CN106633113A - Preparation method of natural macromolecular hollow microspheres - Google Patents
Preparation method of natural macromolecular hollow microspheres Download PDFInfo
- Publication number
- CN106633113A CN106633113A CN201610900731.0A CN201610900731A CN106633113A CN 106633113 A CN106633113 A CN 106633113A CN 201610900731 A CN201610900731 A CN 201610900731A CN 106633113 A CN106633113 A CN 106633113A
- Authority
- CN
- China
- Prior art keywords
- chitin
- solution
- natural polymer
- dried
- reception device
- 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.)
- Pending
Links
Classifications
-
- 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
- C08J3/12—Powdering or granulating
-
- 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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- 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
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention discloses a preparation method of natural macromolecular hollow microspheres. The preparation method comprises the following steps: dissolving natural macromolecules in a mixed solvent of KOH, LiOH, NaOH and urea at a low temperature, and obtaining a chitin, cellulose or chitosan solution by virtue of freezing-thawing circulation; and spraying the chitin solution into liquid nitrogen by virtue of an electrostatic drop method, and obtaining chitin, cellulose and chitosan hollow microspheres with a hollow structure by virtue of freeze drying. According to the preparation method of the invention, the chitin, the cellulose and the chitosan hollow microspheres having good biological compatibility and degradation and having a hollow interior and regular pores on spherical walls can be obtained and have a wide application prospect in various fields such as environmental treatment, tissue engineering, agricultural and biological materials and the like.
Description
Technical field
The invention belongs to natural macromolecular material field, and in particular to a kind of preparation side of natural polymer tiny balloon
Method.
Background technology
Tiny balloon has larger specific surface area, in drug controlled release, artificial cell, catalyst, microreactor, lithium
There is huge application prospect in the fields such as ion battery, environmental treatment, have attracted attention (Zhou, the et of more and more researchers
al.,2016).Natural polymer tiny balloon has good biocompatibility, degradability, nontoxicity, in biological medicine, tissue
Engineering, biotechnology field be widely used (Yang, et al., 2009).
Chitin, shitosan, cellulose are the natural polymers being widely used, based on its superior biological property, such as
Biocompatibility, biological degradability and physical property, such as into gelation, hydrophilic nmature, good mechanical property, they are in biology
Medical and biological technical field have a wide range of applications (Sashiwa ＆ Aiba, 2004).But, these natural polymers are deposited
In a large amount of intermolecular and intramolecular hydrogen bonds, be dissolved only in minority solvent (Ravi Kumar, 2000).Research reports alkali
（NaOH、LiOH、KOH）/ urea, Thiourea can dissolve at low temperature chitin, shitosan, cellulose, based on this solvent,
By emulsion method can prepare micro-sphere material (Zhang, et al., 2015).
However, it is longer the time required to reaction of the emulsion method during natural polymer microballoon is prepared, and yield is relatively low, system
Standby process is complicated, needs to use poisonous crosslinking agent, destroy wherein medicine and molecule activity (Shi, et al., 2014).
The content of the invention
The technical problem to be solved is to provide a kind of chitin of environmental protection, cellulose, shitosan sky
The preparation method of heart microballoon, prepared chitin, cellulose, shitosan tiny balloon have good biocompatibility, make
Standby process is simple, is suitable for large-scale production.
It is provided by the present invention prepare natural polymer tiny balloon method be：
Preparing natural Polymer Solution, the natural polymer is chitin, shitosan or cellulose, the natural polymer for obtaining
The concentration of solution is 0.001 wt%～8 wt%；Solvent used by preparing natural Polymer Solution is in KOH, LiOH, NaOH
A kind of or combination and urea or the mixed solution of thiocarbamide；
Natural polymer tiny balloon is prepared using electrostatic drop generation, natural polymer solution is loaded into syringe, needle point and reception
The distance between device is 3 cm～100 cm, and the voltage of 0Kv～30Kv, the promotion speed of pump are applied between needle point and reception device
Spend for 0.1 ml h-1～1000 ml h-1, the solidification liquid in reception device is liquid nitrogen；
The natural polymer microballoon formed in liquid nitrogen is put into freeze dryer drying all removes to all moisture therein,
Will it is lyophilized after microballoon be put into water and rinse to neutrality, freeze dry be dried to obtain natural polymer tiny balloon again.
Prepare chitin in chitin, shitosan tiny balloon, the source of shitosan can be the oceans such as shrimp, crab, squid
The insects such as animal, fly, silkworm chrysalis, cockroach, and the cell membrane of fungi.
Prepare cellulose in cellulose hollow microballoon source can for fiber crops, straw, straw, bagasse, bacteria cellulose,
Marine alga, timber and cotton.
In the solvent of preparing natural Polymer Solution, it is 5 wt% that the concentration of KOH is the concentration of 5 wt%～20 wt%, LiOH
The concentration of～20 wt%, NaOH is 4 wt%～12 wt% for the concentration of 5wt%～50wt%, urea or thiocarbamide.
The method prepared used by chitin, shitosan, cellulose hollow microballoon is electrostatic drop generation.Needle point and reception device
The distance between be 3 cm～100 cm.Voltage between needle point and reception device is 0 Kv～30 Kv.What driving pump was used
Speed is 0.1 ml h-1～1000 ml h-1。
The chitin of formation, cellulose, chitosan microball drying are all removed to all moisture therein, drying mode is
Freeze-drying, lyophilized temperature is -20～-80 DEG C.
Other materials is added in chitin, cellulose, shitosan, such as macromolecular material, inorganic material can be prepared mixed
Close tiny balloon.
The present invention prepares chitin, shitosan, cellulose microsphere by electrostatic drop generation by coagulator of liquid nitrogen, with behaviour
Make it is simple, can be prepared on a large scale, microspherulite diameter is controllable, environmental protection the advantages of.Using the extremely low temperature of liquid nitrogen（Normal pressure
Under -196 DEG C）, can make the rapid balling-up of Polymer Solution, and any toxic cross-linking agents that undope, can to greatest extent keep medicine
The activity of thing and molecule.Compared to other pelletizing methods, tiny balloon is prepared as coagulator using liquid nitrogen by electrostatic drop generation
With obvious advantage.
Compared with prior art, the present invention has the following advantages that and beneficial effect：
1st, the present invention prepares chitin, cellulose, chitosan microball by electrostatic drop generation, and method is simple, and easy to operate, environment is friendly
It is good, it is adaptable to large-scale production.
2nd, it is liquid nitrogen to prepare the solidification liquid that chitin, cellulose, chitosan microball used, without using poisonous crosslinking
Agent, can to greatest extent keep chitin, cellulose, the structure of shitosan and security.
3rd, the present invention prepares chitin, cellulose, chitosan microball and has hollow-core construction.
4th, the chitin of present invention preparation, cellulose, shitosan tiny balloon have good biocompatibility, can be extensive
It is applied to the fields such as biological medicine, agricultural and environmental protection.
Description of the drawings
The optical microscope photograph of the chitin tiny balloon prepared by Fig. 1 embodiments 8.
The optical microscope photograph of the shitosan tiny balloon prepared by Fig. 2 embodiments 20.
The optical microscope photograph of the cellulose hollow microballoon prepared by Fig. 3 embodiments 29.
Specific embodiment
Technical scheme is described further below in conjunction with specific embodiment, it is impossible to be interpreted as the guarantor of the present invention
Shield scope is limited, and those skilled in the art makes some nonessential changes and adjustment, belongs to according to the content of foregoing invention
In protection scope of the present invention.
Embodiment 1：
Chitin powder is scattered in 20 wt% KOH, 50 wt% NaOH, the mixed liquor of 12 wt% urea, is tied at -30 DEG C
Cheng Bing, places 12 hours, after at room temperature solution be frozen into solution, concentration is 0.001 wt%.Chitin solution is loaded into syringe, pin
The distance between point and reception device are 3 cm, the voltage 0Kv between needle point and reception device, and the driving velocity of pump is 0.1ml
h-1, solidification liquid is liquid nitrogen, chitin balls is put into -20 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water and rinses into
Property, the dry chitin tiny balloon for being dried to obtain neutrality is freezed again.
Embodiment 2：
Chitin powder is scattered in 20 wt% KOH, 50 wt% NaOH, the mixed liquor of 12 wt% thiocarbamides, is tied at -30 DEG C
Cheng Bing, places 12 hours, after at room temperature solution be frozen into solution, concentration is 8 wt%.By chitin solution load syringe, needle point and
The distance between reception device is 3 cm, the voltage 0Kv between needle point and reception device, and the driving velocity of pump is 0.1 ml h-1,
Solidification liquid is liquid nitrogen, chitin balls is put into -20 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water and rinses to neutrality,
The dry chitin tiny balloon for being dried to obtain neutrality is freezed again.
Embodiment 3：
Chitin powder is scattered in 20 wt% KOH, 20 wt% LiOH, the mixed liquor of 12 wt% urea, is tied at -30 DEG C
Cheng Bing, places 12 hours, after at room temperature solution be frozen into solution, concentration is 0.001 wt%.Chitin solution is loaded into syringe, pin
The distance between point and reception device are 100 cm, the voltage 0Kv between needle point and reception device, and the driving velocity of pump is 0.1
ml h-1, solidification liquid is liquid nitrogen, chitin balls is put into -20 DEG C of freeze dryers and is dried.Microballoon after lyophilized be put into water rinse to
Neutrality, freezes again the dry chitin tiny balloon for being dried to obtain neutrality.
Embodiment 4：
Chitin powder is scattered in 20 wt% KOH, 20 wt% LiOH, the mixed liquor of 50 wt% NaOH, at -30 DEG C
Build-up ice, place 12 hours, after at room temperature solution be frozen into solution, concentration is 0.001 wt%.Chitin solution is loaded into syringe,
The distance between needle point and reception device are 100 cm, the voltage 30Kv between needle point and reception device, and the driving velocity of pump is
0.1 ml h-1, solidification liquid is liquid nitrogen, chitin balls is put into -20 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water and floats
Neutrality is washed till, the dry chitin tiny balloon for being dried to obtain neutrality is freezed again.
Embodiment 5：
Chitin powder is scattered in 20 wt% LiOH, 50 wt% NaOH, the mixed liquor of 12 wt% urea, at -30 DEG C
Build-up ice, place 12 hours, after at room temperature solution be frozen into solution, concentration is 0.001 wt%.Chitin solution is loaded into syringe,
The distance between needle point and reception device are 100 cm, the voltage 0Kv between needle point and reception device, and the driving velocity of pump is
1000 ml h-1, solidification liquid is liquid nitrogen, chitin balls is put into -20 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water
Rinse to neutrality, the dry chitin tiny balloon for being dried to obtain neutrality is freezed again.
Embodiment 6：
Chitin powder is scattered in 5 wt% KOH, 8 wt% LiOH, the mixed liquor of 12 wt% urea, is tied at -30 DEG C
Cheng Bing, places 12 hours, after at room temperature solution be frozen into solution, concentration is 0.001 wt%.Chitin solution is loaded into syringe, pin
The distance between point and reception device are 100 cm, the voltage 0Kv between needle point and reception device, and the driving velocity of pump is 0.1
ml h-1, solidification liquid is liquid nitrogen, chitin balls is put into -80 DEG C of freeze dryers and is dried.Microballoon after lyophilized be put into water rinse to
Neutrality, freezes again the dry chitin tiny balloon for being dried to obtain neutrality.
Embodiment 7：
Chitin powder is scattered in 5 wt% LiOH, 8 wt% NaOH, the mixed liquor of 12 wt% urea, is tied at -30 DEG C
Cheng Bing, places 12 hours, after at room temperature solution be frozen into solution, concentration is 0.5 wt%.Chitin solution is loaded into syringe, needle point
It is 100 cm, the Kv of voltage 10 between needle point and reception device with the distance between reception device, the driving velocity of pump is 10
ml h-1, solidification liquid is liquid nitrogen, chitin balls is put into -45 DEG C of freeze dryers and is dried.Microballoon after lyophilized be put into water rinse to
Neutrality, freezes again the dry chitin tiny balloon for being dried to obtain neutrality.
Embodiment 8：
Chitin powder is scattered in 5 wt% LiOH, 8 wt% NaOH, the mixed liquor of 12 wt% urea, is tied at -30 DEG C
Cheng Bing, places 12 hours, after at room temperature solution be frozen into solution, concentration is 2 wt%.By chitin solution load syringe, needle point and
The distance between reception device is 20 cm, the Kv of voltage 9 between needle point and reception device, and the driving velocity of pump is 10 ml h-1, solidification liquid is liquid nitrogen, chitin balls is put into -45 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water and rinses into
Property, the dry chitin tiny balloon for being dried to obtain neutrality is freezed again.
Embodiment 9：
During chitin powder is scattered in into 20 wt% KOH, the mixed liquor of 12 wt% urea, build-up ice at -30 DEG C, place 12
Hour, after at room temperature solution be frozen into solution, concentration is 0.1 wt%.Chitin solution is loaded into syringe, needle point and reception device it
Between distance be 20 cm, the voltage 9Kv between needle point and reception device, the driving velocity of pump is 5 ml h-1, solidification liquid is liquid
Nitrogen, chitin balls is put into -30 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water and rinses to neutrality, freezes again
The dry chitin tiny balloon for being dried to obtain neutrality.
Embodiment 10：
During chitin powder is scattered in into 20 wt% LiOH, the mixed liquor of 12 wt% urea, build-up ice at -30 DEG C, place 12
Hour, after at room temperature solution be frozen into solution, concentration is 2 wt%.Chitin solution is loaded into syringe, between needle point and reception device
Distance be 10 cm, the Kv of voltage 6 between needle point and reception device, the driving velocity of pump is 10 ml h-1, solidification liquid is liquid
Nitrogen, chitin balls is put into -45 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water and rinses to neutrality, freezes again
The dry chitin tiny balloon for being dried to obtain neutrality.
Embodiment 11：
During chitin powder is scattered in into 50 wt% NaOH, the mixed liquor of 12 wt% thiocarbamides, build-up ice at -30 DEG C, place 12
Hour, after at room temperature solution be frozen into solution, concentration is 1 wt%.Chitin solution is loaded into syringe, between needle point and reception device
Distance be 5 cm, the Kv of voltage 15 between needle point and reception device, the driving velocity of pump is 6 ml h-1, solidification liquid is liquid
Nitrogen, chitin balls is put into -80 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water and rinses to neutrality, freezes again
The dry chitin tiny balloon for being dried to obtain neutrality.
Embodiment 12：
Chitin powder is scattered in into the mixed liquor of 20 wt% KOH, 20 wt% LiOH, 50 wt% NaOH, 12 wt% urea
In, build-up ice at -30 DEG C, place 12 hours, after at room temperature solution be frozen into solution, concentration is 1 wt%.By chitin solution dress
Enter syringe, the distance between needle point and reception device are 5 cm, the Kv of voltage 15 between needle point and reception device, the promotion of pump
Speed is 6 ml h-1, solidification liquid is liquid nitrogen, chitin balls is put into -80 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water
In rinse to neutrality, freeze again it is dry be dried to obtain neutrality chitin tiny balloon.
Embodiment 13：
Chitin powder is scattered in into the mixed liquor of 20 wt% KOH, 20 wt% LiOH, 50 wt% NaOH, 12 wt% thiocarbamides
In, build-up ice at -30 DEG C, place 12 hours, after at room temperature solution be frozen into solution, concentration is 1 wt%.By chitin solution dress
Enter syringe, the distance between needle point and reception device are 5 cm, the Kv of voltage 15 between needle point and reception device, the promotion of pump
Speed is 6 ml h-1, solidification liquid is liquid nitrogen, chitin balls is put into -80 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water
In rinse to neutrality, freeze again it is dry be dried to obtain neutrality chitin tiny balloon.
Embodiment 14：
Chitin powder is scattered in 5 wt% KOH, 20 wt% LiOH, 50 wt% NaOH, the mixed liquor of 12 wt% thiocarbamides,
Build-up ice at -30 DEG C, place 12 hours, after at room temperature solution be frozen into solution, concentration is 1 wt%.Chitin solution is loaded
Syringe, the distance between needle point and reception device are 5 cm, and the Kv of voltage 15 between needle point and reception device, the promotion of pump is fast
Spend for 6 ml h-1, solidification liquid is liquid nitrogen, chitin balls is put into -80 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water
Rinse to neutrality, the dry chitin tiny balloon for being dried to obtain neutrality is freezed again.
Embodiment 15：
Chitin powder is scattered in 20 wt% KOH, 5 wt% LiOH, 50 wt% NaOH, the mixed liquor of 12 wt% thiocarbamides,
Build-up ice at -30 DEG C, place 12 hours, after at room temperature solution be frozen into solution, concentration is 1 wt%.Chitin solution is loaded
Syringe, the distance between needle point and reception device are 5 cm, and the Kv of voltage 15 between needle point and reception device, the promotion of pump is fast
Spend for 6 ml h-1, solidification liquid is liquid nitrogen, chitin balls is put into -80 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water
Rinse to neutrality, the dry chitin tiny balloon for being dried to obtain neutrality is freezed again.
Embodiment 16：
Chitin powder is scattered in 20 wt% KOH, 20 wt% LiOH, 5 wt% NaOH, the mixed liquor of 12 wt% thiocarbamides,
Build-up ice at -30 DEG C, place 12 hours, after at room temperature solution be frozen into solution, concentration is 1 wt%.Chitin solution is loaded
Syringe, the distance between needle point and reception device are 5 cm, and the Kv of voltage 15 between needle point and reception device, the promotion of pump is fast
Spend for 6 ml h-1, solidification liquid is liquid nitrogen, chitin balls is put into -80 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water
Rinse to neutrality, the dry chitin tiny balloon for being dried to obtain neutrality is freezed again.
Embodiment 17：
Chitin powder is scattered in 20 wt% KOH, 20 wt% LiOH, 50 wt% NaOH, the mixed liquor of 4 wt% thiocarbamides,
Build-up ice at -30 DEG C, place 12 hours, after at room temperature solution be frozen into solution, concentration is 1 wt%.Chitin solution is loaded
Syringe, the distance between needle point and reception device are 5 cm, and the Kv of voltage 15 between needle point and reception device, the promotion of pump is fast
Spend for 6 ml h-1, solidification liquid is liquid nitrogen, chitin balls is put into -80 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water
Rinse to neutrality, the dry chitin tiny balloon for being dried to obtain neutrality is freezed again.
Embodiment 18：
Chitin powder is scattered in 20 wt% KOH, 20 wt% LiOH, 5 wt% NaOH, the mixed liquor of 4 wt% urea,
Build-up ice at -30 DEG C, place 12 hours, after at room temperature solution be frozen into solution, concentration is 1 wt%.Chitin solution is loaded
Syringe, the distance between needle point and reception device are 5 cm, and the Kv of voltage 15 between needle point and reception device, the promotion of pump is fast
Spend for 6 ml h-1, solidification liquid is liquid nitrogen, chitin balls is put into -80 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water
Rinse to neutrality, the dry chitin tiny balloon for being dried to obtain neutrality is freezed again.
Embodiment 19：
Chitosan powder is scattered in into the mixed liquor of 20 wt% KOH, 20 wt% LiOH, 50 wt% NaOH, 12 wt% thiocarbamides
In, build-up ice at -30 DEG C, place 12 hours, after at room temperature solution be frozen into solution, concentration is 1 wt%.Chitosan solution is filled
Enter syringe, the distance between needle point and reception device are 5 cm, and the Kv of voltage 0 between needle point and reception device, the promotion of pump is fast
Spend for 6 ml h-1, solidification liquid is liquid nitrogen, chitosan bead is put into -30 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water
Rinse to neutrality, the dry shitosan tiny balloon for being dried to obtain neutrality is freezed again.
Embodiment 20：
Chitosan powder is scattered in 5 wt% KOH, 20 wt% LiOH, the mixed liquor of 12 wt% thiocarbamides, is tied at -30 DEG C
Cheng Bing, places 12 hours, after at room temperature solution be frozen into solution, concentration is 1 wt%.Chitosan solution is loaded into syringe, needle point and
The distance between reception device is 5 cm, the Kv of voltage 9 between needle point and reception device, and the driving velocity of pump is 6 ml h-1,
Solidification liquid is liquid nitrogen, chitosan bead is put into -20 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water and rinses to neutrality,
The dry shitosan tiny balloon for being dried to obtain neutrality is freezed again.
Embodiment 21：
Chitosan powder is scattered in 20 wt% KOH, 5 wt% LiOH, 50 wt% NaOH, the mixed liquor of 12 wt% thiocarbamides,
Build-up ice at -30 DEG C, place 12 hours, after at room temperature solution be frozen into solution, concentration is 1 wt%.Chitosan solution is loaded
Syringe, the distance between needle point and reception device are 5 cm, and the Kv of voltage 15 between needle point and reception device, the promotion of pump is fast
Spend for 6 ml h-1, solidification liquid is liquid nitrogen, chitosan bead is put into -45 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water
Rinse to neutrality, the dry shitosan tiny balloon for being dried to obtain neutrality is freezed again.
Embodiment 22：
Chitosan powder is scattered in 20 wt% KOH, 20 wt% LiOH, 5 wt% NaOH, the mixed liquor of 12 wt% thiocarbamides,
Build-up ice at -30 DEG C, place 12 hours, after at room temperature solution be frozen into solution, concentration is 1 wt%.Chitosan solution is loaded
Syringe, the distance between needle point and reception device are 5 cm, and the Kv of voltage 15 between needle point and reception device, the promotion of pump is fast
Spend for 6 ml h-1, solidification liquid is liquid nitrogen, chitosan bead is put into -80 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water
Rinse to neutrality, the dry shitosan tiny balloon for being dried to obtain neutrality is freezed again.
Embodiment 23：
Chitosan powder is scattered in 20 wt% KOH, 20 wt% LiOH, 50 wt% NaOH, the mixed liquor of 4 wt% thiocarbamides,
Build-up ice at -30 DEG C, place 12 hours, after at room temperature solution be frozen into solution, concentration is 1 wt%.Chitosan solution is loaded
Syringe, the distance between needle point and reception device are 5 cm, and the Kv of voltage 15 between needle point and reception device, the promotion of pump is fast
Spend for 6 ml h-1, solidification liquid is liquid nitrogen, chitosan bead is put into -80 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water
Rinse to neutrality, the dry shitosan tiny balloon for being dried to obtain neutrality is freezed again.
Embodiment 24：
Chitosan powder is scattered in 20 wt% KOH, 20 wt% LiOH, 5 wt% NaOH, the mixed liquor of 4 wt% urea,
Build-up ice at -30 DEG C, place 12 hours, after at room temperature solution be frozen into solution, concentration is 1 wt%.Chitosan solution is loaded
Syringe, the distance between needle point and reception device are 5 cm, and the Kv of voltage 15 between needle point and reception device, the promotion of pump is fast
Spend for 6 ml h-1, solidification liquid is liquid nitrogen, chitosan bead is put into -80 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water
Rinse to neutrality, the dry shitosan tiny balloon for being dried to obtain neutrality is freezed again.
Embodiment 25：
Cellulose powder is scattered in into the mixed liquor of 20 wt% KOH, 20 wt% LiOH, 50 wt% NaOH, 12 wt% thiocarbamides
In, build-up ice at -30 DEG C, place 12 hours, after at room temperature solution be frozen into solution, concentration is 1 wt%.Cellulose solution is filled
Enter syringe, the distance between needle point and reception device are 5 cm, and the Kv of voltage 0 between needle point and reception device, the promotion of pump is fast
Spend for 6 ml h-1, solidification liquid is liquid nitrogen, cellulose balls is put into -30 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water
Rinse to neutrality, the dry cellulose hollow microballoon for being dried to obtain neutrality is freezed again.
Embodiment 26：
Cellulose powder is scattered in 5 wt% KOH, 20 wt% LiOH, 50 wt% NaOH, the mixed liquor of 12 wt% thiocarbamides,
Build-up ice at -30 DEG C, place 12 hours, after at room temperature solution be frozen into solution, concentration is 1 wt%.Cellulose solution is loaded
Syringe, the distance between needle point and reception device be 5 cm, the Kv of voltage 9 between needle point and reception device, the driving velocity of pump
For 6 ml h-1, solidification liquid is liquid nitrogen, cellulose balls is put into -45 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water and floats
Neutrality is washed till, the dry cellulose hollow microballoon for being dried to obtain neutrality is freezed again.
Embodiment 27：
Cellulose powder is scattered in 20 wt% KOH, 5 wt% LiOH, 50 wt% NaOH, the mixed liquor of 12 wt% thiocarbamides,
Build-up ice at -30 DEG C, place 12 hours, after at room temperature solution be frozen into solution, concentration is 1 wt%.Cellulose solution is loaded
Syringe, the distance between needle point and reception device are 5 cm, and the Kv of voltage 15 between needle point and reception device, the promotion of pump is fast
Spend for 6 ml h-1, solidification liquid is liquid nitrogen, cellulose balls is put into -80 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water
Rinse to neutrality, the dry cellulose hollow microballoon for being dried to obtain neutrality is freezed again.
Embodiment 28：
Cellulose powder is scattered in 20 wt% KOH, 20 wt% LiOH, 5 wt% NaOH, the mixed liquor of 12 wt% thiocarbamides,
Build-up ice at -30 DEG C, place 12 hours, after at room temperature solution be frozen into solution, concentration is 1 wt%.Cellulose solution is loaded
Syringe, the distance between needle point and reception device be 5 cm, the Kv of voltage 0 between needle point and reception device, the driving velocity of pump
For 6 ml h-1, solidification liquid is liquid nitrogen, cellulose balls is put into -80 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water and floats
Neutrality is washed till, the dry cellulose hollow microballoon for being dried to obtain neutrality is freezed again.
Embodiment 29：
During cellulose powder is scattered in into 10 wt% NaOH, the mixed liquor of 12 wt% thiocarbamides, build-up ice at -30 DEG C, place 12
Hour, after at room temperature solution be frozen into solution, concentration is 1 wt%.Cellulose solution is loaded into syringe, between needle point and reception device
Distance be 5 cm, the Kv of voltage 0 between needle point and reception device, the driving velocity of pump is 6 ml h-1, solidification liquid is liquid nitrogen,
Cellulose balls are put into -45 DEG C of freeze dryers and are dried.Microballoon after lyophilized is put into water and rinses to neutrality, freezes again dry
The dry cellulose hollow microballoon for obtaining neutrality.
Embodiment 30：
Cellulose powder is scattered in 20 wt% KOH, 20 wt% LiOH, 5 wt% NaOH, the mixed liquor of 4 wt% urea,
Build-up ice at -30 DEG C, place 12 hours, after at room temperature solution be frozen into solution, concentration is 1 wt%.Cellulose solution is loaded
Syringe, the distance between needle point and reception device are 5 cm, and the Kv of voltage 15 between needle point and reception device, the promotion of pump is fast
Spend for 6 ml h-1, solidification liquid is liquid nitrogen, cellulose balls is put into -80 DEG C of freeze dryers and is dried.Microballoon after lyophilized is put into water
Rinse to neutrality, the dry cellulose hollow microballoon for being dried to obtain neutrality is freezed again.
Claims (6)
1. a kind of method for preparing natural polymer tiny balloon, it is characterised in that：
Preparing natural Polymer Solution, the natural polymer is chitin, shitosan or cellulose, the natural polymer for obtaining
Wt%～8 wt% of concentration 0.001 of solution；Solvent used by preparing natural Polymer Solution is in KOH, LiOH, NaOH
Plant or combine the mixed solution with urea or thiocarbamide；
Natural polymer tiny balloon is prepared using electrostatic drop generation, natural polymer solution is loaded into syringe, needle point and reception
The distance between device is 3 cm～100 cm, and the voltage of 0 Kv～30 Kv, the promotion of pump are applied between needle point and reception device
Speed is 0.1 ml h-1～1000 ml h-1, the solidification liquid in reception device is liquid nitrogen；
The natural polymer microballoon formed in liquid nitrogen is put into freeze dryer and is dried, extremely all moisture therein all remove and are
Only, will it is lyophilized after microballoon be put into water and rinse to neutrality, freeze dry be dried to obtain natural polymer tiny balloon again.
2. method according to claim 1, it is characterised in that in the solvent of preparing natural Polymer Solution, KOH's is dense
Spend for 5 wt%～20 wt%.
3. method according to claim 1, it is characterised in that in the solvent of preparing natural Polymer Solution, LiOH's
Concentration is 5 wt%～20 wt%.
4. method according to claim 1, it is characterised in that in the solvent of preparing natural Polymer Solution, NaOH's is dense
Spend for 5 wt%～50 wt%.
5. method according to claim 1, it is characterised in that in the solvent of preparing natural Polymer Solution, urea or sulphur
The concentration of urea is 4 wt%～12 wt%.
6. method according to claim 1, it is characterised in that cryodesiccated temperature is -20～-80 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610900731.0A CN106633113A (en) | 2016-10-17 | 2016-10-17 | Preparation method of natural macromolecular hollow microspheres |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610900731.0A CN106633113A (en) | 2016-10-17 | 2016-10-17 | Preparation method of natural macromolecular hollow microspheres |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106633113A true CN106633113A (en) | 2017-05-10 |
Family
ID=58857038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610900731.0A Pending CN106633113A (en) | 2016-10-17 | 2016-10-17 | Preparation method of natural macromolecular hollow microspheres |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106633113A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107189109A (en) * | 2017-07-04 | 2017-09-22 | 浙江理工大学 | A kind of poly- polysaccharide solution of homogeneous and preparation method thereof |
| CN112030206A (en) * | 2020-09-08 | 2020-12-04 | 重庆市真诚电镀有限公司 | Electroplating process for spectacle frame |
| CN113336977A (en) * | 2021-05-19 | 2021-09-03 | 武汉大学 | Chitosan nanofiber microsphere and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921410A (en) * | 2010-09-16 | 2010-12-22 | 武汉工程大学 | Method for preparing cellulose microspheres |
| CN103614756A (en) * | 2013-11-15 | 2014-03-05 | 武汉大学 | Method for preparing hollow multi-layer chitosan hydrogel |
| CN103709416A (en) * | 2013-12-20 | 2014-04-09 | 武汉大学 | Chitosan multilayered gel balls and preparation method thereof |
| CN103804712A (en) * | 2014-01-23 | 2014-05-21 | 北京化工大学常州先进材料研究院 | Preparation of porous and aperture-controllable chitosan microspheres |
| CN104327287A (en) * | 2014-11-20 | 2015-02-04 | 武汉工程大学 | Preparation method of chitosan beads |
| CN104327286A (en) * | 2014-11-20 | 2015-02-04 | 武汉工程大学 | Preparation method of cellulose peaberry |
| CN104525071A (en) * | 2014-11-24 | 2015-04-22 | 张家港保税区鑫和成国际贸易有限公司 | Chitosan microsphere preparation method |
-
2016
- 2016-10-17 CN CN201610900731.0A patent/CN106633113A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921410A (en) * | 2010-09-16 | 2010-12-22 | 武汉工程大学 | Method for preparing cellulose microspheres |
| CN103614756A (en) * | 2013-11-15 | 2014-03-05 | 武汉大学 | Method for preparing hollow multi-layer chitosan hydrogel |
| CN103709416A (en) * | 2013-12-20 | 2014-04-09 | 武汉大学 | Chitosan multilayered gel balls and preparation method thereof |
| CN103804712A (en) * | 2014-01-23 | 2014-05-21 | 北京化工大学常州先进材料研究院 | Preparation of porous and aperture-controllable chitosan microspheres |
| CN104327287A (en) * | 2014-11-20 | 2015-02-04 | 武汉工程大学 | Preparation method of chitosan beads |
| CN104327286A (en) * | 2014-11-20 | 2015-02-04 | 武汉工程大学 | Preparation method of cellulose peaberry |
| CN104525071A (en) * | 2014-11-24 | 2015-04-22 | 张家港保税区鑫和成国际贸易有限公司 | Chitosan microsphere preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 谷军等: ""高压静电喷雾法制备天然纤维素微球及影响因素研究"", 《高分子学报》 * |
| 马骊娜等: ""静电喷雾法制备壳聚糖/康普瑞丁载药微球"", 《材料科学与工程学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107189109A (en) * | 2017-07-04 | 2017-09-22 | 浙江理工大学 | A kind of poly- polysaccharide solution of homogeneous and preparation method thereof |
| CN112030206A (en) * | 2020-09-08 | 2020-12-04 | 重庆市真诚电镀有限公司 | Electroplating process for spectacle frame |
| CN113336977A (en) * | 2021-05-19 | 2021-09-03 | 武汉大学 | Chitosan nanofiber microsphere and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Polyvinyl alcohol/chitosan hydrogels with enhanced antioxidant and antibacterial properties induced by lignin nanoparticles | |
| Rodriguez-Rodriguez et al. | Composite hydrogels based on gelatin, chitosan and polyvinyl alcohol to biomedical applications: A review | |
| Silva et al. | Ionic liquids in the processing and chemical modification of chitin and chitosan for biomedical applications | |
| Zhu et al. | Cellulose/chitosan composite multifilament fibers with two-switch shape memory performance | |
| Zhao et al. | Preparation of nanofibers with renewable polymers and their application in wound dressing | |
| CN103446621B (en) | Preparation method of nano-silver-containing sodium alginate based antibacterial medical dressing | |
| CN101972481B (en) | Macromolecular microcarrier and preparation method thereof | |
| CN105494430B (en) | One kind carries silver-colored low-molecular weight chitoglycan complex microsphere antiseptic and preparation method thereof | |
| CN105903064B (en) | A kind of chitosan microball and its preparation method and application | |
| CN103059319B (en) | Preparation method of chitin nano fiber | |
| CN106467613B (en) | A kind of self-healing polyanion-chitin quarternary ammonium salt aquagel and its application | |
| Wei et al. | Nanocellulose based hydrogel or aerogel scaffolds for tissue engineering | |
| CN111748109B (en) | Chitosan microspheres prepared from chitosan solution with pH value of 6-8 and preparation method thereof | |
| CN106633113A (en) | Preparation method of natural macromolecular hollow microspheres | |
| CN105085943B (en) | A kind of polymer microballoon and preparation method thereof | |
| CN101342381A (en) | Preparation method for anti-inflammation adhesion-proof hemostatic sponge | |
| CN101711893A (en) | Method for preparing bacterial cellulose nerve conduit | |
| CN107118361B (en) | Silk fibroin/carboxymethyl chitosan composite gel and preparation method thereof | |
| CN105617459A (en) | Preparation method for nano polypyrrole chitin nerve conduit | |
| Bi et al. | Homogeneous modification of chitin and chitosan based on an alkali/urea soluble system and their applications in biomedical engineering | |
| CN104624130A (en) | Method for preparing regenerated chitin microspheres | |
| Zhu et al. | Chitin whiskers enhanced methacrylated hydroxybutyl chitosan hydrogels as anti-deformation scaffold for 3D cell culture | |
| Li et al. | Construction of porous structure-based carboxymethyl chitosan/sodium alginate/tea polyphenols for wound dressing | |
| Kavitha et al. | Chitosan polymer used as carrier in various pharmaceutical formulations: brief review | |
| Liu et al. | Electrostimulation of fibroblast proliferation by an electrospun poly (lactide-co-glycolide)/polydopamine/chitosan membrane in a humid environment |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170510 |
|
| RJ01 | Rejection of invention patent application after publication |