CN103319737B - A kind of preparation method of cellulose/zinc oxide nanoparticle composite material - Google Patents
A kind of preparation method of cellulose/zinc oxide nanoparticle composite material Download PDFInfo
- Publication number
- CN103319737B CN103319737B CN201310249687.8A CN201310249687A CN103319737B CN 103319737 B CN103319737 B CN 103319737B CN 201310249687 A CN201310249687 A CN 201310249687A CN 103319737 B CN103319737 B CN 103319737B
- Authority
- CN
- China
- Prior art keywords
- cellulose
- zinc oxide
- preparation
- solution
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a kind of preparation method of cellulose/zinc oxide nanoparticle composite material.Cellulose carbamate is scattered in the NaOH/ZnO aqueous solution, freezing rear thawed at room temperature obtains composite solution, by composite solution through centrifugal removal of impurities, degassed after knifing or spray silk, solidify in organic solvent precipitation bath, then wash, be drying to obtain Mierocrystalline cellulose/zinc oxide composite.This method makes full use of the ZnO component in solvent, is directly prepared the matrix material of Mierocrystalline cellulose and zinc oxide nano-particle by reaction in－situ single stage method.Preparation method of the present invention is simple, and preparation cost is low, and the residual nitrogen quantity of product of preparation is low, non-environmental-pollution, and aftertreatment technology is simple; Prepared Mierocrystalline cellulose/zinc oxide nano-particle composite membrane, the intensity of silk, elongation at break, snappiness keep the performance of regenerated cellulose film and silk, and have good anti-microbial activity and uv-absorbing function, can accomplish scale production.
Description
Technical field
The present invention relates to natural polymer field, particularly a kind of preparation method of cellulose/zinc oxide nanoparticle composite material.
Background technology
In recent years, polymkeric substance, nano composition have become the attractive field of modern material science.Because nanoparticle size is little, produce the features such as small-size effect, surface effects, quantum size effect and macro quanta tunnel effect that general macro object do not have and high inspiratory, high Combination, low density, thus make polymkeric substance, nano composition occur many excellent properties being different from Conventional solid, as mechanics, optics, calorifics, electricity and magnetics etc.But due to the Intermolecular Forces difference of inorganic materials and organic polymer, the interface uncompatibility of the two and adsorptive power lack and bring difficulty to preparing associated materials.According to characteristic and the polymer treatment process of nanoparticle, polymkeric substance, inorganic nano composite material are generally by the in-situ synthesized of nanoparticle, blending method, the preparation such as intercalation compounding and sol-gel method.
Mierocrystalline cellulose is the renewable biomass resource that occurring in nature enriches the most, and its application relates to the fields such as weaving, light industry, chemical industry, national defence, oil, medicine, biotechnology, environment protection, the energy and bio-science.Zinc oxide is a kind of semiconductor material with wide forbidden band, and its energy gap is 3.2ev.Along with Zinc oxide particles size reduces, energy gap increases gradually.Energy gap as 10nm Zinc oxide particles is 4.5ev, and it is that 280 ~ 400nm UV-light has very strong receptivity to wavelength, is desirable ultraviolet screening agent.And it also has the function of antibacterial, mildew-resistant and smelly eliminating.Document (CarbohydratePolymers, 2012,87,1065 – 1072) zinc acetate of 0.2mol is dissolved in the mixed solvent of dimethyl formamide (DMF) and acetone, and then 14wt% cellulose acetate is put into above-mentioned solution stirring within 5 hours, obtain uniform cellulose acetate solution, then carry out electrospinning, by control cellulose acetate concentration finally obtain the conjugated fibre of different zinc oxide content.Document (Cellulose, 2011,18,675 – 680) first by cellulose dissolution in LiCl/DMAc solvent, then casting film-forming be solidify regeneration in the isopropanol water solution of 50% to obtain regenerated cellulose film in volume fraction, finally drops into cellulose membrane and obtains Mierocrystalline cellulose/zinc oxide composite membrane containing with washing drying after 90 DEG C of condition lower magnetic forces stir 6 hours in the zinc nitrate of mol ratio and the trolamine aqueous solution.0.25g Microcrystalline Cellulose is dissolved in the ionic liquid [C of 5g by document (Cellulose, 2013,20,699 – 705) by the mode of microwave heating
4mim] in, and then in cellulose solution, add the mixed solution of zinc acetate and sodium hydroxide and ionic liquid, continue microwave reaction, finally add that distilled water is separated, washing, drying obtain Mierocrystalline cellulose/zinc-oxide nano composite membrane.Document (CrystalGrowth & Design, 2009,9,387) first zinc acetate and sodium hydroxide heating for dissolving in 2-propyl alcohol, cellulosic fibre is put into after cooling, stirred at ambient temperature filters, dry, and for obtaining containing the more conjugated fibre of ZnO, above-mentioned fiber continuation 90 DEG C of reacting by heating in containing the solution of zinc nitrate to be washed, drying obtains Mierocrystalline cellulose/zinc-oxide nano conjugated fibre after 6 hours.Below several methods preparing Mierocrystalline cellulose/zinc oxide composite membrane and fiber reported mostly adopt and first prepare cellulose membrane and fiber, then cellulose membrane and fiber are put in the precursors preparing zinc oxide and finally obtain matrix material, or prepare matrix material adding the precursors co-precipitation preparing zinc oxide after cellulose dissolution.Aforesaid method complex steps, and aftertreatment technology is complicated, and preparation cost is higher, is difficult to accomplish scale production.
Summary of the invention
The object of the invention is for exist in background technology problem provide a kind of preparation technology simple, non-environmental-pollution, and the method preparing cellulose/zinc oxide nanoparticle composite material that cost is low.
The present invention makes full use of the ZnO component in solvent, and adopt in-situ reaction one step to prepare cellulose/zinc oxide nanoparticle composite material, its technical scheme is as follows:
A kind of preparation method of cellulose/zinc oxide nanoparticle composite material, it is characterized in that: cellulose carbamate is scattered in the NaOH/ZnO aqueous solution, freezing rear thawed at room temperature obtains composite solution, by composite solution through centrifugal removal of impurities, degassed after knifing or spray silk, solidify in organic solvent precipitation bath, then wash, be drying to obtain Mierocrystalline cellulose/zinc oxide composite.
Preference as such scheme:
In described composite solution, the mass percent concentration of NaOH is the mass percent concentration of 6 ~ 10wt%, ZnO is 0.4 ~ 4.0wt%, and the mass percent concentration of cellulose carbamate is 3 ~ 10wt%.
Organic solvent in described organic solvent precipitation bath is the mixing solutions of one or more in ethanol, methyl alcohol, ethylene glycol, glycerol, n-propyl alcohol, 2-propyl alcohol, acetone soln.
The coagulation bath temperature of described organic solvent precipitation bath is 0-50 DEG C, and setting time is 5-30min.
Described washing temperature is 10-60 DEG C.
According to above-mentioned technical scheme, its preparation principle be the gained NaOH/ZnO aqueous solution as solvent first dissolving cellulos carbamate obtain the mixing solutions containing cellulose carbamate and ZnO precursors, by composite solution through centrifugal removal of impurities, degassed rear knifing or spray silk, after immersing organic precipitation bath, solvent composition and precipitation bath generation double diffusion in cellulose carbamate solution, there is restructuring regeneration in cellulose carbamate hydrogen bond, simultaneous oxidation zinc precursor in-situ preparation zinc oxide nano-particle also disperses wherein, through washing, Mierocrystalline cellulose/zinc oxide nano-particle composite membrane is finally obtained after drying.
The present invention makes full use of the ZnO component in solvent, can by NaOH/ZnO proportioning, cellulose carbamate concentration, coagulation bath temperature, setting time, washing temperature in control solvent to prepare the matrix material of the ZnO particle of different content, wherein in solution, NaOH, ZnO and cellulose carbamate content are followed successively by 6 ~ 10wt%, 0.4 ~ 4.0wt%ZnO and 3 ~ 10wt%; Coagulation bath temperature is 0-50 DEG C, and setting time is 5-30min, and washing temperature is 10-60 DEG C.
Technical solution of the present invention technique is simple, easy to operate, the NaOH/ZnO aqueous solution both as the direct dissolving cellulos carbamate of solvent, again as generating the precursors of zinc oxide nano-particle.And solidifying, the reaction of regenerative process situ generates nano level zinc oxide particles.Single stage method just can prepare Mierocrystalline cellulose/zinc oxide nano-particle composite membrane, and solvent-free pollution, with low cost.
The present invention, to dissolving the nitrogen content of cellulose carbamate used without explicitly calling for, particularly uses the cellulose carbamate of nitrogen content lower (0.3 ~ 2%) still can reach good effect.And solidifying, regenerate in washing process the carbamate groups major part tieed up on plain molecular chain and can be hydrolyzed, residual nitrogen quantity extremely low (≤0.3%).
In the matrix material that the present invention prepares, the content of zinc oxide nano-particle is 1.2 ~ 16wt%, cellulosic content is 84 ~ 98.8wt%, and content described herein is mass percent.
Substantially namely the intensity of the Mierocrystalline cellulose prepared by the present invention/zinc oxide nano-particle composite membrane, silk, elongation at break, snappiness keep the performance of regenerated cellulose film and silk, and impart again new function, as good anti-microbial activity and uv-absorbing function etc.
Preparation method of the present invention is simple, and preparation cost is low, and the residual nitrogen quantity of product of preparation is low, and non-environmental-pollution, so aftertreatment technology is simple; Prepared Mierocrystalline cellulose/zinc oxide nano-particle composite membrane, the intensity of silk, elongation at break, snappiness keep the performance of regenerated cellulose film and silk; and there is good anti-microbial activity and uv-absorbing function; can accomplish scale production; can be used for the separation in chemical industry, food, environmental protection, weaving, medical field, evaporating-osmosis, ion-exchange, antibacterial deodourizing, uv-absorbing and wrapping material, also can be used as medical material.
Accompanying drawing explanation
The Mierocrystalline cellulose that accompanying drawing 1 prepares for the embodiment of the present invention 1/zinc-oxide nano composite membrane photo.
Accompanying drawing 2 is obtained Mierocrystalline cellulose/zinc-oxide nano crystal grain composite film surface (a) of the embodiment of the present invention 2 and cross section (b) electron scanning micrograph.
The streptococcus aureus (a) of Mierocrystalline cellulose/zinc-oxide nano composite membrane that accompanying drawing 3 prepares for the embodiment of the present invention 2 and the bacteriostatic test photo of intestinal bacteria (b).
The ultraviolet absorpting spectrum of Mierocrystalline cellulose/zinc-oxide nano composite membrane that accompanying drawing 4 prepares for the embodiment of the present invention 1.
Embodiment
Below in conjunction with specific embodiment to technical scheme further instruction of the present invention
Embodiment 1
Get 15 grams of nitrogen contents be 1.441% cellulose carbamate be scattered in 285 grams of 7.0wt%NaOH/0.8wt%ZnO aqueous solution, at-10 DEG C freezing 24 hours, thawing under room temperature condition to dissolve obtained the cellulose carbamate solution that concentration is 5wt%.Use ultracentrifuge 7, evacuation and centrifugal degassing 15 minutes under the rotating speed of 200 revs/min.Centrifugal rear gained solution is poured on casting film-forming on clean poly (methyl methacrylate) plate, and the thickness of controlling diaphragm is 0.5mm, then immerse in ethanol and solidify 15 minutes under 10 DEG C of conditions, 25 DEG C of Water Unders are washed, be fixed on poly (methyl methacrylate) plate and obtain the composite membrane that zinc oxide nano-particle content is 7.0wt% after drying under 25 DEG C of conditions.The tensile strength of dry state composite membrane is 69MPa, and elongation at break is 6%, and ammonia nitrogen detector detects residual nitrogen quantity≤0.3% of composite membrane.
The obtained transmittance of composite membrane within the scope of wavelength 200 ~ 1000nm of the present embodiment is scanned with ultraviolet spectrometer (ShimaduUV-160A).Test result as shown in Figure 4, shows that composite membrane prepared by the present invention has good uv-absorbing function, and along with the increase of nano oxidized Zn content, the uv-absorbing function of film strengthens, and produces significantly " red shift ".This material is for the preparation of the fabric and wrapping material etc. with uv-absorbing function.
Embodiment 2
Get 20 grams of nitrogen contents be 1.441% cellulose carbamate be scattered in 380 grams of 7.0wt%NaOH/1.2wt%ZnO aqueous solution, at-12 DEG C freezing 20 hours, thawing under room temperature condition to dissolve obtained the cellulose carbamate solution that concentration is 5wt%.Use ultracentrifuge 7, evacuation and centrifugal degassing 15 minutes under the rotating speed of 200 revs/min.Centrifugal rear gained solution is poured on casting film-forming on clean poly (methyl methacrylate) plate, and the thickness of controlling diaphragm is 0.5mm, then immerse in ethanol and solidify 15 minutes under 10 DEG C of conditions, 25 DEG C of Water Unders are washed, be fixed on poly (methyl methacrylate) plate and obtain the composite membrane that zinc oxide nano-particle content is 9.0wt% after drying under 25 DEG C of conditions.The tensile strength of composite membrane is 50MPa, and elongation at break is 2%, and ammonia nitrogen detector detects residual nitrogen quantity≤0.3% of composite membrane.
Bacteriostatic experiment
Bacterial classification:
Streptococcus aureus and intestinal bacteria (Staphylococcusaureus) are provided by Wuhan University's China typical culture collection center, are typical biomedical researches with bacterium, and are used to the anti-microbial property of evaluating material for a long time.Peel off the preservation 72 hours at 37 DEG C of the clone body of bacterium.
The present embodiment gained Mierocrystalline cellulose/zinc-oxide nano composite membrane is cut into the circular membrane that diameter is 7mm, and the ethanolic soln soaking disinfection being placed in 93% was cleaned with distilled water after 15 minutes.The sterilizing in 200 DEG C of autoclaves of all laboratory apparatuss.Composite membrane is put in culture dish nutritive medium above streptococcus aureus and intestinal bacteria, observes mould material surface and spore growth situation around to evaluate its anti-microbial property.
The attached streptococcus aureus (a) of Mierocrystalline cellulose/zinc-oxide nano composite membrane and the bacteriostatic test photo of intestinal bacteria (b) that Figure 3 shows that the present embodiment prepares, antibacterial tests result: show this matrix material and have good biocidal property, in culture dish on composite membrane and around do not occur spore circle spot.And along with the increase of zinc-oxide nano crystal grain content, the inhibition zone increase around composite membrane and bacteriostasis property increase.This material can be used for preparing medical, the daily materials such as antibiotic fabric fiber or antibacterial film.
Embodiment 3
Get 18 grams of nitrogen contents be 1.952% cellulose carbamate be scattered in 282 grams of 6.5wt%NaOH/3.0wt%ZnO aqueous solution, at-15 DEG C freezing 24 hours, it was 6wt% cellulose carbamate solution that dissolving of thawing under room temperature condition obtains concentration.Use ultracentrifuge 7, evacuation and centrifugal degassing 15 minutes under the rotating speed of 200 revs/min.Centrifugal rear gained solution is poured on casting film-forming on clean poly (methyl methacrylate) plate, and the thickness of controlling diaphragm is 0.5mm, then immerse in acetone and solidify 30 minutes under 0 DEG C of condition, 10 DEG C of Water Unders are washed, be fixed on poly (methyl methacrylate) plate and obtain the composite membrane that zinc oxide nano-particle content is 14wt% after drying under 20 DEG C of conditions.The tensile strength of composite membrane is 61MPa, and elongation at break is 3%, and ammonia nitrogen detector detects residual nitrogen quantity≤0.3% of composite membrane.
Embodiment 4
Get 12 grams of nitrogen contents be 1.732% cellulose carbamate be scattered in 188 grams of 10.0wt%NaOH/0.4wt%ZnO aqueous solution, at-24 DEG C freezing 8 hours, thawing under room temperature condition to dissolve obtained the cellulose carbamate solution that concentration is 6wt%.Use ultracentrifuge 7, evacuation and centrifugal degassing 15 minutes under the rotating speed of 200 revs/min.Centrifugal rear gained solution is poured on casting film-forming on clean poly (methyl methacrylate) plate, and the thickness of controlling diaphragm is 0.5mm, then immerse in methyl alcohol and solidify 10 minutes under 15 DEG C of conditions, 60 DEG C of Water Unders are washed, be fixed on poly (methyl methacrylate) plate 50 DEG C of conditions under obtain the composite membrane that zinc oxide nano-particle content is 1.2wt% after drying.The tensile strength of composite membrane is 55MPa, and elongation at break is 16%, and ammonia nitrogen detector detects residual nitrogen quantity≤0.3% of composite membrane.
Embodiment 5
Get 24 grams of nitrogen contents be 1.009% cellulose carbamate be scattered in 376 grams of 6.0wt%NaOH/2.5wt%ZnO aqueous solution, at-15 DEG C freezing 18 hours, thawed under room temperature condition the cellulose carbamate solution dissolving and obtain concentration 6wt%.Use ultracentrifuge 7, evacuation and centrifugal degassing 15 minutes under the rotating speed of 200 revs/min.The solution of centrifugal rear gained is poured on clean poly (methyl methacrylate) plate uses glass knifing, and the thickness of controlling diaphragm is 0.5mm, then immerse in ethylene glycol and solidify 5 minutes under 20 DEG C of conditions, 35 DEG C of Water Unders are washed, and are fixed under poly (methyl methacrylate) plate 70 DEG C of conditions and obtain the composite membrane that zinc oxide nano-particle content is 10wt% after drying.The breaking tenacity of composite membrane is 85MPa, and elongation at break is 9%, and ammonia nitrogen detector detects residual nitrogen quantity≤0.3% of composite membrane.
Embodiment 6
Get 18 grams of nitrogen contents be 0.30% cellulose carbamate be dissolved in 282 grams of 10.0wt%NaOH/4.0wt%ZnO aqueous solution, under-23 DEG C of conditions freezing 8 hours, thawed under room temperature condition the cellulose carbamate solution dissolving and obtain 6wt%.Use ultracentrifuge 7, evacuation and centrifugal degassing 15 minutes under the rotating speed of 200 revs/min.Centrifugal rear gained solution is poured on casting film-forming on clean poly (methyl methacrylate) plate, and the thickness of controlling diaphragm is 0.5mm, then immerse in glycerol and solidify 20 minutes under 50 DEG C of conditions, 15 DEG C of Water Unders are washed, be fixed on poly (methyl methacrylate) plate 15 DEG C of conditions under obtain the composite membrane that zinc oxide nano-particle content is 16wt% after drying.The tensile strength of composite membrane is 65MPa, and elongation at break is 6wt%, and ammonia nitrogen detector detects residual nitrogen quantity≤0.3% of composite membrane.
Embodiment 7
Get 18 grams of nitrogen contents be 1.218% cellulose carbamate be scattered in the aqueous solution of 282 grams of 9.0wt%NaOH/3.5wt%ZnO, at-20 DEG C freezing 12 hours, dissolving of thawing under room temperature condition obtained 6wt% cellulose carbamate solution.Use ultracentrifuge 7, evacuation and centrifugal degassing 15 minutes under the rotating speed of 200 revs/min.The solution of centrifugal rear gained is poured on clean poly (methyl methacrylate) plate uses glass knifing, and the thickness of controlling diaphragm is 0.5mm, then immerse in 2-propyl alcohol and solidify 10 minutes under 7 DEG C of conditions, 25 DEG C of Water Unders are washed, and are fixed under poly (methyl methacrylate) plate 45 DEG C of conditions and obtain the composite membrane that zinc oxide nano-particle content is 13wt% after drying.The breaking tenacity of composite membrane is 70MPa, and elongation at break is 12%, and ammonia nitrogen detector detects residual nitrogen quantity≤0.3% of composite membrane.
Embodiment 8
Getting 24 grams of nitrogen contents is that the cellulose carbamate sample dissolution of 1.218% is in the aqueous solution of 376 grams of 10.0wt%NaOH/2.6wt%ZnO, under-17 DEG C of conditions freezing 14 hours, it was 6wt% cellulose carbamate solution that dissolving of thawing under room temperature condition obtains concentration.Use ultracentrifuge 7, evacuation and centrifugal degassing 15 minutes under the rotating speed of 200 revs/min.The solution of centrifugal rear gained is poured on casting film-forming on clean poly (methyl methacrylate) plate, and the thickness of controlling diaphragm is 0.5mm, then immerse in n-propyl alcohol and solidify 10 minutes under 28 DEG C of conditions, 35 DEG C of Water Unders are washed, be fixed on poly (methyl methacrylate) plate 50 DEG C of conditions under obtain the composite membrane that zinc oxide nano-particle content is 12wt% after drying.The tensile strength of composite membrane is 78MPa, and elongation at break is 13%, and ammonia nitrogen detector detects residual nitrogen quantity≤0.3% of composite membrane.
Embodiment 9
Get 9 grams of nitrogen contents be 1.441% cellulose carbamate be scattered in 291 grams of 7.0wt%NaOH/0.8wt%ZnO aqueous solution, at-10 DEG C freezing 24 hours, thawing under room temperature condition to dissolve obtained the cellulose carbamate solution that concentration is 3wt%.Use ultracentrifuge 7, evacuation and centrifugal degassing 15 minutes under the rotating speed of 200 revs/min.Centrifugal rear gained solution is poured on casting film-forming on clean poly (methyl methacrylate) plate, and the thickness of controlling diaphragm is 0.5mm, then immerse in ethanol and solidify 15 minutes under 10 DEG C of conditions, 25 DEG C of Water Unders are washed, be fixed on poly (methyl methacrylate) plate and obtain the composite membrane that zinc oxide nano-particle content is 12.0wt% after drying under 25 DEG C of conditions.The tensile strength of dry state composite membrane is 69MPa, and elongation at break is 6%, and ammonia nitrogen detector detects residual nitrogen quantity≤0.3% of composite membrane.
Embodiment 10
Get 20 grams of nitrogen contents be 1.441% cellulose carbamate be scattered in 180 grams of 7.5wt%NaOH/2.0wt%ZnO aqueous solution, at-12 DEG C freezing 20 hours, thawing under room temperature condition to dissolve obtained the cellulose carbamate solution that concentration is 10wt%.Use ultracentrifuge 7, evacuation and centrifugal degassing 15 minutes under the rotating speed of 200 revs/min.Centrifugal rear gained solution is poured on casting film-forming on clean poly (methyl methacrylate) plate, and the thickness of controlling diaphragm is 0.5mm, then immerse in ethanol and solidify 15 minutes under 10 DEG C of conditions, 40 DEG C of Water Unders are washed, be fixed on poly (methyl methacrylate) plate and obtain the composite membrane that zinc oxide nano-particle content is 3.0wt% after drying under 25 DEG C of conditions.The tensile strength of composite membrane is 80MPa, and elongation at break is 7%, and ammonia nitrogen detector detects residual nitrogen quantity≤0.3% of composite membrane.
Embodiment 11
Get 20 grams of nitrogen contents be 1.591% cellulose carbamate be scattered in 380 grams of 7.0wt%NaOH/0.8wt%ZnO aqueous solution, at-18 DEG C freezing 15 hours, thawing under room temperature condition to dissolve obtained the cellulose carbamate solution that concentration is 5wt%.Use ultracentrifuge 7, evacuation and centrifugal degassing 15 minutes under the rotating speed of 200 revs/min.Centrifugal rear gained solution is poured on spinning on the simple and easy spinning-drawing machine in laboratory, cellulose carbamate solution is ejected in 60wt% ethanol (massfraction in the ethanol) aqueous solution of 30 DEG C through spinning nozzle and solidifies 5 minutes, then through obtaining the conjugated fibre that zinc oxide nano-particle content is 7.0wt% after drying under 40 DEG C of washings, 70 DEG C of conditions.The tensile strength of dry state conjugated fibre is 1.2cN/dtex, and elongation at break is 6%, and ammonia nitrogen detector detects residual nitrogen quantity≤0.3% of composite membrane.
Embodiment 12
Get 20 grams of nitrogen contents be 1.414% cellulose carbamate be scattered in 380 grams of 7.0wt%NaOH/0.6wt%ZnO aqueous solution, at-12 DEG C freezing 24 hours, thawing under room temperature condition to dissolve obtained the cellulose carbamate solution that concentration is 5wt%.Use ultracentrifuge 7, evacuation and centrifugal degassing 15 minutes under the rotating speed of 200 revs/min.Centrifugal rear gained solution is poured on spinning on the simple and easy spinning-drawing machine in laboratory, cellulose carbamate solution is ejected in ethanol and the n-propyl alcohol (1:1 of 20 DEG C through spinning nozzle, mass ratio) mixed solution in solidify 5 minutes, then through obtaining the conjugated fibre that zinc oxide nano-particle content is 4.0wt% after drying under 35 DEG C of washings, 50 DEG C of conditions in the aqueous solution.The tensile strength of dry state conjugated fibre is 0.8cN/dtex, and elongation at break is 5%, and ammonia nitrogen detector detects residual nitrogen quantity≤0.3% of composite membrane.
Above-described embodiment is known, and preparation method of the present invention is simple, and preparation cost is low, and the residual nitrogen quantity of product of preparation is low, and non-environmental-pollution, so aftertreatment technology is simple; Prepared Mierocrystalline cellulose/zinc oxide nano-particle composite membrane, the intensity of silk, elongation at break, snappiness keep the performance of regenerated cellulose film and silk, can accomplish scale production.
Claims (2)
1. the preparation method of a cellulose/zinc oxide nanoparticle composite material, it is characterized in that: cellulose carbamate is scattered in the NaOH/ZnO aqueous solution, freezing rear thawed at room temperature obtains composite solution, by composite solution through centrifugal removal of impurities, degassed after knifing or spray silk, solidify in organic solvent precipitation bath, then wash, be drying to obtain Mierocrystalline cellulose/zinc oxide composite; In described composite solution, the mass percent concentration of NaOH is the mass percent concentration of 6 ~ 10wt%, ZnO is 0.4 ~ 4.0wt%, and the mass percent concentration of cellulose carbamate is 3 ~ 10wt%; Organic solvent in described organic solvent precipitation bath is the mixing solutions of one or more in ethanol, methyl alcohol, ethylene glycol, glycerol, n-propyl alcohol, 2-propyl alcohol, acetone soln, the coagulation bath temperature of described organic solvent precipitation bath is 0-50 DEG C, and setting time is 5-30min.
2. the preparation method of cellulose/zinc oxide nanoparticle composite material as claimed in claim 1, is characterized in that: described washing temperature is 10-60 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310249687.8A CN103319737B (en) | 2013-06-21 | 2013-06-21 | A kind of preparation method of cellulose/zinc oxide nanoparticle composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310249687.8A CN103319737B (en) | 2013-06-21 | 2013-06-21 | A kind of preparation method of cellulose/zinc oxide nanoparticle composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103319737A CN103319737A (en) | 2013-09-25 |
| CN103319737B true CN103319737B (en) | 2015-12-09 |
Family
ID=49188810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310249687.8A Active CN103319737B (en) | 2013-06-21 | 2013-06-21 | A kind of preparation method of cellulose/zinc oxide nanoparticle composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103319737B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103643334B (en) * | 2013-12-17 | 2016-04-13 | 青岛大学 | The preparation method of Fire resistant viscose fiber |
| CN104264258B (en) * | 2014-10-15 | 2015-12-09 | 钱景 | A kind of functional salix monogolica regenerated celulose fibre and preparation method thereof |
| CN104630934B (en) * | 2015-03-06 | 2016-12-07 | 苏州爱立方服饰有限公司 | A kind of retardant fabric material and preparation method thereof |
| EP3323848A4 (en) * | 2015-07-14 | 2019-02-27 | DIC Corporation | Coagulation manufacturing method |
| CN106390188A (en) * | 2016-04-01 | 2017-02-15 | 浙江理工大学 | Hydrogel having wound repair function and preparation method of hydrogel |
| CN106012070A (en) * | 2016-07-04 | 2016-10-12 | 浙江理工大学 | Novel slow-release antibacterial cellulose fibers and preparation method thereof |
| CN106519306A (en) * | 2016-10-09 | 2017-03-22 | 浙江理工大学 | Cellulose based Ag @ ZnO nano composite hydrogel and preparation method thereof |
| CN106810723B (en) * | 2017-01-18 | 2020-05-12 | 浙江理工大学 | Composite hydrogel with protein separation function and preparation method thereof |
| CN107446166A (en) * | 2017-09-17 | 2017-12-08 | 赵兵 | A kind of amphoteric cellulose composite of supported nano zinc oxide and preparation method thereof |
| CN112210126A (en) * | 2019-07-12 | 2021-01-12 | 郭敏 | Preparation method of antibacterial bacterial cellulose |
| CN111082008B (en) * | 2019-12-14 | 2021-07-23 | 莒南凯佳化工有限公司 | Preparation method of nanocellulose/zinc oxide compound for electrochemical energy storage |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432894B (en) * | 2011-10-17 | 2013-09-11 | 武汉大学 | Cellulose carbamate dissolved combined solvent and using method thereof |
| CN102691125B (en) * | 2012-06-19 | 2014-01-01 | 武汉大学 | Method for preparing regenerated cellulose fibers with cellulose carbamate |
| CN103012822B (en) * | 2012-12-11 | 2015-10-21 | 武汉大学 | A kind of method being prepared regenerated cellulose film by cellulose carbamate |
-
2013
- 2013-06-21 CN CN201310249687.8A patent/CN103319737B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103319737A (en) | 2013-09-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103319737B (en) | A kind of preparation method of cellulose/zinc oxide nanoparticle composite material | |
| Song et al. | Antibacterial polyvinyl alcohol/bacterial cellulose/nano-silver hydrogels that effectively promote wound healing | |
| Mokhena et al. | Electrospun alginate nanofibres impregnated with silver nanoparticles: Preparation, morphology and antibacterial properties | |
| Lin et al. | Novel antimicrobial chitosan–cellulose composite films bioconjugated with silver nanoparticles | |
| Abdelgawad et al. | Antimicrobial wound dressing nanofiber mats from multicomponent (chitosan/silver-NPs/polyvinyl alcohol) systems | |
| Li et al. | Preparation of nanocrystalline cellulose via ultrasound and its reinforcement capability for poly (vinyl alcohol) composites | |
| Fu et al. | Construction of cellulose based ZnO nanocomposite films with antibacterial properties through one-step coagulation | |
| RU2669626C2 (en) | Cellulose fibres | |
| Huang et al. | Nanofiber-reinforced bulk hydrogel: preparation and structural, mechanical, and biological properties | |
| KR20180010256A (en) | Multifunctional viscose fiber and manufacturing method thereof | |
| CN111304779A (en) | Preparation method of chitosan/polyvinyl alcohol nanofiber containing nanocellulose | |
| CN103572507A (en) | Preparation method for antibiosis ultraviolet prevention silk fibroin nanofiber membrane | |
| Yang et al. | Designment of polydopamine/bacterial cellulose incorporating copper (II) sulfate as an antibacterial wound dressing | |
| Errokh et al. | Hybrid nanocellulose decorated with silver nanoparticles as reinforcing filler with antibacterial properties | |
| CN103469542B (en) | Bacterial cellulose fiber containing nano-silver chloride particles and preparation method of fiber | |
| Motasadizadeh et al. | Development of PVA/Chitosan-g-Poly (N-vinyl imidazole)/TiO2/curcumin nanofibers as high-performance wound dressing | |
| CN1613900A (en) | Cellulose and nanometer titania composite material, preparation and use thereof | |
| Lv et al. | Overview of preparation, modification, and application of tunicate-derived nanocellulose | |
| KR101551850B1 (en) | Manufacturing method porous paper filter and porous paper filter manufactured by the method | |
| CN110665051A (en) | Preparation method of hemostatic and antibacterial frozen gel stent | |
| Shi et al. | Fabrication of cellulose acetate/gelatin-eugenol core–shell structured nanofiber films for active packaging materials | |
| Yang et al. | A facile, biosynthetic design strategy for high-performance multifunctional bacterial cellulose-based dressing | |
| Ma et al. | Homogeneous silver nanoparticle loaded polydopamine/polyethyleneimine-coated bacterial cellulose nanofibers for wound dressing | |
| Rezaei et al. | Investigating of the influence of zinc oxide nanoparticles morphology on the properties of electrospun polyvinyl alcohol/chitosan (PVA/CS) nanofibers | |
| CN106012070A (en) | Novel slow-release antibacterial cellulose fibers and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |