CN103570946B - A kind of preparation method of polyimide microsphere - Google Patents
A kind of preparation method of polyimide microsphere Download PDFInfo
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- CN103570946B CN103570946B CN201310583099.8A CN201310583099A CN103570946B CN 103570946 B CN103570946 B CN 103570946B CN 201310583099 A CN201310583099 A CN 201310583099A CN 103570946 B CN103570946 B CN 103570946B
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Abstract
The invention provides a kind of preparation method of polyimide microsphere, it comprises the following steps: the acid of (1) synthesizing polyamides; (2) polyamic acid microballoon is prepared; (3) polyimide microsphere is prepared in the imidization of polyamic acid microballoon: add pyridine/diacetyl oxide mixing solutions by step (2) gained polyamic acid microspheres solution, stirring reaction 2 hours, obtain polyimide solution, again by centrifugal for the polyimide solution obtained, filter, washing, dries and obtains polyimide microsphere.The present invention is easy to realize, and the polyimide microsphere particle diameter of preparation is little, and median size is 37.4-110nm.
Description
Technical field
The invention belongs to functional polymer microballoon field, be specifically related to a kind of preparation method of polyimide microsphere.
Background technology
Polyimide microsphere particle has pattern and the size of polymer microsphere uniqueness, and specific surface area is large, and adsorptivity is strong, and surface reaction ability is strong; Also have high temperature resistant, solvent resistant, the natural characteristics that physical strength is high, in support of the catalyst, coating, be separated and sorbing material, biotechnology, biological chemistry and the contour sophisticated technology field of information have a wide range of applications simultaneously.
The preparation method of polyimide microsphere mainly contains nonaqueous emulsion method and reprecipitation method etc.Wherein to there is polyimide microsphere particle diameter comparatively large for nonaqueous emulsion method, and size distribution is wider, cannot obtain the polyimide microsphere of more uniform high sphericity, and in preparation process emulsifying agent add the polyimide microsphere unstable properties causing preparing.Reprecipitation method prepares the solvability difference that polyimide microsphere generally uses polyimide in different solvents, and target substance and poor solvent are mixed to get polyimide microsphere.When this method exists the precipitation agent dripped containing dispersion agent, process is difficult to control, the comparatively large and problem of wider distribution of microspherulite diameter, and the general precipitation agent used is expensive, causes cost high.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, and provide a kind of preparation method of polyimide microsphere, simple process, do not introduce additive, cost is low; Prepared polyimide microsphere particle diameter is little, reaches Nano grade, and specific surface area is large, has the advantage of nanospheres and polyimide material concurrently.
The technical scheme that solution the technology of the present invention problem adopts is that the preparation method of this polyimide microsphere comprises the following steps:
(1) synthesizing polyamides acid: at 0-10 DEG C, monomer diamine is dissolved in organic solvent, is stirred to and dissolves completely, obtain the solution of monomer diamine, then add tetracarboxylic dianhydride's monomer and carry out polyreaction, obtain polyamic acid solution;
(2) polyamic acid microballoon is prepared: step (1) gained polyamic acid solution is added the polyamic acid dilute solution that organic solvent diluting to solid content is 1-2wt%, dropwise water is dripped again in polyamic acid dilute solution, keep in the process dripped stirring, obtain polyamic acid microspheres solution;
(3) polyimide microsphere is prepared in the imidization of polyamic acid microballoon: add pyridine/diacetyl oxide mixing solutions by step (2) gained polyamic acid microspheres solution, stirring reaction 2-3 hour, obtain polyimide solution, again by centrifugal for the polyimide solution obtained, filter, washing, dries and obtains polyimide microsphere.
The present invention utilizes polyimide intermediate polyamic acid not easily to reunite, and the features such as little, the narrowly distributing of polyimide microsphere particle diameter formed add water in polyimide intermediate polyamic acid solution prepares polyamic acid microballoon, then its imidization is obtained polyimide microsphere.The polyimide microsphere that this method obtains all is greatly improved than existing methods in particles size and distribution.Polyimide microsphere particle diameter can reach nano level, compared with large ball diameter material, a large amount of interfaces is had in nano structural material, dielectric confinement, and nanostructured microsphere has very high diffusivity, during for the preparation of polyimide nano-composite material, blended evenly, the mechanical property such as creep, superplasticity is significantly improved.In addition, polyimide material itself has high temperature resistant, corrosion-resistant, physical strength high, therefore nano level polyimide microsphere has Nano microsphere surface effects, dielectric confinement and high temperature resistant, the characteristic such as physical strength is high, has expanded the Application Areas of polyimide material further.
Preferably, step (1) described monomer diamine is the one in 4,4'-diaminodiphenyl oxide, 4,4'-diaminodiphenylmethane, Ursol D, and described organic solvent is N,N-dimethylacetamide, and the strength of solution of described monomer diamine is 5wt%.
Preferably, the described tetracarboxylic dianhydride's monomer of step (1) is pyromellitic acid anhydride, 3,3', 4,4'-bibenzene tetracarboxylic dianhydride or 2,3, one in 3', 4'-bibenzene tetracarboxylic dianhydride, tetracarboxylic dianhydride's monomer and monomer diamine mol ratio are 1.02:1, step (1) described polymeric reaction condition is under 500-700r/min rotating speed, reacts 2-3 hour at 0-10 DEG C of temperature.The polyamic acid solution obtained through step (1) is first diluted to the polyamic acid dilute solution that solid content is 1-2wt%, then adds water further and prepare polyamic acid microspheres solution.Polyamic acid solution solid content greatly easily causes soltion viscosity large, even occurs agglomeration.
Preferably, adding tetracarboxylic dianhydride's monomer described in step (1) is point to add for 3 times, adds tetracarboxylic dianhydride's monomer of 1/3 weight part, every minor tick 30min at every turn.
Preferably, add-on and the polyamic acid dilute solution mass ratio of step (2) described water are 1:1, and described maintenance is stirred as keeping stir speed (S.S.) to be 500-700r/min.The too high meeting of rotating speed causes polyamic acid microballoon mutually to clash into, and causes the polyamic acid microspherulite diameter generated to distribute wide.
Preferably, the described pyridine of step (3)/diacetyl oxide mixing solutions add-on is 10% of polyamic acid microspheres solution volume, and in pyridine/diacetyl oxide mixing solutions, the volume ratio of pyridine and diacetyl oxide is 1:3.
Present invention also offers a kind of preparation method of polyimide microsphere.This preparation method comprises the following steps:
(1) synthesizing polyamides acid: at 0-10 DEG C, monomer diamine is dissolved in organic solvent, is stirred to and dissolves completely, obtain the solution of monomer diamine, then add tetracarboxylic dianhydride's monomer and carry out polyreaction, obtain polyamic acid solution;
(2) polyamic acid microballoon is prepared: step (1) gained polyamic acid solution is added the polyamic acid dilute solution that organic solvent diluting to solid content is 1-2wt%, dropwise water is dripped again in polyamic acid dilute solution, keep in the process dripped stirring, obtain polyamic acid microspheres solution;
(3) polyimide microsphere is prepared in the imidization of polyamic acid microballoon: step (2) gained polyamic acid microspheres solution be coated on base material, and heat 2-3 hour at 240-270 DEG C of temperature, obtain polyimide microsphere coating.Described base material can be glass, tinsel etc.
Adopt the method for heating to the imidization of polyamic acid microballoon, be applicable to polyamic acid microballoon or be coated on base material containing the mixture of polyamic acid microballoon, reheat after carrying out imidization and form the coating containing polyimide microsphere.
Preferably, the median size of the polyimide microsphere prepared by aforesaid method is 37.4-110nm, and particle size polydispersity index is 0.225-0.278.
The invention has the beneficial effects as follows: adopt the method being simple and easy to repetition to prepare polyimide microsphere at a lower temperature, direct in preparation process is precipitation agent with water, does not need to add dispersion agent, does not thus introduce impurity, the polyimide microsphere of preparation is purer, and with low cost.The polyimide microsphere particle diameter prepared is little, and median size is 37.4-100nm, narrow diameter distribution, and particle size polydispersity index is 0.225-0.278.
Can give matrix material better properties when preparing matrix material, and purity is higher, thus the scope of application is wider.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of polyimide microsphere prepared in the present invention's specific embodiment;
Fig. 2 is the particle size distribution figure of polyimide microsphere prepared in embodiment one;
Fig. 3 is the electron-microscope scanning figure of polyimide microsphere prepared in embodiment two.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with accompanying drawing, the present invention is described in further detail.
The embodiment of the present invention provides a kind of preparation method of polyimide microsphere, in organic solvent monomer diamine and tetracarboxylic dianhydride's monomer reaction are obtained polyamic acid, be that polyamic acid microballoon prepared by precipitation agent again with water, and further the imidization of polyamic acid microballoon obtain polyimide microsphere.
Embodiment of the present invention N used, N-N,N-DIMETHYLACETAMIDE purity >=99wt%, monomer diamine 4,4'-diaminodiphenyl oxide used, 4,4-diamino dimethylbenzene alkane and Ursol D purity >=98wt%, tetracarboxylic dianhydride's monomer pyromellitic acid anhydride used, 3,3', 4,4'-bibenzene tetracarboxylic dianhydride or 2,3,3', 4'-bibenzene tetracarboxylic dianhydride purity >=98wt%.
Embodiment one
Under frozen water mixing bath condition (0 DEG C), take 5.0g4, 4'-diaminodiphenyl oxide (0.025mol) is dissolved in 90gN, in N-N,N-DIMETHYLACETAMIDE, after all dissolving, point adding pyromellitic acid anhydride for 3 times carries out polyreaction, add 1.854g pyromellitic acid anhydride at every turn, add 5.562g(0.0255mol altogether), next time (4 are added again after dissolving completely each time, the mol ratio of 4'-diaminodiphenyl oxide and pyromellitic acid anhydride is 1:1.02), reaction times is 3h, stir speed (S.S.) is 700r/min, obtain the polyamic acid solution that solid content is 10%.Take the polyamic acid solution prepared by 20g, then add 180gN, N-N,N-DIMETHYLACETAMIDE, obtain the polyamic acid dilute solution of solid content 1wt%.Take the above-mentioned polyamic acid dilute solution of 20g, under the rotating speed of 700r/min, slowly drip 20g distilled water, time for adding is 5min, prepares polyamic acid microspheres solution.
The polyamic acid microspheres solution obtained is coated with on a glass uniformly, and heats 2 hours at 270 DEG C in retort furnace, obtain polyimide microsphere coating.
Adopt transmission electron microscope to test the polyimide microsphere prepared by the embodiment of the present invention, be illustrated in figure 1 the transmission electron microscope picture of the polyimide microsphere prepared by the present embodiment, polyimide microsphere particle diameter is 40nm.Adopt Britain Malvern company Mastersizer3000 particle-size analyzer to carry out testing graininess to the polyimide microsphere prepared by the present embodiment, its particle size distribution figure as shown in Figure 2.After tested, gained polyimide microsphere median size is 37.4nm, and in normal distribution, particle diameter polydispersity index is 0.225.
Embodiment two
At 10 DEG C, take 5.0g4,4'-diaminodiphenyl oxide (0.025mol) is dissolved in 90gN, in N-N,N-DIMETHYLACETAMIDE, after all dissolving, point adding pyromellitic acid anhydride for 3 times carries out polyreaction, add 1.854g pyromellitic acid anhydride at every turn, add 5.562g(0.0255mol altogether), add next time (mol ratio of 4,4'-diaminodiphenyl oxide and pyromellitic acid anhydride is 1:1.02) after dissolving completely each time, the reaction times is 2h again, stir speed (S.S.) is 500r/min, obtains the polyamic acid solution that solid content is 10%.Take the polyamic acid solution prepared by 20g, then add 80gN, N-N,N-DIMETHYLACETAMIDE, obtain the polyamic acid dilute solution of solid content 2%.Take the above-mentioned polyamic acid dilute solution of 20g, under the rotating speed of 500r/min, slowly drip 20g distilled water, time for adding is 5min, prepares polyamic acid microspheres solution.
4ml pyridine/diacetyl oxide mixing solutions (volume ratio of pyridine and diacetyl oxide is 1:3) will be added in the polyamic acid microspheres solution obtained, stirring reaction 2 hours, obtain polyimide solution, again by centrifugal in the whizzer of 10000r/min for the polyimide solution obtained, filter, washing, dries and obtains polyimide microsphere.
The method identical with embodiment one and electron-microscope scanning is adopted to carry out testing graininess to the polyimide microsphere prepared by the present embodiment.After tested, gained polyimide microsphere median size is 82.1nm, in normal distribution, particle diameter polydispersity index is 0.278, be illustrated in figure 3 the electron-microscope scanning figure of the polyimide microsphere prepared by the present embodiment, polyimide microsphere has good globosity as can be seen from Figure, and is uniformly dispersed, size is homogeneous, and particle diameter is about 70-110nm.
Embodiment three
At 0 DEG C, take 5.0g4, 4 '-diaminodiphenylmethane (0.0252mol) is dissolved in 124gN, in N-N,N-DIMETHYLACETAMIDE, after all dissolving, divide and add 33 times, 3', 4, 4'-bibenzene tetracarboxylic dianhydride carries out polyreaction, add 2.520g3 at every turn, 3', 4, 4'-bibenzene tetracarboxylic dianhydride, add 7.561g(0.0257mol altogether), next time (4 are added again after dissolving completely each time, 4 '-diaminodiphenylmethane and 3, 3', 4, the mol ratio of 4'-bibenzene tetracarboxylic dianhydride is 1:1.02), reaction times is 3h, stir speed (S.S.) is 600r/min, obtain the polyamic acid solution that solid content is 10wt%.Take the polyamic acid solution prepared by 20g, then add 180gN, N-N,N-DIMETHYLACETAMIDE, obtain the polyamic acid dilute solution of solid content 1wt%.Take the above-mentioned polyamic acid dilute solution of 20g, under the rotating speed of 600r/min, slowly drip 20g distilled water, time for adding is 5min, prepares polyamic acid microspheres solution.
The polyamic acid microspheres solution obtained is coated with on a glass uniformly, and heats 3 hours at 240 DEG C of temperature in retort furnace, obtain polyimide microsphere coating.
The method identical with embodiment one is adopted to carry out testing graininess to the polyimide microsphere prepared by the present embodiment.After tested, gained polyimide microsphere median size is 50.7nm, and in normal distribution, particle diameter polydispersity index is 0.258.
Embodiment four
At 5 DEG C, take 5.0g Ursol D (0.0463mol) and be dissolved in 171gN, in N-N,N-DIMETHYLACETAMIDE, after all dissolving, divide and add 2,3,3' 3 times, 4'-bibenzene tetracarboxylic dianhydride, add 4.625g at every turn, add 13.876g(0.0472mol altogether), add next time (Ursol D and 2 again after dissolving completely each time, 3, the mol ratio of 3', 4'-bibenzene tetracarboxylic dianhydride is 1:1.02), the reaction times is 3h, stir speed (S.S.) is 600r/min, obtains the polyamic acid solution that solid content is 10wt%.Take the polyamic acid solution prepared by 20g, then add 180gN, N-N,N-DIMETHYLACETAMIDE, obtain the polyamic acid dilute solution of solid content 1wt%.Take the above-mentioned polyamic acid dilute solution of 20g, under the rotating speed of 600r/min, slowly drip 20g distilled water, time for adding is 5min, prepares polyamic acid microspheres solution.
4ml pyridine/diacetyl oxide mixing solutions (volume ratio of pyridine and diacetyl oxide is 1:3) will be added in the polyamic acid microspheres solution obtained, stirring reaction 2 hours, obtain polyimide solution, again by centrifugal in the whizzer of 10000r/min for the polyimide solution obtained, filter, washing, dries and obtains polyimide microsphere.
The method identical with embodiment two is adopted to carry out testing graininess to the polyimide microsphere prepared by the present embodiment.After tested, gained polyimide microsphere median size is 60.9nm, and in normal distribution, size distribution index is 0.230.
By the above detailed description to the embodiment of the present invention, can understand and the invention solves polyimide microsphere preparation method complexity in prior art, and the polyimide microsphere particle diameter obtained is large or the wide problem that distributes, obtained polyimide microsphere median size be 37.4-110nm, particle size polydispersity index is 0.225-0.278.
Be understandable that, the illustrative embodiments that above embodiment is only used to principle of the present invention is described and adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (5)
1. a preparation method for polyimide microsphere, is characterized in that comprising the following steps:
(1) synthesizing polyamides acid: at 0-10 DEG C, monomer diamine is dissolved in organic solvent, is stirred to and dissolves completely, obtain the solution of monomer diamine, then add tetracarboxylic dianhydride's monomer and carry out polyreaction, obtain polyamic acid solution;
(2) polyamic acid microballoon is prepared: step (1) gained polyamic acid solution is added the polyamic acid dilute solution that organic solvent diluting to solid content is 1-2wt%, dropwise water is dripped again in polyamic acid dilute solution, keep in the process dripped stirring, obtain polyamic acid microspheres solution;
(3) polyimide microsphere is prepared in the imidization of polyamic acid microballoon: add pyridine/diacetyl oxide mixing solutions by step (2) gained polyamic acid microspheres solution, in pyridine/diacetyl oxide mixing solutions, the volume ratio of pyridine and diacetyl oxide is 1:3, stirring reaction 2-3 hour, obtain polyimide solution, again by centrifugal for the polyimide solution obtained, filter, washing, oven dry obtains polyimide microsphere, and the median size of polyimide microsphere is 37.4-110nm;
Step (1) described monomer diamine is 4, 4'-diaminodiphenyl oxide, 4, 4'-diaminodiphenylmethane, one in Ursol D, described organic solvent is N, N-N,N-DIMETHYLACETAMIDE, the strength of solution of described monomer diamine is 5wt%, described tetracarboxylic dianhydride's monomer is pyromellitic acid anhydride, 3, 3', 4, 4'-bibenzene tetracarboxylic dianhydride or 2, 3, 3', one in 4'-bibenzene tetracarboxylic dianhydride, tetracarboxylic dianhydride's monomer and monomer diamine mol ratio are 1.02:1, step (1) described polymeric reaction condition is under 500-700r/min rotating speed, 2-3 hour is reacted at 0-10 DEG C of temperature.
2. the preparation method of polyimide microsphere according to claim 1, it is characterized in that adding described in step (1) tetracarboxylic dianhydride's monomer is point to add for 3 times, adds tetracarboxylic dianhydride's monomer of 1/3 weight part, every minor tick 30min at every turn.
3. the preparation method of polyimide microsphere according to claim 1, is characterized in that the add-on of step (2) described water and polyamic acid dilute solution mass ratio are 1:1, and described maintenance is stirred as keeping stir speed (S.S.) to be 500-700r/min.
4. the preparation method of polyimide microsphere according to claim 1, is characterized in that the described pyridine of step (3)/diacetyl oxide mixing solutions add-on is 10% of polyamic acid microspheres solution volume.
5. a preparation method for polyimide microsphere, is characterized in that comprising the following steps:
(1) synthesizing polyamides acid: at 0-10 DEG C, monomer diamine is dissolved in organic solvent, is stirred to and dissolves completely, obtain the solution of monomer diamine, then add tetracarboxylic dianhydride's monomer and carry out polyreaction, obtain polyamic acid solution;
(2) polyamic acid microballoon is prepared: step (1) gained polyamic acid solution is added the polyamic acid dilute solution that organic solvent diluting to solid content is 1-2wt%, dropwise water is dripped again in polyamic acid dilute solution, keep in the process dripped stirring, obtain polyamic acid microspheres solution;
(3) polyimide microsphere is prepared in the imidization of polyamic acid microballoon: be coated on base material by step (2) gained polyamic acid microspheres solution, and 2-3 hour is heated at 240-270 DEG C of temperature, obtain polyimide microsphere, the median size of polyimide microsphere is 37.4-110nm.
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| CN104130411B (en) * | 2014-08-01 | 2016-08-17 | 黑龙江省科学院高技术研究院 | A kind of preparation method of the polyimides complex microsphere of hollow structure |
| CN104710789A (en) * | 2015-03-16 | 2015-06-17 | 吉林大学 | Preparation method of polyimide molding powder |
| CN105713349B (en) * | 2016-03-21 | 2017-12-29 | 武汉理工大学 | A kind of preparation method of antiwear heat resisting epoxy resin composite material |
| CN106111028B (en) * | 2016-06-28 | 2018-12-18 | 东阳市新意工业产品设计有限公司 | A kind of preparation method of microcapsules battery compound polyimide dielectric material |
| CN113169418B (en) * | 2019-01-22 | 2022-11-18 | 东莞东阳光科研发有限公司 | Polyimide microsphere slurry, composite diaphragm and lithium ion battery |
| CN111057237B (en) * | 2019-12-23 | 2021-10-26 | 华南理工大学 | Polyimide microsphere and preparation method thereof |
| CN111875796B (en) * | 2020-06-28 | 2022-03-18 | 东华大学 | Polyimide nano-microsphere for gas separation membrane |
| CN112266611B (en) * | 2020-10-14 | 2023-05-05 | 中国科学院合肥物质科学研究院 | Functionalized polyimide composite microsphere and preparation method thereof |
| CN113231043B (en) * | 2021-05-06 | 2022-08-02 | 哈尔滨工程大学 | Oximato multi-layer polyimide microsphere adsorption material and preparation method thereof |
| CN117069939B (en) * | 2023-10-17 | 2024-04-09 | 宁德时代新能源科技股份有限公司 | Polyimide microsphere and preparation method thereof, negative electrode plate, battery and power utilization device |
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| CN1246489A (en) * | 1998-08-28 | 2000-03-08 | 大阪府 | Polyamide acid and polyimide micrograin and method for preparing them |
| EP1152021A1 (en) * | 2000-05-04 | 2001-11-07 | Osaka Prefectural Government | Thermosetting polyamic acid microfine particles, thermosetting polyimide microfine particles, crosslinked polyimide microfine particles, and processes for their production |
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