CN115181295A - Controllable preparation method of polymer composite microparticles with various complex morphologies - Google Patents
Controllable preparation method of polymer composite microparticles with various complex morphologies Download PDFInfo
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- CN115181295A CN115181295A CN202210961326.5A CN202210961326A CN115181295A CN 115181295 A CN115181295 A CN 115181295A CN 202210961326 A CN202210961326 A CN 202210961326A CN 115181295 A CN115181295 A CN 115181295A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/21—Urea; Derivatives thereof, e.g. biuret
Abstract
A method for controllably preparing polymer composite microparticles with various complex morphologies comprises the following steps: step 1, dissolving a polymer solution by a solvent system A and dissolving a small molecule solution by a solvent system B; the solvent system A is a mixed solution system comprising acetone, dioxane, dimethyl sulfoxide, dimethyl amide, toluene and water, and the polymer is a polymer molecule of which the polymer chain can be encapsulated in a crystal structure formed by small molecules and the polymerization degree is more than 1; the solvent system B is a mixed solution system comprising methanol, ethanol, isobutanol and water; the small molecule is a molecule which can form a crystalline framework structure and can be used for accommodating or compounding a single chain or a plurality of chains of a polymer; step 2, placing one prepared solution in a homogeneous environment, and dropwise adding the other solution to obtain polymer-small molecule compound microparticles; and 3, collecting and drying the obtained polymer composite microparticles. The invention is easy to form a polymer composite microparticle structure with better uniformity.
Description
Technical Field
The invention belongs to the technical field of polymer micron-sized composite particle preparation, and particularly relates to a method for controllably preparing polymer micron-sized composite particles with complicated shapes such as flower discs and the like by forming host-guest structures of small molecules and polymers and changing the composition of a solvent in a system.
Background
The polymer composite microparticles refer to particles which are composed of polymers and small molecules and have the particle size of micron level. The polymer composite microparticles have wide applications in the fields of medical diagnosis, electronic devices, food industry, chemical industry, environmental engineering and the like. For example, polymer composite microparticles can be used not only as carriers to deliver specific drugs in the medical field, but also to achieve adhesion and sealing in the fields of construction, electronics, and the like.
Besides the chemical composition, the morphology of the polymer composite microparticles is closely related to the function thereof. Common composite microparticles are predominantly spherical or spheroidal. In recent years, composite microparticles having a particular morphology have received much attention. For example, the rod-shaped and cage-shaped composite microparticles have special length-diameter ratio, which is beneficial to effectively and controllably releasing functional small molecules [6,7] (ii) a The hairy or flocculent composite microparticles can carry functional groups and have good biological environmental adaptability [ 3 ,8] (ii) a The disc-shaped composite microparticles have different emulsifying properties from spherical particles [9] (ii) a The flaky composite microparticle filler has higher thermal conductivity [10] (ii) a The fibrous composite microparticles have excellent mechanical properties [11] . Therefore, the preparation of the polymer composite microparticles with special morphology has important application significance in various engineering fields.
At present, the polymer composite microparticles with special morphology can be prepared by methods such as emulsion polymerization, microfluid, electrospray, template method, supercritical fluid and the like. For exampleCage-shaped composite particles can be produced by a polymerization method [6] (ii) a The micro-channel method can prepare porous microspheres; flocculent microparticles can be obtained by a solvent method; the template method can form cylindrical microparticles. However, these methods are complicated to operate, and the same method often only can obtain particles with a single morphology. In other words, the methods are difficult to achieve the purpose of effectively regulating and controlling the microparticles to form various morphologies by simply changing the preparation conditions, and the defect greatly limits the diversified development of the polymer composite microparticle morphology.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for controllably preparing polymer composite microparticles with various complex morphologies, which is used for accurately regulating and controlling the morphology of the polymer composite microparticles by changing the composition of a solvent system used for preparation on the basis of a host-guest structure formed by self-assembly of small molecules and polymers.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for controllably preparing polymer composite microparticles with various complex morphologies comprises the following steps:
step 1, dissolving a polymer solution by a solvent system A and dissolving a small molecule solution by a solvent system B;
the solvent system A is a mixed solution system comprising acetone, dioxane, dimethyl sulfoxide, dimethyl amide, toluene and water, and the polymer is a polymer molecule of which the polymer chain can be encapsulated in a crystal structure formed by small molecules and the polymerization degree is more than 1; the solvent system B is a mixed solution system comprising methanol, ethanol, isobutanol and water; the small molecule is a molecule which can form a crystalline framework structure and can be used for accommodating or compounding a single chain or multiple chains of a polymer;
step 2, placing one solution prepared in the step 1 in a homogeneous environment, and dropwise adding the other solution to obtain polymer-small molecule compound microparticles;
and 3, collecting and drying the obtained polymer composite microparticles.
Further, in the step 1, the polymer is polyester, such as polycaprolactone, polylactic acid, and the like; polyethers such as polyethylene oxide and the like; polyamides such as nylon and the like; polyolefins such as polyethylene, polypropylene, and polybutadiene.
Still further, in the step 1, the small molecule is urea molecule and its analogues (such as thiourea, methylurea, etc.); cyclodextrin molecules and derivatives thereof (e.g., α -, β -, γ -cyclodextrin, etc.); a metal organic framework Material (MOF); a covalent organic framework material (COF); and some drug small molecules (e.g., diflunisal, dapsone, etc.).
In step 1, the solvent systems A and B are generally mutually soluble, A is selected from but not limited to acetone, dioxane, dimethyl sulfoxide, dimethyl amide, toluene, water and the like and mixed solution systems thereof, and B is selected from but not limited to methanol, ethanol, isobutanol, water and the like and mixed solution systems thereof. The choice of solvent system affects the final morphology of the polymer composite particles. Therefore, the morphology of the finally formed polymer composite microparticle is regulated and controlled by a solvent system obtained by mixing the A solvent, the B solvent and the two solvents.
Further, in step 2, the homogenization environment includes, but is not limited to, stirring, ultrasound, homogenization, and the like. If the polymer solution is in a homogeneous environment, the added solution is a small molecule solution. And vice versa.
Preferably, in the step 2, the homogeneous environment can be further regulated. For example: when the homogeneous environment is an ultrasonic environment, the ultrasonic power, the ultrasonic frequency, the ultrasonic temperature, the ultrasonic time and the like can be properly changed or adjusted, so that the effect of accurately adjusting the size and the dispersibility of the microparticles is achieved.
In the step 3, the collection method of the polymer composite microparticles includes, but is not limited to: filtering, centrifuging, decanting, and settling by weight.
In the step 3, the drying method of the polymer composite microparticles includes, but is not limited to: drying at normal temperature, freeze drying, vacuum drying or spray drying.
The invention provides a method for controllably preparing polymer micron-sized composite particles with complicated shapes such as flower discs and the like by forming host-guest structures of small molecules and polymers and changing the composition of a solvent in a system. The method is essentially different from the existing methods for obtaining the polymer composite microparticles by emulsion polymerization, microfluid method, supercritical fluid method and the like. The method has the advantages of simple operation, greenness, mildness, short time consumption, wide selection range of the composite micromolecules and important application value. Moreover, from the aspect of product morphology, the invention can obtain a series of polymer composite particles with complex morphologies such as a flower disc shape, a screw cap shape, a cage shape, a flocculent shape and the like which are difficult to realize by other means.
The invention has the following beneficial effects: 1. the polymer composite microparticle structure with better uniformity is easy to form; 2. the polymer composite microparticles with complex shapes can be easily obtained; 3. the morphology of the polymer particles is easy to adjust so as to meet the requirements of different application environments; 4. the preparation process is easy to operate, the required equipment is simple, and the cost is economic; 5. self-assembly is the main driving force, no harsh external field condition is needed, and the energy consumption is low.
Drawings
FIG. 1 is an infrared image of polycaprolactone-urea composite microparticles prepared in different solvent systems, with a scanning speed of 4cm -1 And the scanning times are 64 times, wherein the number average molecular weight of the polycaprolactone used as the raw material and the polycaprolactone in the composite particles are both 2000.
FIG. 2 is a Scanning Electron Microscope (SEM) picture of the lamellar composite microparticles of polycaprolactone-urea sheet (example 1) at a scale bar of 20 μm.
FIG. 3 is a Scanning Electron Microscope (SEM) picture of polycaprolactone-urea macropattern-shaped composite microparticles (example 2) at a scale bar of 50 μm.
FIG. 4 is a Scanning Electron Microscope (SEM) picture of polycaprolactone-urea screw-cap composite microparticles (example 3) at a scale bar of 500 μm.
Fig. 5 is a Scanning Electron Microscope (SEM) of polycaprolactone-urea caged composite microparticles (example 4) at a scale bar of 5 μm.
FIG. 6 is a Scanning Electron Microscope (SEM) picture of polycaprolactone-urea floriated composite microparticles (example 5) at a scale bar of 50 μm.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
Referring to fig. 1 to 6, a method for controllably preparing polymer composite microparticles having a plurality of complex morphologies, comprising the steps of:
step 1, dissolving a polymer solution by a solvent system A and dissolving a small molecule solution by a solvent system B;
the solvent system A is a mixed solution system comprising acetone, dioxane, dimethyl sulfoxide, dimethyl amide, toluene and water, and the polymer is a polymer molecule of which the polymer chain can be encapsulated in a crystal structure formed by small molecules and the polymerization degree is more than 1; the solvent system B is a mixed solution system comprising methanol, ethanol, isobutanol and water; the small molecule is a molecule which can form a crystalline framework structure and can be used for accommodating or compounding a polymer single chain or a polymer multi-chain;
in the step 1, the polymer is polyester, such as polycaprolactone, polylactic acid and the like; polyethers such as polyethylene oxide and the like; polyamides such as nylon and the like; polyolefins such as polyethylene, polypropylene, and polybutadiene.
In the step 1, the small molecules are urea molecules and analogues thereof (such as thiourea, methylurea and the like); cyclodextrin molecules and derivatives thereof (e.g., α -, β -, γ -cyclodextrin, etc.); a metal organic framework Material (MOF); a covalent organic framework material (COF); and some drug small molecules (e.g., diflunisal, dapsone, etc.).
In step 1, the solvent systems A and B are generally mutually soluble, A is selected from but not limited to acetone, dioxane, dimethyl sulfoxide, dimethyl amide, toluene, water and the like and mixed solution systems thereof, and B is selected from but not limited to methanol, ethanol, isobutanol, water and the like and mixed solution systems thereof. The choice of solvent system affects the final morphology of the polymer composite particles. Therefore, the morphology of the finally formed polymer composite microparticle is regulated and controlled by a solvent system obtained by mixing the A solvent, the B solvent and the two solvents.
Step 2, placing one solution prepared in the step 1 in a homogeneous environment, and dropwise adding the other solution to obtain polymer-small molecule compound microparticles;
in step 2, the homogenization environment includes, but is not limited to, stirring, ultrasound, homogenization, and the like. If the polymer solution is in a homogeneous environment, the added solution is a small molecule solution. And vice versa.
In the step 2, the homogeneous environment can be further regulated. For example: when the homogeneous environment is an ultrasonic environment, the ultrasonic power, the ultrasonic frequency, the ultrasonic temperature, the ultrasonic time and the like can be properly changed or adjusted, so that the effect of accurately adjusting the size and the dispersibility of the microparticles is achieved.
And 3, collecting and drying the obtained polymer composite microparticles.
In step 3, the collection method of the polymer composite microparticles includes, but is not limited to: filtering, centrifuging, decanting, and settling by weight.
In step 3, the drying method of the polymer composite microparticles includes but is not limited to: drying at normal temperature, freeze drying, vacuum drying or spray drying.
As shown in figure 1, the polycaprolactone/urea composite micro-particle prepared under different solvent systems is 3400cm -1 、3350cm -1 、3200cm -1 All have NH 2 Peak shift at 2950cm -1 In the presence of CH 2 Shift of vibration peak at 1735cm -1 There is a blue shift of the peak of polycaprolactone C = O at 1650cm -1 Where is the red shift of the urea C = O peak. The results show that the polycaprolactone-urea host-guest composite structure is prepared and formed in different solvent systems.
As shown in fig. 2, the polycaprolactone-urea composite microparticle prepared in the methanol-acetone system showed a lamellar structure with micron scale as a whole.
As shown in fig. 3, the polycaprolactone-urea composite microparticles prepared in the isobutanol-acetone system generally exhibit a large disc-shaped complex structure of micrometer scale.
As shown in fig. 4, the polycaprolactone-urea composite microparticle prepared in the ethanol-acetone system generally has a micrometer-scale screw-cap-shaped complex structure.
As shown in fig. 5, the polycaprolactone-urea composite microparticles prepared in the methanol/isobutanol-acetone system generally exhibited a cage-like complex structure of micrometer scale.
As shown in fig. 6, the polycaprolactone-urea composite microparticles prepared in isobutanol-acetone system showed a small floral disc complex structure in micron scale overall.
Example 1
Mixing 0.25g polycaprolactone (M) n =2,000) was dissolved in 50mL of an acetone solution. A saturated urea-methanol solution was prepared. The urea-methanol solution is placed in an ultrasonic machine, the ultrasonic power is set to be 140W, the ultrasonic frequency is set to be 40KHz, the temperature is set to be 50 ℃, and the time is set to be 30min. During the ultrasound, the polycaprolactone-acetone solution was added drop-wise to the urea-methanol solution. After the sonication was completed, the sample was cooled to room temperature. Standing and filtering. Obtaining white powdery particles and drying the white powdery particles to obtain the polymer composite microparticle product. Under the condition of the embodiment, the obtained product has good particle dispersibility and uniform shape and size, and shows the appearance of lamellar particles with micron size.
Example 2
Mixing 0.25g polycaprolactone (M) n =2,000) was dissolved in 50mL acetone solution. A saturated urea-isobutanol solution is prepared. And (3) putting the urea-isobutanol solution into an ultrasonic machine, setting the ultrasonic power to be 140W, the ultrasonic frequency to be 40KHz, the temperature to be 50 ℃ and the time to be 30min. After completion, the sample was cooled to room temperature. Standing and filtering. Obtaining white powdery particles and drying the white powdery particles to obtain the polymer composite microparticle product. Under the condition of the example, the obtained product has good particle dispersibility, uniform morphological size and appearance of disc-shaped particles with micron size.
Example 3
Mixing 0.25g polycaprolactone (M) n =2,000) was dissolved in 50mL of an acetone solution. A saturated urea-ethanol solution was prepared. The urea-ethanol solution is placed in an ultrasonic machine, the ultrasonic power is set to be 140W, the ultrasonic frequency is set to be 40KHz, the temperature is set to be 50 ℃, and the time is set to be 30min. During the ultrasonic treatment, polycaprolactone-acetone is addedThe solution was added drop wise to the urea-ethanol solution. After the sonication was completed, the sample was cooled to room temperature. Standing and filtering. Obtaining white powdery particles and drying the white powdery particles to obtain the polymer composite microparticle product. Under the condition of the embodiment, the obtained product has good particle dispersibility and uniform shape and size, and shows the appearance of hexagonal screw cap-shaped particles with the size of micron.
Example 4
Mixing 0.25g polycaprolactone (M) n =2,000) was dissolved in 50mL of an acetone solution. A saturated urea-methanol/isobutanol (50/50) solution was prepared. Putting the urea-methanol/isobutanol solution into an ultrasonic machine, setting the ultrasonic power to be 140W, the ultrasonic frequency to be 40KHz, the temperature to be 50 ℃ and the time to be 30min. During ultrasonic treatment, the polycaprolactone-acetone solution is added dropwise into the urea-methanol/isobutanol solution. After the sonication was completed, the sample was cooled to room temperature. Standing and filtering. Obtaining white powdery particles and drying the white powdery particles to obtain the polymer composite microparticle product. Under the conditions of this example, a cage-like particle morphology with dimensions in the micrometer range is exhibited.
Example 5
Mixing 0.25g of polycaprolactone (M) n =2,000) was dissolved in 50mL of an acetone solution. A saturated urea-isobutanol solution is prepared. And (3) putting the urea-isobutanol solution into an ultrasonic machine, setting the ultrasonic power to be 200W, the ultrasonic frequency to be 40KHz, the temperature to be 50 ℃ and the time to be 30min. During the ultrasonic treatment, the urea-isobutanol solution is added into the polycaprolactone-acetone solution drop by drop. After the sonication was completed, the sample was cooled to room temperature. Standing and filtering. Obtaining white powdery particles and drying the white powdery particles to obtain the polymer composite microparticle product. Under the conditions of this example, the resulting product particles had a smaller particle size than the discoid particles of example 2.
The embodiments described in this specification are merely illustrative of implementations of the inventive concepts, which are intended for purposes of illustration only. The scope of the present invention should not be construed as being limited to the particular forms set forth in the embodiments, but is to be accorded the widest scope consistent with the principles and equivalents thereof as contemplated by those skilled in the art.
Claims (7)
1. A method for controllably producing polymeric composite microparticles having a plurality of complex morphologies, said method comprising the steps of:
step 1, dissolving a polymer solution by a solvent system A and dissolving a small molecule solution by a solvent system B;
the solvent system A is a mixed solution system comprising acetone, dioxane, dimethyl sulfoxide, dimethyl amide, toluene and water, and the polymer is a polymer molecule of which the polymer chain can be encapsulated in a crystal structure formed by small molecules and the polymerization degree is more than 1; the solvent system B is a mixed solution system comprising methanol, ethanol, isobutanol and water; the small molecule is a molecule which can form a crystalline framework structure and can be used for accommodating or compounding a polymer single chain or a polymer multi-chain;
step 2, placing one solution prepared in the step 1 in a homogeneous environment, and dropwise adding the other solution to obtain polymer-small molecule compound microparticles;
and 3, collecting and drying the obtained polymer composite microparticles.
2. The method for controllably preparing polymer composite microparticles with multiple complex morphologies according to claim 1, wherein in step 1, the polymer is polyester, polyether, polyamide or polyolefin.
3. The method for controllably preparing the polymer composite micro-particles with various complex morphologies as claimed in claim 1 or 2, wherein in the step 1, the small molecules are urea molecules and analogues thereof, cyclodextrin molecules and derivatives thereof, metal organic framework materials, covalent organic framework materials and drug small molecules.
4. The method of claim 1 or 2, wherein the homogenizing step 2 comprises stirring, sonication, and homogenizing.
5. The method of claim 1 or 2, wherein the homogeneous environment in step 2 is further controlled.
6. The method for controllably preparing polymer composite microparticles with multiple complex morphologies as claimed in claim 1 or 2, wherein in step 3, the collection method of the polymer composite microparticles comprises filtration, centrifugation, decantation and gravimetric sedimentation.
7. The method for controllably preparing polymer composite microparticles with multiple complex morphologies as claimed in claim 1 or 2, wherein in the step 3, the drying method of the polymer composite microparticles is normal temperature drying, freeze drying, vacuum drying or spray drying.
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Citations (4)
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| WO2016080336A1 (en) * | 2014-11-18 | 2016-05-26 | 国立研究開発法人物質・材料研究機構 | Method for producing porous particle |
| US20200040191A1 (en) * | 2011-09-23 | 2020-02-06 | Dystar Hilton Davis Corp. | Self-assembled nano-structured particle and methods for preparing |
| CN112876701A (en) * | 2021-01-15 | 2021-06-01 | 浙江工业大学 | Method for preparing polymer micro-nano particles with wrinkled or laminated morphology |
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- 2022-08-10 CN CN202210961326.5A patent/CN115181295A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012071013A1 (en) * | 2010-11-24 | 2012-05-31 | Nanyang Technological University | Method for encapsulating particles |
| US20200040191A1 (en) * | 2011-09-23 | 2020-02-06 | Dystar Hilton Davis Corp. | Self-assembled nano-structured particle and methods for preparing |
| WO2016080336A1 (en) * | 2014-11-18 | 2016-05-26 | 国立研究開発法人物質・材料研究機構 | Method for producing porous particle |
| CN112876701A (en) * | 2021-01-15 | 2021-06-01 | 浙江工业大学 | Method for preparing polymer micro-nano particles with wrinkled or laminated morphology |
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