CN103724568B - A kind of Antimicrobial bacterial cellulose and preparation method thereof - Google Patents
A kind of Antimicrobial bacterial cellulose and preparation method thereof Download PDFInfo
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- CN103724568B CN103724568B CN201310751956.0A CN201310751956A CN103724568B CN 103724568 B CN103724568 B CN 103724568B CN 201310751956 A CN201310751956 A CN 201310751956A CN 103724568 B CN103724568 B CN 103724568B
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Abstract
The invention provides a kind of Antimicrobial bacterial cellulose and preparation method thereof, the present invention utilizes a large amount of hydroxy functional group existed on bacteria cellulose, the antibacterial group of quaternary ammonium salt is introduced by surface modification, do not destroy the structure of bacteria cellulose film, maintain the form of its hydrated gums, play effect that it promotes wound healing, simultaneously obtained Antimicrobial bacterial cellulose chemical stability is good, durable antibacterial effect.
Description
Technical field
The invention belongs to biology medical material technical field, be specifically related to a kind of Antimicrobial bacterial cellulose and preparation method thereof.
Background technology
Bacteria cellulose is as the equivalent material of artificial skin or trauma repair, be compared to other material as collagen protein, hyaluronic acid and silica gel etc., bacteria cellulose has the reticulated structure and mechanical holding power that are similar to skin, and do not need the chemical reaction through complexity only to need simple microbial culture just can form the controlled hydrated gums of profile, immunity rejection is low, can promote wound healing well, be a kind of good trauma repair material.But bacteria cellulose itself does not possess antibacterial, be easy to be subject to harmful microbe in air or water and pollute, thus cause a series of infection problems.
In order to make bacteria cellulose possess antibacterial function, bacteria cellulose is placed in microbicide solution by the mode of soaking absorption that adopts more at present, but the adsorption efficiency of sterilant and stability are not high, and sterilization effect is poor.
Summary of the invention
For solving the problem, the invention provides a kind of Antimicrobial bacterial cellulose and preparation method thereof, preparation method's mild condition of described Antimicrobial bacterial cellulose, obtained Antimicrobial bacterial cellulose can promote wound healing, and sterilization effect is good.
First aspect, the invention provides a kind of preparation method of Antimicrobial bacterial cellulose, comprises the following steps:
(1) bacteria cellulose is provided;
(2) described bacteria cellulose is placed in unsaturated carboxylic acid to soak, then stopper is added, obtain mixing solutions, catalyzer is added in described mixing solutions, at room temperature carry out esterification 1 ~ 4h, obtain the esterification bacterial cellulose solution containing unsaturated link(age), after purifying, obtain the dry esterification bacteria cellulose containing unsaturated link(age);
(3) after the esterification bacteria cellulose deionized water containing unsaturated link(age) of described drying being soaked, in an inert atmosphere, add unsaturated quaternary ammonium salt monomer and initiator obtains reaction solution, described reaction solution carries out addition reaction and polyreaction 2h ~ 4h at 50 DEG C ~ 60 DEG C, obtain esterification bacteria cellulose and the Antimicrobial bacterial cellulose of QAS polymer modification, one end of described QAS polymer is connected with esterification bacteria cellulose by covalent linkage.
Preferably, in step (1), the polymerization degree of bacteria cellulose is 10000 ~ 16000.
Preferably, stopper described in step (2) is Resorcinol, 2-Tert. Butyl Hydroquinone or 2,5 di tert butyl hydroquinone, and the quality of described stopper is 0.1% ~ 0.2% of described bacteria cellulose and unsaturated carboxylic acid total mass.
Preferably, unsaturated carboxylic acid described in step (2) is acrylic or methacrylic acid.
Preferably, described in step (2), catalyzer is perchloric acid or tosic acid, and the interpolation volume of described catalyzer is 0.1% ~ 0.2% of described mixed liquor volume.
In order to promote the carrying out of esterification, preferably, step also adds esterifying agent in (2) in esterification reaction process, and described esterifying agent is methacrylic anhydride, and the quality of described esterifying agent is 1 ~ 4 times of described bacteria cellulose quality.
Preferably, unsaturated quaternary ammonium salt monomer described in step (3) is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac or allyl group trimethyl ammonium chloride.
Preferably, the molar weight of unsaturated quaternary ammonium salt monomer described in step (3) is described 1 ~ 3 times of containing glucose monomer molar weight in the esterified cellulose of unsaturated link(age).
Preferably, initiator described in step (3) is the mixture of Potassium Persulphate and sodium bisulfite or the mixture of ammonium persulphate and sodium bisulfite.
Quaternary ammonium salt antiseptic-germicide develops into six generation-quaternary ammonium salt polymer antibacterial agent, because it has higher electric density, compares micromolecular compound antibacterial ability stronger.Quaternary ammonium salt polymer antibacterial agent is except anti-microbial property is good, also have chemical stability high, residual toxicity is low, easy processing, durable antibacterial effect, environmental pollution is little, and non-volatile under low vapour pressure, the advantages such as the skin of people can not be penetrated into, therefore progressively substitute traditional small molecules antiseptic-germicide in many Application Areass.
The molecular weight of bacteria cellulose is large, greatly sterically hindered, bacteria cellulose directly connects QAS polymer more difficult, the present invention introduces unsaturated link(age) by the esterification of bacteria cellulose and unsaturated carboxylic acid on bacteria cellulose molecule, reduce sterically hindered, QAS polymer can be introduced more easily on bacteria cellulose.
The present invention introduces unsaturated link(age) by the esterification of bacteria cellulose and unsaturated carboxylic acid on bacteria cellulose molecule, then addition reaction is passed through, unsaturated link(age) ruptures, unsaturated quaternary ammonium salt monomer is introduced in former unsaturated link(age) position, then, under the effect of initiator, the unsaturated quaternary ammonium salt monomer polymerization reaction take place that esterified cellulose molecule is introduced obtains QAS polymer.The present invention is by covalentlying bind in bacteria cellulose on the surface by QAS polymer, and QAS polymer can not come off, and can reach the sterilization effect of high-efficient and lasting.Compare with small molecules antiseptic-germicide, the bonding force of the esterification bacteria cellulose that described QAS polymer is modified and Antimicrobial bacterial cellulose and bacterial cell membrane is stronger, thus realizes better sterilization effect.
The present invention utilizes a large amount of hydroxy functional group existed on bacteria cellulose, the antibacterial group of quaternary ammonium salt is introduced by surface modification, do not destroy the structure of bacteria cellulose film, maintain the form of its hydrated gums, play effect that it promotes wound healing, simultaneously obtained Antimicrobial bacterial cellulose chemical stability is high, durable antibacterial effect.
Preparation method's mild condition of the present invention, the chemical reagent added mostly is water-soluble, is easily removed by unnecessary chemical reagent.
Second aspect, the invention provides a kind of Antimicrobial bacterial cellulose, and the preparation method that described Antimicrobial bacterial cellulose is provided by first aspect present invention obtains.
Antimicrobial bacterial cellulose of the present invention, while promotion wound healing, also has the antibacterial effect of high-efficient and lasting.
To sum up, beneficial effect of the present invention comprises the following aspects:
(1) preparation method's mild condition of the present invention, preparation method is simple;
(2) Antimicrobial bacterial cellulose that obtains of the present invention is while promotion wound healing, also has the sterilization effect of high-efficient and lasting.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the esterified cellulose containing double bond that the embodiment of the present invention 1 obtains.
Embodiment
The following stated is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
First aspect, the invention provides a kind of preparation method of Antimicrobial bacterial cellulose, comprises the following steps:
(1) bacteria cellulose is provided;
(2) described bacteria cellulose is placed in unsaturated carboxylic acid to soak, then stopper is added, obtain mixing solutions, catalyzer is added in described mixing solutions, at room temperature carry out esterification 1 ~ 4h, obtain the esterification bacterial cellulose solution containing unsaturated link(age), after purifying, obtain the dry esterification bacteria cellulose containing unsaturated link(age);
(3) after the esterification bacteria cellulose deionized water containing unsaturated link(age) of described drying being soaked, in an inert atmosphere, add unsaturated quaternary ammonium salt monomer and initiator obtains reaction solution, described reaction solution carries out addition reaction and polyreaction 2h ~ 4h at 50 DEG C ~ 60 DEG C, obtain esterification bacteria cellulose and the Antimicrobial bacterial cellulose of QAS polymer modification, one end of described QAS polymer is connected with esterification bacteria cellulose by covalent linkage.
Described in step (1), the preparation method of bacteria cellulose is: prepare nutrient solution, bacteria cellulose being produced bacterial strain is inoculated in described nutrient solution in the ratio that the volume ratio with nutrient solution is 1:100, then at 28 DEG C ~ 32 DEG C static fermentations, until obtaining thickness is the bacteria cellulose film of 1 ~ 5mm, described fungin film being placed in concentration is that the sodium hydroxide solution of 0.1mol/L vibrates smudge cells 30 minutes at 80 DEG C, repeatedly after three times, deionized water is used to wash away broken cell and sodium hydroxide, until described fungin film surface p H is neutral, after steam sterilizing, lyophilize is for subsequent use.
The composition of described nutrient solution is: 0.1 ~ 0.4g/mL glucose sugar, 0.03 ~ 0.06g/mL peptone, 0.02 ~ 0.03g/mL yeast powder, 0.01 ~ 0.02g/mL Sodium phosphate dibasic, 0.005 ~ 0.015g/mL magnesium sulfate, 0.005 ~ 0.01g/mL ammonium sulfate, 0.005 ~ 0.015mL/mL maize treacle extracting solution.
Described bacteria cellulose is produced bacterial strain and is acetobacter xylinum, produces acetobacter, acetify bacillus, Acetobacter pasteurianus, glucose bacillus, Agrobacterium, root nodule bacterium, sarcina, pseudomonas cepacia, Pseudomonas cocovenenans or campylobacter jejuni.
Described in step (1), the polymerization degree of bacteria cellulose is 10000 ~ 16000.
Hydroxyl in bacteria cellulose described in step (2) and the carboxyl generation esterification in unsaturated carboxylic acid obtain the esterification bacterial cellulose solution containing unsaturated link(age).
End is adopted to be the unsaturated fatty acids of alkene.
Unsaturated carboxylic acid described in step (2) can be acrylic or methacrylic acid, but is not limited to that these are several.
Acrylic or methacrylic acid obtains for purchase.
In step (2), described bacteria cellulose is placed in unsaturated carboxylic acid and soaks 1 ~ 2h.
In step (2) by described bacteria cellulose by solid-to-liquid ratio be 0.02g/mL ~ 0.03g/mL be placed in unsaturated carboxylic acid soak 1 ~ 2h.Described unsaturated carboxylic acid is excessive.
In order to prevent unsaturated carboxylic acid polymerization reaction take place; add the unsaturated link(age) in stopper protection unsaturated carboxylic acid; stopper described in step (2) is Resorcinol, 2-Tert. Butyl Hydroquinone or 2; 5-di-tert-butyl hydroquinone, the quality of described stopper is 0.1% ~ 0.2% of described bacteria cellulose and unsaturated carboxylic acid total mass.
Described in step (2), catalyzer is perchloric acid or tosic acid, and the interpolation volume of described catalyzer is 0.1% ~ 0.2% of described mixed liquor volume.
When adding described catalyzer, in described mixing solutions, add a certain amount of toluene.
In order to promote the carrying out of esterification, step also adds esterifying agent in (2) in esterification reaction process, and described esterifying agent is methacrylic anhydride, and the quality of described esterifying agent is 1 ~ 4 times of described bacteria cellulose quality.The activity of esterifying agent is large compared with carboxylic acid, promotes the esterification of hydroxyl on sterically hindered larger bacteria cellulose.
The purification process of step (2) is taken out by the esterification bacteria cellulose containing unsaturated link(age), and after then using methyl alcohol and rinsed with deionized water totally successively, lyophilize, obtains the dry esterification bacteria cellulose containing unsaturated link(age).
Unsaturated quaternary ammonium salt monomer described in step (3) and the described esterification bacteria cellulose generation addition reaction containing unsaturated link(age) obtain the esterification bacteria cellulose that unsaturated quaternary ammonium salt monomer is modified, esterification bacteria cellulose polymerization reaction take place under the effect of described initiator that described unsaturated quaternary ammonium salt monomer is modified, obtains esterification bacteria cellulose and the Antimicrobial bacterial cellulose of QAS polymer modification.
In step (3), the esterification bacteria cellulose deionized water containing unsaturated link(age) of described drying is soaked 1 ~ 2h.
Is that 0.04g/mL ~ 0.06g/mL in deionized water soak 1 ~ 2h containing the esterification bacteria cellulose of unsaturated link(age) by solid-to-liquid ratio by described drying in step (3).
Described in step (3), inert atmosphere is nitrogen or argon atmosphere.
Unsaturated quaternary ammonium salt monomer described in step (3) is the quaternary ammonium salt containing unsaturated link(age), preferably, described unsaturated quaternary ammonium salt monomer can be MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac or allyl group trimethyl ammonium chloride, but is not limited to that these are several.
The molar weight of unsaturated quaternary ammonium salt monomer described in step (3) is described 1 ~ 3 times of containing glucose monomer molar weight in the esterified cellulose of unsaturated link(age).
Bacteria cellulose is with β-1 by glucose monomer, the macromolecular polysaccharide of 4 glycosidic link compositions, the each glucose monomer of bacteria cellulose is connected with three hydroxyls, by esterification, the hydroxyl place on glucose monomer introduces unsaturated link(age), then by addition reaction, unsaturated quaternary ammonium salt monomer is partly or entirely introduced in former unsaturated double-bond position.
Initiator described in step (3) is the mixture of Potassium Persulphate and sodium bisulfite or the mixture of ammonium persulphate and sodium bisulfite.
Initiator described in step (3) is ammonium persulphate (NH4)
2s
2o
8, add sodium bisulfite (NaHSO when use ammonium persulphate is as initiator
3) form redox initiation system, thus the activation energy of polyreaction is reduced greatly, the quality of described ammonium persulphate and described sodium bisulfite is described containing the esterification bacteria cellulose of unsaturated link(age) and 0.05% ~ 0.2% of unsaturated quaternary ammonium salt monomer mass sum.
The mol ratio of described ammonium persulphate and sodium bisulfite is 1:1.
Purification process in step (3) is taken out the bacteria cellulose that modify containing QAS polymer, cleans again, preserve after lyophilize with after methanol wash three times with deionized water.
The present invention introduces unsaturated link(age) by the esterification of bacteria cellulose and unsaturated carboxylic acid on bacteria cellulose molecule, then addition reaction is passed through, unsaturated link(age) ruptures, unsaturated quaternary ammonium salt monomer is introduced in former unsaturated double-bond position, then, under the effect of initiator, the unsaturated quaternary ammonium salt monomer polymerization reaction take place that esterified cellulose molecule is introduced obtains QAS polymer.
Quaternary ammonium salt antiseptic-germicide developed into for the 6th generation---quaternary ammonium salt polymer antibacterial agent, because it has higher electric density, compare micromolecular compound antibacterial ability stronger.Polymer antibacterial agent is except anti-microbial property is good, also have chemical stability high, residual toxicity is low, easy processing, durable antibacterial effect, environmental pollution is little, and non-volatile under low vapour pressure, the advantages such as the skin of people can not be penetrated into, therefore progressively substitute traditional small molecules antiseptic-germicide in many Application Areass.
In order to introduce the antibacterial group of quaternary ammonium salt on bacteria cellulose molecule, the present invention selects the unsaturated quaternary ammonium salt monomer-MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride not only containing quaternary ammonium salt group but also containing the unsaturated link(age) that can react, acrylyl oxy-ethyl-trimethyl salmiac or allyl group trimethyl ammonium chloride, on bacteria cellulose molecule, unsaturated link(age) is introduced by the esterification of bacteria cellulose and unsaturated carboxylic acid, so both introduce the unsaturated link(age) that can react, again reduce cellulosic sterically hindered, make it that addition reaction more easily occur and introduce quaternary ammonium salt functional group.
The present invention, by QAS polymer is covalently bind in bacteria cellulose on the surface, makes antibacterial group concentrate on bacteria cellulose surface and concentration is high, and antibacterial group and bacteria cellulose bonding force are strong, and difficult drop-off, can reach the sterilization effect of high-efficient and lasting.
Compare with small molecules antiseptic-germicide, the germ resistance of the Antimicrobial bacterial cellulose that the present invention obtains is improved largely, after mainly combining with bacteria cellulose because of QAS polymer, the density of QAS polymer positive charge improves, stronger with the bonding force of bacterial cell membrane, thus realize better sterilization effect.
Because bacteria cellulose has the dermatoid tridimensional network of class and mechanical property, there is good affinity and cell compatibility, and bacteria cellulose carries suff water, provide good growing environment can to impaired skin, promote impaired skin wound healing.
The present invention utilizes a large amount of hydroxy functional group existed on bacteria cellulose, the antibacterial group of quaternary ammonium salt is introduced by surface modification, do not destroy the tridimensional network of bacteria cellulose film, maintain the form of its hydrated gums, be conducive to maintaining its water holding water retention capacity, play effect that it promotes wound healing, simultaneously to be connected to chemical stability on bacteria cellulose by covalent linkage high for the antibacterial group of quaternary ammonium salt, durable antibacterial effect, and antiseptic-germicide can not penetrate into human body, security is good.
Preparation method's reaction conditions of the present invention is gentle, and reagent is water-soluble, is easy to unnecessary reagent to separate from material.
Second aspect, a kind of Antimicrobial bacterial cellulose of the present invention, the preparation method that described Antimicrobial bacterial cellulose is provided by first aspect present invention obtains.
The present invention utilizes a large amount of hydroxy functional group existed on bacteria cellulose, the antibacterial group of quaternary ammonium salt is introduced by surface modification, do not destroy the structure of bacteria cellulose film, maintain the form of its hydrated gums, play it and promote effect of wound healing, obtained Antimicrobial bacterial cellulose durable antibacterial effect, efficient, security is good.
Below in conjunction with specific embodiment, specific implementation of the present invention is described in detail.
Embodiment 1:
(1) 1mL acetobacter xylinum is inoculated in 100mL nutrient solution, 30 DEG C of static cultivation are until obtaining thickness is the bacteria cellulose film of 5mm, bacteria cellulose film being placed in concentration is that the sodium hydroxide solution of 0.1mol/L vibrates smudge cells 30 minutes at 80 DEG C, repeatedly after three times, deionized water is used to wash away broken cell and sodium hydroxide, until bacteria cellulose film surface p H is neutral, after steam sterilizing, lyophilize is for subsequent use; The composition of described nutrient solution is: 0.1g/mL glucose sugar, 0.03g/mL peptone, 0.02g/mL yeast powder, 0.01g/mL Sodium phosphate dibasic, 0.005g/mL magnesium sulfate, 0.005g/mL ammonium sulfate, 0.005mL/mL maize treacle extracting solution;
(2) the bacteria cellulose film 0.5g that step (1) obtains is got, be placed in 20mL methacrylic acid and soak 2h, add the hydroquinone of polymerization retarder that quality is bacteria cellulose film quality and methacrylic acid total mass 0.1%, obtain mixing solutions, 25mL toluene is added and 0.1mL mass concentration is the perchloric acid solution of 60% in mixing solutions, stir gently and make mixing, drip 2mL methacrylic anhydride again, the quality of methacrylic anhydride is 4 times of bacteria cellulose quality, stir while adding, room temperature leaves standstill 1h, hydroxyl in bacteria cellulose and the carboxyl generation esterification in methacrylic acid obtain the esterification bacterial cellulose solution containing double bond, esterification bacteria cellulose containing double bond is taken out after using methyl alcohol and rinsed with deionized water totally successively, lyophilize, obtain the dry esterification bacteria cellulose containing double bond, Fig. 1 is the infrared spectrogram of the esterification bacteria cellulose containing double bond that bacteria cellulose and the present embodiment obtain, wherein, B is the infrared spectrogram of not carrying out the bacteria cellulose of esterification, C is the esterification bacteria cellulose infrared spectrogram containing double bond that the present embodiment obtains, as can be seen from Figure 1, in C bacteria cellulose at 3350.34cm
-1there is significantly decay in the-OH base stretching vibration peak at place, shows to consume-OH group in reaction process.At 1725.01cm in C
-1having there is sharp-pointed strong absorption peak in place, is judged as the charateristic avsorption band of ester carbonyl stretching vibration.At 1649.78cm in C
-1place is the charateristic avsorption band of C=C double bond, and this illustrates that the carboxyl of bacteria cellulose hydroxyl and methacrylic acid there occurs esterification, and introduces double bond in bacteria cellulose.
Esterification equation is:
(3) the esterification bacteria cellulose containing double bond getting 0.5g drying is placed in three-necked flask, adds 10mL deionized water and soaks 2 hours.Add the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride that molar weight is glucose monomer molar weight 1 times in esterified cellulose containing double bond, after logical 15 minutes nitrogen, add initiator (NH4)
2s
2o
8and NaHSO
3, (NH4)
2s
2o
8and NaHSO
3mol ratio be 1:1, (NH4)
2s
2o
8and NaHSO
3quality be 0.07% of esterification bacteria cellulose containing double bond and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride quality sum, obtain reaction solution, continue to pass into nitrogen, reaction solution is warming up to 50 DEG C of reaction 2h, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and the esterification bacteria cellulose generation addition reaction containing double bond obtain the esterification bacteria cellulose that MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride aqueous monomer is modified, esterification bacteria cellulose polymerization reaction take place under the effect of initiator that MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer is modified, obtain esterification bacteria cellulose and the Antimicrobial bacterial cellulose of the modification of polymethyl acyloxyethyl trimethyl ammonium chloride, clean after reaction product methanol wash three times with deionized water, lyophilize is preserved.
Reaction equation is:
Embodiment 2:
(1) 1mL acetobacter xylinum is inoculated in 100mL nutrient solution, 30 DEG C of static cultivation are until obtaining thickness is the bacteria cellulose film of 5mm, fungin film being placed in concentration is that the sodium hydroxide solution of 0.1mol/L vibrates smudge cells 30 minutes at 80 DEG C, repeatedly after three times, deionized water is used to wash away broken cell and sodium hydroxide, until described fungin film surface p H is neutral, after steam sterilizing, lyophilize is for subsequent use; The composition of described nutrient solution is: 0.4g/mL glucose sugar, 0.06g/mL peptone, 0.03g/mL yeast powder, 0.02g/mL Sodium phosphate dibasic, 0.015g/mL magnesium sulfate, 0.01g/mL ammonium sulfate, 0.015mL/mL maize treacle extracting solution;
(2) the bacteria cellulose film 0.4g that step (1) obtains is got, be placed in 20ml vinylformic acid and soak 1h, add the hydroquinone of polymerization retarder that quality is bacteria cellulose film and vinylformic acid total mass 0.2%, obtain mixing solutions, in mixing solutions, add 25ml toluene and 0.1mL mass concentration is the perchloric acid solution of 60%, stir gently and make mixing.Drip 0.4mL acrylic anhydride again, the quality of acrylic anhydride is 1 times of bacteria cellulose quality, stir while adding, room temperature leaves standstill 4h, hydroxyl in bacteria cellulose and the carboxyl generation esterification in vinylformic acid obtain the esterification bacterial cellulose solution containing double bond, taken out by esterification bacteria cellulose containing double bond after using methyl alcohol and rinsed with deionized water totally successively, lyophilize, obtains the dry esterification bacteria cellulose containing double bond;
(3) the esterification bacteria cellulose containing double bond getting 0.5g drying is placed in three-necked flask, adds 10mL deionized water and soaks 1 hour.Add the allyl group trimethyl ammonium chloride of 3 times that molar weight is glucose monomer molar weight in esterified cellulose containing double bond, after logical 15 minutes nitrogen, add initiator (NH4)
2s
2o
8and NaHSO
3, (NH4)
2s
2o
8and NaHSO
3mol ratio be 1:1, (NH4)
2s
2o
8and NaHSO
3quality be 0.2% of esterification bacteria cellulose containing double bond and allyl group trimethyl ammonium chloride quality sum, continue to pass into nitrogen, obtain reaction solution, reaction solution is warming up to 60 DEG C of reaction 2h.Allyl group trimethyl ammonium chloride and the esterification bacteria cellulose generation addition reaction containing double bond obtain the esterification bacteria cellulose that allyl group trimethyl ammonium chloride monomer is modified, esterification bacteria cellulose polymerization reaction take place under the effect of initiator that allyl group trimethyl ammonium chloride monomer is modified, obtain esterification bacteria cellulose and the Antimicrobial bacterial cellulose of the modification of polyallyl trimethyl ammonium chloride, clean after reaction product methanol wash three times with deionized water, lyophilize is preserved.
Embodiment 3:
(1) 1mL acetobacter xylinum is inoculated in 100mL nutrient solution, 30 DEG C of static cultivation are until obtaining thickness is the bacteria cellulose film of 5mm, fungin film being placed in concentration is that the sodium hydroxide solution of 0.1mol/L vibrates smudge cells 30 minutes at 80 DEG C, repeatedly after three times, deionized water is used to wash away broken cell and sodium hydroxide, until described fungin film surface p H is neutral, after steam sterilizing, lyophilize is for subsequent use; The composition of described nutrient solution is: 0.4g/mL glucose sugar, 0.06g/mL peptone, 0.03g/mL yeast powder, 0.02g/mL Sodium phosphate dibasic, 0.015g/mL magnesium sulfate, 0.01g/mL ammonium sulfate, 0.015mL/mL maize treacle extracting solution;
(2) the bacteria cellulose film 0.4g that step (1) obtains is got, be placed in 20ml vinylformic acid and soak 1h, add the hydroquinone of polymerization retarder that quality is bacteria cellulose film and vinylformic acid total mass 0.2%, obtain mixing solutions, in mixing solutions, add the tosic acid solution that 25mL toluene and 0.1mL mass concentration are 60%, stir gently and make mixing.Drip 0.8mL acrylic anhydride again, the quality of acrylic anhydride is 2 times of bacteria cellulose quality, stir while adding, room temperature leaves standstill 2h, hydroxyl in bacteria cellulose and the carboxyl generation esterification in vinylformic acid obtain the esterification bacterial cellulose solution containing double bond, taken out by esterification bacteria cellulose containing double bond after using methyl alcohol and rinsed with deionized water totally successively, lyophilize, obtains the dry esterification bacteria cellulose containing double bond;
(3) the esterification bacteria cellulose containing double bond getting 0.5g drying is placed in three-necked flask, adds 10mL deionized water and soaks 1 hour.Add the allyl group trimethyl ammonium chloride of 2 times that molar weight is glucose monomer molar weight in esterified cellulose containing double bond, after logical 15 minutes nitrogen, add initiator (NH4)
2s
2o
8and NaHSO
3, (NH4)
2s
2o
8and NaHSO
3mol ratio be 1:1, (NH4)
2s
2o
8and NaHSO
3quality be 0.1% of esterification bacteria cellulose containing double bond and allyl group trimethyl ammonium chloride quality sum, continue to pass into nitrogen, obtain reaction solution, reaction solution is warming up to 60 DEG C of reaction 2h.Allyl group trimethyl ammonium chloride and the esterification bacteria cellulose generation addition reaction containing double bond obtain the esterification bacteria cellulose that allyl group trimethyl ammonium chloride monomer is modified, esterification bacteria cellulose polymerization reaction take place under the effect of initiator that allyl group trimethyl ammonium chloride monomer is modified, obtain esterification bacteria cellulose and the Antimicrobial bacterial cellulose of the modification of polyallyl trimethyl ammonium chloride, clean after reaction product methanol wash three times with deionized water, lyophilize is preserved.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for Antimicrobial bacterial cellulose, is characterized in that, comprises the following steps:
(1) bacteria cellulose is provided;
(2) described bacteria cellulose is placed in unsaturated carboxylic acid to soak, then stopper is added, obtain mixing solutions, catalyzer is added in described mixing solutions, at room temperature carry out esterification 1 ~ 4h, obtain the esterification bacterial cellulose solution containing unsaturated link(age), after purifying, obtain the dry esterification bacteria cellulose containing unsaturated link(age);
(3) after the esterification bacteria cellulose deionized water containing unsaturated link(age) of described drying being soaked, in an inert atmosphere, add unsaturated quaternary ammonium salt monomer and initiator obtains reaction solution, described reaction solution carries out addition reaction and polyreaction 2h ~ 4h at 50 DEG C ~ 60 DEG C, obtain esterification bacteria cellulose and the Antimicrobial bacterial cellulose of QAS polymer modification, one end of described QAS polymer is connected with esterification bacteria cellulose by covalent linkage.
2. the preparation method of Antimicrobial bacterial cellulose as claimed in claim 1, is characterized in that, in step (1), the polymerization degree of bacteria cellulose is 10000 ~ 16000.
3. the preparation method of Antimicrobial bacterial cellulose as claimed in claim 1, it is characterized in that, stopper described in step (2) is Resorcinol, 2-Tert. Butyl Hydroquinone or 2,5-di-tert-butyl hydroquinone, the quality of described stopper is 0.1% ~ 0.2% of described bacteria cellulose and unsaturated carboxylic acid total mass.
4. the preparation method of Antimicrobial bacterial cellulose as claimed in claim 1, is characterized in that, unsaturated carboxylic acid described in step (2) is acrylic or methacrylic acid.
5. the preparation method of Antimicrobial bacterial cellulose as claimed in claim 1, it is characterized in that, described in step (2), catalyzer is perchloric acid or tosic acid, and the interpolation volume of described catalyzer is 0.1% ~ 0.2% of described mixed liquor volume.
6. the preparation method of Antimicrobial bacterial cellulose as claimed in claim 1, it is characterized in that, step also adds esterifying agent in (2) in esterification reaction process, and described esterifying agent is methacrylic anhydride, and the quality of described esterifying agent is 1 ~ 4 times of described bacteria cellulose quality.
7. the preparation method of Antimicrobial bacterial cellulose as claimed in claim 1, it is characterized in that, unsaturated quaternary ammonium salt monomer described in step (3) is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac or allyl group trimethyl ammonium chloride.
8. the preparation method of Antimicrobial bacterial cellulose as claimed in claim 1, it is characterized in that, the molar weight of unsaturated quaternary ammonium salt monomer described in step (3) is described 1 ~ 3 times of containing glucose monomer molar weight in the esterification bacteria cellulose of unsaturated link(age).
9. the preparation method of Antimicrobial bacterial cellulose as claimed in claim 1, it is characterized in that, initiator described in step (3) is the mixture of Potassium Persulphate and sodium bisulfite or the mixture of ammonium persulphate and sodium bisulfite.
10. an Antimicrobial bacterial cellulose, is characterized in that, described Antimicrobial bacterial cellulose is for obtaining according to the preparation method described in any one of claim 1 ~ 9.
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| JP2016023275A (en) * | 2014-07-23 | 2016-02-08 | セイコーエプソン株式会社 | Cellulosic material and cellulosic member |
| CN104826168B (en) * | 2015-04-13 | 2017-01-25 | 王辉 | Preparation method of material for abdominal wall defect intraperitoneal repair, and obtained material thereof |
| CN104892842A (en) * | 2015-05-15 | 2015-09-09 | 深圳先进技术研究院 | Antimicrobial bacterial cellulose, preparation method and application thereof |
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| JP6716841B2 (en) * | 2016-02-10 | 2020-07-01 | 株式会社アルチザンラボ | Hemostatic material |
| CN105860121A (en) * | 2016-04-06 | 2016-08-17 | 东华大学 | Preparation method of antimicrobial bacterial cellulose material |
| CN107254778A (en) * | 2017-07-25 | 2017-10-17 | 安徽亚源印染有限公司 | A kind of flax artificial cotton elastic fabric of antibacterial resistant |
| US20210085820A1 (en) * | 2017-08-01 | 2021-03-25 | Artisan Lab Co., Ltd. | Hemostatic material and wound dressing containing same |
| CN107840895A (en) * | 2017-11-29 | 2018-03-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Cation-modified method of pure plant extraction nano-cellulose and products thereof and application |
| CN109134767B (en) * | 2018-08-08 | 2021-05-28 | 中国科学院长春应用化学研究所 | Antibacterial hydrogel material and preparation method thereof |
| CN110511405B (en) * | 2019-10-11 | 2021-07-02 | 四川大学 | Antibacterial keratin-based hydrogel and preparation method thereof |
| CN114317653A (en) * | 2021-12-23 | 2022-04-12 | 海南盛美诺生物技术有限公司 | Method for extracting elastin by using bovine heart vessels |
| CN117626468B (en) * | 2024-01-26 | 2024-04-16 | 扬州富威尔复合材料有限公司 | Method for preparing regenerated fibers by separating and recycling waste polyester cotton |
| CN117946287B (en) * | 2024-03-27 | 2024-06-11 | 江苏惠利生物科技有限公司 | Preparation method and application of antibacterial amino acid-based cellulose polymer |
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| CN101274107A (en) * | 2008-05-21 | 2008-10-01 | 天津大学 | Bacteria cellulose and Hydroxyethyl methacrylate transparency compound material and preparation thereof |
| CN102178973A (en) * | 2010-01-15 | 2011-09-14 | 东华大学 | Bacterial cellulose based antibacterial dry film for treating acute injury and preparation method and application thereof |
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| CN102178973A (en) * | 2010-01-15 | 2011-09-14 | 东华大学 | Bacterial cellulose based antibacterial dry film for treating acute injury and preparation method and application thereof |
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