CN106084302B - Self-crosslinking hydroformylation nanometer bacteria cellulose functional porous material and preparation method - Google Patents

Self-crosslinking hydroformylation nanometer bacteria cellulose functional porous material and preparation method Download PDF

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CN106084302B
CN106084302B CN201610374542.4A CN201610374542A CN106084302B CN 106084302 B CN106084302 B CN 106084302B CN 201610374542 A CN201610374542 A CN 201610374542A CN 106084302 B CN106084302 B CN 106084302B
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bacteria cellulose
solution
nanometer
nanometer bacteria
porous material
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CN106084302A (en
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郑裕东
王岩森
梁春永
芦海洋
谢亚杰
王彩
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University of Science and Technology Beijing USTB
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Abstract

A kind of self-crosslinking hydroformylation nanometer bacteria cellulose porous material and preparation method, the material include:Bacteria cellulose, polysaccharide or polypeptide, bacteriostatic agent, foaming agent.Preparation method includes dissolving and stirring polysaccharide or polypeptide to form solution, and the aldehyde radical bacteria cellulose of a certain amount of disperse, a certain amount of bacteriostatic agent (or antibacterial colloidal sol) and a certain amount of foaming agent are added into solution, by stirring so that bubble is uniformly present in mixed solution after, pour into mold, chilling is carried out to sample, then sample is placed in vacuum freeze drier, it is vacuum dried, self-crosslinking degradable polysaccharide or the compound hydroformylation nanometer bacteria cellulose functional porous material of polypeptide is made.The present invention is other than the excellent mechanical performances intrinsic with porous material, also have many advantages, such as that good biocompatibility, dry state wetting rate are fast and skin attachment is good and there is bacteria resistance function, can be used as the use such as various medical wound repair materials, multi-functional wound dressing, novel tissue engineering rack.

Description

Self-crosslinking hydroformylation nanometer bacteria cellulose functional porous material and preparation method
Technical field
The present invention relates to be applied to medical hemostatic, biological antibacterial, wound repair, the numerous areas such as tissue engineered porous scaffold The degradable hydroformylation nanometer bacteria cellulose functional porous material of self-crosslinking more particularly to a kind of biocompatibility, permeability It is good, it is degradable and have that the quick local hemostasis of good skin attachment is antibacterial, reduces infected wound rate and has by self-crosslinking Hydroformylation nanometer bacteria cellulose functional porous material of good mechanical strength and preparation method thereof.
Background technique
Porous material be using solid dielectric as material and intrinsic silicon has the poromerics of countless stomatas, can also regard as It is the composite material that gas is filler.It is used as wound dressing, wound repair material, for cell progress in organizational project in recent years The timbering material of vital movement has received widespread attention in the application of pharmacy and field of biomedicine.Applied to biosystem Porous material must meet following requirement:With good biocompatibility, cell compatibility and hygroscopicity, wound infiltration can be absorbed Liquid, antibacterial out, hemostasis, the healing that wound can be accelerated, except the basic demand that should meet general wound repair material or dressing, such as nothing It is malicious outer, it should also be conducive to cell Proliferation, maintain the expression of cell normal function;As biological degradability timbering material, branch is completed It should be able to degrade under the action of human chitinase after frame effect, catabolite copes with cytotoxic evil effect;Medical porous material should have There is three-dimensional stereochemical structure, it is raw to be conducive to cell because this structure can provide roomy surface area and space for higher porosity Long and breeding, extrtacellular matrix deposition, nutriment and oxygen disengaging, metabolite discharge and blood vessel and nerve are grown into;It is more Porous materials should also have good plasticity, certain shapes can be made in advance, and have certain mechanical strength.
Bacteria cellulose (BC) is a kind of natural biopolymer, has good bioactivity, degradability, highly crystalline Much unique physics such as degree, high-purity, high retentiveness, superfine nano network of fibers, high-tensile and elasticity modulus, chemistry And mechanical performance, it is had broad application prospects in biomedical materials field.But bacteria cellulose itself without antibacterial, Anthemorrhagic performance, it is not ideal enough to the facilitation effect of wound healing.Bacteria cellulose is aoxidized, so that bacteria cellulose molecule 2,3 for C-C key be broken, be oxidized into aldehyde radical, research shows that the bacteria cellulose after aldehyde radical have good biocompatibility and Mechanical property is applied to most important.Meanwhile aldehyde radical bacteria cellulose can replace many due to containing a large amount of aldehyde radicals With poly glycan molecule self-crosslinking reaction, elevating mechanism intensity and stabilization occur for toxic aldehyde crosslinking agent, such as formaldehyde, glutaraldehyde Property.
Polysaccharide and polypeptide have excellent biocompatibility, degradability, are degraded under the action of enzyme absorbable low Glycan or amino acid.Polysaccharide material such as chitosan, the property that glycosaminoglycan etc. can be used in wound healing include biocompatibility, Biological degradability, styptic activity, the ability of anti-complications ability and accelerating wound healing.And polypeptide material such as polyaminoacid, Polylysine, polyglutamic acid etc. have for example good water solubility of many excellent performances, adhesiveness, and biodegrade is free of toxicity Deng being not only derived from natural resources but also can largely take, and be a kind of very promising material for regeneration.At present In disclosed patent document, there is patent by glycosaminoglycan formaldehyde or glutaraldehyde cross-linking at porous material;Or use carboxymethyl After chitosan glycerol adding, production technology made of being freeze-dried after being cross-linked into porous material with environment-protective ion exchanger.These The product that technique is produced has used crosslinking agent, is improved polysaccharide polyporous materials mechanical property, but crosslinking agent is residual Staying has certain toxicity to human body, cannot have good performance again without being foamed into porous material.There are also patents to disclose one Kind bacteria cellulose/chitosan composite sponge dressing, bacteria cellulose body is mixed with chitosan solution, manufactured porous material For material due to not having chemical crosslink reaction, products obtained therefrom properties are poor;In addition, molten using bacteria cellulose body and chitosan Liquid mixing, bacteria cellulose dispersion is uneven, porous material existing defects obtained, and different piece performance difference is larger.
Disclosed above is related in the patent document of polysaccharide, polypeptide or bacteria cellulose porous material, the suction of porous material Wet, hemostasis, bacteriostasis property are to be improved;Crosslinking agent is used, residual has certain toxicity to human body;Permeability, skin are viscous Attached property is poor, easy to fall off.In bio-medical field, it is badly in need of moisture absorption, resist blocking and that has good skin adherence and antibacterial, anti-sense Wound repair material and permeability, the good biocompatibility of dye, novel tissue engineering branch that is degradable and having some strength Frame material.
Summary of the invention
The present invention provides that a kind of raw material type is few, preparation process is simple, short preparation period, and low production cost has simultaneously There are good a three-dimensional connected porous structure, good retentiveness, biocompatibility, and the compound hydroformylation of degradable polysaccharide or polypeptide is received Rice bacteria cellulose porous material.The porous material is soft, has certain tension compressive strength, is suitble to do organizational project branch Frame is played a supporting role;Also it can be used as wound repair material, play antibacterial, anastalsis.The present invention is by the aldehyde radical after disperse Nanometer bacteria cellulose is mixed with polysaccharide or polypeptide solution, and with polysaccharide or polypeptide self-crosslinking can occur for aldehyde radical bacteria cellulose Reaction, this self-crosslinking reaction not only eliminate injury of the toxic cross-linking agents to human body, also enhance the water holding of porous material, lead to Permeability and mechanical strength.In addition, to can be used multiple types antibacterial agent compound with porous material by the present invention, make it for varying environment With excellent long-acting stable anti-microbial property.The present invention can adjust the porosity, intensity, water holding of porous material in a wider range The physical performance indexs such as rate meet different application field and require the difference of properties of product.
A kind of functional porous material of polysaccharide or the compound hydroformylation nanometer bacteria cellulose of polypeptide, it is characterised in that the material Material has a self-crosslinking degradable function, raw material include polysaccharide or polypeptide, foaming agent, bacteria cellulose and its derivative, oxidant, Bacteriostatic agent or antibacterial colloidal sol;Each material amounts are by weight percentage:Polysaccharide or polypeptide 5%~8%, bacteria cellulose and its Derivative 6%~10%, bacteriostatic agent or antibacterial colloidal sol 4%~8%, foaming agent 0.3%~0.6%, surplus are water.
The foaming agent is one of sodium bicarbonate, sodium carbonate, calcium carbonate, compressed air or a variety of.
The bacteria cellulose is the hydroformylation nanometer bacteria cellulose of hydroformylation nanometer bacteria cellulose or disperse.
The bacteriostatic agent or antibacterial colloidal sol are one of inorganic antiseptic, photocatalysis antibacterial agent and silver-series antibacterial agent.
The preparation method of polysaccharide as described above or the compound hydroformylation nanometer bacteria cellulose functional porous material of polypeptide, technology Scheme is as follows:
A certain amount of polysaccharide or polypeptide are uniformly dissolved in a solvent, the aldehyde radical bacterial fibers after disperse are added thereto Element, bacteriostatic agent and foaming agent, are stirred at room temperature, mold are poured into after bacteria cellulose is uniformly dispersed in mixed solution, will Mixed liquor carries out chilling, is dried in vacuo certain time, forms porous material.Sample is washed again, after dry, it is suitable to be cut into Size shape to get arrive target product.
Specifically preparation process is:
Step 1: the preparation of polysaccharide or polypeptide solution
It takes a certain amount of polysaccharide or polypeptide Solution into appropriate solvent, is made into polysaccharide or polypeptide solution.Solution is set In on magnetic stirrer, stirring at low speed to being uniformly dissolved, after ultrasonic wave disperses 30min, it is placed in 2~4h of standing in climatic chamber Defoaming.
Step 2: the pretreatment of nanometer bacteria cellulose
Nanometer bacteria cellulose is soaked in the NaOH solution of 0.1mol/L, boils 90~120min at 80~90 DEG C, It is repeatedly rinsed with distilled water, then passes through disinfection by ultraviolet light;By the distilled water immersion 2~4 of the nanometer bacteria cellulose after disinfection It is secondary, pH value is surveyed with the light press mold of PH test paper, control nanometer bacteria cellulose pH value is 7.2;
Step 3: the dispersion of nanometer bacteria cellulose
It weighs weight in wet base and accounts for the above-mentioned nanometer bacteria cellulose of system gross mass 6%~10% in a certain amount of deionized water In, it is evenly dispersed with high speed disperser, the nanometer bacteria cellulose of dispersion is obtained, is placed in centrifuge tube and is centrifuged.
Step 4: the addition of nanometer bacteria cellulose aldehyde grouping and bacteriostatic agent, foaming agent
It is 0.02~0.10mol/L sodium periodate solution that nanometer bacteria cellulose after taking a certain amount of disperse, which is soaked in concentration, In, solution temperature is controlled at 20~30 DEG C.Mixed liquor is immediately placed in and is protected from light place's natural reaction.Nanometer bacteria cellulose is through aoxidizing After form aldehyde radical, by the nanometer bacteria cellulose of aldehyde radical 2~4 times wash with distilled water.Polysaccharide or polypeptide are placed into after centrifugation Mixed low speed stirs evenly in solution, and self-crosslinking reaction occurs for polysaccharide or polypeptide and the aldehyde radical nanometer bacteria cellulose of disperse. 5~10min is stirred, the bacteriostatic agent or antibacterial colloidal sol for accounting for system gross mass 4%~8% is added, stirring at low speed keeps grain dissolution equal It is even;0.3%~0.6% foaming agent is added, speed of agitator is turned up rapidly, stirring is until obtain viscous solution.
Step 5: self-crosslinking degradable polysaccharide or the compound hydroformylation nanometer bacteria cellulose functional porous material molding of polypeptide
In viscous solution obtained in step 4 injection mold, after solution chilling, it is immediately placed in vacuum freeze drying Machine after vacuum freeze drying, porous material is removed from the molds, is washed with deionized 2~5 times, and in ultrasonic cleaning tank In be cleaned by ultrasonic.It is cut into suitable shape after drying, is placed in 25 DEG C of climatic chambers, it is degradable more to obtain self-crosslinking Sugar or the compound hydroformylation nanometer bacteria cellulose functional porous material finished product of polypeptide.
Compared with prior art, the invention has the advantages that and beneficial effect
1, present invention self-crosslinking degradable polysaccharide obtained or the compound hydroformylation nanometer bacteria cellulose of polypeptide are functional more Self-crosslinking reaction occurs for Porous materials, the bacteria cellulose and polysaccharide or polypeptide of aldehyde radical, not only can be common chemical to avoid using Crosslinking agent causes toxicity to human body, moreover it is possible to improve the moisture absorption of material, water retention property, mechanical strength and penetrating by self-crosslinking Property.
2, present invention self-crosslinking degradable polysaccharide obtained or the compound hydroformylation nanometer bacteria cellulose of polypeptide are functional more Porous materials have excellent biocompatibility and cellular affinity, have good adhesion with skin, and have part fast The effect of short stopping blood, resist blocking and that.
3, the obtained self-crosslinking degradable polysaccharide of the present invention or the compound hydroformylation nanometer bacteria cellulose of polypeptide are functional porous Material, degradable under the action of enzyme using natural biological macromolecular, catabolite acts on cytotoxic evil and can be biological Body absorbs.
4, present invention self-crosslinking degradable polysaccharide obtained or the compound hydroformylation nanometer bacteria cellulose of polypeptide are functional more Porous materials have excellent bacteriostasis, may be implemented to improve as antibacterial agent the significant fungistatic effect of various bacteria Application range.
5, it using foaming agent, is blistered using churned mechanically method, and thin by adding different amounts of aldehyde radical nanometer Fungin is crosslinked with polysaccharide or polypeptide to react, and realizes that aperture of porous material size is controllable, controlled porosity;And it can pass through It adjusts the shape of mold or sample is cut, meet different actual demands.
Detailed description of the invention
Fig. 1 is aldehyde radical nanometer bacteria cellulose chemical structure schematic diagram
Specific embodiment
Below in conjunction with specific implementation case, the present invention is further explained.It will be appreciated that these case study on implementation are used only for The bright present invention rather than for limiting the scope of the invention.In addition, it should also be understood that, those skilled in the art is reading the present invention After the content of instruction, the change of various equivalent forms is done to the present invention, is equally fallen into required by the claim of this application book Within the scope of.
Embodiment 1
Step 1: a certain amount of chitosan is taken to be dissolved in acetum, it is poly- to be made into the shell that chitosan mass score is 5% Sugar juice.Solution is placed on magnetic stirrer, stirs at low speed to chitosan and is uniformly dissolved, after ultrasonic wave disperses 30min, is placed in Defoaming is stood in climatic chamber.
Step 2: flake nano bacteria cellulose is soaked in the NaOH solution of 0.1mol/L, boiled at 90 DEG C 120min is repeatedly rinsed with distilled water, then passes through disinfection by ultraviolet light;By the distillation water logging of the nanometer bacteria cellulose after disinfection Bubble 2~4 times surveys pH value with the light press mold of PH test paper, and control nanometer bacteria cellulose pH value is 7.2;
Step 3: weighing a certain amount of above-mentioned nanometer bacteria cellulose in a certain amount of deionized water, high speed dispersion is used Machine is evenly dispersed, obtains the nanometer bacteria cellulose of dispersion, is placed in centrifuge tube and is centrifuged.Take receiving for a certain amount of dispersion It is in 0.02mol/L sodium periodate solution that rice bacteria cellulose, which is soaked in concentration, and solution temperature is controlled at 25 DEG C.Mixed liquor is fast Speed, which is placed in, is protected from light place's natural reaction.Nanometer bacteria cellulose forms aldehyde radical after aoxidizing, by the nanometer bacteria cellulose of aldehyde radical 2~4 times wash with distilled water.
Step 4: weighing weight in wet base accounts for the aldehyde radical nanometer bacteria cellulose after the above-mentioned disperse of system gross mass 6%, it is put into Mixed low speed stirs evenly in chitosan solution, and chitosan is crosslinked with aldehyde radical nanometer bacteria cellulose to react.After stirring The TiO for accounting for system gross mass 6% is added2Particle, stirring at low speed keeps grain dissolution uniform;0.4% sodium bicarbonate is added, rapidly Speed of agitator stirring foaming is turned up, until obtaining thick solution.
Step 5:, with liquid nitrogen by after solution chilling, being immediately placed in viscous solution obtained in step 4 injection mold Vacuum freeze drier after vacuum freeze drying, the porous material of formation is removed from the molds, is washed with deionized 2~5 It is secondary, and be cleaned by ultrasonic in ultrasonic cleaning tank.It is cut into suitable shape after drying, is placed in 25 DEG C of climatic chambers, Obtain the degradable hydroformylation nanometer bacteria cellulose of self-crosslinking/chitosan functional porous material finished product.
Embodiment 2
Step 1: a certain amount of glycosaminoglycan is taken to be dissolved in acid solution, it is made into the amino that chitosan mass score is 6% Polysaccharide solution.Solution is placed on magnetic stirrer, stirs at low speed to glycosaminoglycan and is uniformly dissolved, after ultrasonic wave disperses 30min, It is placed in climatic chamber and stands defoaming.
Step 2: flake nano bacteria cellulose is soaked in the NaOH solution of 0.1mol/L, boiled at 90 DEG C 120min is repeatedly rinsed with distilled water, then passes through disinfection by ultraviolet light;By the distillation water logging of the nanometer bacteria cellulose after disinfection Bubble 2~4 times surveys pH value with the light press mold of PH test paper, and control nanometer bacteria cellulose pH value is 7.2;
Step 3: weighing a certain amount of above-mentioned nanometer bacteria cellulose in a certain amount of deionized water, high speed dispersion is used Machine is evenly dispersed, obtains the nanometer bacteria cellulose of dispersion, is placed in centrifuge tube and is centrifuged.Take receiving for a certain amount of dispersion It is in 0.06mol/L sodium periodate solution that rice bacteria cellulose, which is soaked in concentration, and solution temperature is controlled at 25 DEG C.Mixed liquor is fast Speed, which is placed in, is protected from light place's natural reaction.Nanometer bacteria cellulose forms aldehyde radical after aoxidizing, by the nanometer bacteria cellulose of aldehyde radical 2~4 times wash with distilled water.
Step 4: the aldehyde radical nanometer bacteria cellulose for weighing the above-mentioned disperse that weight in wet base accounts for system gross mass 8% is put into ammonia Mixed low speed stirs evenly in the sugar juice of Quito, and glycosaminoglycan and sheet aldehyde radical nanometer bacteria cellulose generation self-crosslinking are anti- It answers.The Nano silver solution (colloidal sol) for accounting for system gross mass 5% is added after 5~10min of stirring, stirs at low speed 2~5min;It is added 0.3% calcium carbonate is turned up rapidly speed of agitator and stirs 6~15min, until obtaining thick liquid.
Step 5: after refrigerator freezing, it is cold to be immediately placed in vacuum in thick liquid obtained in step 4 injection mold Lyophilizer after vacuum freeze drying, the porous material of formation is removed from the molds, is washed with deionized 2~5 times, and It is cleaned by ultrasonic in ultrasonic cleaning tank.It is cut into suitable shape after drying, is placed in 25 DEG C of climatic chambers, obtains certainly It is crosslinked degradable hydroformylation nanometer bacteria cellulose/glycosaminoglycan functional porous material finished product.
Embodiment 3
Step 1: a certain amount of polylysine is taken to be dissolved in aqueous solution, be made into polylysine mass fraction be 8% it is poly- Lysine solution.Solution is placed on magnetic stirrer, stirs at low speed to polylysine and is uniformly dissolved, ultrasonic wave disperses 30min Afterwards, it is placed in climatic chamber and stands defoaming.
Step 2: nanometer bacteria cellulose is soaked in the NaOH solution of 0.1mol/L, boiled at 80~90 DEG C 120min is repeatedly rinsed with distilled water, then passes through disinfection by ultraviolet light;By the distillation water logging of the nanometer bacteria cellulose after disinfection Bubble 2~4 times surveys pH value with the light press mold of PH test paper, and control nanometer bacteria cellulose pH value is 7.2;
Step 3: weighing a certain amount of above-mentioned nanometer bacteria cellulose in a certain amount of deionized water, high speed dispersion is used Machine is evenly dispersed, obtains the nanometer bacteria cellulose of dispersion, is placed in centrifuge tube and is centrifuged.Take receiving for a certain amount of dispersion It is in 0.08mol/L sodium periodate solution that rice bacteria cellulose, which is soaked in concentration, and solution temperature is controlled at 25 DEG C.Mixed liquor is fast Speed, which is placed in, is protected from light place's natural reaction.Nanometer bacteria cellulose forms aldehyde radical after aoxidizing, by the nanometer bacteria cellulose of aldehyde radical 2~4 times wash with distilled water.
It is put into Step 4: weighing the aldehyde radical nanometer bacteria cellulose that weight in wet base accounts for after the above-mentioned disperse of system gross mass 10% Mixed low speed stirs evenly in polylysin solution, and self-crosslinking occurs for the aldehyde radical nanometer bacteria cellulose of polylysine and disperse Reaction.5~10min is stirred, the quaternary ammonium salt solution for accounting for system gross mass 7% is added, 5min is stirred in the slow-speed of revolution;0.6% carbon is added Sour sodium is turned up rapidly speed of agitator and stirs 10min, until obtaining thick liquid.
Step 5:, with liquid nitrogen by after solution chilling, being immediately placed in thick liquid obtained in step 4 injection mold Vacuum freeze drier after vacuum freeze drying, the porous material of formation is removed from the molds, is washed with deionized 2~5 It is secondary, and be cleaned by ultrasonic in ultrasonic cleaning tank.It is cut into suitable shape after drying, is placed in 25 DEG C of climatic chambers, Obtain the degradable hydroformylation nanometer bacteria cellulose of self-crosslinking/polylysine functional porous material finished product.
Embodiment 4
Step 1: a certain amount of polyaminoacid is taken to be dissolved in aqueous solution, it is molten to be made into the polyaminoacid that mass fraction is 7% Liquid.Solution is placed on magnetic stirrer, stirs at low speed to polyaminoacid and is uniformly dissolved, after ultrasonic wave disperses 30min, is placed in perseverance Defoaming is stood in constant temperature and humidity case.
Step 2: nanometer bacteria cellulose is soaked in the NaOH solution of 0.1mol/L, boiled at 80~90 DEG C 120min is repeatedly rinsed with distilled water, then passes through disinfection by ultraviolet light;By the distillation water logging of the nanometer bacteria cellulose after disinfection Bubble 2~4 times surveys pH value with the light press mold of PH test paper, and control nanometer bacteria cellulose pH value is 7.2;
Step 3: weighing a certain amount of above-mentioned nanometer bacteria cellulose in a certain amount of deionized water, high speed dispersion is used Machine is evenly dispersed, obtains the nanometer bacteria cellulose of dispersion, is placed in centrifuge tube and is centrifuged.Take receiving for a certain amount of dispersion It is in 0.1mol/L sodium periodate solution that rice bacteria cellulose, which is soaked in concentration, and solution temperature is controlled at 25 DEG C.Mixed liquor is fast Speed, which is placed in, is protected from light place's natural reaction.Nanometer bacteria cellulose forms aldehyde radical after aoxidizing, by the nanometer bacteria cellulose of aldehyde radical 2~4 times wash with distilled water.
Polyaminoacid is put into Step 4: weighing weight in wet base and accounting for the above-mentioned aldehyde radical nanometer bacteria cellulose of system gross mass 7% Mixed low speed stirs evenly in solution, and self-crosslinking reaction occurs for the aldehyde radical nanometer bacteria cellulose of polyaminoacid and disperse.It stirs 5~10min is mixed, the nano-zinc oxide powder for accounting for system gross mass 6% is added, the slow-speed of revolution stirs 5min, keeps grain dissolution uniform; Speed of agitator is turned up rapidly, while being constantly passed through compressed air, until obtaining viscous liquid.
Step 5: after refrigerator freezing, it is cold to be immediately placed in vacuum in thick liquid obtained in step 4 injection mold Lyophilizer after vacuum freeze drying, the porous material of formation is removed from the molds, is washed with deionized 2~5 times, and It is cleaned by ultrasonic in ultrasonic cleaning tank.It is cut into suitable shape after drying, is placed in 25 DEG C of climatic chambers, obtains certainly It is crosslinked degradable hydroformylation nanometer bacteria cellulose/polyaminoacid functional porous material finished product.

Claims (4)

1. a kind of self-crosslinking hydroformylation nanometer bacteria cellulose functional porous material, it is characterised in that the material has self-crosslinking Degradable function, raw material include chitosan or polypeptide, foaming agent, bacteria cellulose or derivatives thereof, bacteriostatic agent;Each material amounts It is by weight percentage:Chitosan or polypeptide 5%~8%, bacteria cellulose or derivatives thereof 6%~10%, bacteriostatic agent 4%~8%, Foaming agent 0.3%~0.6%, surplus are water;
The foaming agent is one of sodium bicarbonate, sodium carbonate, calcium carbonate, compressed air or a variety of;
The bacteria cellulose is hydroformylation nanometer bacteria cellulose;
The bacteriostatic agent is one of inorganic antiseptic, organic antibacterial agent, photocatalysis antibacterial agent and silver-series antibacterial agent.
2. the preparation method of hydroformylation nanometer bacteria cellulose functional porous material according to claim 1, feature exist In, a certain amount of chitosan or polypeptide are uniformly dissolved, thereto be added disperse after aldehyde radical bacteria cellulose, bacteriostatic agent with Foaming agent is stirred at room temperature, and mold is poured into after aldehyde radical bacteria cellulose is uniformly dispersed in mixed solution, by mixed liquor Chilling is carried out, certain time is dried in vacuo, forms porous material;Sample is washed again, after dry, is cut into suitably sized shape Shape to get arrive target product;
Specifically preparation process is:
Step 1: the preparation of chitosan or polypeptide solution
Take a certain amount of chitosan to be dissolved in acid solution or take a certain amount of polypeptide to be dissolved in aqueous solution, be made into chitosan or Peptide masses score is 5%~8% solution;Solution is placed on magnetic stirrer, is stirred at low speed to being uniformly dissolved, ultrasonic wave disperses After 30min, it is placed in climatic chamber and stands 2~4h defoaming;
Step 2: the pretreatment of nanometer bacteria cellulose
Nanometer bacteria cellulose is soaked in NaOH solution and boils certain time, is repeatedly rinsed with distilled water, then passes through purple Outside line disinfection;By the nanometer bacteria cellulose distilled water immersion after disinfection, pH value is surveyed with the light press mold of PH test paper, control nanometer is thin Fungin pH value;
Step 3: the dispersion of nanometer bacteria cellulose
It weighs weight in wet base and accounts for the above-mentioned nanometer bacteria cellulose of system gross mass 6%~10% in a certain amount of deionized water, with height Fast dispersion machine is evenly dispersed, obtains the nanometer bacteria cellulose of dispersion, is placed in centrifuge tube and is centrifuged;
Step 4: the addition of nanometer bacteria cellulose aldehyde grouping and bacteriostatic agent, foaming agent
Nanometer bacteria cellulose after taking a certain amount of disperse is soaked in the sodium periodate solution of certain temperature;Mixed liquor is rapid It is placed in and is protected from light place's natural reaction;Nanometer bacteria cellulose forms aldehyde radical after aoxidizing, and the nanometer bacteria cellulose of aldehyde radical is used Distilled water cleans 2~4 times;It places into mixed on low speed in chitosan or polypeptide solution after centrifugation to stir evenly, chitosan or polypeptide Self-crosslinking reaction occurs with the aldehyde radical nanometer bacteria cellulose of disperse;Stir 5~10min, addition account for system gross mass 4%~ 8% bacteriostatic agent, stirring at low speed keeps grain dissolution uniform;0.3%~0.6% foaming agent is added, speed of agitator is turned up rapidly, stirs It mixes until obtaining viscous solution;
Step 5: the degradable hydroformylation nanometer bacteria cellulose/chitosan of self-crosslinking or the molding of polypeptide functional porous material
In viscous solution obtained in step 4 injection mold, after solution chilling, it is immediately placed in vacuum freeze drier, very After vacuum freecing-dry, porous material is removed from the molds, is washed with deionized 2~5 times, and carried out in ultrasonic cleaning tank Ultrasonic cleaning;It is cut into suitable shape after drying, is placed in 25 DEG C of climatic chambers, obtains the degradable hydroformylation nanometer of self-crosslinking Bacteria cellulose functional porous material finished product.
3. the preparation method of hydroformylation nanometer bacteria cellulose functional porous material according to claim 2, feature exist In NaOH solution concentration described in step 2 is 0.1mol/L, 80~90 DEG C of boiling temps, 90~120min of boiling time, is distilled Water impregnates number 2~4 times, and control nanometer bacteria cellulose pH value is 7.2.
4. the preparation method of hydroformylation nanometer bacteria cellulose functional porous material according to claim 2, feature exist In step 4 sodium periodate solution concentration is 0.02~0.10mol/L, and solution temperature is controlled at 20~30 DEG C.
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