precipitating 1h, filters, and precipitation washing, finally dries, obtain soluble polyimide at temperature is 130 DEG C.
The structural formula of soluble polyimide prepared by the present embodiment is:
Permanent magnet described in step 4 is magnetic induction density is 0.3 tesla;
High magnetic response polyimide/Fe described in step one
3o
4the particle diameter of composite magnetic nanoparticle is 1um.
High magnetic response polyimide/Fe described in step one
3o
4in composite magnetic nanoparticle, the structural formula of polyimide is:
In soluble polyamide acid solution described in described step one, the structural formula of soluble polyamide acid is:
Described soluble polyamide acid solution is specifically prepared according to the following steps:
In a nitrogen atmosphere, under room temperature, two for 2.45g (8.38mmol) 1,3-(3-amino-benzene oxygen) benzene and 45g N,N-dimethylacetamide are placed in three-necked bottle, stirring and dissolving 3h, then in three-necked bottle, 2.55g (8.22mmol) 3,3,4 ' is added with the rate of addition of 10mg/s, 4 '-phenyl ether tetracarboxylic dianhydride, obtain reaction system, reaction system is continued stir and dissolve 1h ~ 5h, obtains soluble polyamide acid solution.
Contrast experiment one:
The preparation method that this contrast experiment prepares soluble polyimide carries out according to the following steps:
One, the three-necked bottle that woven asbesto wraps up is placed in the heating toroidal coil of HF induction heating apparatus, then logical nitrogen atmosphere in three-necked bottle, then in three-necked bottle, add 50g soluble polyamide acid solution and 15g toluene, low whipping speed is 100rpm, stir 1h, obtain mixing solutions;
Two, heating jacket power is regulated to make mixing solutions be warming up to 125 DEG C, and at temperature is 125 DEG C back flow reaction 1h, discharge toluene and water, then regulate the output rating of HF induction heating apparatus to make mixing solutions be warming up to 149 DEG C, stopped reaction after being warming up to 149 DEG C, obtains reacted solution;
Three, reacted solution is down to room temperature, obtains the solution after lowering the temperature, then be added drop-wise in distilled water by the solution after cooling, precipitating 1h, filter, precipitation washing, finally dries, obtains soluble polyimide at temperature is 130 DEG C.
The structural formula of soluble polyimide prepared by this contrast experiment one 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 specifically prepared according to the following steps:
In a nitrogen atmosphere, under room temperature, two for 2.45g (8.38mmol) 1,3-(3-amino-benzene oxygen) benzene and 45g DMF are placed in three-necked bottle, stirring and dissolving 3h, then in three-necked bottle, 2.55g (8.22mmol) 3,3,4 ' is added with the rate of addition of 10mg/s, 4 '-phenyl ether tetracarboxylic dianhydride, obtain reaction system, reaction system is continued stir and dissolve 2h, obtains soluble polyamide acid solution.
Contrast experiment two:
The preparation method of the soluble polyimide described in this contrast experiment carries out according to the following steps:
One, the three-necked bottle that woven asbesto wraps up is placed in the heating toroidal coil of HF induction heating apparatus, then logical nitrogen atmosphere in three-necked bottle, then in three-necked bottle, add 50g soluble polyamide acid solution and 15g dimethylbenzene, low whipping speed is 100rpm, stir 1h, obtain mixing solutions;
Two, heating jacket power is regulated to make mixing solutions be warming up to 145 DEG C, and at temperature is 145 DEG C back flow reaction 10h, discharge dimethylbenzene and water, the output rating of HF induction heating apparatus is regulated to make mixing solutions be warming up to 164 DEG C again, stopped reaction after being warming up to 164 DEG C, obtains reacted solution;
Three, reacted solution is down to room temperature, obtains the solution after lowering the temperature, then be added drop-wise in distilled water by the solution after cooling, precipitating 1h, filter, precipitation washing, finally dries, obtains soluble polyimide at temperature is 130 DEG C.
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 specifically prepared according to the following steps:
In a nitrogen atmosphere, under room temperature, two for 2.45g (8.38mmol) 1,3-(3-amino-benzene oxygen) benzene and 45g N,N-dimethylacetamide are placed in three-necked bottle, stirring and dissolving 1h ~ 3h, then in three-necked bottle, 2.55g (8.22mmol) 3,3,4 ' is added with the rate of addition of 10mg/s, 4 '-phenyl ether tetracarboxylic dianhydride, obtain reaction system, reaction system is continued stir and dissolve 2h, obtains soluble polyamide acid solution.
Fig. 1 is high magnetic response polyimide/Fe prepared by embodiment one
3o
4the scanning electron microscope diagram of composite magnetic nanoparticle.As seen from the figure, microballoon is high magnetic response polyimide/Fe
3o
4composite magnetic microballoon, uneven surface and larger Microsphere Size are polyimide covered effect.
Fig. 2 is high magnetic response polyimide/Fe prepared by embodiment one
3o
4the X-ray diffraction graphic representation of composite magnetic nanoparticle, as seen from the figure, in figure, 15deg ~ 20deg fills the air peak is unformed polyimide, and indicating peak in figure is Fe
3o
4the characteristic peak of lattice.
Fig. 3 is high magnetic response polyimide/Fe prepared by embodiment one
3o
4the infrared graphic representation of composite magnetic nanoparticle.As seen from the figure, 1779cm
-1and 1720cm
-1for carbonyl symmetric vibration peak, 570cm
-1for Fe
3o
4the infrared signature absorption peak of Fe-O key in crystal.
Fig. 4 is high magnetic response polyimide/Fe prepared by embodiment one
3o
4the vibrating sample magnetometer graphic representation of composite magnetic nanoparticle.As seen from the figure, high magnetic response polyimide/Fe
3o
4the saturation magnetization of composite magnetic nanoparticle still reaches 70emu/g, has the corresponding effect of good magnetic.
Fig. 6 is infrared graphic representation; 1 is soluble polyimide prepared by embodiment one; 2 is soluble polyimide prepared by embodiment two; 3 is soluble polyimide prepared by embodiment three; 4 is soluble polyimide prepared by embodiment four; 5 is soluble polyimide prepared by embodiment five; 6 is soluble polyimide prepared by contrast experiment one; 7 is soluble polyimide prepared by contrast experiment two.Soluble polyimide prepared by the soluble polyimide utilizing Fourier infrared spectrograph to prepare embodiment one to five and contrast experiment one to two is tested, FT-IR (KBr, cm
-1): 1780cm
-1and1718cm
-1(C=O), 1591cm
-1imines symmetric vibration peak; At 1591cm
-1for C=C stretching vibration peak; At 1370cm
-1c-N symmetry (C=C), 1370cm
-1(C-N).It can thus be appreciated that, from structure, 1780cm
-1and 1718cm
-1for acyl stretching vibration peak, at 1231cm
-1and 1031cm
-1be symmetry and the asymmetrical stretching vibration peak of ehter bond respectively, therefore, soluble type polyimide prepared by provable embodiment one to five meets structural formula.But the infrared curve of contrast experiment one, at 1660cm
-1have the sub-asymmetric absorption vibration peak of acyl, under proving this condition, polyimide imidization degree is incomplete, does not find, illustrate that imidization is complete in other embodiment and comparative example.
Table 1 second-order transition temperature test data
Table 1 is second-order transition temperature test data.Polyimide prepared by the soluble type polyimide prepare embodiment one to embodiment five and contrast experiment one to two carries out DSC test data, utilizes differential scanning calorimeter, temperature rise rate 10 DEG C/min, N
2atmosphere, tests the second-order transition temperature difference that same batch of resin repeatedly samples; Embodiment is compared to comparative example, there is more good numerical stability, second-order transition temperature is all within ± 2 DEG C, and except the second-order transition temperature of embodiment three is except 212 DEG C, all the other are all at 213 DEG C ~ 214 DEG C, show imidization complete, polyimide backbone structure is stablized.But the polyreaction second-order transition temperature that simultaneous test one shows under same time only has 195 DEG C ~ 203 DEG C, imidization is incomplete, simultaneously the less stable of resin.
Table 2 thermal weight loss test data
Table 2 is thermal weight loss test data, and soluble type polyimide prepared by the soluble type polyimide prepare embodiment one to embodiment five and contrast experiment one to two carries out thermal weight loss test; Thermal weight loss: test adopts thermal gravimetric analyzer (TGA), temperature rise rate: 10 DEG C/min, N
2atmosphere, tests thermal weight loss performance in its nitrogen; As seen from table, embodiment one to five is far above contrast experiment one, 600 DEG C of carbon yields under its nitrogen bring up to more than 70%, 5% thermal weight loss temperature is more than 500 DEG C, equivalent or higher than standard manufacturing method, i.e. contrast experiment two, can reach the thermal characteristics of polyimide, meets the demand to temperature resistant grade and thermostability.
The performance of table 3 polyimide material plate
Polyimide prepared by soluble type polyimide embodiment one to embodiment five prepared and contrast experiment one to two, as in mould, enters thermocompressor in ambient temperatare, is heated up gradually by grinding tool.When mould is warming up to 300 DEG C, pressurization 2MPa, is then warming up to 370 DEG C by temperature from 300 DEG C, and the 15MPa that exerts pressure, under temperature is 370 DEG C and pressure is the condition of 15MPa, solidify 1h, then after being down to room temperature, pressure relief takes out mould, obtains polyimide material plate.By the test of GB/T 2567-2008 casting resin method for testing performance, the results are shown in Table 3.
Table 3 is the performance of polyimide material plate, the sheet material that the soluble type polyimide prepared by embodiment one to five is made, its mechanical property (tensile strength and flexural strength) is all far away higher than the polyimide sheet material that identical preparation time adopts simple hot imidization method to synthesize, and polyimide sheet material that is equivalent or that obtain higher than the conventional preparation time of employing.
Claims (6)
1. adopt magnetic particle induction heating to prepare a method for soluble polyimide, it is characterized in that a kind of method adopting magnetic particle induction heating to prepare soluble polyimide is carried out according to the following steps:
One, 1., at nitrogen atmosphere, under room temperature and agitation condition, high bp polar solvent and aromatic diamines is added in three-necked bottle, reaction 0.5h ~ 1h, aromatic dianhydride is added again in three-necked bottle, reaction 1h ~ 5h, then in three-necked bottle, tertiary amine is added, reaction 2h ~ 3h, stop stirring, obtain reaction solution, under agitation, by reaction solution with in the speed of 2mL/s ~ 10mL/s instillation acetone, after being added dropwise to complete, continue to stir 1h ~ 6h, then 3 days ~ 10 days are left standstill, obtain the standing liquid containing filament, take out containing filament in the standing liquid of filament, be in the vacuum drying oven of 20 DEG C ~ 30 DEG C, filament is dried in temperature, obtain polyamic acid amine salt,
The mol ratio of described aromatic diamines and aromatic diamines acid anhydride is 1:(0.90 ~ 0.95); Described aromatic diamines and the mol ratio of tertiary amine are 1:(1.90 ~ 2.10); The mass ratio of described aromatic dianhydride and the total mass of aromatic diamines and high bp polar solvent is 1:5;
Described aromatic diamines is 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, two (3-amino-benzene oxygen) benzophenone or 2-(3-aminophenyl)-5-An base benzoxazole;
Described aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3,4 ', 4 '-phenyl ether tetracarboxylic dianhydride or 3,3,4 ', 4 '-two sulfuryl tetracarboxylic dianhydride;
Described tertiary amine is a kind of or wherein several mixture in triethylamine, trialkyl tertiary amine and Dodecyl Dimethyl Amine;
Described high bp polar solvent is a kind of or wherein several mixture in N,N-dimethylacetamide, DMF and N-Methyl pyrrolidone;
2., under agitation, polyamic acid amine salt is placed in hydrothermal reaction kettle, and add molysite, polyoxyethylene glycol and ethylene glycol solvent, reaction 5h ~ 10h, then hydrothermal reaction kettle being warming up to temperature is 190 DEG C ~ 210 DEG C, and 3h ~ 7h is incubated at temperature is 190 DEG C ~ 210 DEG C, again hydrothermal reaction kettle is naturally cooled to room temperature, obtain crude product, adopt outer strong magnet crude product to be separated washing 3 times ~ 5 times, and dry at temperature is 80 DEG C ~ 120 DEG C, obtain high magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle;
Described polyamic acid amine salt and the mass ratio of molysite are 10:(1 ~ 50); Described polyamic acid amine salt and the mass ratio of polyoxyethylene glycol are 10:(0.1 ~ 3.0); Described polyamic acid amine salt and the mass ratio of ethylene glycol are 10:(80 ~ 300);
Described molysite is a kind of or wherein several mixture in Iron(III) chloride hexahydrate, Iron dichloride tetrahydrate and four ferrous sulfate hydrates;
Described high magnetic response polyimide/Fe
3o
4in composite magnetic nanoparticle, the general structure of polyimide is:
described n is 9 ~ 49;
Described R
1for-O-or
described R
2for
Or described high magnetic response polyimide/Fe
3o
4in composite magnetic nanoparticle, the general structure of polyimide is:
described n is 9 ~ 49;
Described R
2for
Two, the three-necked bottle that woven asbesto wraps up is placed in the heating toroidal coil of HF induction heating apparatus, then logical nitrogen atmosphere in three-necked bottle, then in three-necked bottle, adds soluble polyamide acid solution, water entrainer and high magnetic response polyimide/Fe
3o
4composite magnetic nanoparticle, low whipping speed is 25rpm ~ 100rpm, stirs 1h ~ 5h, obtains mixing solutions;
Described soluble polyamide acid solution and the mass ratio of water entrainer are 10:(2 ~ 4.8); Described high magnetic response polyimide/Fe
3o
4the mass ratio of composite magnetic nanoparticle and soluble polyamide acid solution is (0.1 ~ 0.5): 1;
Three, under the frequency of alternating magnetic field is the condition of 80kHz ~ 200kHz, the output rating of HF induction heating apparatus is regulated to make mixing solutions 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, the output rating of HF induction heating apparatus is regulated to make mixing solutions be warming up to 146 DEG C ~ 164 DEG C again, 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, utilizes permanent magnet by magnetic response polyimide/Fe high in three-necked bottle
3o
4composite magnetic nanoparticle shifts out, and obtains the solution after removing magnetic nano-particle, then is added drop-wise in distilled water by removing the solution after magnetic nano-particle, precipitating 1h ~ 4h, filters, precipitation washing, last oven dry at temperature is 130 DEG C ~ 140 DEG C, obtains soluble polyimide;
Described soluble polyimide general structure is:
described n is 3 ~ 49;
Described R
1for:
Described R
2for:
2. a kind of method adopting magnetic particle induction heating to prepare soluble polyimide according to claim 1, is characterized in that the permanent magnet described in step 4 be magnetic induction density is 0.1 tesla ~ 1.5 tesla.
3. a kind of method adopting magnetic particle induction heating to prepare soluble polyimide according to claim 1, is characterized in that the water entrainer described in step 2 is a kind of in toluene and dimethylbenzene or the wherein mixture of two kinds.
4. a kind of method adopting magnetic particle induction heating to prepare soluble polyimide according to claim 1, is characterized in that the high magnetic response polyimide/Fe described in step one
3o
4the particle diameter of composite magnetic nanoparticle is 50nm ~ 3um.
5. a kind of method adopting magnetic particle induction heating to prepare soluble polyimide according to claim 1, is characterized in that the general structure of soluble polyamide acid in the soluble polyamide acid solution described in step 2 is:
described n is 3 ~ 49;
Described R
1for:
Described R
2for:
6. a kind of method adopting magnetic particle induction heating to prepare soluble polyimide according to claim 1, is characterized in that what the soluble polyamide acid solution described in step 2 was specifically prepared 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, aromatic series tetracarboxylic dianhydride is added with the rate of addition of 1mg/s ~ 10mg/s, obtain reaction system, reaction system is continued stir and dissolve 1h ~ 5h, obtains soluble polyamide acid solution;
The mol ratio of described aromatic diamines and aromatic series tetracarboxylic dianhydride is 1:(0.75 ~ 0.98); The quality summation of described aromatic diamines and aromatic series tetracarboxylic dianhydride accounts for 10% ~ 15% of reaction system quality;
Described intensive polar solvent is one or both the mixture in DMF and N,N-dimethylacetamide;
Described aromatic diamines is 2,2'-two (trifluoromethyl)-4,4-benzidine, 1, two (3-amino-benzene oxygen) benzene, 1 of 3-, 3-two (4-amino-benzene oxygen) benzene, 3,3'-diaminodiphenyl oxides or 3,3'-diaminobenzophenone;
Described aromatic series tetracarboxylic dianhydride is 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3,4 ', 4 '-phenyl ether tetracarboxylic dianhydride, Bisphenol A Type Diether Dianhydride or 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids.
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| CN106498545A (en) * | 2016-06-13 | 2017-03-15 | 杨磊 | A kind of preparation technology of polyamic acid magnetic nano composite fibre |
| CN112480404A (en) * | 2020-11-27 | 2021-03-12 | 株洲时代新材料科技股份有限公司 | Magnetic heat-conducting polyimide composite material and preparation method thereof |
| CN113731376A (en) * | 2021-09-01 | 2021-12-03 | 大同共聚(西安)科技有限公司 | Preparation method of polyimide and aluminum ion complex |
| CN113731377A (en) * | 2021-09-02 | 2021-12-03 | 大同共聚(西安)科技有限公司 | Preparation method of ferroferric oxide/polyimide composite material |
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| CN112480404A (en) * | 2020-11-27 | 2021-03-12 | 株洲时代新材料科技股份有限公司 | Magnetic heat-conducting polyimide composite material and preparation method thereof |
| CN112480404B (en) * | 2020-11-27 | 2022-12-13 | 株洲时代新材料科技股份有限公司 | Magnetic heat-conducting polyimide composite material and preparation method thereof |
| CN113731376A (en) * | 2021-09-01 | 2021-12-03 | 大同共聚(西安)科技有限公司 | Preparation method of polyimide and aluminum ion complex |
| CN113731376B (en) * | 2021-09-01 | 2023-07-25 | 大同共聚(西安)科技有限公司 | Preparation method of polyimide and aluminum ion complex |
| CN113731377A (en) * | 2021-09-02 | 2021-12-03 | 大同共聚(西安)科技有限公司 | Preparation method of ferroferric oxide/polyimide composite material |
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