CN102276876A - Bacterial cellulose porous foam material and preparation method thereof - Google Patents
Bacterial cellulose porous foam material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a bacterial cellulose porous foam material and a preparation method thereof, and in particular relates to a foam material used for preparing a moulded bacterial cellulose membrane by utilizing azodicarbonamide (AC foaming agent) and a preparation method thereof. In the bacterial cellulose porous foam material provided by the invention, internal structure of the bacterial cellulose membrane is shown as ellipse holes, the holes are interpenetrated, and hole diameter is 5-10 mu m. The preparation method of the bacterial cellulose porous foam material provided by the invention comprises the following steps of: preparing foaming solution by taking azodicarbonamide as a foaming agent and adding a surfactant and a foam stabilizer, fully soaking the moulded bacterial cellulose membrane into the foaming solution and then heating and foaming so as to prepare the bacterial cellulose porous foam material. In the process, the AC foaming agent is effectively introduced into the moulded bacterial cellulose membrane, decomposition temperature of the AC foaming agent is appropriate, a technological process is simple, preparation period is short, and the original chemical structure of the bacterial cellulose is not damaged, thus the bacterial cellulose porous foam material can be applied to multiple industrial fields.
Description
Technical field
The present invention relates to a kind of bacteria cellulose perforated foams and preparation method thereof, specifically be meant a kind of foam materials that utilizes Cellmic C 121 (AC whipping agent) preparation moulding bacteria cellulose film and preparation method thereof.
Background technology
Bacteria cellulose is a kind ofly to be secreted into extracellular filamentary fibers by bacterium, and it is formed by simple glucose polycondensation, and forms the network structure of random ordering, and its Fibre diameter is about 10～100nm, and the width between the fiber is about 70～80nm.Therefore bacteria cellulose have many very excellent physics and chemical property as the nano grade biological fiber.Water absorbing properties, good mechanical performance and excellent biocompatibility thereof etc. as the three-dimensional net structure of uniqueness, nano-scale fiber size, superelevation make bacterial fibers can be widely used in functional materials, nano-hybrid material, mould material, sorbing material, strongthener, degradable material, medical applications material etc.Bacteria cellulose still is subjected to certain restriction when being used in material for water treatment, tissue engineering material and protective material, its chief reason is that the random hole of nano level can't satisfy actual application requiring, for example the membrane for water treatment flux reaches the micron number magnitude with regard to the hole that needs film, tissue scaffold design material micron level hole then has the growth that utilizes cell, protective material then needs by keeping certain Air permenbility etc. than macroscopic void, therefore these all need the original nano level three-dimensional net structure of bacteria cellulose is modified, and form micron-sized regular hole.
Cellmic C 121 (AC whipping agent) has been widely used in the foam materialss such as preparation plastics, rubber owing to have good characteristics such as gas forming amount is big, nontoxic, tasteless.Himself heat decomposition temperature can reach 195～220 ℃, also can suitably add its heat decomposition temperature of the compound reduction of promoting agent.Usually the AC whipping agent is that form with pressed powder joins in the raw material dispersion of not moulding, for example when preparation polyvinyl chloride (PVC) foam materials, earlier the PVC screw rod is melt extruded the back and add after AC whipping agent solid particulate and promoting agent thereof carry out thorough mixing, carry out foamable after pouring the mould film-making into; The preparation of polypropylene (PP) foam materials is to add AC whipping agent and other auxiliary agents when the PP raw materials melt, pours into after mixing and forms the moulding sample in the mould, makes foam sample 187～190 ℃ of foaming then.In a word, the AC whipping agent is by in the raw material that adds not moulding with the pressed powder state to and then carry out foamable, rather than directly adds and be distributed in the molded product and the preparation foam material.Reported that at present the AC whipping agent can decompose and discharge a large amount of gases under alkaline NaOH solution condition, but this method remains the AC whipping agent added to and foams after mixing in the raw material dispersion of not moulding again, therefore need utilize a kind of novel preparation technology's method that the AC whipping agent is distributed to the moulding bacteria cellulose film equably and forms perforated foams.
Summary of the invention
The present invention is in order to overcome the existing in prior technology problem, foam materials and concrete processing method thereof that a kind of AC of utilization whipping agent prepares at the moulding bacteria cellulose film are proposed, for in type bacteria cellulose film, its main difficult point is that bacteria cellulose is a kind of aquagel membrane of moulding, and be difficult to be dissolved in the usual vehicle, if dissolving also can cause the mechanical property of bacteria cellulose film to reduce significantly and be difficult to repairs, therefore can not adopt prior art to make the bacteria cellulose foam material simultaneously.AC whipping agent solid powder particle is to be difficult to well disperse and enter in the fine and close bacteria cellulose film of moulding simultaneously, and higher AC heat decomposition temperature can destroy the structure of bacteria cellulose film self.The present invention by Cellmic C 121 (AC whipping agent) as whipping agent and add surfactant dissolves in NaOH solution, the bacteria cellulose film of moulding fully is immersed in this basic solution, the AC whipping agent is adsorbed fully be dispersed in the moulding bacteria cellulose film, add at last suds-stabilizing agent polyvinyl alcohol (PVA) afterwards foamable prepare the bacteria cellulose perforated foams, made bacteria cellulose foam materials hole is regular, and the aperture can reach 5～20 μ m.The present invention introduces the AC whipping agent in the bacteria cellulose film that has been shaped effectively, and its decomposition temperature is suitable, and processing method is simple, and preparation cycle is short, and does not destroy original bacteria cellulose self chemical structure, can be applicable to multiple practical field.
A kind of bacteria cellulose perforated foams internal structure of the present invention presents oval hole, connects mutually between the hole, and its aperture is 5～20 μ m.
The present invention also provides a kind of preparation method of bacteria cellulose foam materials, comprises the steps:
(1) pre-treatment: at first bacteria cellulose film is washed several times with deionized water, until the pH of bacteria cellulose film value is neutral, then bacteria cellulose film is immersed in mass concentration and is 12～24h in 1～3% the NaOH basic solution, take out behind the bacteria cellulose film standby;
(2) preparation frothing solution: add AC whipping agent, NaOH and deionized water in reaction vessel, its mass ratio is 3～10: 1～5: 100, until becoming glassy yellow solution, promptly be mixed with frothing solution after the abundant stirring and dissolving;
Perhaps add low quantity of surfactant simultaneously, until becoming glassy yellow solution, promptly be mixed with frothing solution after the abundant stirring and dissolving; The mass ratio of described tensio-active agent and AC whipping agent is 1: 10～15;
(3) soak the pre-treatment film: the bacteria cellulose film after step (1) is handled is immersed in the described frothing solution, and constantly stirs 3～5h;
(4) preparation polyvinyl alcohol solution: take by weighing the polyvinyl alcohol solid (PVA) of certain mass, be positioned in the deionized water and be heated to 80～100 ℃, until dissolving fully and being incubated; The mass ratio of described polyvinyl alcohol solid and AC whipping agent is 2～6: 1;
(5) foamable: the described immersion of the polyvinyl alcohol solution for preparing being poured into step (3) has in the frothing solution of bacteria cellulose film, and be warming up to 50～120 ℃ and make reaction, constantly stir simultaneously, when question response solution fades to clear, colorless by glassy yellow, finish reaction, obtain the bacteria cellulose film that foams;
(6) washing lyophilize: for several times with the described foaming bacteria cellulose film of absolute ethanol washing, when dehydrated alcohol no longer becomes muddy, residuals dissolves removal fully, use deionized water wash then 5～10 times, freezing 6～12h under-20～-40 ℃ of conditions, again it is carried out lyophilize 24～48h, promptly obtain the bacteria cellulose perforated foams;
Wherein, described tensio-active agent is a nonionogenic tenside, polyoxyethylene sorbitan monooleate (tween-80) or sorbitol anhydride oleate (Span-80).
Advantage of the present invention is to utilize the AC whipping agent can prepare bacteria cellulose film perforated foams after molded.
Another advantage of the present invention is that the AC whipping agent can be dispersed in the bacterial fibers film that has been shaped uniformly, rather than adds to and reach effective dispersion AC whipping agent in the bacteria cellulose raw material of dissolving back and foam.
An advantage more of the present invention be the AC whipping agent be at alkaline NaOH solution to the bacteria cellulose film drilling of foaming, temperature is controlled at 50～120 ℃ optimum range.
An advantage more of the present invention is when having added the AC whipping agent, has also added tensio-active agent (tween-80 and Span-80) and PVA suds-stabilizing agent thereof and has controlled the release of bubble in the foaming process and the formation of hole.Its resulting hole is regular, and the aperture can reach 5～20 μ m, and good mechanical properties.
Beneficial effect
The present invention utilizes the AC whipping agent to prepare a kind of in type bacteria cellulose film perforated foams, has proposed a kind of novel process method for preparing the moulding product perforated foams.This bacteria cellulose foam materials has regular micron order hole structure and mechanical property, can still keep bigger water regain after lyophilize.In preparation technology, the AC whipping agent is by being dissolved in the NaOH basic solution, be dispersed in the bacteria cellulose film that has been shaped, and under tensio-active agent (tween-80 and Span-80) and stablizer (PVA) effect, thermal degradation discharges a large amount of gases and prepares the bacteria cellulose foam materials, and formed foam hole is arranged very regular even, and pore size can reach 5～20 μ m, it is good that fibrous texture keeps, and have good water flux.Its preparation technology is simple, efficient, the time cycle is short, can be applicable to popular domains such as water treatment, protective material, organizational project.
Description of drawings
Fig. 1 is a bacteria cellulose local surfaces sem photograph
Fig. 2 is the local nanometer three-dimensional net structure of a bacteria cellulose mimic diagram
Fig. 3 is that whipping agent, emulsifying agent and suds-stabilizing agent are adsorbed on mimic diagram on the bacteria cellulose
Fig. 4 is a bacteria cellulose foam materials Local Porous three-dimensional net structure mimic diagram
Fig. 5 is a bacteria cellulose foam materials Local Porous three-dimensional net structure sem photograph
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
A kind of bacteria cellulose perforated foams internal structure of the present invention presents oval hole, and the regular arrangement that is parallel to each other, and connects mutually between the hole, and its aperture is 5～20 μ m; Outward appearance is the white foam shape.
A kind of bacteria cellulose perforated foams provided by the present invention and preparation method thereof, its drilling principle is as described below: bacteria cellulose itself has unique three-dimensional network space structure (as shown in Figure 1), about 100～the 200nm of bore clearance, curve shown in Figure 2 are the mimic diagrams of local structure among Fig. 1.By after abundant absorption AC whipping agent, emulsifying agent and the suds-stabilizing agent (as shown in Figure 3), at high temperature the AC whipping agent decomposes, discharge a large amount of nitrogen, carbon monoxide and ammonia and in the aqueous solution, form bubble, make the internal networking structure of bacteria cellulose be subjected to the influence of pressure in bubbles and form regular network structure.Tensio-active agent (tween-80, Arlacel-80) and suds-stabilizing agent (PVA) mainly play the effect of control bubble stabilizes time and gas release rate in the process of preparation.As shown in Figure 4,, formed the porous bacteria cellulose three-dimensional net structure by under the effect of whipping agent, and regular orderly, and pore size can reach 5～20 μ m.This bacteria cellulose perforated foams can keep still keeping bigger suction content after mechanical property, the lyophilize preferably, and Fig. 5 is a bacteria cellulose foam materials Local Porous three-dimensional net structure sem photograph.
Embodiment 1
(1) pre-treatment: at first with deionized water bacteria cellulose film being washed several times, is neutral until the pH of bacteria cellulose film value, then bacteria cellulose film is immersed in mass concentration and is 24h in 1% the NaOH basic solution, takes out behind the bacteria cellulose film standby;
(2) preparation frothing solution: add AC whipping agent, NaOH and deionized water in reaction vessel, its mass ratio is 3: 1: 100, until becoming glassy yellow solution, promptly is mixed with frothing solution after the abundant stirring and dissolving;
(3) soak the pre-treatment film: the bacteria cellulose film after step (1) is handled is immersed in the described frothing solution, and constantly stirs 3h;
(4) preparation polyvinyl alcohol solution: take by weighing the polyvinyl alcohol solid of certain mass, the mass ratio of itself and AC whipping agent is 2: 1, is positioned in the deionized water and is heated to 80 ℃, until dissolving fully and being incubated;
(5) foamable: the described immersion of the polyvinyl alcohol solution for preparing being poured into step (3) has in the frothing solution of bacteria cellulose film, and be warming up to 50 ℃ and make reaction, constantly stir simultaneously, when question response solution fades to clear, colorless by glassy yellow, finish reaction, obtain the bacteria cellulose film that foams;
(6) washing lyophilize: for several times with the described foaming bacteria cellulose film of absolute ethanol washing, when dehydrated alcohol no longer becomes muddy, residuals dissolves removal fully, use deionized water wash then 5 times, freezing 12h under-20 ℃ of conditions, again it is carried out lyophilize 24h, promptly obtain the bacteria cellulose perforated foams;
(1) pre-treatment: at first with deionized water bacteria cellulose film being washed several times, is neutral until the pH of bacteria cellulose film value, then bacteria cellulose film is immersed in mass concentration and is 24h in 1% the NaOH basic solution, takes out behind the bacteria cellulose film standby;
(2) preparation frothing solution: in reaction vessel, add AC whipping agent, NaOH and deionized water, its mass ratio is 3: 1: 100, add the tensio-active agent tween-80 simultaneously, the mass ratio of itself and AC whipping agent is 1: 10, until becoming glassy yellow solution, promptly be mixed with frothing solution after the abundant stirring and dissolving;
(3) soak the pre-treatment film: the bacteria cellulose film after step (1) is handled is immersed in the described frothing solution, and constantly stirs 3h;
(4) preparation polyvinyl alcohol solution: take by weighing the polyvinyl alcohol solid of certain mass, the mass ratio of itself and AC whipping agent is 2: 1, is positioned in the deionized water and is heated to 80 ℃, until dissolving fully and being incubated;
(5) foamable: the described immersion of the polyvinyl alcohol solution for preparing being poured into step (3) has in the frothing solution of bacteria cellulose film, and be warming up to 50 ℃ and make reaction, constantly stir simultaneously, when question response solution fades to clear, colorless by glassy yellow, finish reaction, obtain the bacteria cellulose film that foams;
(6) washing lyophilize: for several times with the described foaming bacteria cellulose film of absolute ethanol washing, when dehydrated alcohol no longer becomes muddy, residuals dissolves removal fully, use deionized water wash then 5 times, freezing 12h under-20 ℃ of conditions, again it is carried out lyophilize 24h, promptly obtain the bacteria cellulose perforated foams;
Embodiment 3
(1) pre-treatment: at first with deionized water bacteria cellulose film being washed several times, is neutral until the pH of bacteria cellulose film value, then bacteria cellulose film is immersed in mass concentration and is 24h in 1% the NaOH basic solution, takes out behind the bacteria cellulose film standby;
(2) preparation frothing solution: in reaction vessel, add AC whipping agent, NaOH and deionized water, its mass ratio is 3: 1: 100, add the tensio-active agent Span-80 simultaneously, the mass ratio of itself and AC whipping agent is 1: 10, until becoming glassy yellow solution, promptly be mixed with frothing solution after the abundant stirring and dissolving;
(3) soak the pre-treatment film: the bacteria cellulose film after step (1) is handled is immersed in the described frothing solution, and constantly stirs 3h;
(4) preparation polyvinyl alcohol solution: take by weighing the polyvinyl alcohol solid of certain mass, the mass ratio of itself and AC whipping agent is 2: 1, is positioned in the deionized water and is heated to 80 ℃, until dissolving fully and being incubated;
(5) foamable: the described immersion of the polyvinyl alcohol solution for preparing being poured into step (3) has in the frothing solution of bacteria cellulose film, and be warming up to 50 ℃ and make reaction, constantly stir simultaneously, when question response solution fades to clear, colorless by glassy yellow, finish reaction, obtain the bacteria cellulose film that foams;
(6) washing lyophilize: for several times with the described foaming bacteria cellulose film of absolute ethanol washing, when dehydrated alcohol no longer becomes muddy, residuals dissolves removal fully, use deionized water wash then 5 times, freezing 12h under-20 ℃ of conditions, again it is carried out lyophilize 24h, promptly obtain the bacteria cellulose perforated foams;
Embodiment 4
(1) pre-treatment: at first with deionized water bacteria cellulose film being washed several times, is neutral until the pH of bacteria cellulose film value, then bacteria cellulose film is immersed in mass concentration and is 18h in 2% the NaOH basic solution, takes out behind the bacteria cellulose film standby;
(2) preparation frothing solution: add AC whipping agent, NaOH and deionized water in reaction vessel, its mass ratio is 5: 3: 100, until becoming glassy yellow solution, promptly is mixed with frothing solution after the abundant stirring and dissolving;
(3) soak the pre-treatment film: the bacteria cellulose film after step (1) is handled is immersed in the described frothing solution, and constantly stirs 4h;
(4) preparation polyvinyl alcohol solution: take by weighing the polyvinyl alcohol solid of certain mass, the mass ratio of itself and AC whipping agent is 4: 1, is positioned in the deionized water and is heated to 90 ℃, until dissolving fully and being incubated;
(5) foamable: the described immersion of the polyvinyl alcohol solution for preparing being poured into step (3) has in the frothing solution of bacteria cellulose film, and be warming up to 80 ℃ and make reaction, constantly stir simultaneously, when question response solution fades to clear, colorless by glassy yellow, finish reaction, obtain the bacteria cellulose film that foams;
(6) washing lyophilize: for several times with the described foaming bacteria cellulose film of absolute ethanol washing, when dehydrated alcohol no longer becomes muddy, residuals dissolves removal fully, use deionized water wash then 7 times, freezing 18h under-30 ℃ of conditions, again it is carried out lyophilize 36h, promptly obtain the bacteria cellulose perforated foams;
Embodiment 5
(1) pre-treatment: at first with deionized water bacteria cellulose film being washed several times, is neutral until the pH of bacteria cellulose film value, then bacteria cellulose film is immersed in mass concentration and is 24h in 2% the NaOH basic solution, takes out behind the bacteria cellulose film standby;
(2) preparation frothing solution: in reaction vessel, add AC whipping agent, NaOH and deionized water, its mass ratio is 5: 3: 100, add the tensio-active agent tween-80 simultaneously, the mass ratio of itself and AC whipping agent is 1: 13, until becoming glassy yellow solution, promptly be mixed with frothing solution after the abundant stirring and dissolving;
(3) soak the pre-treatment film: the bacteria cellulose film after step (1) is handled is immersed in the described frothing solution, and constantly stirs 4h;
(4) preparation polyvinyl alcohol solution: take by weighing the polyvinyl alcohol solid of certain mass, the mass ratio of itself and AC whipping agent is 4: 1, is positioned in the deionized water and is heated to 90 ℃, until dissolving fully and being incubated;
(5) foamable: the described immersion of the polyvinyl alcohol solution for preparing being poured into step (3) has in the frothing solution of bacteria cellulose film, and be warming up to 80 ℃ and make reaction, constantly stir simultaneously, when question response solution fades to clear, colorless by glassy yellow, finish reaction, obtain the bacteria cellulose film that foams;
(6) washing lyophilize: for several times with the described foaming bacteria cellulose film of absolute ethanol washing, when dehydrated alcohol no longer becomes muddy, residuals dissolves removal fully, use deionized water wash then 7 times, freezing 18h under-30 ℃ of conditions, again it is carried out lyophilize 36h, promptly obtain the bacteria cellulose perforated foams;
Embodiment 6
(1) pre-treatment: at first with deionized water bacteria cellulose film being washed several times, is neutral until the pH of bacteria cellulose film value, then bacteria cellulose film is immersed in mass concentration and is 24h in 2% the NaOH basic solution, takes out behind the bacteria cellulose film standby;
(2) preparation frothing solution: in reaction vessel, add AC whipping agent, NaOH and deionized water, its mass ratio is 5: 3: 100, add the tensio-active agent Span-80 simultaneously, the mass ratio of itself and AC whipping agent is 1: 13, until becoming glassy yellow solution, promptly be mixed with frothing solution after the abundant stirring and dissolving;
(3) soak the pre-treatment film: the bacteria cellulose film after step (1) is handled is immersed in the described frothing solution, and constantly stirs 4h;
(4) preparation polyvinyl alcohol solution: take by weighing the polyvinyl alcohol solid of certain mass, the mass ratio of itself and AC whipping agent is 4: 1, is positioned in the deionized water and is heated to 90 ℃, until dissolving fully and being incubated;
(5) foamable: the described immersion of the polyvinyl alcohol solution for preparing being poured into step (3) has in the frothing solution of bacteria cellulose film, and be warming up to 80 ℃ and make reaction, constantly stir simultaneously, when question response solution fades to clear, colorless by glassy yellow, finish reaction, obtain the bacteria cellulose film that foams;
(6) washing lyophilize: for several times with the described foaming bacteria cellulose film of absolute ethanol washing, when dehydrated alcohol no longer becomes muddy, residuals dissolves removal fully, use deionized water wash then 7 times, freezing 18h under-30 ℃ of conditions, again it is carried out lyophilize 36h, promptly obtain the bacteria cellulose perforated foams;
Embodiment 7
(1) pre-treatment: at first with deionized water bacteria cellulose film being washed several times, is neutral until the pH of bacteria cellulose film value, then bacteria cellulose film is immersed in mass concentration and is 24h in 3% the NaOH basic solution, takes out behind the bacteria cellulose film standby;
(2) preparation frothing solution: add AC whipping agent, NaOH and deionized water in reaction vessel, its mass ratio is 10: 5: 100, until becoming glassy yellow solution, promptly is mixed with frothing solution after the abundant stirring and dissolving;
(3) soak the pre-treatment film: the bacteria cellulose film after step (1) is handled is immersed in the described frothing solution, and constantly stirs 5h;
(4) preparation polyvinyl alcohol solution: take by weighing the polyvinyl alcohol solid of certain mass, the mass ratio of itself and AC whipping agent is 6: 1, is positioned in the deionized water and is heated to 100 ℃, until dissolving fully and being incubated;
(5) foamable: the described immersion of the polyvinyl alcohol solution for preparing being poured into step (3) has in the frothing solution of bacteria cellulose film, and be warming up to 120 ℃ and make reaction, constantly stir simultaneously, when question response solution fades to clear, colorless by glassy yellow, finish reaction, obtain the bacteria cellulose film that foams;
(6) washing lyophilize: for several times with the described foaming bacteria cellulose film of absolute ethanol washing, when dehydrated alcohol no longer becomes muddy, residuals dissolves removal fully, use deionized water wash then 10 times, freezing 24h under-40 ℃ of conditions, again it is carried out lyophilize 48h, promptly obtain the bacteria cellulose perforated foams;
Embodiment 8
(1) pre-treatment: at first with deionized water bacteria cellulose film being washed several times, is neutral until the pH of bacteria cellulose film value, then bacteria cellulose film is immersed in mass concentration and is 24h in 3% the NaOH basic solution, takes out behind the bacteria cellulose film standby;
(2) preparation frothing solution: in reaction vessel, add AC whipping agent, NaOH and deionized water, its mass ratio is 10: 5: 100, add the tensio-active agent tween-80 simultaneously, the mass ratio of itself and AC whipping agent is 1: 15, until becoming glassy yellow solution, promptly be mixed with frothing solution after the abundant stirring and dissolving;
(3) soak the pre-treatment film: the bacteria cellulose film after step (1) is handled is immersed in the described frothing solution, and constantly stirs 5h;
(4) preparation polyvinyl alcohol solution: take by weighing the polyvinyl alcohol solid of certain mass, the mass ratio of itself and AC whipping agent is 6: 1, is positioned in the deionized water and is heated to 100 ℃, until dissolving fully and being incubated;
(5) foamable: the described immersion of the polyvinyl alcohol solution for preparing being poured into step (3) has in the frothing solution of bacteria cellulose film, and be warming up to 120 ℃ and make reaction, constantly stir simultaneously, when question response solution fades to clear, colorless by glassy yellow, finish reaction, obtain the bacteria cellulose film that foams;
(6) washing lyophilize: for several times with the described foaming bacteria cellulose film of absolute ethanol washing, when dehydrated alcohol no longer becomes muddy, residuals dissolves removal fully, use deionized water wash then 10 times, freezing 24h under-40 ℃ of conditions, again it is carried out lyophilize 48h, promptly obtain the bacteria cellulose perforated foams;
Embodiment 9
(1) pre-treatment: at first with deionized water bacteria cellulose film being washed several times, is neutral until the pH of bacteria cellulose film value, then bacteria cellulose film is immersed in mass concentration and is 24h in 3% the NaOH basic solution, takes out behind the bacteria cellulose film standby;
(2) preparation frothing solution: in reaction vessel, add AC whipping agent, NaOH and deionized water, its mass ratio is 10: 5: 100, add the tensio-active agent Span-80 simultaneously, the mass ratio of itself and AC whipping agent is 1: 15, until becoming glassy yellow solution, promptly be mixed with frothing solution after the abundant stirring and dissolving;
(3) soak the pre-treatment film: the bacteria cellulose film after step (1) is handled is immersed in the described frothing solution, and constantly stirs 5h;
(4) preparation polyvinyl alcohol solution: take by weighing the polyvinyl alcohol solid of certain mass, the mass ratio of itself and AC whipping agent is 6: 1, is positioned in the deionized water and is heated to 100 ℃, until dissolving fully and being incubated;
(5) foamable: the described immersion of the polyvinyl alcohol solution for preparing being poured into step (3) has in the frothing solution of bacteria cellulose film, and be warming up to 120 ℃ and make reaction, constantly stir simultaneously, when question response solution fades to clear, colorless by glassy yellow, finish reaction, obtain the bacteria cellulose film that foams;
(6) washing lyophilize: for several times with the described foaming bacteria cellulose film of absolute ethanol washing, when dehydrated alcohol no longer becomes muddy, residuals dissolves removal fully, use deionized water wash then 10 times, freezing 24h under-40 ℃ of conditions, again it is carried out lyophilize 48h, promptly obtain the bacteria cellulose perforated foams;
Claims (2)
1. bacteria cellulose perforated foams, it is characterized in that: the bacteria cellulose film internal structure presents oval hole, connects mutually between the hole, and its aperture is 5～20 μ m.
2. the preparation method of a kind of bacteria cellulose foam materials as claimed in claim 1 is characterized in that comprising the steps:
(1) pre-treatment: at first bacteria cellulose film is washed several times with deionized water, until the pH of bacteria cellulose film value is neutral, then bacteria cellulose film is immersed in mass concentration and is 12～24h in 1～3% the NaOH solution, take out behind the bacteria cellulose film standby;
(2) preparation frothing solution: add AC whipping agent, NaOH and deionized water in reaction vessel, its mass ratio is 3～10: 1～5: 100, until becoming glassy yellow solution, promptly be mixed with frothing solution after the abundant stirring and dissolving;
Perhaps add low quantity of surfactant simultaneously, until becoming glassy yellow solution, promptly be mixed with frothing solution after the abundant stirring and dissolving; The mass ratio of described tensio-active agent and AC whipping agent is 1: 10～15;
(3) soak the pre-treatment film: the bacteria cellulose film after step (1) is handled is immersed in the described frothing solution, and constantly stirs 3～5h;
(4) preparation polyvinyl alcohol solution: take by weighing the polyvinyl alcohol solid of certain mass, be positioned in the deionized water and be heated to 80～100 ℃, until dissolving fully and being incubated; The mass ratio of described polyvinyl alcohol solid and AC whipping agent is 2～6: 1;
(5) foamable: the described immersion of the polyvinyl alcohol solution for preparing being poured into step (3) has in the frothing solution of bacteria cellulose film, and be warming up to 50～120 ℃ and make reaction, constantly stir simultaneously, when question response solution fades to clear, colorless by glassy yellow, finish reaction, obtain the bacteria cellulose film that foams;
(6) washing lyophilize: for several times with the described foaming bacteria cellulose film of absolute ethanol washing, when dehydrated alcohol no longer becomes muddy, use deionized water wash then 5～10 times, freezing 6～12h under-20～-40 ℃ of conditions, again it is carried out lyophilize 24～48h, promptly obtain the bacteria cellulose perforated foams;
Wherein, described tensio-active agent is a nonionogenic tenside, is polyoxyethylene sorbitan monooleate or sorbitol anhydride oleate.
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| CN104958782A (en) * | 2015-06-08 | 2015-10-07 | 东华大学 | Bacterial cellulose porous foamed material and preparation method thereof |
| CN106191165A (en) * | 2016-08-05 | 2016-12-07 | 山东纳美德生物科技有限公司 | A kind of Bacterial cellulose bubble fermentation method |
| CN106190819A (en) * | 2016-08-05 | 2016-12-07 | 山东纳美德生物科技有限公司 | A kind of bacterial cellulose product bubble fermentation Apparatus and method for |
| CN109414055A (en) * | 2016-07-11 | 2019-03-01 | 虹霓机械制造有限公司 | For handling the method for tobacco-containing material, the device of processed tobacco-containing material and the tobacco industry |
| WO2022178698A1 (en) * | 2021-02-24 | 2022-09-01 | 海南光宇生物科技有限公司 | Bacterial cellulose-based porous foam dressing, preparation method therefor and use thereof |
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| CN102671236A (en) * | 2012-05-03 | 2012-09-19 | 北京科技大学 | Method for preparing nanofiber reinforcement hydrogel bionic artificial meniscus composite material |
| CN103772749A (en) * | 2013-12-25 | 2014-05-07 | 湖北工业大学 | Plant fiber porous composite material |
| CN104958782A (en) * | 2015-06-08 | 2015-10-07 | 东华大学 | Bacterial cellulose porous foamed material and preparation method thereof |
| CN104958782B (en) * | 2015-06-08 | 2018-01-02 | 东华大学 | A kind of bacterial cellulose porous foam material and preparation method thereof |
| CN109414055A (en) * | 2016-07-11 | 2019-03-01 | 虹霓机械制造有限公司 | For handling the method for tobacco-containing material, the device of processed tobacco-containing material and the tobacco industry |
| CN106191165A (en) * | 2016-08-05 | 2016-12-07 | 山东纳美德生物科技有限公司 | A kind of Bacterial cellulose bubble fermentation method |
| CN106190819A (en) * | 2016-08-05 | 2016-12-07 | 山东纳美德生物科技有限公司 | A kind of bacterial cellulose product bubble fermentation Apparatus and method for |
| CN106191165B (en) * | 2016-08-05 | 2019-11-22 | 山东纳美德生物科技有限公司 | A kind of bacteria cellulose bubble fermentation method |
| WO2022178698A1 (en) * | 2021-02-24 | 2022-09-01 | 海南光宇生物科技有限公司 | Bacterial cellulose-based porous foam dressing, preparation method therefor and use thereof |
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