CN108440794A - A kind of preparation method of chitosan nano fiber element nanometer titanium dioxide composite membrane - Google Patents
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Abstract
The invention discloses a kind of preparation methods of chitosan nano fiber element nanometer titanium dioxide composite membrane.The present invention is with nano-cellulose, nano-titanium dioxide is functional filler, chitosan/nano-cellulose/nano-titanium dioxide tri compound film is made using the method for solution blending, systematically its preparation process condition and material formula are optimized, pass through nano-cellulose, the blending and modifying of nano-titanium dioxide is expected to realize nano-cellulose and nano-titanium dioxide polymolecularity and then the high intensity of performance nano-cellulose and the good anti-microbial property of nano-titanium dioxide in composite membrane, improve the mechanical property and antibiotic property of composite film material, basic data and technical support are provided for degradable anti-bacterial packaging film of the research and development based on chitosan.
Description
Technical field
The invention belongs to antibacterial degradable technical field of composite materials, and in particular to a kind of chitosan nano fiber element nanometer
The preparation method of titanium dioxide composite film.
Background technology
Chitin is second largest natural organic-compound of yield present on the earth, and chitosan is the de- second of chitin
Acyl product is that a kind of having many advantages, such as biodegradability, biocompatibility and nontoxic cationic polysaccharide.Band in chitosan
The group of positive charge can form tridimensional network with the matter interaction with negative electrical charge.Chitosan has good
Film forming, antibiotic property, hygroscopicity, moisture retention, anticoagulation and the effect and the antitumor action that promote wound healing.Chitosan has
These advantageous properties having become in food fresh keeping and the very promising packaging material of packaging field.In recent years, people
A series of researchs about food fresh keeping membrane have been carried out by matrix of chitosan, have found the property of chitosan film by chitosan
Source, molecular weight, deacetylation, the influence for preparing the factors such as film method and plasticizer.It, can using chitosan as lapping
It is exchanged with gas in air with playing the role of barrier package object to a certain extent, moisture and nutriment is prevented to be lost in.
However, the structure and characteristic of chitosan itself determine chitosan film material when food packaging and fresh-keeping aspect are applied there is also
The problems such as mechanical performance is not high, thermal stability is poor, in addition the antibacterial ability of chitosan is also by the hydrophily of film and use environment
The influence of condition, antibacterial efficacy time are short.Therefore, further carry out the study on the modification of chitosan for pushing it in food packaging
It has been extremely urgent vital task with the application in fresh-keeping.
Blending and modifying is the common method of polymer modification, be added in single polymers component other polymer modifications at
Point, it can learn from other's strong points to offset one's weaknesses, eliminate the weakness on each single polymers component property, obtain the high molecular material of excellent combination property.
In order to improve the performance of chitosan, can by with other organic or inorganic material blending and modifyings, and then improve its mechanical performance,
Production cost is reduced simultaneously and obtains new function.
Cellulose origin is extensive, is natural polymers most abundant in nature.Cellulose origin in cellulose,
It is a kind of diameter between 1~100nm, rigid rod fiber element of the length between tens to hundreds of nanometers.Due to Nanowire
The excellent properties such as high intensity, high-crystallinity, high Young's modulus, the high-purity of element are tieed up, high intensity is shown on materials synthesis
With Young's modulus etc., nano-cellulose has the characteristics such as lightweight, biocompatibility, the degradable and regeneration of biomaterial in addition,
It is set to show huge application prospect in high-performance composite materials.The intensity of nano-cellulose be the intensity that produces so far most
The 25% of high carbon nanotube intensity makes it have the potential quality of substituted metal and ceramics.
Nano-titanium dioxide is the environmentally friendly inorganic material of a kind of novel photocatalysis to grow up nearly ten years, can be used
In air purification, sewage disposal etc., the inorganic antibacterial scavenging material of a new generation is become, has increasingly been valued by people.
Nano-titanium dioxide is nontoxic, tasteless and nonirritant, thermal stability with it is heat-resist and with prompt effect good, strong antibacterial,
The advantages that has a broad antifungal spectrum, durable antibacterial effect.Nano-titanium dioxide can not only generate under the excitation of ultraviolet light to be made with sterilization
Hydroxyl radical free radical, under visible light and faint light source, nano-titanium dioxide modified also shows good kill
Bacterium acts on.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of chitosan nano fiber element nanometer titanium dioxide composite membrane.
Technical scheme is as follows：
A kind of preparation method of chitosan nano fiber element nanometer titanium dioxide composite membrane, includes the following steps：
(1) nano-cellulose suspension is prepared, it is specific as follows：
A, in ice-water bath, microcrystalline cellulose is mixed with sulfuric acid solution while stirring, obtains suspension, wherein crystallite is fine
The mass ratio of dimension element and sulfuric acid solution is 1: 8~9, a concentration of 50~70wt% of sulfuric acid solution；
B, above-mentioned suspension is continued into 90~120min of stirring in 40~50 DEG C, obtains acidolysis material；
C, it is gone after centrifuging above-mentioned acidolysis material, removes supernatant, must precipitate；
D, it is deposited in 30~90min of supersound process in ice-water bath by above-mentioned, then adjusts pH into sodium hydroxide solution
Property is to get the nano-cellulose suspension；
(2) chitosan nano fiber element nanometer titanium dioxide composite membrane is prepared, it is specific as follows：
A, in the acetic acid solution that chitosan is dissolved completely in a concentration of 1.5~2.5wt% in 48~52 DEG C, the first liquid is obtained
Material；
B, the nano-cellulose suspension obtained by step (1) is stirred into 25~40min in 48~52 DEG C, obtains the second liquid material；
C, the second liquid material is added in the first liquid material, after 48~52 DEG C are stirred 8~12min, sequentially adds modification and receive
Rice titanium dioxide and glycerine, stirring 50~70min postcoolings are subsequently ultrasonicated for 25~40min, then vacuum is removed to room temperature
Bubble, obtains composite membrane film liquid, above-mentioned microcrystalline cellulose, chitosan, modified nano-titanium dioxide and glycerine ratio be 2.2~
2.3g: 0.4~1.2g: 0.04~0.036g: 0.004~0.16mL；
D, above-mentioned composite membrane film liquid is cast and in 48~50 DEG C of drying, is subsequently placed in after being impregnated in NaOH solution with distillation
Water is rinsed well to get the chitosan nano fiber element nanometer titanium dioxide composite membrane.
In a preferred embodiment of the invention, in a of the step (1), microcrystalline cellulose and sulfuric acid solution
Mass ratio is 1: 8.75, a concentration of 63.5wt% of sulfuric acid solution.
In a preferred embodiment of the invention, the b of the step (1) is：By above-mentioned suspension in 45 DEG C of continuation
110min is stirred, acidolysis material is obtained.
In a preferred embodiment of the invention, in the c of the step (1), the number of centrifugation is 5 times, every time
20min, rotating speed 4000rpm.
In a preferred embodiment of the invention, in the d of the step (1), the supersonic frequency of the supersound process
For 50KHz, time 30min.
In a preferred embodiment of the invention, a of the step (2) is：Chitosan is completely dissolved in 50 DEG C
In the acetic acid solution of a concentration of 2wt%, the first liquid material is obtained.
In a preferred embodiment of the invention, the b of the step (2) is：By the nanofiber obtained by step (1)
Plain suspension stirs 30min in 50 DEG C, obtains the second liquid material.
In a preferred embodiment of the invention, the c of the step (2) is：Second liquid material is added to the first liquid
In material, after 50 DEG C are stirred 10min, modified nano-titanium dioxide and glycerine are sequentially added, stirring 60min postcoolings to room temperature,
It is subsequently ultrasonicated for 30min, then froth in vacuum, obtains composite membrane film liquid.
It is further preferred that the supersonic frequency of the supersound process in the c of the step (2) is 50KHz, time 30min.
In a preferred embodiment of the invention, the drying temperature in the d of the step (2) is 50 DEG C.
The beneficial effects of the invention are as follows：
Shell is made using nano-cellulose, nano-titanium dioxide as functional filler, using the method for solution blending in the present invention
Glycan/nano-cellulose/nano-titanium dioxide tri compound film systematically (is added its preparation process condition and material formula
Plasticizer glycerine appropriate, crosslinking agent glutaraldehyde) it optimizes, pass through nano-cellulose, the blending and modifying of nano-titanium dioxide
It is expected to realize the high-strength of nano-cellulose and nano-titanium dioxide polymolecularity and then performance nano-cellulose in composite membrane
The good anti-microbial property of degree and nano-titanium dioxide, improves the mechanical property and antibiotic property of composite film material, is based on for research and development
The degradable anti-bacterial packaging film of chitosan provides basic data and technical support.
Specific implementation mode
Technical scheme of the present invention is further detailed and is described below by way of specific implementation mode.
Embodiment 1
(1) nano-cellulose suspension is prepared, it is specific as follows：
A, in ice-water bath, while stirring by the sulfuric acid solution of 4.57g microcrystalline celluloses and a concentration of 63.5wt% of 40mL
Mixing, obtains suspension；
B, above-mentioned suspension is continued to stir 110min in 45 DEG C, obtains acidolysis material；
C, it is gone after centrifuging above-mentioned acidolysis material, removes supernatant, must precipitate, the number of centrifugation is 5 times, each 20min, rotating speed
For 4000rpm (or gained supernatant is muddy after centrifugation, can stop centrifuging)；
D, above-mentioned be deposited in ice-water bath being ultrasonically treated, the supersonic frequency of supersound process is 50KHz, time 30min,
Then pH is adjusted to neutrality to get the nano-cellulose suspension with sodium hydroxide solution；
(2) chitosan nano fiber element nanometer titanium dioxide composite membrane is prepared, it is specific as follows：
A, in the acetic acid solution that 1.2g chitosans are dissolved completely in a concentration of 2wt% of 40mL in 50 DEG C, the first liquid material is obtained；
B, the nano-cellulose suspension obtained by step (1) is stirred into 30min in 50 DEG C, obtains the second liquid material；
C, the second liquid materials of 20mL are added in the first liquid material, after 50 DEG C are stirred 10min, sequentially add 0.036g modifications
Nano-titanium dioxide and 0.16mL glycerine, stirring 60min postcoolings to room temperature are subsequently ultrasonicated for 30min, and supersound process surpasses
Acoustic frequency is 50KHz, time 30min, and then froth in vacuum, obtains composite membrane film liquid；
D, then above-mentioned composite membrane film liquid curtain coating is taken off on a diameter of 9.3cm glass culture dish and in 50 DEG C of drying
Film is placed in 0.1mol/L NaOH solutions after immersion 30min~1h with distilled water flushing totally to get chitosan nano fibre
It is needed by different experiments that sample is made, and is put down under room temperature and 75% ambient humidity by the plain nanometer titanium dioxide composite membrane of dimension
It is used after weighing apparatus 48h.
Embodiment 2
(1) nano-cellulose suspension is prepared, it is specific as follows：
A, in ice-water bath, while stirring by the sulfuric acid solution of 4.57g microcrystalline celluloses and a concentration of 63.5wt% of 40mL
Mixing, obtains suspension；
B, above-mentioned suspension is continued to stir 110min in 45 DEG C, obtains acidolysis material；
C, it is gone after centrifuging above-mentioned acidolysis material, removes supernatant, must precipitate, the number of centrifugation is 5 times, each 20min, rotating speed
For 4000rpm (or gained supernatant is muddy after centrifugation, can stop centrifuging)；
D, above-mentioned be deposited in ice-water bath being ultrasonically treated, the supersonic frequency of supersound process is 50KHz, time 30min,
Then pH is adjusted to neutrality to get the nano-cellulose suspension with sodium hydroxide solution；
(2) chitosan nano fiber element nanometer titanium dioxide composite membrane is prepared, it is specific as follows：
A, in the acetic acid solution that 0.8g chitosans are dissolved completely in a concentration of 2wt% of 40mL in 50 DEG C, the first liquid material is obtained；
B, the nano-cellulose suspension obtained by step (1) is stirred into 30min in 50 DEG C, obtains the second liquid material；
C, the second liquid materials of 20mL are added in the first liquid material, after 50 DEG C are stirred 10min, sequentially add 0.036g modifications
Nano-titanium dioxide and 0.16mL glycerine, stirring 60min postcoolings to room temperature are subsequently ultrasonicated for 30min, and supersound process surpasses
Acoustic frequency is 50KHz, time 30min, and then froth in vacuum, obtains composite membrane film liquid；
D, then above-mentioned composite membrane film liquid curtain coating is taken off on a diameter of 9.3cm glass culture dish and in 50 DEG C of drying
Film is placed in 0.1mol/LNaOH solution after immersion 30min~1h with distilled water flushing totally to get chitosan nano fibre
It is needed by different experiments that sample is made, and is put down under room temperature and 75% ambient humidity by the plain nanometer titanium dioxide composite membrane of dimension
It is used after weighing apparatus 48h.
Embodiment 3
(1) nano-cellulose suspension is prepared, it is specific as follows：
A, in ice-water bath, while stirring by the sulfuric acid solution of 4.57g microcrystalline celluloses and a concentration of 63.5wt% of 40mL
Mixing, obtains suspension；
B, above-mentioned suspension is continued to stir 110min in 45 DEG C, obtains acidolysis material；
C, it is gone after centrifuging above-mentioned acidolysis material, removes supernatant, must precipitate, the number of centrifugation is 5 times, each 20min, rotating speed
For 4000rpm (or gained supernatant is muddy after centrifugation, can stop centrifuging)；
D, above-mentioned be deposited in ice-water bath being ultrasonically treated, the supersonic frequency of supersound process is 50KHz, time 30min,
Then pH is adjusted to neutrality to get the nano-cellulose suspension with sodium hydroxide solution；
(2) chitosan nano fiber element nanometer titanium dioxide composite membrane is prepared, it is specific as follows：
A, in the acetic acid solution that 0.4g chitosans are dissolved completely in a concentration of 2wt% of 40mL in 50 DEG C, the first liquid material is obtained；
B, the nano-cellulose suspension obtained by step (1) is stirred into 30min in 50 DEG C, obtains the second liquid material；
C, the second liquid materials of 20mL are added in the first liquid material, after 50 DEG C are stirred 10min, sequentially add 0.036g modifications
Nano-titanium dioxide and 0.16mL glycerine, stirring 60min postcoolings to room temperature are subsequently ultrasonicated for 30min, and supersound process surpasses
Acoustic frequency is 50KHz, time 30min, and then froth in vacuum, obtains composite membrane film liquid；
D, then above-mentioned composite membrane film liquid curtain coating is taken off on a diameter of 9.3cm glass culture dish and in 50 DEG C of drying
Film is placed in 0.1mol/L NaOH solutions after immersion 30min~1h with distilled water flushing totally to get chitosan nano fibre
It is needed by different experiments that sample is made, and is put down under room temperature and 75% ambient humidity by the plain nanometer titanium dioxide composite membrane of dimension
It is used after weighing apparatus 48h.
Film dynamic performance survey is carried out to the chitosan nano fiber element nanometer titanium dioxide composite membrane obtained by above-described embodiment
Examination and antimicrobial sample test, the specific test method is as follows：
(1) film dynamic performance test method：
Test method is cut into 15mm × 150mm according to GB/T 1040.3-2006, by smooth, clean, flawless film
Horizontal stripe tested, the distance between fixture is 100mm to testing machine up and down.Each formula measures 15 groups of valid data, takes it flat
Mean value.The thickness of film is surveyed, every film surveys 5.
The calculation formula of tensile strength is：σ=F/ (b × d)
In formula：σ-tensile strength, MPa；F- pulling force maximum values, N；B- specimen widths, mm；D- sample thickness, mm.
The calculation formula of elongation at break is：E=100 × (G-G0)/G0
In formula：E- elongation at breaks, %；Distance when G- sample fractures between fixture, mm；G0- samples stretch between front jig
Distance, mm.
(2) antimicrobial sample test method：
1. antibacterial test standard：QB/T2591-2003A《Antibiotic plastic Anti-microbial Performance Tests method and antibacterial effect》；Inspection
Bacterium is used in survey：Escherichia coli, staphylococcus aureus.
2, antibacterial experiment step is tested with reference to antibiotic plastic examination criteria QB/T2591-2003A.Specific steps are such as
Under：Sample to be tested is handled and dried with 75% ethanol disinfection, the bacteria suspension that strain is diluted with water to debita spissitudo is spare.It takes
The bacteria suspension of 0.2mL drops in sample surfaces, is overlying on thereon, is made with the polyethylene packaging film (4.0cm × 4.0cm) of 0.1mm thickness
Bacteria suspension forms uniform liquid film between sample and film.It is cultivated 18~24 hours in 37 DEG C, relative humidity 90% time.With sterile
Water washes down bacterium solution, is diluted to concentration gradient appropriate, and 0.1mL is taken to be uniformly coated on the sterile agar culture prepared
On.It is cultivated 18~24 hours in 37 DEG C, observes result.Negative control is substituted with sterilized petri dishes, other operations are identical.
It is specific that test result is as follows：
The mechanical experimental results of chitosan nano fiber element nanometer titanium dioxide composite membrane：
The antibiotic rate testing result of chitosan nano fiber element nanometer titanium dioxide composite membrane：
The foregoing is only a preferred embodiment of the present invention, therefore cannot limit the scope of implementation of the present invention according to this, i.e.,
According to equivalent changes and modifications made by the scope of the claims of the present invention and description, all should still belong in the range of the present invention covers.
Claims (10)
1. a kind of preparation method of chitosan nano fiber element nanometer titanium dioxide composite membrane, it is characterised in that：Including walking as follows
Suddenly：
(1) nano-cellulose suspension is prepared, it is specific as follows：
A, in ice-water bath, microcrystalline cellulose is mixed with sulfuric acid solution while stirring, obtains suspension, wherein microcrystalline cellulose
Mass ratio with sulfuric acid solution is 1: 8~9, a concentration of 50~70wt% of sulfuric acid solution；
B, above-mentioned suspension is continued into 90~120min of stirring in 40~50 DEG C, obtains acidolysis material；
C, it is gone after centrifuging above-mentioned acidolysis material, removes supernatant, must precipitate；
D, it is deposited in 30~90min of supersound process in ice-water bath by above-mentioned, then adjusts pH to neutrality, i.e., with sodium hydroxide solution
Obtain the nano-cellulose suspension；
(2) chitosan nano fiber element nanometer titanium dioxide composite membrane is prepared, it is specific as follows：
A, in the acetic acid solution that chitosan is dissolved completely in a concentration of 1.5~2.5wt% in 48~52 DEG C, the first liquid material is obtained；
B, the nano-cellulose suspension obtained by step (1) is stirred into 25~40min in 48~52 DEG C, obtains the second liquid material；
C, the second liquid material is added in the first liquid material, after 48~52 DEG C are stirred 8~12min, sequentially adds modified Nano two
Titanium oxide and glycerine, stirring 50~70min postcoolings are subsequently ultrasonicated for 25~40min, then froth in vacuum, obtain to room temperature
Obtain composite membrane film liquid；
D, above-mentioned composite membrane film liquid is cast and in 48~50 DEG C of drying, is subsequently placed in after being impregnated in NaOH solution and is rushed with distilled water
Wash clean is to get the chitosan nano fiber element nanometer titanium dioxide composite membrane, above-mentioned microcrystalline cellulose, chitosan, modification
The ratio of nano-titanium dioxide and glycerine is 2.2~2.3g: 0.4~1.2g: 0.004~0.036g: 0.04~0.16mL.
2. preparation method as described in claim 1, it is characterised in that：In a of the step (1), microcrystalline cellulose and sulfuric acid
The mass ratio of solution is 1: 8.75, a concentration of 63.5wt% of sulfuric acid solution.
3. preparation method as described in claim 1, it is characterised in that：The b of the step (1) is：By above-mentioned suspension in 45
DEG C continue to stir 110min, obtains acidolysis material.
4. preparation method as described in claim 1, it is characterised in that：In the c of the step (1), the number of centrifugation is 5 times,
Each 20min, rotating speed 4000rpm.
5. preparation method as described in claim 1, it is characterised in that：In the d of the step (1), the supersound process surpasses
Acoustic frequency is 50KHz, time 30min.
6. preparation method as described in claim 1, it is characterised in that：The a of the step (2) is：Chitosan is complete in 50 DEG C
Fully dissolved obtains the first liquid material in the acetic acid solution of a concentration of 2wt%.
7. preparation method as described in claim 1, it is characterised in that：The b of the step (2) is：By receiving obtained by step (1)
Rice cellulose suspension stirs 30min in 50 DEG C, obtains the second liquid material.
8. preparation method as described in claim 1, it is characterised in that：The c of the step (2) is：Second liquid material is added to
In first liquid material, after 50 DEG C are stirred 10min, modified nano-titanium dioxide and glycerine are sequentially added, stirring 60min postcoolings are extremely
Room temperature is subsequently ultrasonicated for 30min, then froth in vacuum, obtains composite membrane film liquid.
9. the preparation method as described in claim 1 or 8, it is characterised in that：Supersound process in the c of the step (2) it is super
Acoustic frequency is 50KHz, time 30min.
10. preparation method as described in claim 1, it is characterised in that：Drying temperature in the d of the step (2) is 50 DEG C.
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| CN111138698A (en) * | 2020-01-22 | 2020-05-12 | 陈昭桦 | Method for preparing cellulose membrane based on chitosan |
| CN112442262A (en) * | 2019-09-04 | 2021-03-05 | 罗惠民 | Titanium dioxide modified biodegradable composite material and preparation method and application thereof |
| CN112549594A (en) * | 2020-12-03 | 2021-03-26 | 宁波东旭成新材料科技有限公司 | Preparation method of optical composite film with diffusion and reflection functions |
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| CN114369292A (en) * | 2021-12-08 | 2022-04-19 | 广东无穷食品集团有限公司 | Carboxymethyl chitosan/bacterial cellulose/nano silicon dioxide active packaging film and preparation method thereof |
| CN114369292B (en) * | 2021-12-08 | 2023-08-29 | 广东无穷食品集团有限公司 | Carboxymethyl chitosan/bacterial cellulose/nano silicon dioxide active packaging film and preparation method thereof |
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