CN104130411A - Preparation method of hollow polyimide composite microspheres - Google Patents
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Abstract
The invention discloses a preparation method of hollow polyimide composite microspheres, relates to a preparation method of the polyimide composite microspheres, and solves the problems that according to preparation methods of the polyimide composite microsphere in the prior art, solvent consumption is large, the microsphere morphology is difficult to control, part of the internal structure is easy to be damaged by a solvent, and a surfactant introduced into the preparation process for avoiding of reduction of the thermal properties of materials is difficult to remove. The preparation method is as follows: 1, coating; 2, preparation of a polyamide acid solution; 3, preparation of polyamide acid composite microspheres; and 4, the preparation of the polyimide composite microspheres. The preparation method can well control the composite microsphere morphology, can avoid the polyimide shell collapse phenomenon, and enables the polyimide composite microspheres to have a hollow structure so as to reduce the dielectric constant characteristics. The hollow polyimide composite microspheres are suitable for high temperature resistant and low dielectric materials, wave absorbing material and catalyst carriers and other aspects.
Description
Technical field
The present invention relates to a kind of preparation method of polyimide complex microsphere.
Background technology
Along with the progressively development of nano science, a lot of people concentrate on the center of gravity of research in micro-dimension structure.And in fact, the material consisting of the super tiny powder of micro-dimension has very large potentiality on functional.And hollow microsphere is because it has low density and the higher excellent specific properties such as specific surface area, make it aspect catalysis and functional materials, there is good application prospect.
Polyimide is prepared into micro-nano spheroid and will contributes to increase the specific surface area of polyimide material, increase it in the ordinary organic solvents dispersive ability in water even, contribute to reduce the difficulty of processing of polyimide material, meanwhile, each species specific micro-nano pattern will give this traditional special engineering plastics more wide application prospect.Based on above several reasons, polyimide microsphere material has become the Hot Contents of polyimide research in recent years.Due to thermotolerance and the solvent resistance of polyimide excellence, the various microballoon pattern of polyimide also will give polyimide microsphere more kinds of complex functions.The research of polyimide microsphere is a lot, but the research of the compound hollow microsphere of polyimide also seldom, this is the rigid structure mainly due to polyimide segment, be prepared into hollow structure and will be difficult point in its preparation process, the hollow structure of polyimide complex microsphere, can be applicable to the various high-technology fields such as preparation of polyimide dielectric materials.
The employing precipitation polymerization process such as Asao are dissolved in respectively two kinds of solvents by dianhydride and diamines, then two kinds of solution are mixed, thereby are settled out polyamic acid particle, but this method is to the having relatively high expectations of solvent, and imidization aftertreatment is more difficult.
Kawaguchi etc. are with pyromellitic dianhydride (PMDA) and 4, and 4 '-diaminodiphenyl oxide (ODA) is raw material, take triethylamine and acetone as solvent, by precipitation polymerization method, prepared polyamic acid microballoon, but the more difficult control of product pattern.
Jiang Yuanyuan etc. also adopt the precipitator method, diamines is dissolved in to PVP and N, in the solution of N-N,N-DIMETHYLACETAMIDE, then progressively add dianhydride polycondensation, through splashing into PVP in chemical imidization backward system and precipitation agent (water or ethanol) is separated out polyimide, and by PVP, serve as tensio-active agent and make the polymer formation microballoon of separating out.Due to the thermal characteristics that membership reduces material that adds of tensio-active agent, so people are seeking how under the prerequisite of not adding tensio-active agent, to prepare polyimide micro-nano ball always.
The polyimide hollow ball of nucleocapsid structure prepared by traditional dispersion copolymerization method, the process of stoning by bring shell subside, or part is because polyimide shell is thinner, is difficult to depart from core.
Summary of the invention
The present invention will solve existing method to prepare polyimide complex microsphere and exist the solvent amount of expending large, microballoon pattern is difficult to control, solvent destructible partial interior structure and the tensio-active agent of introducing for fear of reducing material thermal characteristics in preparation process are difficult to the problem of removing, and a kind of preparation method of polyimide complex microsphere of hollow structure is provided.
The preparation method of the polyimide complex microsphere of a kind of hollow structure of the present invention carries out according to the following steps:
One, under the condition of magnetic agitation, polystyrene microsphere solution and pyrrole monomer are mixed, add again iron trichloride, magnetic agitation 8h～12h, obtain the coated polystyrene complex microsphere solution of polypyrrole, the coated polystyrene complex microsphere solution of the polypyrrole obtaining is carried out to centrifugation, after centrifugation, solid is dried for 2～4 times afterwards by washing with alcohol, obtains the coated polystyrene complex microsphere of polypyrrole; The solid content of described polystyrene microsphere is 5%; The volume ratio of described polystyrene microsphere solution and pyrrole monomer is 1:(0.1～0.5); The volume ratio of the quality of described iron trichloride and polystyrene microsphere solution is 1g:5mL;
Two, diamines is dissolved in N,N-dimethylacetamide, then adding wherein quality is the dianhydride of M, and under room temperature, mechanical stirring 12h～20h, obtains polyamic acid solution; The quality of described diamines and the volume ratio of N,N-dimethylacetamide are 1g:(10～15mL); Described diamines is 1:(1～1.2 with dianhydride amount of substance ratio); The dosing method of described dianhydride is to divide and add for 8 times at 4h, primary dosage is 1/2M, secondary dosage is 1/4M, dosage is for the third time 1/8M, the dosage of the 4th time is 1/16M, and the dosage of the 5th time is 1/32M, and the dosage of the 6th time is 1/64M, the dosage of the 7th time is 1/128M, and the dosage of the 8th time is 1/128M;
Three, the coated polystyrene complex microsphere of the polypyrrole that step 1 obtained is to be placed in retort furnace calcination under the condition of 300 ℃～500 ℃ in temperature, calcination time is 2h～4h, after calcination, be scattered in N, in N-dimethylacetamide solvent, then the polyamic acid solution that adds wherein step 2 to obtain, carries out centrifugation, by solid N after magnetic agitation 12h～24h, the washing of N-dimethylacetamide solvent is dried for 2～4 times afterwards, obtains polyamic acid complex microsphere; The coated polystyrene complex microsphere of polypyrrole that described step 1 obtains and the mass ratio of polyamic acid solution are 1:(3～5), in described N,N-dimethylacetamide solvent and step 1, the volume ratio of polystyrene microsphere solution is (2～4): 1;
Four, polyamic acid complex microsphere step 3 being obtained carries out imidization processing, obtains the polyimide complex microsphere of hollow structure.
The invention has the beneficial effects as follows:
One, the present invention reacts simple and easy to do, and process is simple, easy handling.
Two, the present invention adopts hollow template to prepare polyimide hollow ball, after the coated polystyrene complex microsphere calcination of polypyrrole, the carbon skeleton of hollow ball is prepared polyamic acid hollow ball to the physisorption of polyamic acid, then imidization obtains polyimide hollow ball, makes the pattern of product also be easy to control.
Three, the present invention can obtain the globosity that stable diameter is about 300nm～500nm, before polyamic acid is coated, has just removed nuclear structure, does not exist and is difficult to depart from the problem that in core or After Enucleation, big area is subsided.
Four, in preparation process of the present invention, do not add additive, thereby avoided reducing in preparation method the defect of material thermal characteristics.
The present invention is for the preparation of a kind of polyimide complex microsphere of hollow structure.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of polystyrene microsphere in embodiment mono-step 1;
Fig. 2 is the scanning electron microscope (SEM) photograph of the coated polystyrene complex microsphere of the polypyrrole that obtains of embodiment mono-step 1;
Fig. 3 is the scanning electron microscope (SEM) photograph of the polyimide complex microsphere of the hollow structure that makes of embodiment mono-;
Fig. 4 is the outside drawing of the polyimide complex microsphere of the hollow structure that makes of embodiment mono-.
Embodiment
Embodiment one: the preparation method of the polyimide complex microsphere of a kind of hollow structure described in present embodiment carries out according to the following steps:
One, under the condition of magnetic agitation, polystyrene microsphere solution and pyrrole monomer are mixed, add again iron trichloride, magnetic agitation 8h～12h, obtain the coated polystyrene complex microsphere solution of polypyrrole, the coated polystyrene complex microsphere solution of the polypyrrole obtaining is carried out to centrifugation, after centrifugation, solid is dried for 2～4 times afterwards by washing with alcohol, obtains the coated polystyrene complex microsphere of polypyrrole; The solid content of described polystyrene microsphere is 5%; The volume ratio of described polystyrene microsphere solution and pyrrole monomer is 1:(0.1～0.5); The volume ratio of the quality of described iron trichloride and polystyrene microsphere solution is 1g:5mL;
Two, diamines is dissolved in N,N-dimethylacetamide, then adding wherein quality is the dianhydride of M, and under room temperature, mechanical stirring 12h～20h, obtains polyamic acid solution; The quality of described diamines and the volume ratio of N,N-dimethylacetamide are 1g:(10～15mL); Described diamines is 1:(1～1.2 with dianhydride amount of substance ratio); The dosing method of described dianhydride is to divide and add for 8 times at 4h, primary dosage is 1/2M, secondary dosage is 1/4M, dosage is for the third time 1/8M, the dosage of the 4th time is 1/16M, and the dosage of the 5th time is 1/32M, and the dosage of the 6th time is 1/64M, the dosage of the 7th time is 1/128M, and the dosage of the 8th time is 1/128M;
Three, the coated polystyrene complex microsphere of the polypyrrole that step 1 obtained is to be placed in retort furnace calcination under the condition of 300 ℃～500 ℃ in temperature, calcination time is 2h～4h, after calcination, be scattered in N, in N-dimethylacetamide solvent, then the polyamic acid solution that adds wherein step 2 to obtain, carries out centrifugation, by solid N after magnetic agitation 12h～24h, the washing of N-dimethylacetamide solvent is dried for 2～4 times afterwards, obtains polyamic acid complex microsphere; The coated polystyrene complex microsphere of polypyrrole that described step 1 obtains and the mass ratio of polyamic acid solution are 1:(3～5), in described N,N-dimethylacetamide solvent and step 1, the volume ratio of polystyrene microsphere solution is (2～4): 1;
Four, polyamic acid complex microsphere step 3 being obtained carries out imidization processing, obtains the polyimide complex microsphere of hollow structure.
Present embodiment reaction is simple and easy to do, and process is simple, easy handling.
Present embodiment adopts hollow template to prepare polyimide hollow ball, after the coated polystyrene complex microsphere calcination of polypyrrole, the carbon skeleton of hollow ball is prepared polyamic acid hollow ball to the physisorption of polyamic acid, then imidization obtains polyimide hollow ball, makes the pattern of product also be easy to control.
Present embodiment can obtain the globosity that stable diameter is about 300nm～500nm, before polyamic acid is coated, has just removed nuclear structure, does not exist and is difficult to depart from the problem that in core or After Enucleation, big area is subsided.
In present embodiment preparation process, do not add additive, thereby avoided additive in preparation method to be difficult to the defect of removing.
The hollow ball that present embodiment is prepared by hollow template is unicellular structure, and this structure will can be applicable to the preparation of polyimide dielectric materials.Can carbonization after template pyroprocessing, so the hollow ball that we prepare become polyimide/carbon composite hollow ball, because polyimide material itself is the polymkeric substance that a kind of remaining carbon is higher, this compound ball can be applicable to the preparation of hollow carbon balls.
The polyimide complex microsphere of hollow structure prepared by present embodiment has good dispersiveness in water He in ethanol
Present embodiment is for the preparation of polyimide complex microsphere.
Embodiment two: present embodiment is different from embodiment one: the volume ratio of polystyrene microsphere and pyrrole monomer described in step 1 is 1:0.125.Other is identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two: the volume ratio of polystyrene microsphere and pyrrole monomer described in step 1 is 1:0.2.Other is identical with embodiment one or two.
Embodiment four: present embodiment is different from embodiment one to three: diamines described in step 2 is diaminodiphenyl oxide.Other is identical with embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four: dianhydride described in step 2 is pyromellitic acid dianhydride, phenyl ether tetracarboxylic dianhydride or benzophenone tetracarboxylic dianhydride.Other is identical with one of embodiment one to four.
Embodiment six: present embodiment is different from one of embodiment one to five: diamines described in step 2 is 1:1.02 with the amount of substance ratio of dianhydride.Other is identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six: the method for imidization described in step 4 is: the polyamic acid complex microsphere obtaining to step 3 adds diacetyl oxide and pyridine, after reaction 24h～48h, add second alcohol and water; In described diacetyl oxide and step 1, the volume ratio of polystyrene microsphere is 1:(3～6); In described pyridine and step 1, the volume ratio of polystyrene microsphere is 1:(9～18); The volume ratio of described ethanol and water is 1:1; In the cumulative volume of described second alcohol and water and step 1, the volume ratio of polystyrene microsphere is 1:(0.4～0.8).Other is identical with one of embodiment one to six.
Embodiment eight: present embodiment is different from one of embodiment one to seven: the method for imidization described in step 4 is: the polyamic acid complex microsphere obtaining to step 3 adds diacetyl oxide and pyridine, after reaction 24h～48h, under nitrogen atmosphere, be placed in temperature and be the retort furnace calcination 2h of 350 ℃; In described diacetyl oxide and step 1, the volume ratio of polystyrene microsphere is 1:(3～6); In described pyridine and step 1, the volume ratio of polystyrene microsphere is 1:(9～18).Other is identical with one of embodiment one to seven.
Embodiment nine: present embodiment is different from one of embodiment one to eight: the method for imidization described in step 4 is: it is the retort furnace calcination 2h of 350 ℃ that the polyamic acid complex microsphere that step 3 is obtained is placed in temperature under nitrogen atmosphere.Other is identical with one of embodiment one to eight.
By following examples, verify beneficial effect of the present invention:
Embodiment mono-: the preparation method of the polyimide complex microsphere of a kind of hollow structure described in the present embodiment carries out according to the following steps:
One, under the condition of magnetic agitation, 10mL polystyrene microsphere and 1mL pyrrole monomer are mixed, adding concentration is the liquor ferri trichloridi 20mL of 0.1g/mL, magnetic agitation is 12h, obtain the coated polystyrene complex microsphere solution of polypyrrole, the coated polystyrene complex microsphere solution of the polypyrrole obtaining is carried out to centrifugation, after centrifugation, solid is dried for 3 times afterwards by washing with alcohol, obtains the coated polystyrene complex microsphere of polypyrrole; The solid content of described polystyrene microsphere is 5%;
Two, 37.5g diamines is dissolved in to 500mLN, in N-N,N-DIMETHYLACETAMIDE, then adds wherein the dianhydride of 40g, under room temperature, mechanical stirring 12h, obtains polyamic acid solution; The dosing method of described dianhydride is to divide and add for 8 times at 4h, primary dosage is 20g, secondary dosage is 10g, dosage is for the third time 5g, the dosage of the 4th time is 2.5g, and the dosage of the 5th time is 1.25g, and the dosage of the 6th time is 0.625g, the dosage of the 7th time is 0.3125g, and the dosage of the 8th time is 0.3125g;
Three, the coated polystyrene complex microsphere of the polypyrrole that step 1 obtained is to be placed in retort furnace calcination under the condition of 300 ℃ in temperature, calcination time is 2h, after calcination, be scattered in 40mLN, in N-dimethylacetamide solvent, then the polyamic acid solution that adds wherein step 2 to obtain, carries out centrifugation, by solid N after magnetic agitation 24h, the washing of N-dimethylacetamide solvent is dried for 3 times afterwards, obtains polyamic acid complex microsphere;
Four,, in polyamic acid complex microsphere imidization step 3 being obtained, obtain the polyimide complex microsphere of hollow structure; The method of described imidization is: the polyamic acid complex microsphere obtaining to step 3 adds 3mL diacetyl oxide and 1mL pyridine, after reaction 24h, adds 10mL ethanol and 10mL water.
The color of the polyimide complex microsphere of the hollow structure of embodiment mono-preparation is brown color.
Embodiment bis-: the preparation method of the polyimide complex microsphere of a kind of hollow structure described in the present embodiment carries out according to the following steps:
One, under the condition of magnetic agitation, 9.6mL polystyrene microsphere and 1.2mL pyrrole monomer mix, adding concentration is the liquor ferri trichloridi 20mL of 0.1g/mL, magnetic agitation is 12h, obtain the coated polystyrene complex microsphere solution of polypyrrole, the coated polystyrene complex microsphere solution of the polypyrrole obtaining is carried out to centrifugation, after centrifugation, solid is dried for 3 times afterwards by washing with alcohol, obtains the coated polystyrene complex microsphere of polypyrrole; The solid content of described polystyrene microsphere is 5%;
Two, 40g diamines is dissolved in to 500mLN, in N-N,N-DIMETHYLACETAMIDE, then adds wherein the dianhydride of 40g, under room temperature, mechanical stirring 12h, obtains polyamic acid solution; The dosing method of described dianhydride is to divide and add for 8 times at 4h, primary dosage is 20g, secondary dosage is 10g, dosage is for the third time 5g, the dosage of the 4th time is 2.5g, and the dosage of the 5th time is 1.25g, and the dosage of the 6th time is 0.625g, the dosage of the 7th time is 0.3125g, and the dosage of the 8th time is 0.3125g;
Three, the coated polystyrene complex microsphere of the polypyrrole that step 1 obtained is to be placed in retort furnace calcination under the condition of 300 ℃ in temperature, calcination time is 2h, after calcination, be scattered in 40mLN, in N-dimethylacetamide solvent, then the polyamic acid solution that adds wherein step 2 to obtain, carries out centrifugation, by solid N after magnetic agitation 24h, the washing of N-dimethylacetamide solvent is dried for 3 times afterwards, obtains polyamic acid complex microsphere;
Four,, in polyamic acid complex microsphere imidization step 3 being obtained, obtain the polyimide complex microsphere of hollow structure; The method of described imidization is: the polyamic acid complex microsphere 1. obtaining to step 3 adds 3mL diacetyl oxide and 1mL pyridine, after reaction 24h, is placed in temperature and is the retort furnace calcination 2h of 350 ℃ under nitrogen atmosphere.
Embodiment tri-: the preparation method of a kind of polyimide complex microsphere described in the present embodiment carries out according to the following steps:
One, under the condition of magnetic agitation, 10mL polystyrene microsphere and 1mL pyrrole monomer are mixed, adding concentration is the liquor ferri trichloridi 20mL of 0.1g/mL, magnetic agitation is 12h, obtain the coated polystyrene complex microsphere solution of polypyrrole, the coated polystyrene complex microsphere solution of the polypyrrole obtaining is carried out to centrifugation, after centrifugation, solid is dried for 3 times afterwards by washing with alcohol, obtains the coated polystyrene complex microsphere of polypyrrole; The solid content of described polystyrene microsphere is 5%;
Two, 40g diamines is dissolved in to 500mLN, in N-N,N-DIMETHYLACETAMIDE, then adds wherein the dianhydride of 40g, under room temperature, mechanical stirring 12h, obtains polyamic acid solution; The dosing method of described dianhydride is to divide and add for 8 times at 4h, primary dosage is 20g, secondary dosage is 10g, dosage is for the third time 5g, the dosage of the 4th time is 2.5g, and the dosage of the 5th time is 1.25g, and the dosage of the 6th time is 0.625g, the dosage of the 7th time is 0.3125g, and the dosage of the 8th time is 0.3125g;
Three, the coated polystyrene complex microsphere of the polypyrrole that step 1 obtained is to be placed in retort furnace calcination under the condition of 300 ℃ in temperature, calcination time is 2h, after calcination, be scattered in 40mLN, in N-dimethylacetamide solvent, then the polyamic acid solution that adds wherein step 2 to obtain, carries out centrifugation, by solid N after magnetic agitation 24h, the washing of N-dimethylacetamide solvent is dried for 3 times afterwards, obtains polyamic acid complex microsphere;
Four,, in polyamic acid complex microsphere imidization step 3 being obtained, obtain the polyimide complex microsphere of hollow structure; The method of described imidization is: it is the retort furnace calcination 2h of 350 ℃ that the polyamic acid complex microsphere that step 3 is obtained is placed in temperature under nitrogen atmosphere.
Fig. 1 is the scanning electron microscope (SEM) photograph of polystyrene microsphere in embodiment mono-step 1; Fig. 2 is the scanning electron microscope (SEM) photograph of the coated polystyrene complex microsphere of the polypyrrole that obtains of embodiment mono-step 1; Fig. 3 is the scanning electron microscope (SEM) photograph of the polyimide complex microsphere that makes of embodiment mono-; Fig. 4 is the outside drawing of the polyimide complex microsphere of the hollow structure that makes of embodiment mono-.As can be seen from Figure 1, coated Surfaces of Polystyrene Microparticles smoother before, favorable dispersity, size homogeneous; Surface is more coarse compared with polystyrene microsphere as can be seen from Figure 2, and the size of microballoon and pattern all to compare homogeneous complete, illustrate that polypyrrole is successfully coated on polystyrene surface.As can be seen from Figure 3 the size of microballoon compares homogeneous, and surface is more coarse, and this is the result of imidization.Although can see and have slight bonding phenomenon, the surface of microballoon is relatively complete, from the microballoon of minority breakage, we exactly can clearly see the hollow structure of microballoon.The polyimide complex microsphere of the hollow structure that embodiment mono-makes is as seen from Figure 4 very loose, does not have agglomeration.
Claims (9)
1. a preparation method for the polyimide complex microsphere of hollow structure, the preparation method who it is characterized in that the polyimide complex microsphere of hollow structure carries out according to the following steps:
One, under the condition of magnetic agitation, polystyrene microsphere solution and pyrrole monomer are mixed, add again iron trichloride, magnetic agitation 8h～12h, obtain the coated polystyrene complex microsphere solution of polypyrrole, the coated polystyrene complex microsphere solution of the polypyrrole obtaining is carried out to centrifugation, after centrifugation, solid is dried for 2～4 times afterwards by washing with alcohol, obtains the coated polystyrene complex microsphere of polypyrrole; The solid content of described polystyrene microsphere is 5%; The volume ratio of described polystyrene microsphere solution and pyrrole monomer is 1:(0.1～0.5); The volume ratio of the quality of described iron trichloride and polystyrene microsphere solution is 1g:5mL;
Two, diamines is dissolved in N,N-dimethylacetamide, then adding wherein quality is the dianhydride of M, and under room temperature, mechanical stirring 12h～20h, obtains polyamic acid solution; The quality of described diamines and the volume ratio of N,N-dimethylacetamide are 1g:(10～15mL); Described diamines is 1:(1～1.2 with dianhydride amount of substance ratio); The dosing method of described dianhydride is to divide and add for 8 times at 4h, primary dosage is 1/2M, secondary dosage is 1/4M, dosage is for the third time 1/8M, the dosage of the 4th time is 1/16M, and the dosage of the 5th time is 1/32M, and the dosage of the 6th time is 1/64M, the dosage of the 7th time is 1/128M, and the dosage of the 8th time is 1/128M;
Three, the coated polystyrene complex microsphere of the polypyrrole that step 1 obtained is to be placed in retort furnace calcination under the condition of 300 ℃～500 ℃ in temperature, calcination time is 2h～4h, after calcination, be scattered in N, in N-dimethylacetamide solvent, then the polyamic acid solution that adds wherein step 2 to obtain, carries out centrifugation, by solid N after magnetic agitation 12h～24h, the washing of N-dimethylacetamide solvent is dried for 2～4 times afterwards, obtains polyamic acid complex microsphere; The coated polystyrene complex microsphere of polypyrrole that described step 1 obtains and the mass ratio of polyamic acid solution are 1:(3～5), in described N,N-dimethylacetamide solvent and step 1, the volume ratio of polystyrene microsphere solution is (2～4): 1;
Four, polyamic acid complex microsphere step 3 being obtained carries out imidization processing, obtains the polyimide complex microsphere of hollow structure.
2. the preparation method of the polyimide complex microsphere of a kind of hollow structure according to claim 1, the volume ratio that it is characterized in that polystyrene microsphere described in step 1 and pyrrole monomer is 1:0.125.
3. the preparation method of the polyimide complex microsphere of a kind of hollow structure according to claim 1, the volume ratio that it is characterized in that polystyrene microsphere described in step 1 and pyrrole monomer is 1:0.2.
4. the preparation method of the polyimide complex microsphere of a kind of hollow structure according to claim 1, is characterized in that diamines described in step 2 is diaminodiphenyl oxide.
5. the preparation method of the polyimide complex microsphere of a kind of hollow structure according to claim 1, is characterized in that dianhydride described in step 2 is pyromellitic acid dianhydride, phenyl ether tetracarboxylic dianhydride or benzophenone tetracarboxylic dianhydride.
6. the preparation method of the polyimide complex microsphere of a kind of hollow structure according to claim 1, is characterized in that diamines described in step 2 and the amount of substance ratio of dianhydride are 1:1.02.
7. the preparation method of the polyimide complex microsphere of a kind of hollow structure according to claim 1, the method that it is characterized in that imidization described in step 4 is: the polyamic acid complex microsphere obtaining to step 3 adds diacetyl oxide and pyridine, after reaction 24h～48h, add second alcohol and water; In described diacetyl oxide and step 1, the volume ratio of polystyrene microsphere is 1:(3～6); In described pyridine and step 1, the volume ratio of polystyrene microsphere is 1:(9～18); The volume ratio of described ethanol and water is 1:1; In the cumulative volume of described second alcohol and water and step 1, the volume ratio of polystyrene microsphere is 1:(0.4～0.8).
8. the preparation method of the polyimide complex microsphere of a kind of hollow structure according to claim 1, the method that it is characterized in that imidization described in step 4 is: the polyamic acid complex microsphere obtaining to step 3 adds diacetyl oxide and pyridine, after reaction 24h～48h, under nitrogen atmosphere, be placed in temperature and be the retort furnace calcination 2h of 350 ℃; In described diacetyl oxide and step 1, the volume ratio of polystyrene microsphere is 1:(3～6); In described pyridine and step 1, the volume ratio of polystyrene microsphere is 1:(9～18).
9. the preparation method of the polyimide complex microsphere of a kind of hollow structure according to claim 1, is characterized in that the method for imidization described in step 4 is: it is the retort furnace calcination 2h of 350 ℃ that the polyamic acid complex microsphere that step 3 is obtained is placed in temperature under nitrogen atmosphere.
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| CN110229355A (en) * | 2019-06-20 | 2019-09-13 | 青岛科思姆新材料有限公司 | A kind of preparation method of polyimides hollow microsphere |
| CN113231043A (en) * | 2021-05-06 | 2021-08-10 | 哈尔滨工程大学 | Oximato multi-layer polyimide microsphere adsorption material and preparation method thereof |
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