CN103319737A - Preparation method of cellulose/zinc oxide nanoparticle composite material - Google Patents
Preparation method of cellulose/zinc oxide nanoparticle composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a cellulose/zinc oxide nanoparticle composite material, and the preparation method comprises the following steps of: dispersing cellulose carbamate into an NaOH/ZnO water solution, freezing, and then unfreezing at room temperature to obtain a composite solution; carrying out centrifugalization, impurity removal and desaeration on the composite solution, and then knifing a membrane or spinning; solidifying in an organic solvent coagulating bath, and then washing and drying to obtain the cellulose/zinc oxide nanoparticle composite material. The method disclosed by the invention can be used for directly preparing the cellulose and zinc oxide nanoparticle composite material through an in-situ reaction one-step method by sufficiently utilizing a ZnO component contained in a solvent, has the advantages of simplicity, low preparation cost, low remaining nitrogen quantity of a prepared product, no environment pollution and simple post-processing process; the prepared cellulose/zinc oxide nanoparticle composite membrane and filament keep the properties of a regenerated cellulose membrane and filament on strength, breaking elongation and flexibility, has very good antibacterial activity and ultraviolet absorption function and can realize the large-scale production.
Description
Technical field
The present invention relates to the natural polymer field, particularly a kind of Mierocrystalline cellulose/zinc oxide nano-particle composite manufacture method.
Background technology
In recent years, polymkeric substance, nano composition have become the attractive field of modern material science.Because the nanoparticle size is little, produce the characteristics such as small-size effect, surface effects, quantum size effect and macro quanta tunnel effect that general macro object do not have and high air-breathing property, high Combination, low density, thereby make polymkeric substance, nano composition many excellent properties that are different from conventional solid occur, such as mechanics, optics, calorifics, electricity and magnetics etc.But because the Intermolecular Forces difference of inorganic materials and organic polymer, the interface uncompatibility of the two and adsorptive power lack to the preparation associated materials has brought difficulty.According to characteristic and the polymer treatment process of nanoparticle, polymkeric substance, inorganic nano composite material generally can be by the preparations such as original position method of formation, blending method, intercalation compounding and sol-gel method of nanoparticle.
Mierocrystalline cellulose is the abundantest renewable biomass resource of occurring in nature, 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 3.2 ev.Along with the Zinc oxide particles size reduction, energy gap increases gradually.Energy gap such as 10 nm Zinc oxide particles is 4.5 ev, and it is that 280 ~ 400 nm UV-light have very strong receptivity to wavelength, is desirable ultraviolet screening agent.And it also has the function of antibiotic, mildew-resistant and smelly eliminating.Document (Carbohydrate Polymers, 2012,87,1065 – 1072) zinc acetate with 0.2 mol is dissolved in the mixed solvent of dimethyl formamide (DMF) and acetone, and then 14 wt% cellulose acetates are put into mentioned solution stir and to obtain uniform cellulose acetate solution in 5 hours, then carry out electrospinning, by the control cellulose acetate concentration finally obtain the conjugated fibre of different zinc oxide contents.Document (Cellulose, 2011,18,675 – 680) at first with cellulose dissolution in the LiCl/DMAc solvent, then casting film-forming and solidify regeneration obtain regenerated cellulose film in volume fraction is 50% isopropanol water solution drops into cellulose membrane to contain at last and stirs with 90 ℃ of condition lower magnetic forces in the zinc nitrate of mol ratio and the trolamine aqueous solution that the washing drying obtains Mierocrystalline cellulose/zinc oxide composite membrane after 6 hours.Document (Cellulose, 2013,20,699 – 705) is dissolved in 0.25 g Microcrystalline Cellulose the ionic liquid [C of 5 g by the mode of microwave heating
4Mim] in, and then add the mixed solution of zinc acetate and sodium hydroxide and ionic liquid in the cellulose solution, continue microwave reaction, add at last distilled water separation, washing, drying and obtain Mierocrystalline cellulose/zinc-oxide nano composite membrane.Document (Crystal Growth ﹠amp; Design, 2009,9,387) at first zinc acetate and sodium hydroxide heating for dissolving in the 2-propyl alcohol, put into cellulosic fibre after the cooling, agitation and filtration, oven dry under the room temperature for obtaining containing the more conjugated fibre of ZnO, continue above-mentioned fiber in containing the solution of zinc nitrate that 90 ℃ of reacting by heating were washed after 6 hours, drying obtains Mierocrystalline cellulose/the zinc-oxide nano conjugated fibre.Several methods that prepare Mierocrystalline cellulose/zinc oxide composite membrane and fiber of below having reported mostly adopt and prepare first cellulose membrane and fiber, then cellulose membrane and fiber are put in the precursors of preparation zinc oxide and obtained at last matrix material, or prepare matrix material adding the precursors co-precipitation for preparing zinc oxide behind the cellulose dissolution.The 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 objective of the invention is for exist in the background technology problem provide a kind of preparation technology simple, non-environmental-pollution, and the low method for preparing Mierocrystalline cellulose/zinc oxide nano-particle matrix material of cost.
The present invention takes full advantage of the ZnO component in the solvent, adopts in-situ reaction one step preparation Mierocrystalline cellulose/zinc oxide nano-particle matrix material, and its technical scheme is as follows:
A kind of Mierocrystalline cellulose/zinc oxide nano-particle composite manufacture method, it is characterized in that: cellulose carbamate is scattered in the NaOH/ ZnO aqueous solution, thaw under the freezing rear room temperature and obtain composite solution, with composite solution through centrifugal removal of impurities, degassed after knifing or spray silk, in the organic solvent precipitation bath, solidify, then wash, be drying to obtain Mierocrystalline cellulose/zinc oxide composite.
Preference as such scheme:
The mass percent concentration of NaOH is 6 ~ 10 wt% in the described composite solution, and the mass percent concentration of ZnO is 0.4 ~ 4.0 wt%, and the mass percent concentration of cellulose carbamate is 3 ~ 10 wt%.
Organic solvent in the described organic solvent precipitation bath is one or more the mixing solutions in ethanol, methyl alcohol, ethylene glycol, glycerol, n-propyl alcohol, 2-propyl alcohol, the acetone soln.
The coagulation bath temperature of described organic solvent precipitation bath is 0-50 ℃, and setting time is 5-30 min.
Described washing temperature is 10-60 ℃.
According to above-mentioned technical scheme, its preparation principle be the gained NaOH/ZnO aqueous solution as solvent at first the dissolving cellulos carbamate obtain containing the mixing solutions of cellulose carbamate and ZnO precursors, with the centrifugal removal of impurities of composite solution process, degassed rear knifing or spray silk, after immersing organic precipitation bath, solvent composition and precipitation bath generation double diffusion in the cellulose carbamate solution, restructuring regeneration occurs in the cellulose carbamate hydrogen bond, simultaneous oxidation zinc precursor body original position generates zinc oxide nano-particle and disperses wherein, through washing, finally obtain Mierocrystalline cellulose/zinc oxide nano-particle composite membrane after the drying.
The present invention takes full advantage of the ZnO component in the solvent, can be by NaOH/ZnO proportioning, cellulose carbamate concentration, coagulation bath temperature, setting time, washing temperature in the control solvent with the matrix material of the ZnO particle of preparation different content, wherein NaOH, ZnO and cellulose carbamate content are followed successively by 6 ~ 10 wt% in the solution, 0.4 ~ 4.0 wt% ZnO and 3 ~ 10 wt%; Coagulation bath temperature is 0-50 ℃, and setting time is 5-30min, and washing temperature is 10-60 ℃.
Technical solution of the present invention technique is simple, easy to operate, and the NaOH/ZnO aqueous solution is both as the direct dissolving cellulos carbamate of solvent, again as the precursors that generates zinc oxide nano-particle.And solidify, regenerative process situ reaction generates nano level zinc oxide particle.Single stage method just can prepare Mierocrystalline cellulose/zinc oxide nano-particle composite membrane, and solvent-free pollution, and is with low cost.
The present invention without explicitly calling for, particularly uses the cellulose carbamate of nitrogen content lower (0.3 ~ 2 %) still can reach preferably effect to the nitrogen content that dissolves used cellulose carbamate.And the carbamate groups major part in the washing process that solidifies, regenerates on the plain molecular chain of dimension can be hydrolyzed residual nitrogen amount extremely low (≤0.3 %).
The content of zinc oxide nano-particle is that 1.2 ~ 16 wt%, cellulosic content are 84 ~ 98.8 wt% in the matrix material that the present invention prepares, and content described herein is mass percent.
Substantially namely the performance that is kept regenerated cellulose film and silk by intensity, elongation at break, the snappiness of the prepared Mierocrystalline cellulose of the present invention/zinc oxide nano-particle composite membrane, silk, and given again new function, such 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 amount of the product of preparation is low, and non-environmental-pollution is so aftertreatment technology is simple; The intensity of prepared Mierocrystalline cellulose/zinc oxide nano-particle composite membrane, silk, elongation at break, snappiness keep the performance of regenerated cellulose film and silk; and have good anti-microbial activity and a uv-absorbing function; can accomplish scale production; can be used for separation, evaporating-osmosis, ion-exchange, antibacterial deodourizing, uv-absorbing and wrapping material in chemical industry, food, environmental protection, weaving, the medical field, also can be used as medical material.
Description of drawings
The Mierocrystalline cellulose that accompanying drawing 1 prepares for the embodiment of the invention 1/zinc-oxide nano composite membrane photo.
The Mierocrystalline cellulose that accompanying drawing 2 makes for the embodiment of the invention 2/zinc-oxide nano crystal grain composite membrane surface (a) and cross section (b) electron scanning micrograph.
The streptococcus aureus (a) of the Mierocrystalline cellulose that accompanying drawing 3 prepares for the embodiment of the invention 2/zinc-oxide nano composite membrane and the bacteriostatic test photo of intestinal bacteria (b).
The ultraviolet absorpting spectrum of the Mierocrystalline cellulose that accompanying drawing 4 prepares for the embodiment of the invention 1/zinc-oxide nano composite membrane.
Embodiment
Below in conjunction with specific embodiment to technical scheme further instruction of the present invention
Embodiment 1
Getting 15 gram nitrogen contents is that 1.441% cellulose carbamate is scattered in 285 grams, the 7.0 wt% NaOH/0.8 wt% ZnO aqueous solution ,-10 ℃ lower freezing 24 hours, the dissolving of thawing under the room temperature condition obtains the cellulose carbamate solution that concentration is 5 wt%.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed.Centrifugal rear gained solution is poured on casting film-forming on the clean poly (methyl methacrylate) plate, and the thickness of controlling diaphragm is 0.5 mm, then immerse in the ethanol and solidified 15 minutes under 10 ℃ of conditions, 25 ℃ of Water Unders are washed, are fixed on the poly (methyl methacrylate) plate under 25 ℃ of conditions and obtain the composite membrane that zinc oxide nano-particle content is 7.0 wt% after the drying.The tensile strength of dry state composite membrane is 69 MPa, and elongation at break is 6%, the residual nitrogen amount of ammonia nitrogen detector detection composite membrane≤0.3%.
Scan the transmittance of composite membrane in wavelength 200 ~ 1000 nm scopes that the present embodiment makes with ultraviolet spectrometer (Shimadu UV-160A).Test result shows that the composite membrane that the present invention prepares has good uv-absorbing function as shown in Figure 4, and along with the increase of nano zine oxide content, the uv-absorbing increased functionality of film, and produce significantly " red shift ".This material is for the preparation of the fabric with uv-absorbing function and wrapping material etc.
Embodiment 2
Getting 20 gram nitrogen contents is that 1.441% cellulose carbamate is scattered in 380 grams, the 7.0 wt% NaOH/1.2 wt% ZnO aqueous solution ,-12 ℃ lower freezing 20 hours, the dissolving of thawing under the room temperature condition obtains the cellulose carbamate solution that concentration is 5 wt%.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed.Centrifugal rear gained solution is poured on casting film-forming on the clean poly (methyl methacrylate) plate, and the thickness of controlling diaphragm is 0.5 mm, then immerse in the ethanol and solidified 15 minutes under 10 ℃ of conditions, 25 ℃ of Water Unders are washed, are fixed on the poly (methyl methacrylate) plate under 25 ℃ of conditions and obtain the composite membrane that zinc oxide nano-particle content is 9.0 wt% after the drying.The tensile strength of composite membrane is 50 MPa, and elongation at break is 2%, the residual nitrogen amount of ammonia nitrogen detector detection composite membrane≤0.3%.
Bacteriostatic experiment
Bacterial classification:
Streptococcus aureus and intestinal bacteria (Staphylococcus aureus) are provided by Wuhan University Chinese Typical Representative culture collection center, are that bacterium is used in typical biomedical research, and are used to for a long time the anti-microbial property of evaluating material.Peel off the clone body of bacterium in 37 ℃ of lower preservations 72 hours.
The present embodiment gained Mierocrystalline cellulose/zinc-oxide nano composite membrane is cut into the circular membrane that diameter is 7 mm, and places 93% ethanolic soln soaking disinfection to clean with distilled water after 15 minutes.All laboratory apparatuss are sterilized in 200 ℃ of autoclaves.Composite membrane is put in streptococcus aureus and intestinal bacteria top in the culture dish nutritive medium, observes mould material surface and spore growing state on every side to estimate its anti-microbial property.
Accompanying drawing 3 is depicted as the Mierocrystalline cellulose that the present embodiment prepares/streptococcus aureus (a) of zinc-oxide nano composite membrane and bacteriostatic test photo of intestinal bacteria (b), antibacterial tests result: show that this matrix material has good biocidal property, in the culture dish on the composite membrane and do not occur spore circle spot on every side.And along with the increase of zinc-oxide nano crystal grain content, it is that bacteriostasis property increases that the inhibition zone around the composite membrane increases.This material can be used for preparing medical, the daily materials such as antibiotic fabric fiber or antibacterial film.
Embodiment 3
Getting 18 gram nitrogen contents is that 1.952% cellulose carbamate is scattered in 282 grams, 6.5 wt% NaOH/3., the 0 wt% ZnO aqueous solution ,-15 ℃ lower freezing 24 hours, it is 6 wt% cellulose carbamate solutions that the dissolving of thawing under the room temperature condition obtains concentration.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed.Centrifugal rear gained solution is poured on casting film-forming on the clean poly (methyl methacrylate) plate, and the thickness of controlling diaphragm is 0.5 mm, then immerse in the acetone and solidified 30 minutes under 0 ℃ of condition, 10 ℃ of Water Unders are washed, are fixed on the poly (methyl methacrylate) plate under 20 ℃ of conditions and obtain the composite membrane that zinc oxide nano-particle content is 14 wt% after the drying.The tensile strength of composite membrane is 61 MPa, and elongation at break is 3%, the residual nitrogen amount of ammonia nitrogen detector detection composite membrane≤0.3%.
Embodiment 4
Getting 12 gram nitrogen contents is that 1.732% cellulose carbamate is scattered in 188 grams, the 10.0 wt% NaOH/0.4 wt% ZnO aqueous solution ,-24 ℃ lower freezing 8 hours, the dissolving of thawing under the room temperature condition obtains the cellulose carbamate solution that concentration is 6 wt%.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed.Centrifugal rear gained solution is poured on casting film-forming on the clean poly (methyl methacrylate) plate, and the thickness of controlling diaphragm is 0.5 mm, then immerse in the methyl alcohol and solidified 10 minutes under 15 ℃ of conditions, 60 ℃ of Water Unders are washed, are fixed under 50 ℃ of conditions of poly (methyl methacrylate) plate and obtain the composite membrane that zinc oxide nano-particle content is 1.2 wt% after the drying.The tensile strength of composite membrane is 55 MPa, and elongation at break is 16%, the residual nitrogen amount of ammonia nitrogen detector detection composite membrane≤0.3 %.
Embodiment 5
Getting 24 gram nitrogen contents is that 1.009% cellulose carbamate is scattered in 376 grams, the 6.0 wt% NaOH/2.5 wt% ZnO aqueous solution ,-15 ℃ lower freezing 18 hours, the dissolving of thawing under the room temperature condition obtains the cellulose carbamate solution of concentration 6 wt%.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed.The solution of centrifugal rear gained is poured on and uses the glass knifing on the clean poly (methyl methacrylate) plate, and the thickness of controlling diaphragm is 0.5mm, then immerse in the ethylene glycol and solidified 5 minutes under 20 ℃ of conditions, 35 ℃ of Water Unders are washed, and are fixed under 70 ℃ of conditions of poly (methyl methacrylate) plate to obtain the composite membrane that zinc oxide nano-particle content is 10 wt% after the drying.The breaking tenacity of composite membrane is 85 MPa, and elongation at break is 9%, the residual nitrogen amount of ammonia nitrogen detector detection composite membrane≤0.3%.
Embodiment 6
Getting 18 gram nitrogen contents is that 0.30% cellulose carbamate is dissolved in 282 grams, the 10.0 wt% NaOH/4.0 wt% ZnO aqueous solution, and under-23 ℃ of conditions freezing 8 hours, the dissolving of thawing under the room temperature condition obtained the cellulose carbamate solution of 6 wt%.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed.Centrifugal rear gained solution is poured on casting film-forming on the clean poly (methyl methacrylate) plate, and the thickness of controlling diaphragm is 0.5 mm, then immerse in the glycerol and solidified 20 minutes under 50 ℃ of conditions, 15 ℃ of Water Unders are washed, are fixed under 15 ℃ of conditions of poly (methyl methacrylate) plate and obtain the composite membrane that zinc oxide nano-particle content is 16 wt% after the drying.The tensile strength of composite membrane is 65 MPa, and elongation at break is 6 wt%, the residual nitrogen amount of ammonia nitrogen detector detection composite membrane≤0.3%.
Embodiment 7
Getting 18 gram nitrogen contents is that 1.218% cellulose carbamate is scattered in the aqueous solution of 282 grams, 9.0 wt% NaOH/3.5 wt% ZnO ,-20 ℃ lower freezing 12 hours, the dissolving of thawing under the room temperature condition obtains 6 wt% cellulose carbamate solutions.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed.The solution of centrifugal rear gained is poured on and uses the glass knifing on the clean poly (methyl methacrylate) plate, and the thickness of controlling diaphragm is 0.5 mm, then immerse in the 2-propyl alcohol and solidified 10 minutes under 7 ℃ of conditions, 25 ℃ of Water Unders are washed, and are fixed under 45 ℃ of conditions of poly (methyl methacrylate) plate to obtain the composite membrane that zinc oxide nano-particle content is 13 wt% after the drying.The breaking tenacity of composite membrane is 70 MPa, and elongation at break is 12%, the residual nitrogen amount of ammonia nitrogen detector detection composite membrane≤0.3%.
Embodiment 8
Getting 24 gram nitrogen contents is that 1.218% cellulose carbamate sample dissolution is in the aqueous solution of 376 grams, 10.0 wt% NaOH/2.6 wt% ZnO, under-17 ℃ of conditions freezing 14 hours, it was 6 wt% cellulose carbamate solutions that the dissolving of thawing under the room temperature condition obtains concentration.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed.The solution of centrifugal rear gained is poured on casting film-forming on the clean poly (methyl methacrylate) plate, and the thickness of controlling diaphragm is 0.5 mm, then immerse in the n-propyl alcohol and solidified 10 minutes under 28 ℃ of conditions, 35 ℃ of Water Unders are washed, are fixed under 50 ℃ of conditions of poly (methyl methacrylate) plate and obtain the composite membrane that zinc oxide nano-particle content is 12 wt% after the drying.The tensile strength of composite membrane is 78 MPa, and elongation at break is 13%, the residual nitrogen amount of ammonia nitrogen detector detection composite membrane≤0.3%.
Embodiment 9
Getting 9 gram nitrogen contents is that 1.441% cellulose carbamate is scattered in 291 grams, the 7.0 wt% NaOH/0.8 wt% ZnO aqueous solution ,-10 ℃ lower freezing 24 hours, the dissolving of thawing under the room temperature condition obtains the cellulose carbamate solution that concentration is 3 wt%.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed.Centrifugal rear gained solution is poured on casting film-forming on the clean poly (methyl methacrylate) plate, and the thickness of controlling diaphragm is 0.5 mm, then immerse in the ethanol and solidified 15 minutes under 10 ℃ of conditions, 25 ℃ of Water Unders are washed, are fixed on the poly (methyl methacrylate) plate under 25 ℃ of conditions and obtain the composite membrane that zinc oxide nano-particle content is 12.0 wt% after the drying.The tensile strength of dry state composite membrane is 69 MPa, and elongation at break is 6%, the residual nitrogen amount of ammonia nitrogen detector detection composite membrane≤0.3%.
Embodiment 10
Getting 20 gram nitrogen contents is that 1.441% cellulose carbamate is scattered in 180 grams, the 7.5 wt% NaOH/2.0 wt% ZnO aqueous solution ,-12 ℃ lower freezing 20 hours, the dissolving of thawing under the room temperature condition obtains the cellulose carbamate solution that concentration is 10wt%.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed.Centrifugal rear gained solution is poured on casting film-forming on the clean poly (methyl methacrylate) plate, and the thickness of controlling diaphragm is 0.5 mm, then immerse in the ethanol and solidified 15 minutes under 10 ℃ of conditions, 40 ℃ of Water Unders are washed, are fixed on the poly (methyl methacrylate) plate under 25 ℃ of conditions and obtain the composite membrane that zinc oxide nano-particle content is 3.0 wt% after the drying.The tensile strength of composite membrane is 80 MPa, and elongation at break is 7%, the residual nitrogen amount of ammonia nitrogen detector detection composite membrane≤0.3%.
Embodiment 11
Getting 20 gram nitrogen contents is that 1.591% cellulose carbamate is scattered in 380 grams, the 7.0 wt% NaOH/0.8wt% ZnO aqueous solution ,-18 ℃ lower freezing 15 hours, the dissolving of thawing under the room temperature condition obtains the cellulose carbamate solution that concentration is 5 wt%.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed.Centrifugal rear gained solution is poured on spinning on the simple and easy spinning-drawing machine in laboratory, cellulose carbamate solution solidified 5 minutes in spinning nozzle is ejected in 30 ℃ 60 wt% ethanol (in the massfraction of the ethanol) aqueous solution, then through obtaining the conjugated fibre that zinc oxide nano-particle content is 7.0 wt% after the drying under 40 ℃ of washings, the 70 ℃ of conditions.The tensile strength of dry state conjugated fibre is 1.2 cN/dtex, and elongation at break is 6 %, the residual nitrogen amount of ammonia nitrogen detector detection composite membrane≤0.3%.
Embodiment 12
Getting 20 gram nitrogen contents is that 1.414% cellulose carbamate is scattered in 380 grams, the 7.0 wt% NaOH/0.6 wt% ZnO aqueous solution ,-12 ℃ lower freezing 24 hours, the dissolving of thawing under the room temperature condition obtains the cellulose carbamate solution that concentration is 5 wt%.Use ultracentrifuge evacuation and centrifugal degassing 15 minutes under 7,200 rev/mins rotating speed.Centrifugal rear gained solution is poured on spinning on the simple and easy spinning-drawing machine in laboratory, cellulose carbamate solution is ejected in 20 ℃ ethanol and n-propyl alcohol (1:1 through spinning nozzle, mass ratio) solidified in the aqueous solution 5 minutes in the mixed solution, then through obtaining the conjugated fibre that zinc oxide nano-particle content is 4.0 wt% after the drying under 35 ℃ of washings, the 50 ℃ of conditions.The tensile strength of dry state conjugated fibre is 0.8 cN/dtex, and elongation at break is 5 %, the residual nitrogen amount of ammonia nitrogen detector detection composite membrane≤0.3%.
Above-described embodiment as can be known, preparation method of the present invention is simple, preparation cost is low, the residual nitrogen amount of the product of preparation is low, non-environmental-pollution is so aftertreatment technology is simple; The intensity of prepared Mierocrystalline cellulose/zinc oxide nano-particle composite membrane, silk, elongation at break, snappiness keep the performance of regenerated cellulose film and silk, can accomplish scale production.
Claims (5)
1. Mierocrystalline cellulose/zinc oxide nano-particle composite manufacture method, it is characterized in that: cellulose carbamate is scattered in the NaOH/ZnO aqueous solution, thaw under the freezing rear room temperature and obtain composite solution, with composite solution through centrifugal removal of impurities, degassed after knifing or spray silk, in the organic solvent precipitation bath, solidify, then wash, be drying to obtain Mierocrystalline cellulose/zinc oxide composite.
2. Mierocrystalline cellulose as claimed in claim 1/zinc oxide nano-particle composite manufacture method, it is characterized in that: the mass percent concentration of NaOH is 6 ~ 10 wt% in the described composite solution, the mass percent concentration of ZnO is 0.4 ~ 4.0 wt%, and the mass percent concentration of cellulose carbamate is 3 ~ 10 wt%.
3. Mierocrystalline cellulose as claimed in claim 1/zinc oxide nano-particle composite manufacture method is characterized in that: the organic solvent in the described organic solvent precipitation bath is one or more the mixing solutions in ethanol, methyl alcohol, ethylene glycol, glycerol, n-propyl alcohol, 2-propyl alcohol, the acetone soln.
4. Mierocrystalline cellulose as claimed in claim 1/zinc oxide nano-particle composite manufacture method, it is characterized in that: the coagulation bath temperature of described organic solvent precipitation bath is 0-50 ℃, setting time is 5-30min.
5. Mierocrystalline cellulose as claimed in claim 1/zinc oxide nano-particle composite manufacture method, it is characterized in that: described washing temperature is 10-60 ℃.
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| 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 |
| CN106810723A (en) * | 2017-01-18 | 2017-06-09 | 浙江理工大学 | A kind of composite aquogel with separation protein effect 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 |
| CN111082008A (en) * | 2019-12-14 | 2020-04-28 | 浙江农林大学 | Preparation method of nanocellulose/zinc oxide compound for electrochemical energy storage |
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