CN106674612A - Preparation method of antibacterial and hydrophobic biodegradable membrane - Google Patents
Preparation method of antibacterial and hydrophobic biodegradable membrane Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
- C08L1/28—Alkyl ethers
- C08L1/286—Alkyl ethers substituted with acid radicals, e.g. carboxymethyl cellulose [CMC]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
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- B65D65/466—Bio- or photodegradable packaging materials
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- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/04—Alginic acid; Derivatives thereof
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- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
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Abstract
The invention provides a preparation method of an antibacterial and hydrophobic biodegradable membrane. The preparation method comprises the following steps: 1) weighing a certain amount of modified chitosan powder and sodium carboxymethyl cellulose powder; adding a certain amount of de-ionized water into the powder respectively; swelling at constant temperature and stirring uniformly; placing for 24h at a room temperature, so as to finally obtain a modified chitosan solution and a sodium carboxymethyl cellulose solution; 2) mixing the two prepared solutions at a certain mass ratio and mixing under a certain condition to prepared a uniform water solution; pouring the mixed solution into a mold and putting the mold into an air blowing drying box; drying to obtain a modified chitosan/sodium carboxymethyl cellulose composite membrane. Compared with the prior art, the preparation method of the antibacterial and hydrophobic biodegradable membrane, provided by the invention, is simple to operate and has no corrosion to equipment; the composite membrane prepared by the invention has good biodegradability, sterilization and bacterium-inhibition performances and hydrophobic property; meanwhile, the tensile strength and the elongation at break are remarkably increased.
Description
Technical field
The present invention relates to composite membrane technology field, and in particular to a kind of preparation side of antibacterial hydrophobic biological degradable membrane
Method.
Background technology
For a long time, the thin film with oil as raw material, in packaging for foodstuff and other industrial circles leading position, example are accounted for
Such as biological medicine, wastewater treatment and cosmetics.Although they have a good mechanical performance and toughness, preparation process it is simple and
Inexpensively, but this polymer of synthesis is difficult to degrade, cause severe contamination to environment, thus more researcheres utilized can
It is prepared by degradable polymer.
Shitosan is a kind of natural degradable biomaterial, is had in fields such as agricultural, food, cosmetics, printing and dyeing, medical science
Extensively application.Shitosan is the derivant of chitin deacetylase base, and chitin is the master of Crustacean and insect cell wall
Want composition, yield to be only second to cellulose, be second largest Renewable resource on the earth.Shitosan can prepare solution, gel, sponge
Shape and thin film etc., but there is and have the disadvantage that solution and gel easily flow, are difficult being partially formed higher concentration, thin film and
Its mechanical performance of sponge and toughness are poor.Existing document report, is crosslinked with glutaraldehyde, Biformyl, difunctional anhydride etc.
Agent with it is chitosan crosslinked, can improve the mechanical strength of film, but aldehyde crosslinking agent has chemistry with the Schiff that shitosan is generated
Unstability；Difunctional anhydride need to be carried out at high temperature with chitosan crosslinked, easily make degradation of chitosan；And, shitosan point
Substantial amounts of hydroxyl and amino define the intramolecular and intermolecular hydrogen bonding of complexity in sub so as to water insoluble and alkaline solution, only
Weakly acidic solution can be dissolved in, its application in more wide pH value scope is which has limited.
Sodium carboxymethyl cellulose with good film property, biological degradability and biocompatibility because being widely used in food
In product coating preservation.But single sodium carboxymethyl cellulose film quality is crisp, poor water resistance, fungistatic effect be not obvious, limit its
The application of fresh-keeping aspect.Although sodium alginate and sodium carboxymethyl cellulose to be blended the report for making food package film,
It is obtained sodium alginate and sodium carboxymethyl cellulose blend film, mechanical property is poor, can only do the inner packing of some food.
The content of the invention
For the defect of above-mentioned prior art, one of purpose of the present invention is to provide a kind of antibacterial hydrophobic biology can
The preparation method of degradative membrane, comprises the following steps：
1) a certain amount of modification of chitosan powder and sodium carboxymethyl cellulose powder are weighed, a certain amount of going is added thereto to respectively
Ionized water, prior to constant temperature under 60 DEG C of water-baths swelling certain hour is stood, and is then stirred until homogeneous, and is stirred after terminating at room temperature
24 h are placed, the modification of chitosan solution that mass fraction is 0.5 ~ 5% and the carboxylic first that mass fraction is 0.5 ~ 5% is finally respectively obtained
Base sodium cellulosate solution；
2) the modification of chitosan solution of above-mentioned configuration and carboxymethylcellulose sodium solution are pressed into certain Solute mass proportioning certain
Under the conditions of mix, homogeneous modification of chitosan/sodium carboxymethyl cellulose solution is obtained, then pour mixed solution into film tool,
Air dry oven drying is put into, after solvent evaporating completely, that is, dry modification of chitosan/sodium carboxymethyl cellulose is obtained and is combined
Film.
Preferably, in step 2) in, the Solute mass of described modification of chitosan solution and carboxymethylcellulose sodium solution
Than for 0.5:10~3:10, be more highly preferred to for 1:10~2:10, such as 1:10~1.2:10、1:10~1.5:10、1:10~1.8:
10、1.2:10~1.5:10、1.2:10~1.8:10、1.2:10~2:10、1.5:10~1.8:10、1.5:10~2:10 or 1.8:10~
2:10。
Preferably, in step 2) in, temperature when described modification of chitosan solution mixes with carboxymethylcellulose sodium solution
Spend for 15 ~ 60 DEG C.
Preferably, in step 2) in, temperature when described modification of chitosan solution mixes with carboxymethylcellulose sodium solution
Spend for 20 ~ 50 DEG C, be more highly preferred to for 25 ~ 40 DEG C, such as 25 ~ 30 DEG C, 25 ~ 35 DEG C, 30 ~ 35 DEG C, 30 ~ 40 DEG C, 35 ~
40 ℃、25 ℃、26 ℃、27 ℃、28 ℃、29 ℃、30 ℃、31 ℃、32 ℃、33 ℃、34 ℃、35 ℃、36
DEG C, 37 DEG C, 38 DEG C, 39 DEG C or 40 DEG C.
Preferably, in step 2) in, the drying condition be 35 ~ 60 DEG C of baking temperature, drying time 24 ~ 120 h.
Preferably, in step 2) in, the drying condition is 35 ~ 55 DEG C of baking temperature, be more highly preferred to for 35 ~ 45
DEG C, such as 35 ~ 40 DEG C, 40 ~ 45 DEG C, 35 DEG C, 36 DEG C, 37 DEG C, 38 DEG C, 39 DEG C, 40 DEG C, 41 DEG C, 42 DEG C, 43
DEG C, 44 DEG C or 45 DEG C；Drying time 36 ~ 90 h, be more highly preferred to for 48 ~ 90 h, such as 48 ~ 60 h, 48 ~ 72 h, 48 ~ 90
H, 60 ~ 72 h, 60 ~ 90 h, 72 ~ 90 h, 48 h, 50 h, 55 h, 60 h, 65 h, 70 h, 72 h, 75 h, 80 h, 85 h or
90 h。
Preferably, in step 1) in, the substitution value of the modification of chitosan powder is 0.56 ~ 0.93, and what is be more highly preferred to is
0.70 ~ 0.93, such as 0.70 ~ 0.75,0.70 ~ 0.80,0.70 ~ 0.85,0.70 ~ 0.90,0.75 ~ 0.80,0.75 ~ 0.85,
0.75~0.90、0.75~0.93、0.80~0.85、0.80~0.90、0.80~0.93、0.85~0.90、0.85~0.93、0.70、
0.71、0.72、0.73、0.74、0.75、0.76、0.77、0.78、0.79、0.80、0.81、0.82、0.83、0.84、0.85、
0.86th, 0.87,0.88,0.89,0.90,0.91,0.92 or 0.93.
Preferably, in step 1) in, the modification of chitosan powder is obtained by alkyl quaternary ammonium saltss with chitosan reaction, or by
Alkyl quaternary ammonium saltss replace shitosan carboxylic acid reactant salt to be obtained with oxygen.
Preferably, it is O- alkyl carboxyl shitosans that the oxygen replaces shitosan carboxylate, wherein the alkyl is methyl, second
Base or propyl group.
Preferably, the alkyl quaternary ammonium saltss are 2,3- epoxypropyltrimethylchloride chlorides, 2, the 3- glycidyl dimethyl last of the ten Heavenly stems
Ammonium chloride, 2,3- glycidyl dimethyl dodecyl ammonium chlorides, 2,3- glycidyl dimethyl tetradecyl ammonium chlorides, 2,
3- glycidyl dimethyl hexadecyl ammonium chlorides, 2,3- glycidyl dimethyl stearyl ammonium chloride or the chloro- 2- hydroxypropyls of 3-
One kind in base trimethyl ammonium chloride.
Preferably, the modification of chitosan powder is obtained by a kind of following method：
A) add chitosan in ionic liquid, in 60 ~ 100 DEG C, under conditions of 0.01 ~ 0.06 MPa negative pressure, constant temperature stirring
1 ~ 6 h, makes shitosan be dissolved in ionic liquid, mass percent of the shitosan in shitosan/ionic liquid solution
Concentration is 0.5 ~ 2.5%；
B) alkyl quaternary ammonium saltss are added in the shitosan/ionic liquid solution, in 60 ~ 120 DEG C, 0.01 ~ 0.06 MPa
Under conditions of negative pressure, 0.5 ~ 10 h, the n are reacted（Alkyl quaternary ammonium saltss）:n(shitosan)For 1:1~6:1, wherein n(shitosan)Refer to shitosan
Number of repeat unit；
C) reaction terminate after, 2 the step of room temperature is cooled to) reactant liquor in add acetone-ethanol mixed solution, centrifugation separate out
Precipitate, the precipitate acetone-ethanol mixed solution repeated washing 2 ~ 3 times, and it is dried 8 ~ 24 under the conditions of 50 ~ 80 DEG C
H, obtains nitrogen and replaces chitosan quaternary ammonium salt；
D) ionic liquid of acetone and ethanol will be mixed with, separated is separately recovered acetone, ethanol and ionic liquid；
Wherein described ionic liquid is 1- butyl -3- methylimidazolium chlorides, 1- butyl -3- methy limidazoliums, 1- pi-allyl -3-
One kind in methylimidazolium chloride or 1- ethyl-3-methylimidazole acetate.
Preferably, in step b), described n（Alkyl quaternary ammonium saltss）:n(shitosan)For 2:1~4:1, reaction temperature is 80 ~ 100 DEG C,
Response time is 6 ~ 8 h, the n(shitosan)Refer to the number of repeat unit of shitosan.
Preferably, in step a), described solution temperature is 80 DEG C, the h of dissolution time 4.
Preferably, the deacetylation of the shitosan is 75 ~ 95%, and mean molecule quantity is 200 ~ 2000 mPa.s.
Preferably, in the acetone-ethanol mixed solution of the step c), acetone is 1 with the volume ratio of ethanol:1~1:4.
Preferably, in step c), described baking temperature is 60 DEG C, and drying time is 12 h.
Preferably, the step d) concrete operations are：The ionic liquid solution for being mixed with ethanol and acetone is placed in into electrical heating
Put, air-distillation condensation separation acetone and ethanol；Ionic liquid is reclaimed, after being extracted with ethyl acetate, three revolving removings are more
Remaining ethyl acetate, is dried 10 ~ 24 h under 0.06 ~ 0.1 MPa negative pressure in 60 ~ 100 DEG C of vacuum drying oven.
One kind passes through modification of chitosan powder obtained in another kind of method, in above-mentioned modification of chitosan powder preparation method
In, replace shitosan carboxylate to replace the shitosan with oxygen.
It is a further object of the present invention to provide a kind of preparation method of antibacterial hydrophobic biological degradable membrane, uses sodium alginate
Replace the sodium carboxymethyl cellulose in above-mentioned preparation method.
Heretofore described sodium carboxymethyl cellulose be USP levels, the mPa.s of viscosity 400 ~ 1400；The sodium alginate is purchased from
Qingdao Mingyue Marine Alga Group Corp., Ltd., viscosity is divided into 60 mPa.s, 370 mPa.s, tri- kinds of 540 mPa.s；Remaining is used former
The unreceipted production firm person such as material, reagent, be can pass through city available from conventional products.
Another object of the present invention is to provide the antibacterial hydrophobic biodegradable that a kind of utilization said method is prepared
Film.
A further object of the present invention is to provide above-mentioned antibacterial hydrophobic biological degradable membrane in packaging for foodstuff, is particularly existed
Application in the packaging of wet provision.
The Mechanics Performance Testing of antibacterial hydrophobic biological degradable membrane prepared by the present invention：Using the electricity of Jinan Tian Chen companies
The tensile elongation and elongation at break of antibacterial hydrophobic biological degradable membrane prepared by the sub- tensilon test present invention.Tool
Gymnastics conduct：HTCC films, the CMC films for selecting the sample and comparative sample of uniform, clean, flawless present invention preparation pure.Sample
The mm of the thickness of product about 0.07, by sample cutting rectangularity, long 100 mm, wide 16 mm.Folder is away from 50 mm, stretching speed during test
The mm/min of rate 10.
The anti-microbial property test of antibacterial hydrophobic biological degradable membrane prepared by the present invention：Escherichia coli and golden yellow Fructus Vitis viniferae
Coccus is common gram negative bacteria and gram positive bacteria, therefore the antibacterial for selecting this 2 kinds of bacterium to test present invention preparation is dredged
The anti-microbial property of aqueous biological degradable membrane.Concrete operations are the disk that quantitative filter paper piece is cut into 8mm sizes, are put into sterilizing
Sterilize 20 min at 121 DEG C in pot.By the filter paper for sterilizing on clean bench, different Solute mass proportionings are picked
Composite membrane solution example and comparative sample solution, and be compacted with slide, it is then careful to be attached on plating medium surface, finally
Flat board is placed in biochemical cultivation case and cultivates 24 h, the anti-microbial property of test sample in 36 DEG C.
Compared with prior art, what the preparation method of the antibacterial hydrophobic biological degradable membrane that the present invention is provided was utilized is to change
Property shitosan and sodium carboxymethyl cellulose or sodium alginate react, and unconventional shitosan, due to connecing in the shitosan that is modified
Enter quaternary ammonium salt group, give shitosan good water solublity, this causes the method in operation without the need for by adding hydrochloric acid, vinegar
The methods such as acid make shitosan protonation, dissolving, easy operation, eliminate the sour corrosion to consersion unit and are lost；And
And the composite membrane for preparing of method provided by the present invention has good biodegradability, bactericidal performance and hydrophobic
Property, form a sharp contrast with not possessing bactericidal, hydrophobic Carboxymethyl-chitosan Membranes；What simultaneously prepared by the present invention answers
The tensile strength and elongation at break of conjunction film is compared with single carboxymethyl cellulose film, sodium alginate film or Chitosan film
Dramatically increase.
Description of the drawings
Fig. 1 is that 2,3- epoxypropyltrimethylchloride chlorides modification of chitosan/carboxymethyl prepared by the embodiment of the present invention 2 ~ 4 is fine
The plain sodium film of dimension（HTCC/CMC films）And pure HTCC films, the light transmission comparison diagram of pure CMC films, wherein a) represent pure CMC films
Light transmission comparison diagram；B) the light transmission comparison diagram of HTCC and CMC mass ratioes as 0.05 film is represented；C) HTCC and CMC matter are represented
Light transmission comparison diagram of the amount than the film for 0.10；D) the light transmission comparison diagram of HTCC and CMC mass ratioes as 0.15 film is represented；e)
Represent the light transmission comparison diagram of pure HTCC films.
Fig. 2 is HTCC/CMC film and pure HTCC films, the scanning of the tangent plane of pure CMC films prepared by the embodiment of the present invention 2 ~ 4
Electron micrograph, wherein a) represents the electromicroscopic photograph of pure CMC films；B) HTCC and CMC mass ratioes are represented as 0.05 film
Electromicroscopic photograph；C) electromicroscopic photograph of HTCC and CMC mass ratioes as 0.10 film is represented；D) HTCC and CMC mass ratioes are represented as
The electromicroscopic photograph of 0.15 film；E) electromicroscopic photograph of pure HTCC films is represented.
Fig. 3 is the infrared spectrum of HTCC/CMC films prepared by the embodiment of the present invention 2 ~ 4, wherein i) represents the red of pure CMC films
Outer spectrogram；Ii the infrared spectrum of HTCC and CMC mass ratioes as 0.05 film) is represented；Iii HTCC and CMC mass ratioes) are represented as
The infrared spectrum of 0.10 film；Iv the infrared spectrum of HTCC and CMC mass ratioes as 0.15 film) is represented；V) pure HTCC films are represented
Infrared spectrum.
Fig. 4 is that HTCC/CMC films prepared by the embodiment of the present invention 2 ~ 4 and pure HTCC films, the stress-strain of pure CMC films are bent
Line, wherein i) represents the load-deformation curve of pure CMC films；Ii HTCC and CMC mass ratioes) are represented as 0.05 film stress-should
Varied curve；Iii the load-deformation curve of HTCC and CMC mass ratioes as 0.10 film) is represented；Iv HTCC and CMC mass) are represented
Than the load-deformation curve of the film for 0.15；V) load-deformation curve of pure HTCC films is represented.
Fig. 5 is HTCC/CMC film and pure HTCC films, the contact angle figure of pure CMC films prepared by the embodiment of the present invention 2 ~ 4,
Wherein a) represent the contact angle figure of pure HTCC films；B) the contact angle figure of HTCC and CMC mass ratioes as 0.05 film is represented；C) represent
HTCC and CMC mass ratioes are the contact angle figure of 0.10 film；D) contact angle of HTCC and CMC mass ratioes as 0.15 film is represented
Figure；E) the contact angle figure of pure CMC films is represented.
Fig. 6 is HTCC/CMC films prepared by the embodiment of the present invention 2 ~ 6 and pure HTCC films to staphylococcus aureuses（Black
Square dot）And escherichia coli（Red circular point）Antibacterial activity result figure.
Specific embodiment
With reference to specific embodiment, describe the present invention.Unreceipted actual conditions person in embodiment, according to
Normal condition or the condition of manufacturer's suggestion are carried out.
Embodiment 1
The modification of chitosan that example below is used is prepared according to the following steps：
20 g ionic liquid 1- butyl -3- methy limidazoliums and 0.5 g viscositys is added to be 300 in the single-necked flask of 100 mL
The shitosan of mPa.s, the shitosan is that the pretreatment of Jing hydrobromic acids and lyophilization are obtained, will be close after single-necked flask evacuation
Envelope, under 0.06 MPa condition of negative pressure, stirs, and is placed in constant temperature in 100 DEG C of oil bath and stirs 4 h.By polarizing microscope
After observation shitosan is completely dissolved, n (alkyl quaternary ammonium saltss) is added in single-necked flask:N (shitosan) is 6:1 epoxide equivalent
For 0.85 2,3- epoxypropyltrimethylchloride chlorides（GTMAS）, 0.06 MPa negative pressure is kept again and is placed in single-necked flask
The h of isothermal reaction 8 in 80 DEG C of oil bath, to ensure that shitosan and GTMAS fully react.
Reaction is completed, and the acetone-ethanol mixed liquor of 60 mL is added in single-necked flask, acetone and second in the mixed liquor
The volume ratio of alcohol is 1:4, it is sufficiently stirred for, stands, salt out chitosan quaternary ammonium, in the same way repeated washing product 2 times.
Final product is placed in 60 DEG C of vacuum drying oven and is dried 24 h, obtains final product epoxypropyltrimethylchloride chloride modification of chitosan.
Cleaning mixture is reclaimed, distillation, is divided to fraction acetone and 78-79 DEG C of fraction that two sections of temperature collect respectively 55-56 DEG C
Ethanol, residual liquid is ionic liquid.After residual liquid ionic liquid is extracted with ethyl acetate, three times revolving removes unnecessary acetic acid second
Ester, in 60 DEG C of vacuum drying oven, is dried 24 h under 0.06 MPa negative pressure.
The substitution value of obtained modification of chitosan is 0.93 in the present embodiment.
Embodiment 2
HTCC powder and CMC powder that a certain amount of substitution value is 0.56 are weighed, a certain amount of deionization is added thereto to respectively
Water, prior to the swelling certain hour of constant temperature under 60 DEG C of water-baths, is then stirred until homogeneous, and stirring terminates to place 24 h under room temperature,
Finally respectively obtain the HTCC solution that mass fraction is 2% and the CMC solution that mass fraction is 2%；
It is 0.5 by Solute mass ratio:10 ratio weighs the HTCC solution and CMC solution of above-mentioned configuration, and under 25 DEG C of water-baths
Mixing, is obtained homogeneous HTCC/CMC aqueous solutions, then pours mixed solution into film tool, makes the thickness of mixed solution as equal as possible
It is even, 45 DEG C of h of drying 24 of air dry oven are put into, after solvent evaporating completely, that is, obtain dry HTCC/CMC composite membranes.
Composite membrane manufactured in the present embodiment has good light transmission, and the tangent plane of film and Fourier's change infrared spectrum show
There is the good compatibility and significant interaction between HTCC molecules and CMC molecules in composite membrane.The anti-tensile of composite membrane
Intensity is 26.45 MPa, and compared with 11.95 MPa of pure CMC films, its tensile strength increased 121%；Elongation at break is by pure
The 1.55% of CMC films increases to 2.82%.Under room temperature, water is 119 in the contact angle of HTCC/CMC composite membraneso, and water is in pure CMC films
Contact angle be only 72.5o.According to document report, single CMC films do not have bactericidal, and pure HTCC films are to golden yellow Fructus Vitis viniferae
Coccus and colibacillary suppression loop diameter are respectively 1.23 cm and 1.07 cm, and HTCC/CMC composite membranes are to golden yellow Fructus Vitis viniferae
The antibacterial circle diameter of coccus is 1.13 cm, is 1.00 cm to colibacillary antibacterial circle diameter, with pure HTCC films to above-mentioned two
The rejection ability for planting bacterium is suitable.
Embodiment 3
The Solute mass of the HTCC solution for having configured and CMC solution, with case study on implementation 2, is simply compared 0.5 by implementation condition with step:
10 replace with 1:10.
Composite membrane manufactured in the present embodiment has good light transmission, and the tangent plane of film and Fourier's change infrared spectrum show
There is the good compatibility and significant interaction between HTCC molecules and CMC molecules in composite membrane；The anti-tensile of composite membrane
Intensity is 28.56 MPa, and than the tensile strength of pure CMC films 139% is increased；Elongation at break is 2.86%；Water is in composite membrane
Contact angle is 90o, more than the contact angle in pure CMC films, show good hydrophobicity；HTCC/CMC composite membranes are to golden yellow Portugal
The antibacterial circle diameter of grape coccus is 1.28 cm, is 1.03 cm to colibacillary antibacterial circle diameter.
Embodiment 4
The Solute mass of the HTCC solution for having configured and CMC solution, with case study on implementation 2, is simply compared 0.5 by implementation condition with step:
10 replace with 1.5:10.
Composite membrane manufactured in the present embodiment has good light transmission, and the tangent plane of film and Fourier's change infrared spectrum show
There is the good compatibility and significant interaction between HTCC molecules and CMC molecules in composite membrane；The anti-tensile of composite membrane
Intensity is 21.82 MPa, and than the tensile strength of pure CMC films 82.6% is increased；Elongation at break is 2.27%；Water is in composite membrane
Contact angle is 117o, more than the contact angle in pure CMC films, show good hydrophobicity；HTCC/CMC composite membranes are to golden yellow
Staphylococcic antibacterial circle diameter is 1.43 cm, is 1.07 cm to colibacillary antibacterial circle diameter.
Embodiment 5
The Solute mass of the HTCC solution for having configured and CMC solution, with case study on implementation 2, is simply compared 0.5 by implementation condition with step:
10 replace with 2:10.
Composite membrane manufactured in the present embodiment has good light transmission, and the tangent plane of film and Fourier's change infrared spectrum show
There is the good compatibility and significant interaction between HTCC molecules and CMC molecules in composite membrane；The anti-tensile of composite membrane
Intensity is 27.82 MPa, and than the tensile strength of pure CMC films 132.8% is increased；Elongation at break is 2.57%；Water is in composite membrane
Contact angle be 114o, more than the contact angle in pure CMC films, show good hydrophobicity；HTCC/CMC composite membranes are to golden yellow
The staphylococcic antibacterial circle diameter of color is 1.53 cm, is 1.10 cm to colibacillary antibacterial circle diameter.
Embodiment 6
The Solute mass of the HTCC solution for having configured and CMC solution, with case study on implementation 2, is simply compared 0.5 by implementation condition with step:
10 replace with 2.5:10.
Composite membrane manufactured in the present embodiment has good light transmission, and the tangent plane of film and Fourier's change infrared spectrum show
There is the good compatibility and significant interaction between HTCC molecules and CMC molecules in composite membrane；The anti-tensile of composite membrane
Intensity is 28.95 MPa, and than the tensile strength of pure CMC films 142.2% is increased；Elongation at break is 3.02%；Water is in composite membrane
Contact angle be 120o, more than the contact angle in pure CMC films, show good hydrophobicity；HTCC/CMC composite membranes are to golden yellow
The staphylococcic antibacterial circle diameter of color is 1.67 cm, is 1.17 cm to colibacillary antibacterial circle diameter.
Embodiment 7
Weigh the 2- hydroxypropyl-N- dimethyl stearyl ammonium chloride Chitosan powders that a certain amount of substitution value is 0.56
And sodium alginate（Sodium alginate, SA）Powder, is added thereto to respectively a certain amount of deionized water, prior to 60 DEG C
The swelling certain hour of constant temperature, is then stirred until homogeneous under water-bath, and stirring terminates to place 24 h under room temperature, finally respectively obtains
Mass fraction is 0.5 2- hydroxypropyl-N- dimethyl stearyl ammonium chloride chitosan solutions and mass fraction is 0.5
Sodium alginate soln；
It is 0.5 by Solute mass ratio:10 ratio weighs the 2- hydroxypropyl-N- dimethyl stearyl ammonium chloride of above-mentioned configuration
Modification of chitosan solution and sodium alginate soln, and mix under 25 DEG C of water-baths, homogeneous 2- hydroxypropyl-N- diformazans are obtained
Base octadecyl ammonium chloride modification of chitosan/SA aqueous solutions, then pours mixed solution into film tool, and the thickness for making mixed solution is use up
May be uniform, 55 DEG C of h of drying 90 of air dry oven are put into, after solvent evaporating completely, that is, obtain dry 2- hydroxypropyl-N-
Dimethyl stearyl ammonium chloride shitosan/SA composite membranes.
Composite membrane manufactured in the present embodiment has good light transmission, and the tangent plane of film and Fourier's change infrared spectrum show
Deposit between 2- hydroxypropyl-N- dimethyl stearyl ammonium chloride chitosan molecule and sodium alginate molecule in composite membrane
In the good compatibility and significant interaction；The tensile strength of composite membrane is 17.32 MPa, than the tensile strength of pure SA films
Increased 102.3%；Elongation at break is 5.81%.Water is 93 in the contact angle of composite membraneo, more than the contact angle in pure SA films,
Show good hydrophobicity.2- hydroxypropyl-N- dimethyl stearyls ammonium chloride shitosans/SA composite membranes are to golden yellow
The staphylococcic antibacterial circle diameter of color is 1.17 cm, is 1.15 centimetres to colibacillary antibacterial circle diameter.
Embodiment 8
Weigh the 2- hydroxypropyl-N- dimethyl dodecyl ammonium chlorides modification of chitosan powder that a certain amount of substitution value is 0.65
With sodium carboxymethyl cellulose powder, a certain amount of deionized water is added thereto to respectively, prior to constant temperature swelling one under 60 DEG C of water-baths
Fix time, be then stirred until homogeneous, stirring terminates to place 24 h under room temperature, and it is 1.5 finally to respectively obtain mass fraction
2- hydroxypropyl-N- dimethyl dodecyl ammonium chlorides modification of chitosan solution and the carboxymethyl cellulose that mass fraction is 1.5
Sodium solution；
It is 1.5 by Solute mass ratio:10 ratio weighs the 2- hydroxypropyl-N- dimethyl dodecyl ammonium chlorides of above-mentioned configuration
Modification of chitosan solution and carboxymethylcellulose sodium solution, and mix under 15 DEG C of water-baths, prepared homogeneous 2- hydroxypropyls-
N- dimethyl dodecyl ammonium chlorides modification of chitosan/CMC aqueous solutions, then pours mixed solution into film tool, makes mixed solution
Thickness it is as uniform as possible, be put into 37 DEG C of h of drying 36 of air dry oven, after solvent evaporating completely, that is, obtain dry 2- hydroxyls
Base propyl group-N- dimethyl dodecyl ammonium chlorides modification of chitosan/CMC composite membranes.
Composite membrane manufactured in the present embodiment has good light transmission, and the tangent plane of film and Fourier's change infrared spectrum show
2- hydroxypropyl-N- dimethyl dodecyl ammonium chlorides modification of chitosan molecules and sodium carboxymethyl cellulose molecule in composite membrane
Between there is the good compatibility and significant interaction；The tensile strength of composite membrane is 31.53MPa, more anti-than pure CMC films
Zhang Qiangdu increased 163.8%；Elongation at break is 10.81%.Water is 133 in the contact angle of composite membraneo, more than in pure CMC films
Contact angle, show good hydrophobicity.2- hydroxypropyl-N- dimethyl dodecyl ammonium chlorides modification of chitosan/CMC is multiple
It is 2.07 cm that film is closed to the antibacterial circle diameter of staphylococcus aureuses, is 1.63 cm to colibacillary antibacterial circle diameter.
Embodiment 9
Weigh 2- hydroxypropyl-N- dimethyl decyl ammonium chloride Chitosan powders and sea that a certain amount of substitution value is 0.80
Alginate powder, is added thereto to respectively a certain amount of deionized water, prior to the swelling certain hour of constant temperature under 60 DEG C of water-baths, so
After be stirred until homogeneous, stirring terminate 24 h are placed under room temperature, finally respectively obtain the 2- hydroxyls third that mass fraction is 2.5
Base-N- dimethyl decyl ammonium chloride chitosan solutions and the sodium alginate soln that mass fraction is 2.5；
It is 2 by Solute mass ratio:10 ratio weighs the 2- hydroxypropyl-N- dimethyl decyl ammonium chloride shells of above-mentioned configuration
Polysaccharide solution and sodium alginate soln, and mix under 50 DEG C of water-baths, homogeneous 2- hydroxypropyl-N- dimethyl decyls are obtained
Ammonium chloride shitosan/SA aqueous solutions, then pours mixed solution into film tool, makes the thickness of mixed solution as uniform as possible,
48 DEG C of h of drying 100 of air dry oven are put into, after solvent evaporating completely, that is, the dry 2- hydroxypropyl-N- dimethyl last of the ten Heavenly stems is obtained
Ammonium chloride modification of chitosan/SA composite membranes.
Composite membrane manufactured in the present embodiment has good light transmission, and the tangent plane of film and Fourier's change infrared spectrum show
Exist between 2- hydroxypropyl-N- dimethyl decyl ammonium chloride chitosan molecule and sodium alginate molecule in composite membrane good
The good compatibility and significant interaction；The tensile strength of composite membrane is 19.20MPa, is increased than the tensile strength of pure SA films
124.3%；Elongation at break is 9.81%.Water is 123 in the contact angle of composite membraneo, more than the contact angle in pure SA films, performance
Go out good hydrophobicity.2- hydroxypropyl-N- dimethyl stearyls ammonium chloride shitosans/SA composite membranes are to golden yellow Portugal
The antibacterial circle diameter of grape coccus is 2.17 cm, is 1.65 cm to colibacillary antibacterial circle diameter.
Embodiment 10
Weigh 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride modification of chitosan powder and carboxymethyl that a certain amount of substitution value is 0.70
Sodium cellulosate powder, is added thereto to respectively a certain amount of deionized water, prior to the swelling certain hour of constant temperature under 60 DEG C of water-baths,
Then it is stirred until homogeneous, stirring terminates to place 24 h under room temperature, finally respectively obtains the chloro- 2- of 3- that mass fraction is 3.5
Hydroxypropyl-trimethyl ammonium chloride modification of chitosan solution and mass fraction are 3.5 carboxymethylcellulose sodium solution；
It is 1.2 by Solute mass ratio:10 ratio weighs the modified shell of 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides of above-mentioned configuration and gathers
Sugar juice and carboxymethylcellulose sodium solution, and mix under 60 DEG C of water-baths, the homogeneous chloro- 2- Hydroxyproyl Trimethyls of 3- are obtained
Ammonium chloride shitosan/CMC aqueous solutions, then pours mixed solution into film tool, makes the thickness of mixed solution as uniform as possible,
38 DEG C of h of drying 48 of air dry oven are put into, after solvent evaporating completely, that is, the chloro- 2- Hydroxyproyl Trimethyls chlorine of dry 3- is obtained
Change ammonium modification of chitosan/CMC composite membranes.
Composite membrane manufactured in the present embodiment has good light transmission, and the tangent plane of film and Fourier's change infrared spectrum show
Exist between 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride modification of chitosan molecules and CMC molecules in composite membrane good compatible
Property and significant interaction；The tensile strength of composite membrane is 28.05 MPa, be increased than the tensile strength of pure CMC films
134.7%；Elongation at break is 3.82%.Water is 118 in the contact angle of composite membraneo, more than the contact angle in pure CMC films, performance
Go out good hydrophobicity.3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides modification of chitosan/CMC composite membranes are to staphylococcus aureuses
Antibacterial circle diameter be 1.79 cm, to colibacillary antibacterial circle diameter be 1.28 cm.
Embodiment 11
Weigh the 2- hydroxypropyl-N- dimethyl tetradecyl ammonium chloride modification of chitosan powder that a certain amount of substitution value is 0.93
And sodium alginate powder, a certain amount of deionized water is added thereto to respectively, a timing swelling prior to constant temperature under 60 DEG C of water-baths
Between, then it is stirred until homogeneous, stirring terminates to place 24 h under room temperature, finally respectively obtains the 2- hydroxyls that mass fraction is 4.5
Base propyl group-N- dimethyl tetradecyls ammonium chloride modification of chitosan solution and the sodium alginate soln that mass fraction is 4.5；
It is 1 by Solute mass ratio:10 ratio weighs the 2- hydroxypropyl-N- dimethyl tetradecyl ammonium chlorides of above-mentioned configuration and changes
Property chitosan solution and sodium alginate soln, and mix under 35 DEG C of water-baths, homogeneous 2- hydroxypropyl-N- dimethyl is obtained
Tetradecyl ammonium chloride modification of chitosan/SA aqueous solutions, then pours mixed solution into film tool, and the thickness for making mixed solution to the greatest extent may be used
Can be uniform, 52 DEG C of h of drying 80 of air dry oven are put into, after solvent evaporating completely, that is, obtain dry 2- hydroxypropyls-N- two
Methyltetradecylphosphine ammonium chloride modification of chitosan/SA composite membranes.
Composite membrane manufactured in the present embodiment has good light transmission, and the tangent plane of film and Fourier's change infrared spectrum show
Deposit between 2- hydroxypropyls-N- dimethyl tetradecyls ammonium chloride modification of chitosan molecule and sodium alginate molecule in composite membrane
In the good compatibility and significant interaction；The tensile strength of composite membrane is 23.20 MPa, than the tensile strength of pure SA films
Increased 171.0%；Elongation at break is 9.91%.Water is 130 in the contact angle of composite membraneo, more than the contact angle in pure SA films,
Show good hydrophobicity.2- hydroxypropyl-N- dimethyl tetradecyls ammonium chloride modification of chitosan/SA composite membranes are to golden yellow
The staphylococcic antibacterial circle diameter of color is 2.37 cm, is 1.75 cm to colibacillary antibacterial circle diameter.
Embodiment 12
Weigh the 2- hydroxypropyl-N- dimethyl hexadecyl ammonium chloride modification of chitosan powder that a certain amount of substitution value is 0.60
With sodium carboxymethyl cellulose powder, a certain amount of deionized water is added thereto to respectively, prior to constant temperature swelling one under 60 DEG C of water-baths
Fix time, be then stirred until homogeneous, stirring terminates to place 24 h under room temperature, and it is 5.0 finally to respectively obtain mass fraction
2- hydroxypropyls-N- dimethyl hexadecyls ammonium chloride modification of chitosan solution and the carboxymethyl cellulose that mass fraction is 5.0
Sodium solution；
It is 3 by Solute mass ratio:10 ratio weighs the 2- hydroxypropyl-N- dimethyl hexadecyl ammonium chlorides of above-mentioned configuration and changes
Property chitosan solution and carboxymethylcellulose sodium solution, and mix under 20 DEG C of water-baths, homogeneous 2- hydroxypropyl-N- are obtained
Dimethyl hexadecyl ammonium chloride modification of chitosan/CMC aqueous solutions, then pours mixed solution into film tool, makes mixed solution
Thickness is as uniform as possible, is put into 42 DEG C of h of drying 24 of air dry oven, after solvent evaporating completely, that is, obtains dry 2- hydroxyls
Propyl group-N- dimethyl hexadecyls ammonium chloride modification of chitosan/CMC composite membranes.
Composite membrane manufactured in the present embodiment has good light transmission, and the tangent plane of film and Fourier's change infrared spectrum show
2- hydroxypropyls-N- dimethyl hexadecyls ammonium chloride modification of chitosan molecule and sodium carboxymethyl cellulose molecule in composite membrane
Between there is the good compatibility and significant interaction；The tensile strength of composite membrane is 29.53 MPa, than pure CMC films
Tensile strength increased 147.1%；Elongation at break is 10.16%.Water is 143 in the contact angle of composite membraneo, more than in pure CMC
The contact angle of film, shows good hydrophobicity.2- hydroxypropyl-N- dimethyl hexadecyls ammonium chloride modification of chitosan/CMC
Composite membrane is 2.57 cm to the antibacterial circle diameter of staphylococcus aureuses, is 1.85 cm to colibacillary antibacterial circle diameter.
Embodiment 13
Weigh 2,3- epoxypropyltrimethylchloride chloride modification of chitosan powder and alginic acid that a certain amount of substitution value is 0.75
Sodium powder end, is added thereto to respectively a certain amount of deionized water, prior to the swelling certain hour of constant temperature under 60 DEG C of water-baths, then stirs
Mix to uniform, stir and terminate to place 24 h under room temperature, finally respectively obtain 2, the 3- glycidyl three that mass fraction is 2.5
Ammonio methacrylate modification of chitosan solution and mass fraction are 2.5 sodium alginate soln；
It is 0.8 by Solute mass ratio:10 ratio weighs the modified shell of 2,3- epoxypropyltrimethylchloride chlorides of above-mentioned configuration and gathers
Sugar juice and sodium alginate soln, and mix under 18 DEG C of water-baths, homogeneous 2,3- epoxypropyltrimethylchloride chlorides are obtained and change
Property shitosan/SA aqueous solutions, then by mixed solution pour into film tool, make the thickness of mixed solution as uniform as possible, be put into air blast
40 DEG C of h of drying 120 of drying baker, after solvent evaporating completely, that is, obtain dry 2,3- epoxypropyltrimethylchloride chlorides and are modified
Shitosan/SA composite membranes.
Composite membrane manufactured in the present embodiment has good light transmission, and the tangent plane of film and Fourier's change infrared spectrum show
Exist between 2,3- epoxypropyltrimethylchloride chloride modification of chitosan molecules and sodium alginate molecule in composite membrane good
The compatibility and significant interaction；The tensile strength of composite membrane is 15.16 MPa, be increased than the tensile strength of pure SA films
77.10%；Elongation at break is 2.23%.Water is 86 in the contact angle of composite membraneo, more than the contact angle in pure SA films, show
Good hydrophobicity.2,3- epoxypropyltrimethylchloride chlorides modification of chitosan/suppression of the SA composite membranes to staphylococcus aureuses
Bacterium loop diameter is 1.08 cm, is 0.97 cm to colibacillary antibacterial circle diameter.
Embodiment 14
Weigh the O- methyl carboxyl -3- chloro-2-hydroxypropyl-trimethyl ammonium chloride modification of chitosan that a certain amount of substitution value is 0.91
Powder and sodium carboxymethyl cellulose powder, are added thereto to respectively a certain amount of deionized water, molten prior to constant temperature under 60 DEG C of water-baths
Swollen certain hour, is then stirred until homogeneous, and stirring terminates to place 24 h under room temperature, and finally respectively obtaining mass fraction is
3.0 O- methyl carboxyl -3- chloro-2-hydroxypropyl-trimethyl ammonium chloride modification of chitosan solution and the carboxylic first that mass fraction is 3.0
Base sodium cellulosate solution；
It is 1.8 by Solute mass ratio:10 ratio weighs the chloro- 2- Hydroxyproyl Trimethyls chlorine of O- methyl carboxyl -3- of above-mentioned configuration
Change ammonium modification of chitosan solution and carboxymethylcellulose sodium solution, and mix under 30 DEG C of water-baths, homogeneous O- methyl carboxylics are obtained
Base -3- chloro-2-hydroxypropyl-trimethyl ammonium chloride modification of chitosan/CMC aqueous solutions, then pours mixed solution into film tool, makes to mix
The thickness for closing solution is as uniform as possible, is put into 45 DEG C of h of drying 30 of air dry oven, after solvent evaporating completely, that is, is done
O- methyl carboxyl -3- chloro-2-hydroxypropyl-trimethyl ammonium chloride modification of chitosan/CMC composite membranes.
Composite membrane manufactured in the present embodiment has good light transmission, and the tangent plane of film and Fourier's change infrared spectrum show
Exist between O- methyl carboxyl -3- chloro-2-hydroxypropyl-trimethyl ammonium chloride modification of chitosan molecules and CMC molecules in composite membrane
The good compatibility and significant interaction；The tensile strength of composite membrane is 20.63 MPa, than the tensile strength of pure CMC films
Increased 72.64%；Elongation at break is 6.82%.Water is 90 in the contact angle of composite membraneo, more than the contact angle in pure CMC films,
Show good hydrophobicity.O- methyl carboxyl -3- chloro-2-hydroxypropyl-trimethyl ammonium chloride modification of chitosan/CMC composite membranes pair
The antibacterial circle diameter of staphylococcus aureuses is 2.67 cm, is 2.57 cm to colibacillary antibacterial circle diameter.
Embodiment 15
Weigh the O- methyl carboxyl -2,3- epoxypropyltrimethylchloride chloride modification of chitosan powder that a certain amount of substitution value is 0.88
End and sodium alginate powder, are added thereto to respectively a certain amount of deionized water, a timing swelling prior to constant temperature under 60 DEG C of water-baths
Between, then it is stirred until homogeneous, stirring terminates to place 24 h under room temperature, finally respectively obtains the O- first that mass fraction is 4.0
Base carboxyl -2,3- epoxypropyltrimethylchloride chloride modification of chitosan solution and the sodium alginate soln that mass fraction is 4.0；
It is 2.5 by Solute mass ratio:10 ratio weighs the O- methyl carboxyl -2,3- epoxypropyl trimethylammonium chlorides of above-mentioned configuration
Ammonium modification of chitosan solution and sodium alginate soln, and mix under 55 DEG C of water-baths, homogeneous O- methyl carboxyl -2,3- is obtained
Epoxypropyltrimethylchloride chloride modification of chitosan/SA aqueous solutions, then pours mixed solution into film tool, makes the thickness of mixed solution
Degree is as uniform as possible, is put into 58 DEG C of h of drying 40 of air dry oven, after solvent evaporating completely, that is, obtains dry O- methyl carboxylics
Base -2,3- epoxypropyltrimethylchloride chloride modification of chitosan/SA composite membranes.
Composite membrane manufactured in the present embodiment has good light transmission, and the tangent plane of film and Fourier's change infrared spectrum show
O- methyl carboxyl -3- chloro-2-hydroxypropyl-trimethyl ammonium chloride modification of chitosan molecules and sodium alginate molecule in composite membrane it
Between there is the good compatibility and significant interaction；The tensile strength of composite membrane is 18.33 MPa, than the anti-tensile of pure SA films
Intensity increased 114.1%；Elongation at break is 15.36%.Water is 97 in the contact angle of composite membraneo, more than connecing in pure SA films
Feeler, shows good hydrophobicity.O- methyl carboxyl -3- chloro-2-hydroxypropyl-trimethyl ammonium chloride modification of chitosan/SA is combined
Film is 2.07 cm to the antibacterial circle diameter of staphylococcus aureuses, is 1.83 cm to colibacillary antibacterial circle diameter.
Embodiment 16
Weigh the O- alkylcarboxy -2,3- glycidyl dimethyl tetradecyls ammonium chloride that a certain amount of substitution value is 0.58 to be modified
Chitosan powder and sodium alginate powder, are added thereto to respectively a certain amount of deionized water, molten prior to constant temperature under 60 DEG C of water-baths
Swollen certain hour, is then stirred until homogeneous, and stirring terminates to place 24 h under room temperature, and finally respectively obtaining mass fraction is
2.0 O- alkylcarboxy -2,3- glycidyl dimethyl tetradecyl ammonium chloride modification of chitosan solution and mass fraction are 2.0
Sodium alginate soln；
It is 2.8 by Solute mass ratio:10 ratio weighs the O- alkylcarboxy -2,3- glycidyl dimethyl 14 of above-mentioned configuration
Alkyl ammomium chloride modification of chitosan solution and sodium alginate soln, and mix under 25 DEG C of water-baths, homogeneous O- ethyl carboxylics are obtained
Base -2,3- glycidyl dimethyl tetradecyl ammonium chloride modification of chitosan/SA aqueous solutions, then pour mixed solution into film
Tool, makes the thickness of mixed solution as uniform as possible, is put into 60 DEG C of h of drying 70 of air dry oven, after solvent evaporating completely, i.e.,
Obtain dry O- alkylcarboxy -2,3- glycidyl dimethyl tetradecyl ammonium chloride modification of chitosan/SA composite membranes.
Composite membrane manufactured in the present embodiment has good light transmission, and the tangent plane of film and Fourier's change infrared spectrum show
O- alkylcarboxy -2,3- glycidyl dimethyl tetradecyl ammonium chloride modification of chitosan molecules and sodium alginate in composite membrane
There is the good compatibility and significant interaction between molecule；The tensile strength of composite membrane is 17.33 MPa, than pure SA films
Tensile strength increased 102.4%；Elongation at break is 13.30%.Water is 128 in the contact angle of composite membraneo, more than in pure SA
The contact angle of film, shows good hydrophobicity.O- alkylcarboxy -2,3- glycidyl dimethyl tetradecyls ammonium chloride is modified
Shitosan/SA composite membranes are 2.37 cm to the antibacterial circle diameter of staphylococcus aureuses, are to colibacillary antibacterial circle diameter
2.15 cm。
Embodiment 17
Weigh the O- propyl group carboxyl -2,3- glycidyl dimethyl stearyl ammonium chlorides that a certain amount of substitution value is 0.90
Chitosan powder and sodium alginate powder, are added thereto to respectively a certain amount of deionized water, molten prior to constant temperature under 60 DEG C of water-baths
Swollen certain hour, is then stirred until homogeneous, and stirring terminates to place 24 h under room temperature, and finally respectively obtaining mass fraction is
1.0 O- propyl group carboxyl -2,3- glycidyl dimethyl stearyl ammonium chloride chitosan solutions and mass fraction are 1.0
Sodium alginate soln；
It is 2.2 by Solute mass ratio:10 ratio weighs the O- propyl group carboxyl -2,3- glycidyl dimethyl 18 of above-mentioned configuration
Alkyl ammomium chloride modification of chitosan solution and sodium alginate soln, and mix under 45 DEG C of water-baths, homogeneous O- propyl group carboxylics are obtained
Base -2,3- glycidyl dimethyl stearyl ammonium chloride shitosans/SA aqueous solutions, then pour mixed solution into film
Tool, makes the thickness of mixed solution as uniform as possible, is put into 35 DEG C of h of drying 110 of air dry oven, after solvent evaporating completely,
Obtain dry O- propyl group carboxyl -2,3- glycidyl dimethyl stearyl ammonium chloride shitosans/SA composite membranes.
Composite membrane manufactured in the present embodiment has good light transmission, and the tangent plane of film and Fourier's change infrared spectrum show
O- propyl group carboxyl -2,3- glycidyl dimethyl stearyl ammonium chloride chitosan molecule and sodium alginate in composite membrane
There is the good compatibility and significant interaction between molecule；The tensile strength of composite membrane is 17.90 MPa, than pure SA films
Tensile strength increased 109.1%；Elongation at break is 14.63%.Water is 115 in the contact angle of composite membraneo, more than in pure SA
The contact angle of film, shows good hydrophobicity.O- propyl group carboxyl -2,3- glycidyl dimethyl stearyl ammonium chlorides
Shitosan/SA composite membranes are 2.07 cm to the antibacterial circle diameter of staphylococcus aureuses, are to colibacillary antibacterial circle diameter
2.05 cm。
Embodiment 18
Weigh the O- alkylcarboxy -2,3- glycidyl dimethyl decyl ammonium chlorides shell that a certain amount of substitution value is 0.85 to gather
Icing Sugar end and sodium carboxymethyl cellulose powder, are added thereto to respectively a certain amount of deionized water, prior to constant temperature under 60 DEG C of water-baths
Swelling certain hour, is then stirred until homogeneous, and stirring terminates to place 24 h under room temperature, and finally respectively obtaining mass fraction is
4.5 O- alkylcarboxies -2,3- glycidyl dimethyl decyl ammonium chloride chitosan solution and the carboxylic that mass fraction is 4.5
Methylcellulose sodium solution；
It is 2.7 by Solute mass ratio:10 ratio weighs the O- alkylcarboxy -2,3- glycidyl dimethyl decyls of above-mentioned configuration
Ammonium chloride chitosan solution and carboxymethylcellulose sodium solution, and mix under 58 DEG C of water-baths, homogeneous O- ethyls are obtained
Then carboxyl -2,3- glycidyl dimethyl decyl ammonium chloride shitosans/CMC aqueous solutions pour mixed solution into film tool,
Make the thickness of mixed solution as uniform as possible, be put into 50 DEG C of h of drying 60 of air dry oven, after solvent evaporating completely, obtain final product
To dry O- alkylcarboxy -2,3- glycidyl dimethyl decyl ammonium chloride shitosans/CMC composite membranes.
Composite membrane manufactured in the present embodiment has good light transmission, and the tangent plane of film and Fourier's change infrared spectrum show
O- alkylcarboxies -2,3- glycidyl dimethyl decyl ammonium chloride chitosan molecule and carboxymethyl cellulose in composite membrane
There is the good compatibility and significant interaction between sodium molecule；The tensile strength of composite membrane is 27.90 MPa, than pure
The tensile strength of CMC films increased 133.5%；Elongation at break is 15.06%.Water is 120 in the contact angle of composite membraneo, it is more than
In the contact angle of pure CMC films, good hydrophobicity is shown.O- alkylcarboxy -2,3- glycidyl dimethyl decyl ammonium chloride
Modification of chitosan/CMC composite membranes are 2.10 cm to the antibacterial circle diameter of staphylococcus aureuses, to colibacillary inhibition zone
A diameter of 2.15 cm.
The above, is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention, any to be familiar with this specialty
Technical staff is changed or is modified as the Equivalent embodiments of equivalent variations possibly also with the technology contents of the disclosure above.For example,
Specifically use 2,3- glycidyl dimethyl stearyl ammonium chloride, 2,3- glycidyl dimethyl decyl ammonium chloride, 2,3- rings
Oxygen propyl-dimethyl lauryl ammonium chloride, 2,3- glycidyl dimethyl tetradecyl ammonium chlorides, 2,3- glycidyl diformazans
A kind of replacement 2,3- epoxypropyl trimethylammonium chlorides in base cetyl chloride ammonium or 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides
Ammonium, with the one kind in the carboxy-modified shitosan of O- methyl, O- alkylcarboxies modification of chitosan or the carboxy-modified shitosan of O- propyl group
Shitosan is replaced, with 1- pi-allyl -3- methylimidazolium chlorides, 1- butyl -3- methylimidazolium chlorides or 1- ethyl-3-methylimidazoles
A kind of replacement 1- butyl -3- methy limidazoliums in acetate, still according to the above-mentioned method for preparing modification of chitosan, in difference
Under the conditions of prepare the corresponding modified quaternary ammonium salt of chitosan of different degree of substitution.But it is every without departing from technical solution of the present invention
Hold, according to any simple modification, equivalent variations and remodeling that the technical spirit of the present invention is made to above example, still fall within this
The protection domain of inventive technique scheme.
Claims (10)
1. a kind of preparation method of antibacterial hydrophobic biological degradable membrane, it is characterised in that comprise the following steps：
1) a certain amount of modification of chitosan powder and sodium carboxymethyl cellulose powder are weighed, a certain amount of going is added thereto to respectively
Ionized water, prior to constant temperature under 60 DEG C of water-baths swelling certain hour is stood, and is then stirred until homogeneous, and is stirred after terminating at room temperature
24 h are placed, the modification of chitosan solution that mass fraction is 0.5 ~ 5% and the carboxylic first that mass fraction is 0.5 ~ 5% is finally respectively obtained
Base sodium cellulosate solution；
2) the modification of chitosan solution of above-mentioned configuration and carboxymethylcellulose sodium solution are pressed into certain Solute mass proportioning certain
Under the conditions of mix, homogeneous modification of chitosan/sodium carboxymethyl cellulose solution is obtained, then pour mixed solution into film tool,
Air dry oven drying is put into, after solvent evaporating completely, that is, dry modification of chitosan/sodium carboxymethyl cellulose is obtained and is combined
Film.
2. a kind of preparation method of antibacterial hydrophobic biological degradable membrane as claimed in claim 1, it is characterised in that in step
2) in, described modification of chitosan solution and the Solute mass ratio of carboxymethylcellulose sodium solution is 0.5:10~3:10.
3. a kind of preparation method of antibacterial hydrophobic biological degradable membrane as claimed in claim 2, it is characterised in that in step
2) in, temperature when described modification of chitosan solution mixes with carboxymethylcellulose sodium solution is 15 ~ 60 DEG C.
4. a kind of preparation method of antibacterial hydrophobic biological degradable membrane as claimed in claim 3, it is characterised in that in step
2) in, the drying condition be 35 ~ 60 DEG C of baking temperature, drying time 24 ~ 120 h.
5. a kind of preparation method of antibacterial hydrophobic biological degradable membrane as claimed in claim 4, it is characterised in that in step
1) in, the substitution value of the modification of chitosan powder is 0.56 ~ 0.93.
6. a kind of preparation method of the antibacterial hydrophobic biological degradable membrane as described in arbitrary in claim 1-5, its feature exists
In in step 1) in, the modification of chitosan powder is obtained by alkyl quaternary ammonium saltss with chitosan reaction, or by alkyl quaternary ammonium saltss with
Oxygen replaces shitosan carboxylic acid reactant salt to be obtained.
7. a kind of preparation method of antibacterial hydrophobic biological degradable membrane as claimed in claim 6, it is characterised in that the alkane
Based quaternary ammonium salt is 2,3- epoxypropyltrimethylchloride chlorides, 2,3- glycidyl dimethyl decyl ammonium chloride, 2,3- glycidyl
Dimethyl dodecyl ammonium chlorides, 2,3- glycidyl dimethyl tetradecyl ammonium chlorides, 2,3- glycidyl dimethyl 16
In alkyl ammomium chloride, 2,3- glycidyl dimethyl stearyl ammonium chloride or 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides one
Kind.
8. a kind of preparation method of antibacterial hydrophobic biological degradable membrane as claimed in claim 7, it is characterised in that described to change
Property Chitosan powder is obtained by the following method：
A) add chitosan in ionic liquid, in 60 ~ 100 DEG C, under conditions of 0.01 ~ 0.06 MPa negative pressure, constant temperature stirring
1 ~ 6 h, makes shitosan be dissolved in ionic liquid, mass percent of the shitosan in shitosan/ionic liquid solution
Concentration is 0.5 ~ 2.5%；
B) alkyl quaternary ammonium saltss are added in the shitosan/ionic liquid solution, in 60 ~ 120 DEG C, 0.01 ~ 0.06 MPa
Under conditions of negative pressure, 0.5 ~ 10 h, the n are reacted（Alkyl quaternary ammonium saltss）:n(shitosan)For 1:1~6:1, wherein the n(shitosan)Refer to shell to gather
The number of repeat unit of sugar；
C) after reaction terminates, 2 the step of room temperature is cooled to）Reactant liquor in add acetone-ethanol mixed solution, centrifugation separate out
Precipitate, the precipitate acetone-ethanol mixed solution repeated washing 2 ~ 3 times, and it is dried 8 ~ 24 under the conditions of 50 ~ 80 DEG C
H, obtains nitrogen and replaces chitosan quaternary ammonium salt；
D) ionic liquid of acetone and ethanol will be mixed with, separated is separately recovered acetone, ethanol and ionic liquid；
Wherein described ionic liquid is 1- butyl -3- methylimidazolium chlorides, 1- butyl -3- methy limidazoliums, 1- pi-allyl -3-
One kind in methylimidazolium chloride or 1- ethyl-3-methylimidazole acetate.
9. a kind of preparation method of antibacterial hydrophobic biological degradable membrane as claimed in claim 8, it is characterised in that taken with oxygen
The shitosan is replaced for shitosan carboxylate.
10. a kind of preparation method of the antibacterial hydrophobic biological degradable membrane as described in arbitrary in claim 1-9, its feature exists
In with the sodium alginate replacement sodium carboxymethyl cellulose.
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