CN112480320B - Tadpole-shaped hollow polymer particles and preparation method and application thereof - Google Patents
Tadpole-shaped hollow polymer particles and preparation method and application thereof Download PDFInfo
- Publication number
- CN112480320B CN112480320B CN202011387141.5A CN202011387141A CN112480320B CN 112480320 B CN112480320 B CN 112480320B CN 202011387141 A CN202011387141 A CN 202011387141A CN 112480320 B CN112480320 B CN 112480320B
- Authority
- CN
- China
- Prior art keywords
- tadpole
- styrene
- polymer particles
- shaped hollow
- divinylbenzene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K45/00—Medicinal preparations containing active ingredients not provided for in groups A61K31/00 - A61K41/00
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
-
- 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
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Pharmacology & Pharmacy (AREA)
- Polymers & Plastics (AREA)
- Epidemiology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention discloses tadpole-shaped hollow polymer particles and a preparation method and application thereof. The preparation method comprises the following steps: (1) dissolving a stabilizer in a mixed solvent of ethanol and toluene, and adding polystyrene seed microspheres to obtain a suspension; (2) dissolving styrene, divinylbenzene and an initiator in a mixed solvent of ethanol and toluene to obtain a precursor mixed solution; (3) and (2) heating the mixed solution in the step (1) to 75 +/-1 ℃ under the inert gas atmosphere, then dropwise adding the precursor mixed solution obtained in the step (2) into the suspension in the step (1) by using a peristaltic pump for carrying out dispersion polymerization reaction, cooling to room temperature after the reaction is finished, centrifuging, washing, and freeze-drying to obtain the tadpole-shaped hollow polymer particles. The method disclosed by the invention is simple in process, low in environmental pollution, low in cost and high in yield, and the prepared tadpole-shaped hollow polymer particles have a hollow structure, are adjustable in shape and have a wide application prospect.
Description
Technical Field
The invention relates to the technical field of polymer particles, and particularly relates to tadpole-shaped hollow polymer particles and a preparation method and application thereof.
Background
The tadpole-shaped structure is a unique geometric shape with two parts, a head and a tail. Organisms with tadpole-shaped structures in nature include tadpoles, sperm cells, bacteria, phages and the like, and the tadpole-shaped structures endow the organisms with the specific biological functions. Inspired by the tadpole-shaped structure possessed by organisms in nature, researchers have prepared various tadpole-shaped nanoparticles, which mainly include tadpole-shaped metal nanoparticles (Hu Jian qi ang, Zhang Yong, Liu Bo, Liu Jinxuan, Zhou Haihui, Xu Yunfeng, Jiang Yuxiong, Yang Zhilin, Tian Zhong-Qun, j.am.chem.soc, 2004,126, 9470-one 9471, camaro Pedro h.c., Xiong Yujie, Ji Li vit, Zuo Jian m., Xia Younan, j.am.chem.c., 2007,129, 15452-one 53, Yamada lilik, siderson g.m., m, Yang yellow 124514, j.am.c., 2007,129, 15452-one 53, Yamada lik, yao, Wang, Yang g, wang. m, wang. tm, Wang, Yang wo, lang et al, cheng. 5, lang et h, lang et al, chen et al, lang et al, lang et al, 12, lang et al, lang et al, lang, 12, lang et al, 2, lang et al, lang et al, 12, lang et al, 2, lang et al, lang et al, lang et al, lang et al, lang, 45-48; yu Taekyung, Joo Jin, Park Yong Il, Hyeon Taeghwan, Angew. chem. int. Ed.,2005,44, 7411-7414.) and tadpole-shaped inorganic non-metallic nanoparticles (Ni Wei, Liang Fuxin, Liu Juiguang, Qu Xiiaozhong, Zhang Chengliang, Li Jianioli, Wang Qian, Yang Zhenzhong, chem. Commun.,2011,47, 4727-4729; ni Zifeng, Wang Yongkuang, Advanced Materials Research,2011,194-196, 614-617; jia hooping, Gao Lian, j.phys.chem.b,2007,111, 5337-one 5343.). The tadpole-shaped nanoparticles of different types have unique physical, chemical, mechanical, optical and electrical properties and are widely applied to the fields of interface catalysis, local surface plasma resonance, sensors and propellers, nonlinear optical and photoresponsive devices, solar cells, tissue engineering, medical imaging, drug delivery, tumor treatment, biological enzyme immobilization, oil-water separation, emulsion stabilization and the like. Scientists have also developed a variety of methods for preparing tadpole-shaped metal nanoparticles, tadpole-shaped metal oxide nanoparticles, and tadpole-shaped inorganic non-metal nanoparticles, including precursor reduction and Ostwald ripening, local in situ substitution, pyrolysis, aqueous phase chemical seeding, direct current arc plasma jet chemical vapor deposition, solvothermal methods, sol-gel methods, laser fragmentation, metal droplet catalysis, microfluidic focused gel methods, and microemulsion synthesis, among others.
However, there are currently more reports on the synthesis of tadpole-shaped polymers, and fewer reports on the preparation of tadpole-shaped polymer particles. A common method of making tadpole-shaped polymer particles is to control the folding of the individual polymer chains, so the tadpole-shaped polymer particles are typically less than 10nm in size. Among the methods currently used for preparing tadpole-shaped polymer particles are cationic polymerization (Ni Wei, Liang Fuxin, Liu Jigueang, Qu Xiaozhong, Zhang Chengliang, Li Jianioli, Wang Qian, Yang Zhenzhoung, chem. Commun, 2011,47, 4727-the method), emulsion block copolymerization (Bobrin Valentin A., Chen Sung-Po R., Jia Zhongfan, Monteiro Michael J., Macro Lett.,2017,6, 1047-the 1051), dynamic control self-assembly of block copolymers (Zhu Jianhua, Zhuang Shiyi, Zhang g Kejujun, Waxiajun, Mays Jimmy W., Woolen L., Poren, Ju J., Ju Hua J., Ju Hua, Ju Hua J., Wan Ju Hua Hao Ha, Ju Hua Ju Huan J., Ju Huan, Ju Hua Ju Wan Huan J., Ju Hao, Ju Ka, Ju Ka Ha, Ju Ka Ha Ka, Ju Ha Ka Ha Ka, K ü Ka Ha Ka, K ü Ka, K ü Ka, K ü Ka, K ü Ka e, K ü Ka, K ü Ka, K ü e, K ü Ka, K # H, K # 52, K ü Ka e, K # H, K # H K # H # K # H # K # H # K # H # K # H # K # H # K # H #. However, the methods or processes for preparing the tadpole-shaped polymer particles are complicated, the yield is low, the cost is high, or the tadpole-shaped polymer particles are small in size and unclear in morphology.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of tadpole-shaped hollow polymer particles.
Another object of the present invention is to provide tadpole-shaped hollow polymer particles prepared by the method.
It is still another object of the present invention to provide applications of the tadpole-shaped hollow polymer particles.
The purpose of the invention is realized by the following technical scheme:
a preparation method of tadpole-shaped hollow polymer particles comprises the following steps:
(1) dissolving a stabilizer in a mixed solvent of ethanol and toluene, and adding polystyrene seed microspheres to obtain a suspension;
(2) dissolving styrene (monomer), divinylbenzene (cross-linking agent) and an initiator in a mixed solvent of ethanol and toluene to obtain a precursor mixed solution;
(3) and (2) heating the suspension obtained in the step (1) to 75 +/-1 ℃ under the inert gas atmosphere, then dropwise adding the precursor mixed solution obtained in the step (2) into the suspension obtained in the step (1) by using a peristaltic pump for carrying out dispersion polymerization reaction, cooling to room temperature after the reaction is finished, centrifuging, washing, and freeze-drying to obtain the tadpole-shaped hollow polymer particles.
The stabilizer in the step (1) is polyvinylpyrrolidone (PVP).
The molecular weight of the polyvinylpyrrolidone is 40000-58000; preferably 58000.
The polystyrene seed microsphere in the step (1) is prepared by the following method:
s1, dissolving polyvinylpyrrolidone (stabilizer) in ethanol to obtain a mixed solution I; dissolving styrene and an initiator in ethanol to obtain a precursor mixed solution II;
s2, heating the mixed solution I to 75 +/-1 ℃ under the inert gas atmosphere, then dropwise adding the precursor mixed solution II into the mixed solution I by using a peristaltic pump for dispersion polymerization reaction, cooling to room temperature after the reaction is finished, centrifuging, washing, and freeze-drying to obtain the polystyrene seed microspheres.
The molecular weight of the polyvinylpyrrolidone (stabilizer) in the step S1 is 40000-58000; preferably 58000.
The ratio (mass to volume) of polyvinylpyrrolidone to ethanol in the mixed solution I described in step S1 is 0.75 g: (35-40) mL; preferably 0.75 g: 38 mL.
The dosage of the polyvinylpyrrolidone (stabilizer) in the step S1 is 20-30% of the mass of the styrene; preferably 25% by mass of styrene.
The ethanol in step S1 is absolute ethanol.
The ratio (mass to volume ratio) of styrene to ethanol in the precursor mixed solution II described in step S1 is 3.0 g: 12 mL.
The initiator used in step S1 is Azobisisobutyronitrile (AIBN).
The dosage of the initiator in the step S1 is 1.0-1.5% of the total mass of the styrene; preferably 1.28%.
The inert gas in step S2 is nitrogen or argon.
The dropping speed in the step S2 is 4.5-6.0 mL.h-1(ii) a Preferably 4.7 mL. h-1。
The reaction time in the step S2 is 5-10 h; preferably 7 h.
The polystyrene seed microspheres in the step S2 are polystyrene microspheres with the diameter of 2.0 +/-0.5 mu m.
The proportion (mass-volume ratio) of the stabilizer to the mixed solvent in the step (1) is 0.75 g: (35-40) mL; preferably 0.75 g: 38 mL.
The ethanol in the steps (1) and (2) is absolute ethanol.
The volume ratio of ethanol to toluene in the mixed solvent in the step (1) is (29: 9) - (37: 1); preferably 33: 5.
The mass ratio of the stabilizer to the polystyrene seed microspheres in the step (1) is 0.75: 0.15 to 0.9; preferably 0.75: 0.3.
the dosage of the stabilizer in the step (1) is 20-30% of the total mass of the styrene (monomer) and the divinylbenzene (cross-linking agent); preferably 25% of the total mass of the styrene and divinylbenzene.
The mass ratio of the polystyrene seed microspheres in the step (1) to the total mass of the styrene and the divinylbenzene is 0.05-0.3: 1.0; preferably 0.1: 1.0.
the mass ratio of the styrene to the divinylbenzene (crosslinking agent) in the step (2) is (82: 18) to (94: 6); preferably 88: 12.
The initiator in the step (2) is Azobisisobutyronitrile (AIBN).
The amount of the initiator in the step (2) is 1.0-1.5% of the total mass of the styrene (monomer) and the divinylbenzene (cross-linking agent); preferably 1.28%.
The volume ratio of the mixed solvent ethanol to the toluene in the step (2) is 8-12: 2; preferably 10: 2.
the dosage of the styrene in the step (2) is calculated according to the proportion of 3.788-5.303 mL of mixed solvent (mixed solvent of ethanol and toluene) to each gram of styrene (g); it is preferable to calculate the ratio of 4.545mL of the mixed solvent (mixed solvent of ethanol and toluene) per gram (g) of styrene.
The dosage of the divinylbenzene in the step (2) is calculated according to the proportion of 27.78-38.89 mL of mixed solvent (mixed solvent of ethanol and toluene) to each gram of divinylbenzene (crosslinking agent); preferably, the amount of the solvent mixture (mixed solvent of ethanol and toluene) is 33.33mL per gram (g) of divinylbenzene (crosslinking agent).
And (3) the inert gas in the step (3) is nitrogen or argon.
The dropping speed in the step (3) is 4.5-6.0 mL.h-1(ii) a Preferably 4.7 mL. h-1。
The reaction time in the step (3) is 5-10 h; preferably 7 h.
The washing in the step (3) is realized by the following steps: adding the white product obtained after centrifugation into an organic solvent for soaking, and then carrying out centrifugal washing by using the organic solvent; preferably by the following steps: the white product obtained after centrifugation was added to Tetrahydrofuran (THF) for soaking, and then centrifuged and washed with ethanol.
The soaking time is 4.0-8.0 h; preferably 5.0 h.
Tadpole-shaped hollow polymer particles prepared by the method of any one of the above.
The tadpole-shaped hollow polymer particles are applied to the fields of magnetic materials, photoelectric materials, solar cells, interface catalysis, oil-water separation, emulsion stabilization, local surface plasma resonance, sensors, propellers, nonlinear optical and photoresponsive devices, biological enzyme immobilization and the like.
The tadpole-shaped hollow polymer particles are applied to preparation of drug carriers, antitumor drugs (preparations) or medical imaging reagents.
Compared with the prior art, the invention has the following advantages and effects:
(1) the invention provides a method for preparing tadpole-shaped hollow polymer particles by one-step seed dispersion polymerization, aiming at overcoming the defects of complicated process steps, low yield, high cost, small tadpole-shaped polymer particle size, unclear morphology and the like in the conventional preparation method, and the morphology of the tadpole-shaped hollow polymer particles can be regulated and controlled by changing the total mass ratio of seed microspheres to monomers and cross-linking agents.
(2) The preparation method disclosed by the invention is simple in process (one-step seed dispersion polymerization), low in environmental pollution, low in cost, high in yield (large-scale preparation is realized), hollow in structure and adjustable in shape (the tail length of the tadpole-shaped particles is adjustable and is several micrometers to dozens of micrometers).
(3) The polymer particles are tadpole-shaped hollow polymer particles, wherein the diameter of the head of most of the polymer particles is 1.0 +/-0.50 mu m, the length of the head of most of the polymer particles is 4.0 +/-2.0 mu m, the head of most of the polymer particles has a hollow structure, and the length of the polymer particles can be adjusted by changing the total mass ratio of the polystyrene seed microspheres to styrene and divinylbenzene.
(4) The tadpole-shaped hollow polymer particles prepared by the method can be widely applied to the fields of magnetic materials, photoelectric materials, solar cells, interface catalysis, oil-water separation, emulsion stabilization, local surface plasma resonance, sensors, propellers, nonlinear optical and photoresponsive devices, drug carriers, medical imaging, biological enzyme immobilization and the like.
Drawings
Fig. 1 is an SEM image of tadpole-shaped hollow polymer particles prepared in example 1.
Fig. 2 is an SEM image of tadpole-shaped hollow polymer particles prepared in example 2.
Fig. 3 is an SEM image of tadpole-shaped hollow polymer particles prepared in example 3.
Fig. 4 is an SEM image of tadpole-shaped hollow polymer particles prepared in example 4.
Fig. 5 is an SEM image of tadpole-shaped hollow polymer particles prepared in example 5.
Fig. 6 is an SEM image of tadpole-shaped hollow polymer particles prepared in example 6.
Fig. 7 is a diagram of tadpole-shaped hollow polymer particles prepared in example 2; wherein a, c and e are SEM, TEM and AFM images of the tadpole-shaped hollow polymer particles respectively; b, d and f are partial enlarged views of the tadpole-shaped hollow polymer particles SEM, TEM and AFM respectively.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. The test methods in the following examples, in which specific experimental conditions are not specified, are generally performed according to conventional experimental conditions or according to the experimental conditions recommended by the manufacturer. Unless otherwise specified, reagents and starting materials for use in the present invention are commercially available.
The polystyrene seed microspheres involved in the embodiment of the invention are synthesized by one-step dispersion polymerization, and specifically comprise the following steps:
(1) 0.7500g of stabilizer polyvinylpyrrolidone (PVP) (molecular weight of 58000) was dissolved in 38mL of absolute ethanol to obtain a mixed solution;
(2) dissolving 3.0000g of styrene and 0.0384g of initiator Azobisisobutyronitrile (AIBN) in 12mL of absolute ethyl alcohol to obtain a precursor mixed solution;
(3) heating the mixed solution in the step (1) to 75 +/-1 ℃ under the inert gas atmosphere, and then dropwise adding the precursor mixed solution obtained in the step (2) into the mixed solution in the step (1) by using a peristaltic pump for dispersion polymerizationThe reaction mixture was mixed (the dropping rate was 4.7 mL. multidot.h)-1Dripping within 3h, continuing to react for 4h), cooling to room temperature after the reaction is finished, centrifuging, washing, and freeze-drying to obtain polystyrene seed microspheres with the diameter of 2.0 +/-0.5 mu m, and the weighing calculation yield is about 70%.
Example 1 (polystyrene seed microspheres to styrene and divinylbenzene mass ratio of 5.0%)
(1) 0.7500g of polyvinylpyrrolidone (PVP, molecular weight of 58000) is weighed into a 100mL round-bottom flask with two mouths, 33mL of absolute ethyl alcohol and 5mL of toluene are added, the mixture is stirred uniformly, and then 0.1500g of polystyrene seed microspheres (diameter is 2.0 +/-0.5 mu m) are added to obtain a suspension of the polystyrene seed microspheres in a mixed solvent of the ethyl alcohol and the toluene in which the polyvinylpyrrolidone is dissolved;
(2) weighing 0.0384g of Azobisisobutyronitrile (AIBN) into a 25mL single-neck round-bottom flask, adding 0.3600g of Divinylbenzene (DVB), 2.6400g of Styrene (Styrene), 10mL of absolute ethyl alcohol and 2mL of toluene, and uniformly stirring by using magnetons to obtain a precursor mixed solution;
(3) under the condition of mechanical stirring (250rpm) and nitrogen atmosphere (1 h of nitrogen is introduced), the suspension of the polystyrene seed microspheres obtained in the step (1) in the mixed solvent of ethanol and toluene (with the polyvinylpyrrolidone stabilizer dissolved therein) is heated to 75 +/-1 ℃, and the precursor mixed solution obtained in the step (2) is dropwise added into the suspension by using a peristaltic pump (the dropping speed is 4.7 mL. h)-1And the dropwise addition is completed within 3 hours), the reaction is continued for 4 hours after the dropwise addition is completed (the reaction is carried out until the reaction solution is milky), and the reaction is finished and cooled to room temperature;
(4) firstly, centrifuging to obtain a white product, then washing with Tetrahydrofuran (THF), soaking at room temperature for 5.0h, centrifuging, washing with absolute ethyl alcohol, centrifuging repeatedly for three times, and then freeze-drying to obtain white powder of the tadpole-shaped hollow polymer particles.
The SEM image of the tadpole-shaped hollow polymer particles prepared in this example is shown in fig. 1, in which most of the polymer particles have a length of 9.83 ± 1.52 μm and have a hollow structure inside.
Example 2 (polystyrene seed microspheres to styrene and divinylbenzene mass ratio 10.0%)
1) 0.7500g of polyvinylpyrrolidone (PVP, molecular weight of 58000) is weighed into a 100mL round-bottom flask with two mouths, 33mL of absolute ethyl alcohol and 5mL of toluene are added, the mixture is stirred uniformly, and then 0.3000g of polystyrene seed microspheres (diameter is 2.0 +/-0.5 mu m) are added to obtain a suspension of the polystyrene seed microspheres in a mixed solvent of the ethyl alcohol and the toluene in which the polyvinylpyrrolidone is dissolved;
(2) weighing 0.0384g of Azobisisobutyronitrile (AIBN) into a 25mL single-neck round-bottom flask, adding 0.3600g of Divinylbenzene (DVB), 2.6400g of Styrene (Styrene), 10mL of absolute ethyl alcohol and 2mL of toluene, and uniformly stirring by using magnetons to obtain a precursor mixed solution;
(3) under the condition of mechanical stirring (250rpm) and nitrogen atmosphere (1 h of nitrogen is introduced), the suspension of the polystyrene seed microspheres obtained in the step (1) in the mixed solvent of ethanol and toluene (with the polyvinylpyrrolidone stabilizer dissolved therein) is heated to 75 +/-1 ℃, and the precursor mixed solution obtained in the step (2) is dropwise added into the suspension by using a peristaltic pump (the dropping speed is 4.7 mL. h)-1And the dropwise addition is completed within 3 h), the reaction is continued for 4h after the dropwise addition is completed, and the reaction is finished and cooled to room temperature;
(4) firstly, centrifuging to obtain a white product, then washing with Tetrahydrofuran (THF), soaking at room temperature for 5.0h, centrifuging, then washing with absolute ethyl alcohol, centrifuging repeatedly for three times, and then freeze-drying to obtain white powder of the tadpole-shaped hollow polymer particles.
The SEM image of the tadpole-shaped hollow polymer particles prepared in this example is shown in fig. 2, in which most of the polymer particles have a length of 6.28 ± 1.26 μm and have a hollow structure inside.
Example 3 (polystyrene seed microspheres 15.0% by mass of styrene and divinylbenzene)
1) 0.7500g of polyvinylpyrrolidone (PVP, molecular weight of 58000) is weighed into a 100mL round-bottom flask with two mouths, 33mL of absolute ethyl alcohol and 5mL of toluene are added, the mixture is stirred uniformly, 0.4500g of polystyrene seed microspheres (diameter is 2.0 +/-0.5 mu m) are added, and suspension of the polystyrene seed microspheres in a mixed solvent of the ethyl alcohol and the toluene in which the polyvinylpyrrolidone is dissolved is obtained;
(2) weighing 0.0384g of Azobisisobutyronitrile (AIBN) into a 25mL single-neck round-bottom flask, adding 0.3600g of Divinylbenzene (DVB), 2.6400g of Styrene (Styrene), 10mL of absolute ethyl alcohol and 2mL of toluene, and uniformly stirring by using magnetons to obtain a precursor mixed solution;
(3) under the condition of mechanical stirring (250rpm) and nitrogen atmosphere (1 h of nitrogen is introduced), the suspension of the polystyrene seed microspheres obtained in the step (1) in the mixed solvent of ethanol and toluene (with the polyvinylpyrrolidone stabilizer dissolved therein) is heated to 75 +/-1 ℃, and the precursor mixed solution obtained in the step (2) is dropwise added into the suspension by using a peristaltic pump (the dropping speed is 4.7 mL. h)-1And the dropwise addition is completed within 3 h), the reaction is continued for 4h after the dropwise addition is completed, and the reaction is finished and cooled to room temperature;
(4) firstly, centrifuging to obtain a white product, then washing with Tetrahydrofuran (THF), soaking at room temperature for 5.0h, centrifuging, then washing with absolute ethyl alcohol, centrifuging repeatedly for three times, and then freeze-drying to obtain white powder of the tadpole-shaped hollow polymer particles.
The SEM image of the tadpole-shaped hollow polymer particles prepared in this example is shown in fig. 3, in which most of the polymer particles have a length of 4.30 ± 1.12 μm and have a hollow structure inside.
Example 4 (polystyrene seed microspheres to styrene and divinylbenzene mass ratio of 20.0%)
1) 0.7500g of polyvinylpyrrolidone (PVP, molecular weight of 58000) is weighed into a 100mL round-bottom flask with two mouths, 33mL of absolute ethyl alcohol and 5mL of toluene are added, the mixture is stirred uniformly, and then 0.6000g of polystyrene seed microspheres (diameter is 2.0 +/-0.5 mu m) are added to obtain a suspension of the polystyrene seed microspheres in a mixed solvent of the ethyl alcohol and the toluene in which the polyvinylpyrrolidone is dissolved;
(2) weighing 0.0384g of Azobisisobutyronitrile (AIBN) into a 25mL single-neck round-bottom flask, adding 0.3600g of Divinylbenzene (DVB), 2.6400g of Styrene (Styrene), 10mL of absolute ethyl alcohol and 2mL of toluene, and uniformly stirring by using magnetons to obtain a precursor mixed solution;
(3) the polystyrene obtained in step (1) was seeded under mechanical stirring (250rpm) and under nitrogen atmosphere (1 h nitrogen feed)Heating the suspension of the microspheres in the mixed solvent of ethanol and toluene (dissolved with polyvinylpyrrolidone stabilizer) to 75 +/-1 ℃, and dropwise adding the precursor mixed solution obtained in the step (2) into the suspension by using a peristaltic pump (the dropping speed is 4.7 mL. h)-1And the dropwise addition is completed within 3 h), the reaction is continued for 4h after the dropwise addition is completed, and the reaction is finished and cooled to room temperature;
(4) firstly, centrifuging to obtain a white product, then washing with Tetrahydrofuran (THF), soaking at room temperature for 5.0h, centrifuging, then washing with absolute ethyl alcohol, centrifuging repeatedly for three times, and then freeze-drying to obtain white powder of the tadpole-shaped hollow polymer particles.
The SEM image of the tadpole-shaped hollow polymer particles prepared in this example is shown in fig. 4, in which most of the polymer particles have a length of 4.25 ± 0.83 μm and have a hollow structure inside.
Example 5 (polystyrene seed microspheres with a mass ratio of styrene to divinylbenzene of 25.0%)
1) 0.7500g of polyvinylpyrrolidone (PVP, molecular weight of 58000) is weighed into a 100mL round-bottom flask with two mouths, 33mL of absolute ethyl alcohol and 5mL of toluene are added, the mixture is stirred uniformly, 0.7500g of polystyrene seed microspheres (diameter is 2.0 +/-0.5 mu m) are added, and suspension of the polystyrene seed microspheres in a mixed solvent of the absolute ethyl alcohol and the toluene in which the polyvinylpyrrolidone is dissolved is obtained;
(2) weighing 0.0384g of Azobisisobutyronitrile (AIBN) into a 25mL single-neck round-bottom flask, adding 0.3600g of Divinylbenzene (DVB), 2.6400g of Styrene (Styrene), 10mL of ethanol and 2mL of toluene, and uniformly stirring by using magnetons to obtain a precursor mixed solution;
(3) under the condition of mechanical stirring (250rpm) and nitrogen atmosphere (1 h of nitrogen is introduced), the suspension of the polystyrene seed microspheres obtained in the step (1) in the mixed solvent of ethanol and toluene (with the polyvinylpyrrolidone stabilizer dissolved therein) is heated to 75 +/-1 ℃, and the precursor mixed solution obtained in the step (2) is dropwise added into the suspension by using a peristaltic pump (the dropping speed is 4.7 mL. h)-1And the dropwise addition is completed within 3 h), the reaction is continued for 4h after the dropwise addition is completed, and the reaction is finished and cooled to room temperature;
(4) firstly, centrifuging to obtain a white product, then washing with Tetrahydrofuran (THF), soaking at room temperature for 5.0h, centrifuging, then washing with absolute ethyl alcohol, centrifuging repeatedly for three times, and then freeze-drying to obtain white powder of the tadpole-shaped hollow polymer particles.
The SEM image of the tadpole-shaped hollow polymer particles prepared in this example is shown in fig. 5, in which most of the polymer particles have a length of 4.22 ± 1.34 μm and have a hollow structure inside.
Example 6 (polystyrene seed microspheres to styrene and divinylbenzene mass ratio of 30.0%)
1) 0.7500g of polyvinylpyrrolidone (PVP, molecular weight of 58000) is weighed into a 100mL round-bottom flask with two mouths, 33mL of absolute ethyl alcohol and 5mL of toluene are added, the mixture is stirred uniformly, and then 0.9000g of polystyrene seed microspheres (diameter is 2.0 +/-0.5 mu m) are added to obtain a suspension of the polystyrene seed microspheres in a mixed solvent of the ethyl alcohol and the toluene in which the polyvinylpyrrolidone is dissolved;
(2) weighing 0.0384g of Azobisisobutyronitrile (AIBN) into a 25mL single-neck round-bottom flask, adding 0.3600g of Divinylbenzene (DVB), 2.6400g of Styrene (Styrene), 10mL of absolute ethyl alcohol and 2mL of toluene, and uniformly stirring by using magnetons to obtain a precursor mixed solution;
(3) under the condition of mechanical stirring (250rpm) and nitrogen atmosphere (1 h of nitrogen is introduced), the suspension of the polystyrene seed microspheres obtained in the step (1) in the mixed solvent of ethanol and toluene (with the polyvinylpyrrolidone stabilizer dissolved therein) is heated to 75 +/-1 ℃, and the precursor mixed solution obtained in the step (2) is dropwise added into the suspension by using a peristaltic pump (the dropping speed is 4.7 mL. h)-1And the dropwise addition is completed within 3 h), the reaction is continued for 4h after the dropwise addition is completed, and the reaction is finished and cooled to room temperature;
(4) firstly, centrifuging to obtain a white product, then washing with Tetrahydrofuran (THF), soaking at room temperature for 5.0h, centrifuging, then washing with absolute ethyl alcohol, centrifuging repeatedly for three times, and then freeze-drying to obtain white powder of the tadpole-shaped hollow polymer particles.
An SEM image of the tadpole-shaped hollow polymer particles prepared in this example is shown in fig. 6, in which most of the polymer particles have a length of 2.63 ± 1.25 μm and have a hollow structure inside.
Effects of the embodiment
(1) The tadpole-shaped hollow polymer particles prepared in example 2 were characterized by a Scanning Electron Microscope (SEM), a Transmission Electron Microscope (TEM), and an Atomic Force Microscope (AFM), and the results are shown in fig. 7.
(2) The tadpole-shaped hollow polymer particles prepared in examples 1-6 all had a yield of 81-87% by weight.
In summary, the polymer particles prepared in examples 1 to 6 are tadpole-shaped hollow polymer particles, wherein the diameters of the heads of most of the polymer particles are 1.0 ± 0.50 μm, and the interior of the polymer particles has a hollow structure; in addition, with the increasing mass ratio of the polystyrene seed microspheres to the total mass of the styrene and the divinylbenzene, the tail length of the tadpole-shaped polymer particles is reduced from 9.83 +/-1.52 mu m to 6.28 +/-1.26 mu m, then is reduced to 4.30 +/-1.12 mu m, 4.25 +/-0.83 mu m and 4.22 +/-1.34 mu m, and finally is reduced to 2.63 +/-1.25 mu m.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of tadpole-shaped hollow polymer particles is characterized by comprising the following steps:
(1) dissolving a stabilizer in a mixed solvent of ethanol and toluene, and adding polystyrene seed microspheres to obtain a suspension;
(2) dissolving styrene, divinylbenzene and an initiator in a mixed solvent of ethanol and toluene to obtain a precursor mixed solution;
(3) heating the suspension obtained in the step (1) to 75 +/-1 ℃ under the inert gas atmosphere, then dropwise adding the precursor mixed solution obtained in the step (2) into the suspension obtained in the step (1) by using a peristaltic pump for carrying out dispersion polymerization reaction, cooling to room temperature after the reaction is finished, centrifuging, washing, and freeze-drying to obtain tadpole-shaped hollow polymer particles;
the volume ratio of ethanol to toluene in the mixed solvent in the step (1) is 29: 9-37: 1;
the proportion of the stabilizer to the mixed solvent in the step (1) is 0.75 g: 35-40 mL;
the mass ratio of the stabilizer to the polystyrene seed microspheres in the step (1) is 0.75: 0.15 to 0.9;
the dosage of the stabilizer in the step (1) is 20-30% of the total mass of the styrene and the divinylbenzene;
the stabilizer in the step (1) is polyvinylpyrrolidone; the molecular weight of the polyvinylpyrrolidone is 40000-58000;
the initiator in the step (2) is azobisisobutyronitrile;
the mass ratio of styrene to divinylbenzene in the step (2) is 82: 18-94: 6;
the amount of the initiator in the step (2) is 1.0-1.5% of the total mass of the styrene and the divinylbenzene;
the volume ratio of the mixed solvent ethanol to the toluene in the step (2) is 8-12: 2;
the dosage of the styrene in the step (2) is calculated according to the proportion of 3.788-5.303 mL of mixed solvent in each gram of styrene;
the dosage of the divinylbenzene in the step (2) is calculated according to the proportion of 27.78-38.89 mL of mixed solvent per gram of divinylbenzene;
the reaction time in the step (3) is 5-10 h.
2. The method of making tadpole-shaped hollow polymer particles of claim 1, wherein:
the polystyrene seed microsphere in the step (1) is prepared by the following method:
s1, dissolving polyvinylpyrrolidone in ethanol to obtain a mixed solution I; dissolving styrene and an initiator in ethanol to obtain a precursor mixed solution II;
s2, heating the mixed solution I to 75 +/-1 ℃ under the inert gas atmosphere, then dropwise adding the precursor mixed solution II into the mixed solution I by using a peristaltic pump for dispersion polymerization reaction, cooling to room temperature after the reaction is finished, centrifuging, washing, and freeze-drying to obtain the polystyrene seed microspheres.
3. The method of making tadpole-shaped hollow polymer particles of claim 2, wherein:
the molecular weight of the polyvinylpyrrolidone in the step S1 is 40000-58000;
the dosage of the polyvinylpyrrolidone in the step S1 is 20-30% of the mass of the styrene;
the initiator in the step S1 is azobisisobutyronitrile;
the dosage of the initiator in the step S1 is 1.0-1.5% of the total mass of the styrene;
the inert gas in the step S2 is nitrogen or argon;
the dropping speed in the step S2 is 4.5-6.0 mL.h-1；
The reaction time in the step S2 is 5-10 h;
the polystyrene seed microspheres in the step S2 are polystyrene microspheres with the diameter of 2.0 +/-0.5 mu m.
4. The method of making tadpole-shaped hollow polymer particles of claim 1, wherein:
the volume ratio of ethanol to toluene in the mixed solvent in the step (1) is 33: 5;
the proportion of the stabilizer to the mixed solvent in the step (1) is 0.75 g: 38 mL;
the mass ratio of the stabilizer to the polystyrene seed microspheres in the step (1) is 0.75: 0.3;
the using amount of the stabilizer in the step (1) is 25% of the total mass of the styrene and the divinylbenzene;
the mass ratio of the styrene to the divinylbenzene in the step (2) is 88: 12;
the using amount of the initiator in the step (2) is 1.28 percent of the total mass of the styrene and the divinylbenzene;
the volume ratio of the mixed solvent ethanol to the toluene in the step (2) is 10: 2;
the dosage of the styrene in the step (2) is calculated according to the proportion of 4.545mL of mixed solvent in each gram of styrene;
the dosage of the divinylbenzene in the step (2) is calculated according to the proportion of 33.33mL of mixed solvent per gram of divinylbenzene.
5. The method of making tadpole-shaped hollow polymer particles of claim 1, wherein:
the inert gas in the step (3) is nitrogen or argon;
the dropping speed in the step (3) is 4.5-6.0 mL.h-1；
The washing in the step (3) is realized by the following steps: adding the white product obtained after centrifugation into tetrahydrofuran for soaking, and then carrying out centrifugal washing by using ethanol; wherein the soaking time is 4.0-8.0 h.
6. A tadpole-shaped hollow polymer particle, characterized in that: prepared by the method of any one of claims 1 to 5.
7. The tadpole-shaped hollow polymer particle of claim 6, for use in the fields of magnetic materials, optoelectronic materials, interfacial catalysis, oil-water separation, emulsion stabilization, local surface plasmon resonance, sensors, propellers, nonlinear optical and photoresponsive devices, or biological enzyme immobilization.
8. Use according to claim 7, characterized in that: the photoelectric material is a solar cell.
9. Use of the tadpole-shaped hollow polymer particles of claim 6 in the preparation of a pharmaceutical carrier, an anti-neoplastic pharmaceutical formulation, or a medical imaging agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011387141.5A CN112480320B (en) | 2020-12-02 | 2020-12-02 | Tadpole-shaped hollow polymer particles and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011387141.5A CN112480320B (en) | 2020-12-02 | 2020-12-02 | Tadpole-shaped hollow polymer particles and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112480320A CN112480320A (en) | 2021-03-12 |
| CN112480320B true CN112480320B (en) | 2022-04-05 |
Family
ID=74938747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011387141.5A Active CN112480320B (en) | 2020-12-02 | 2020-12-02 | Tadpole-shaped hollow polymer particles and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112480320B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5216096A (en) * | 1991-09-24 | 1993-06-01 | Japan Synthetic Rubber Co., Ltd. | Process for the preparation of cross-linked polymer particles |
| CN101434673A (en) * | 2008-12-22 | 2009-05-20 | 中国科学院长春应用化学研究所 | Preparation of monodisperse porous polymer microsphere |
| CN103819584A (en) * | 2014-02-24 | 2014-05-28 | 苏州大学 | Cyclic azobenzene amphiphilic segmented copolymer and its preparation method |
| CN105622852A (en) * | 2015-12-31 | 2016-06-01 | 西北工业大学 | Preparing method for synthesizing shape-controlled anisotropic particles through emulsion polymerization based on asymmetry monomer-swelling non-crosslinking seed particles |
| CN106467591A (en) * | 2016-09-06 | 2017-03-01 | 常州大学 | A kind of synthetic method of the cyclic polymer containing multi-ring and linear segment |
| CN106750058A (en) * | 2017-03-03 | 2017-05-31 | 中国科学院化学研究所 | A kind of polymer is single-stranded/and the Janus materials of Nanocomposites structure and its cation trigger double-bond polymerization preparation method |
| CN109400828A (en) * | 2017-08-17 | 2019-03-01 | 天津大学 | The amphipathic magnetic ion polymer of tadpole-shaped, synthetic method and its self assembly object, self-assembling method |
-
2020
- 2020-12-02 CN CN202011387141.5A patent/CN112480320B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5216096A (en) * | 1991-09-24 | 1993-06-01 | Japan Synthetic Rubber Co., Ltd. | Process for the preparation of cross-linked polymer particles |
| CN101434673A (en) * | 2008-12-22 | 2009-05-20 | 中国科学院长春应用化学研究所 | Preparation of monodisperse porous polymer microsphere |
| CN103819584A (en) * | 2014-02-24 | 2014-05-28 | 苏州大学 | Cyclic azobenzene amphiphilic segmented copolymer and its preparation method |
| CN105622852A (en) * | 2015-12-31 | 2016-06-01 | 西北工业大学 | Preparing method for synthesizing shape-controlled anisotropic particles through emulsion polymerization based on asymmetry monomer-swelling non-crosslinking seed particles |
| CN106467591A (en) * | 2016-09-06 | 2017-03-01 | 常州大学 | A kind of synthetic method of the cyclic polymer containing multi-ring and linear segment |
| CN106750058A (en) * | 2017-03-03 | 2017-05-31 | 中国科学院化学研究所 | A kind of polymer is single-stranded/and the Janus materials of Nanocomposites structure and its cation trigger double-bond polymerization preparation method |
| CN109400828A (en) * | 2017-08-17 | 2019-03-01 | 天津大学 | The amphipathic magnetic ion polymer of tadpole-shaped, synthetic method and its self assembly object, self-assembling method |
Non-Patent Citations (6)
| Title |
|---|
| ATRC法合成蝌蚪型及杠铃型环状聚合物;薛小强等;《高分子材料科学与工程》;20170831;第33卷(第8期);第22-26页 * |
| Melt Rheology of Tadpole-Shaped Polystyrenes;Yuya Doi et al.;《Macromolecules》;20151117;第48卷;第8667-8674页 * |
| Precise Synthesis and Characterization of Tadpole-Shaped Polystyrenes with High Purity;Yuya Doi et al.;《Macromolecules》;20130118;第46卷;第1075-1081页 * |
| Synthesis and Characterization of Well-Defined, Tadpole-Shaped Polystyrene with a Single Atom Junction Point;Fan Zhang et al.;《Macromolecules》;20181119;第51卷;第9509-9518页 * |
| Tadpole-shaped polymers based on UV-induced strain promoted azide-alkyne cycloaddition reaction;Jinghui Hu et al.;《Science China Chemistry》;20160725;第59卷(第10期);第1277-1282页 * |
| 用活性阴离子聚合设计合成高分子链构造的新进展;李爱香等;《高分子通报》;20051231(第01期);第6-13页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112480320A (en) | 2021-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107299417B (en) | A kind of WO3/ZnWO4The preparation method and products thereof of composite micro-nano rice fiber | |
| Wang et al. | Facile fabrication of nanocomposite microspheres with polymer cores and magnetic shells by Pickering suspension polymerization | |
| CN101633499B (en) | PAN-base carbon hollow nanospheres preparation method | |
| Yuan et al. | Nano-sized silica hollow spheres: Preparation, mechanism analysis and its water retention property | |
| CN101092484A (en) | Surface modified microballons of containing phosphazene, and preparation method | |
| CN102049225A (en) | Method for preparing superparamagnetic polymer microspheres | |
| CN109985584B (en) | Preparation method of adjustable and controllable strawberry-shaped silicon dioxide-organic hybrid composite microspheres | |
| CN113336215A (en) | Preparation method and application of monodisperse hydrothermal carbon spheres | |
| Wang et al. | Hollow polyphosphazene microspheres with cross-linked chemical structure: synthesis, formation mechanism and applications | |
| CN112480320B (en) | Tadpole-shaped hollow polymer particles and preparation method and application thereof | |
| CN110526588B (en) | Method for initiating growth of crystalline block copolymer micelle brush based on material surface | |
| CN113045780B (en) | Polymer material with light-regulated reversible morphology transformation and preparation method and application thereof | |
| CN114591726A (en) | Method for preparing stable single-dispersion crosslinked polystyrene magnetic microspheres | |
| CN113929599B (en) | Precise block polymer nano assembly and preparation method thereof | |
| CN108816162B (en) | Preparation method of inorganic polymer hybrid microspheres with Yolk-Shell structure | |
| WO2017084124A1 (en) | Method for preparing water-soluble polystyrene nano microspheres | |
| Xue et al. | Controlled fabrication of polypyrrole capsules and nanotubes in the presence of Rhodamine B | |
| CN112357905B (en) | Nitrogen-doped mesoporous carbon nanosphere material as well as preparation method and application thereof | |
| CN110028611B (en) | Monodisperse shell-core polystyrene microsphere and preparation method thereof | |
| Gao et al. | Growth from spherical to rod-like SiO2: Impact on microstructure and performance of nanocomposite | |
| CN108854871B (en) | Cyclic colloid and preparation method thereof | |
| Cai et al. | Fabrication of polystyrene hollow spheres in W/O/W multiple emulsions | |
| CN112724305A (en) | Monodisperse quantum dot coded magnetic microspheres | |
| Yamamoto et al. | Nucleation and growth process of polystyrene particle investigated by AFM | |
| CN112499615B (en) | Nano polymer ring, nano carbon ring and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 512400 area B, No.3 Ping'an 1st Road, Dongguan Dalingshan (Nanxiong) industrial transfer industrial park, Nanxiong City, Shaoguan City, Guangdong Province Patentee after: Guoke Guanghua fine chemical incubator (Nanxiong) Co.,Ltd. Patentee after: GUANGZHOU CHEMISTRY Co.,Ltd. CHINESE ACADEMY OF SCIENCES Patentee after: Guoke Guanghua (Nanxiong) New Materials Research Institute Co.,Ltd. Patentee after: Shaoguan Institute of new materials Patentee after: University OF CHINESE ACADEMY OF SCIENCES Address before: 512400 area B, No.3 Ping'an 1st Road, Dongguan Dalingshan (Nanxiong) industrial transfer industrial park, Nanxiong City, Shaoguan City, Guangdong Province Patentee before: NANXIONG CAS INCUBATOR OPERATION CO.,LTD. Patentee before: GUANGZHOU CHEMISTRY Co.,Ltd. CHINESE ACADEMY OF SCIENCES Patentee before: Guoke Guanghua (Nanxiong) New Materials Research Institute Co.,Ltd. Patentee before: GUANGZHOU CHEMICAL INSTITUTE SHAOGUAN TECHNOLOGY INNOVATION AND BREEDING CENTER, CHINESE ACADEMY OF SCIENCES Patentee before: University OF CHINESE ACADEMY OF SCIENCES |
|
| CP01 | Change in the name or title of a patent holder |