CN103387687A - Preparation method of chitosan nanometer fiber resin composite film material - Google Patents
Preparation method of chitosan nanometer fiber resin composite film material Download PDFInfo
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Abstract
The invention discloses a preparation method of a chitosan nanometer fiber resin composite film material. The preparation method comprises the following steps of: (1), preparing chitosan by deacetylation chemical treatment of commercially purchased pure chitin; (2), grinding, ultrasonically treating, high-pressure homogenizing and centrifugally and mechanically treating the chitosan to prepare the chitosan nanometer fiber; (3), preparing a chitosan nanometer fiber film from the chitosan nanometer fiber; and (4), compounding the chitosan nanometer fiber film with the resin to prepare the chitosan nanometer fiber resin composite film material. The chitosan nanometer fiber resin composite film material which is prepared by the preparation method disclosed by the invention is not only good in optical transparency, but also high in strength and small in thermal expansion, and can be used for the fields of a substrate material, a flexible display material of a solar photovoltaic cell, and the like.
Description
Technical field
The present invention relates to a kind of preparation method of chitosan nano fiber resin compounded mould material, belong to the natural macromolecular material field, also possession is in chemistry, Forestry Engineering, Packaging Engineering, field of new.
Technical background
1859, French scientist C.Rouget processed chitin with the concentrated base heated and boiled, obtained Chitosan, is named as chitosan chitosan, and it is unique alkaline natural polysaccharide.It has been generally acknowledged that, the chitin of deacetylation more than 55% can be dissolved in the hydrochloric acid of 1% acetic acid or 1%, so deacetylation reaches 55% and is called as chitosan.Take off N-acetyl degree and still be referred to as chitin below 50%.This shows, chitin is only that N one deacetylation is different and own from the difference of chitosan.
Chitosan (Chitosan) can be dissolved in diluted acid, is the product of chitin after the deacetylated processing of sodium hydroxide, water soluble; It is the rare positively charged high molecular polymer of occurring in nature.These character make chitosan all play the part of very important role in the fields such as medicine, macromolecular material.
Chitosan, as a kind of nontoxic, pollution-free and biodegradable environmental friendliness shaped material, shows tempting prospect in film industry.Because China shrimp, crab resource are very abundant, the chitosan wide material sources, cheap and easy to get, therefore develop the chitosan film material, its development and application prospect will be very wide
Active hydroxyl and amino are arranged in the chitosan macromole, have stronger chemical reaction ability.Following reaction can occur hydroxyl under alkaline condition on C-6: hydroxyethylation-chitosan and oxyethane react, and can obtain hydroxyethylated derivative.Carboxymethylation-chitosan and chloroacetate reaction just carboxymethylated derivative.
Using the chemical modification chitin to carry out deacetylation, to prepare deacetylated chitin be chitosan, and then chitosan is carried out the fiber nanometer, obtains chitosan nano fiber.
Summary of the invention
That the present invention proposes is a kind of preparation method of chitosan nano fiber resin compounded mould material; its purpose: thereby the pure chitin that uses business to buy carries out chemical treatment, be that deacetylated chitin obtains chitosan; preparing required chitosan nano fiber through mechanical treatment; after obtaining nanofiber, the resin compounded such as the chitosan nano fiber film prepared and polyethersulfone, polymethylmethacrylate are prepared nano compound film.
Technical solution of the present invention: a kind of preparation method of chitosan nano fiber resin compounded mould material, the method comprises the steps:
(1) the pure chitin of business being bought is prepared into chitosan by deacetylated chemical treatment with chitin;
(2) to chitosan grind, ultrasonic, high-pressure homogeneous, centrifugal machine processes and prepares chitosan nano fiber;
(3) chitosan nano fiber is prepared the chitosan nano fiber film;
(4) chitosan nano fiber film and resin compounded are prepared chitosan nano fiber resin compounded mould material.
Advantage of the present invention:Because the diameter of gained chitosan nano fiber has reached nanoscale, the rich surface of fiber contains a large amount of hydroxyls, make fiber mutually be woven into netted tangled structure, the biocompatibility and the degradability that have of chitosan self, make its nanofiber have excellent application potential in fields such as strengthening polymer nanocomposites, flexible electrical equipment light-transmissive film in addition.Concrete characteristics show:
(1) width of chitosan after milled processed reached the rank of nanometer, mutually be wound around between fiber and fiber, and present three-dimensional space reticulated structure, this is under the effect of lower millstone on shredder, chitin fiber has been subject to impartial mechanical shock reactive force in all directions, nanofiber is intactly separated from chitin fiber is intrafascicular, the chitosan nano fiber surface of the high length-diameter ratio that obtains is exposing a large amount of hydroxyls, attracts each other between hydroxyl and makes fiber be intertwined to form netted tangled structure.But, because reactive force between hydroxyl is larger, also make the part fiber mutually overlap in the vertical, formed fiber aggregate, increased the diameter width of fiber, but do not have influence on the whole the reticulated structure of chitosan nano fiber.The high length-diameter ratio of chitosan nano fiber, high specific surface area and netted tangled structure make it when strengthening polymkeric substance, can play good toughening effect.When add the ultrasonic processing that adds after centrifugal through grinding after, owing to having increased other more mechanical forces on the basis at the grinding machinery reactive force, thereby can further destroy the hydrogen bond force between chitosan nano fiber, the thicker bundles of nanofibers of the width that flocks together is opened into single thinner nanofiber, due to the connection of hydrogen bond still being arranged between single nanofiber, so still form three-dimensional space net structure between them;
(2) cavatition that produces by high-strength ultrasonic, fiber is carried out break process, also obtained the fibril of diameter at nanoscale, the dispersion state of gained fibril suspension liquid is very even, but also have certain micron order fiber in the gained fibril, the diameter Distribution scope of fiber is larger;
(3) the high-strength ultrasonic cavitation process is as a kind of succinct nanofibrils extracting method efficiently, play an important role in the fine process of machinery solution of fiber, when chitin fiber/water termination is subject to hyperacoustic used time of doing, far from it with the cavitation in pure water liquid in cavitation at the interface.Because the asymmetry of near interface can make bubble generation deformation, more flat near fiber one side, this just plays a kind of strengthening effect, produces the microjet of rapid movement while making collapse, and with the speed directive fiber/water interface greater than 100 m/s, and then make fiber surface localized attack occur and degrade.Whether relevant with the size on adjacent fiber cellulose fiber surface the appearance of this microjet is, and the size that the size of fiber surface must be several times as much as bubble just can;
(4), for improving the efficiency of ul-trasonic irradiation, need carry out grinding to a certain degree before supersound process,, tentatively to open robust fibre, improve the specific surface area of fiber.During this time, little solid particulate under the ordering about of turbulent flow and shockwave, can make solids produce at a high speed and collide.When the fibrous suspension that contains size and be several times as much as cavitation bubble is subject to hyperacoustic used time of doing, the microjet shockwave that ultrasonic cavitation produces will play machinery and separate fine effect, and nanofibrils is separated from coarse fiber bundle;
(5) size of ultrasonic cavitation intensity depends on the size of its output rating, the final cavitation effect of fiber is somewhat dependent upon again the length of supersound process time, need consider simultaneously the energy great question in ultrasonic procedure.Therefore, selecting ultrasonic time is set is 30min/ time, and power is 80%;
(6) the cavatition power that process to produce due to high-strength ultrasonic, far below this high-strength mechanical processing mode of high-pressure homogeneous processing, makes simple dependence high-strength ultrasonic process, and nanofibrils intactly can not be separated from biomass fiber.And because a large amount of hydroxyls is contained on the surface of the nanofibrils after grinding-supersound process, make fibril easily reunite in drying process, the feature that can not keep individual filaments, needing that for this reason the gained nanofibrils is carried out high pressure homogenization processes, to avoid fibril to produce clustering phenomena in drying process, and then the chitosan nano fibril that obtains nanoscale, high length-diameter ratio, is separated from each other and is woven into a mesh structure;
(7) after utilizing high pressure homogenization to process chitosan nano fibril 30min, obtained having high length-diameter ratio, the uniform Mierocrystalline cellulose nanofibrils of diameter size distribution.Only amplify in the situation of 20000 times, with the sample after grinding-supersound process, carry out step by step the fibril of gained after high-pressure homogeneous processing and have the very good fine effect of machinery solution, fibril is separated from each other each other, can observe clearly the feature of individual filaments, almost not observe the existence of a large amount of bunches of shape fibril aggregates, but be interweaved again between fibril, be overlapped into netted tangled structure, can when improving polymer strength, improve its toughness;
(8) the chitosan nano fiber diameter Distribution after milled processed is more inhomogeneous, but fiber is mostly in the 100nm scope, and the Fiber Distribution over 70% is in 60 to 100nm scope, and approximately 10% Fibre diameter is greater than 100nm, near micron order, the coarse fiber bundle of namely not opening temporarily after milled processed.The chitin fiber that carries out subsequently supersound process has further obtained refinement, the diameter of fiber mainly is distributed in the scope of 20-60nm, and quantity accounts for 72%, and wherein 49% Fibre diameter is in 40-60nm, robust fibre is less, and sample reaches being uniformly distributed of Nano grade substantially.
Description of drawings
Fig. 1 is chitosan preparation flow figure.
Fig. 2 is the preparation process figure of chitosan nano fiber.
Fig. 3 is the chitin fiber figure after milled processed.
Fig. 4 is the diameter Distribution figure of chitin fiber after milled processed.
Fig. 5 is the chitin fiber figure after grinding+supersound process.
Fig. 6 is the diameter Distribution figure of the chitin fiber after grinding+supersound process.
Fig. 7 is the chitin fiber figure after grinding+ultrasonic+high-pressure homogeneous processing.
Fig. 8 is the diameter Distribution figure of the chitin fiber after grinding+ultrasonic+high-pressure homogeneous processing.
Embodiment
A kind of preparation method of chitosan nano fiber resin compounded mould material, comprise the steps:
(1) the pure chitin of business being bought is prepared into chitosan by deacetylated chemical treatment with chitin;
(2) to chitosan grind, ultrasonic, high-pressure homogeneous, centrifugal machine processes and prepares chitosan nano fiber;
(3) chitosan nano fiber is prepared the chitosan nano fiber film;
(4) chitosan nano fiber film and resin compounded are prepared chitosan nano fiber resin compounded mould material.
Described deacetylated chemical treatment is that chitin is prepared into chitosan, specifically comprises 1) acid treatment of learning from else's experience removes inorganic salt; 2) alkaline purification deproteination matter and ethanolic soln remove the chitin powder of pigment, pour in sodium hydroxide solution, put into heat collecting type magnetic force heating stirrer and stir; Heated and stirred in water-bath, keep, and changes alkaline solution one time; 3) the chitin powder after deacetylated is washed to neutrality,, then to its drying, has just obtained chitosan; The hot alkaline solution that 4) will contain chitosan fully washs through vacuumfilter, namely obtains the chitosan sample.
Described chitosan obtains: get chitin powder 10g.Preparation 300 ~ 400ml concentration is 45% ~ 50% sodium hydroxide alkaline solution 300 ml, pours in the beaker that the chitin powder is housed, and 65 ~ 90 ℃ of heated and stirred 12h in water-bath, kept every 4 ~ 8 hours, changes alkaline solution one time.Finally with the hot alkaline solution of chitosan-containing through vacuumfilter fully wash to pH be 7, can obtain the chitosan sample,, then to its drying, just obtained chitosan.
Described to chitosan grind, ultrasonic, high-pressure homogeneous, centrifugal machine processes, specifically: (1) first milled processed 20 times or 30min, then with diluted sample and carry out supersound process, each 250ml, ultrasonic time is each 30min, gets the sample after ultrasonic, carry out high-pressure homogeneous processing, time is 30min, and pressure on average can reach 1500bar, and final gained sample is nano level chitin fiber suspension; (2) chitosan solution after ultrasonic is carried out centrifugal treating, the centrifugal speed of sedimentator is set to 8000r/min, and centrifugation time is 10min, and gets centrifugal supernatant liquid.
Described final gained nano level chitin fiber suspension, specifically 1) take the chitosan sample of 3g oven dry, add 300ml distilled water, be mixed with mass concentration and be 1% suspension; 2) after milled processed 20 times with diluted sample, to mass concentration, be 0.1% suspension; 3) carry out supersound process, each 250ml, ultrasonic time is each 30min; 4) get sample after ultrasonic, carry out high-pressure homogeneous processing, the time is 30min, and pressure on average reaches 1500bar.
The preparation of described chitosan nano fiber is 1) the chitosan powder that will prepare takes 5g, is mixed with weight concentration and is 1% chitosan solution; 2) use speed lapping to carry out 30min and grind pre-treatment, make chitosan reach the rank of nanometer; 3) in process of lapping, mill is slowly contacted, then pour chitosan solution into, rotating speed is 1500r/min.
Described various mechanical treatment is that the solution after grinding is made into concentration again is 0.4% solution, carries out supersound process 30min, and selecting ultrasonic frequency in ultrasonic procedure is 75%, and ultrasonic solution is carried out ice-water bath, prevents the ultrasonic effect of ultrasonic excess Temperature impact.
Described various mechanical treatment is that the chitosan solution after ultrasonic is carried out centrifugal treating, and the centrifugal speed of sedimentator is set to 8000r/min, and centrifugation time is 10min, and gets centrifugal supernatant liquid.We have just obtained to use the chitosan nano fiber solution after three kinds of mechanical bond are processed like this.
Described chitosan nano fiber is prepared the chitosan nano fiber film; Specifically will add and ultrasonicly add prepared concentration after centrifugal treating and be about 0.4% chitosan nano fiber solution 450ml and filter at vacuum apparatus through grinding, the filter membrane aperture of using is 0.2 μ m, diameter is 9mm, the diameter of Büchner funnel is 12mm, first pad the filter paper of two-layer 12mm diameter in Büchner funnel, again filter membrane fully is attached to the filter paper surface, use the wetting filter membrane of distilled water, and open vacuum pump make filter membrane fully with the Büchner funnel laminating, pour chitin nanofiber solution in Büchner funnel filtering coating at this moment; After to be filmed, filter membrane is taken out, on the filter membrane surface with chitin film, paste a filter membrane again, be clipped in the middle of two layers of filter paper, put into vacuum drying oven, drying temperature is 60 ℃, has just obtained the chitosan nano fiber film after dry 24 ~ 48 hours.
Described chitosan nano fiber is prepared the chitosan nano fiber film, or adopt graduated cylinder accurately to measure the 500ml mass concentration to be 0.1% suspension, to pour in Büchner funnel, open vacuum pump and carry out extracting, obtain a wet chitosan nano fiber film.Film is taken out, two-sided covering release paper, then with sheet glass, suppress post-drying, can obtain smooth, dry chitosan nano fiber film.
Described chitosan nano fiber resin compounded mould material is to use electronics sky chessboard to take the pulverous polyethersulfone resin of 5g, the preparation mass concentration is 5% polyethersulfone resin solution, use N, N-dimethylacetamide solution is as the solvent of polyethersulfone resin and take 95gN, N-dimethylacetamide solution joins in the beaker that the polyethers powder is housed, and beaker is put into heat collecting type magnetic force heating stirrer stir 60min.The chitosan nano fiber film of mechanical treatment preparation is placed in the glass culture dish that diameter is 6cm, then add the 20g polyethersulfone resin in culture dish, nano-fiber film is fully flooded 12h in resin solution, the culture dish that then will contain film and polyethersulfone solution is placed on dry 12h in vacuum drying oven, takes out and just can obtain chitin nanofiber/polyethersulfone resin matrix material afterwards.
Chitosan nano resin fibre composite film material refers to polyethersulfone resin solution; Polyvinyl alcohol resin solution; Polycarbonate resin solution; Polylactic resin fuses liquid; The resins such as the fused liquid of plexiglass.
Described chitosan nano fiber film sample, impregnated in PMMA or polyethersulfone resin solution, is placed in the vacuum drying oven impregnating by pressure 24h of 60 ℃, after solvent evaporates, obtain chitosan nano fiber thin with resin compounded prepare the optical clear mould material.
Described chitosan nano resin fibre composite film material refers to polyethersulfone resin solution; Polyvinyl alcohol resin solution; Polycarbonate resin solution; Polylactic resin fuses liquid; The resins such as the fused liquid of plexiglass.
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Embodiment 1
The preparation of chitosan: the acid treatment of learning from else's experience removes inorganic salt, alkaline purification deproteination matter and ethanolic soln and removes the chitin powder 10g of pigment.Preparation 400ml concentration is 45% sodium hydroxide alkaline solution, pour in the beaker that the chitin powder is housed, 90 ℃ of heated and stirred 12h in water-bath, during every 4h change alkaline solution one time.Finally with the hot alkaline solution of chitosan-containing through vacuumfilter fully wash to pH be 7, can obtain the chitosan sample.See Fig. 1 chitosan preparation flow figure.
Embodiment 2
The method of using preparing chitosan from chitin is to make chitin can produce chitosan through deacetylation; massfraction commonly used is that 45 ~ 50% sodium hydroxide solutions soak chitin and are heated to 105 ° of C; be incubated 2 h, be washed to neutrality, suction filtration, drying and can obtain the slightly nacreous chitosan of white.Wherein concentration of lye, temperature of reaction and reaction times are the principal elements of the performance index (deacetylation and relative molecular weight) that affect chitosan.Different material (crayfish shell, sea crab shell, prawn shell, river prawn shell and silkworm chrysalis) with Same Way under the same conditions, prepares chitosan in addition, and yield is respectively 13.6%, 12.3%, 10.5%, 8.70%, 1.8%, and visible crayfish shell and sea crab shell are preferred raw materials.
Embodiment 3
The preparation of chitosan nano fiber: take the chitosan sample of 3g oven dry, add approximately 300ml distilled water, be mixed with massfraction and be 1% suspension.With diluted sample, to massfraction, be 0.1% suspension after milled processed 20 times, carry out supersound process, each 250ml, ultrasonic time is each 30min.Get the sample after ultrasonic, carry out high-pressure homogeneous processing, the time is 30min, and pressure on average can reach 1500bar.Final gained sample is nano level chitin fiber suspension.See the preparation process of Fig. 2 chitosan nano fiber.
Fig. 3 is that massfraction is 1% the fibre shape of chitosan after 20 milled processed.Can be observed from figure, amplifying under the condition of 30000 times, totally it seems and have to a certain degree directional property.Have the robust fibre aggregate of micron level, fibril totally presents the netted structure that interweaves.Cavatition by the high-strength ultrasonic generation, fiber is carried out break process, arrived the fibril of diameter at nanoscale, the dispersion state of gained fibril suspension liquid is very even, but also have certain micron order fiber in the gained fibril, the diameter Distribution scope of fiber is larger.The high-strength ultrasonic cavitation process is as a kind of succinct nanofibrils extracting method efficiently, play an important role in the fine process of machinery solution of fiber, when chitin fiber/water termination is subject to hyperacoustic used time of doing, far from it with the cavitation in pure water liquid in cavitation at the interface.Because the asymmetry of near interface can make bubble generation deformation, more flat near fiber one side, this just plays a kind of strengthening effect, produces the microjet of rapid movement while making collapse, and with the speed directive fiber/water interface greater than 100 m/s, and then make fiber surface localized attack occur and degrade.Whether relevant with the size on adjacent fiber cellulose fiber surface the appearance of this microjet is, and the size that the size of fiber surface must be several times as much as bubble just can.Therefore,, for improving the efficiency of ul-trasonic irradiation, need carry out grinding to a certain degree before supersound process,, tentatively to open robust fibre, improve the specific surface area of fiber.During this time, little solid particulate under the ordering about of turbulent flow and shockwave, can make solids produce at a high speed and collide.When the fibrous suspension that contains size and be several times as much as cavitation bubble is subject to hyperacoustic used time of doing, the microjet shockwave that ultrasonic cavitation produces will play machinery and separate fine effect, and nanofibrils is separated from coarse fiber bundle.The size of ultrasonic cavitation intensity depends on the size of its output rating, the final cavitation effect of fiber is somewhat dependent upon again the length of supersound process time, need consider simultaneously the energy great question in ultrasonic procedure.Therefore, it is 30min/ time that the present invention preferably arranges ultrasonic time, and power is 80%.
The diameter Distribution of chitin fiber after Fig. 4 milled processed.Chitosan nano fiber diameter Distribution after milled processed is more inhomogeneous, but fiber is mostly in the 100nm scope, and the Fiber Distribution over 70% is in 60 to 100nm scope, and approximately 10% Fibre diameter is greater than 100nm, near micron order, the coarse fiber bundle of namely not opening temporarily after milled processed.The chitin fiber that carries out subsequently supersound process has further obtained refinement, the diameter of fiber mainly is distributed in the scope of 20-60nm, and quantity accounts for 72%, and wherein 49% Fibre diameter is in 40-60nm, robust fibre is less, and sample reaches being uniformly distributed of Nano grade substantially.
Chitin fiber after Fig. 5 grinding+supersound process.Be the chitin fiber after grinding-supersound process shown in figure, magnification is 50000 times.Than the sample of milled processed only, the chitin fiber distribution uniform after supersound process, only a small amount of fiber is the gathering shape, and the diameter of most of fiber below 100nm, is not almost observed the fibril of micron level.Illustrate that the further nanometer that supersound process after grinding is conducive to fiber is uniformly distributed.The cavatition power that process to produce due to high-strength ultrasonic, far below this high-strength mechanical processing mode of high-pressure homogeneous processing, makes simple dependence high-strength ultrasonic process, and nanofibrils intactly can not be separated from biomass fiber.And because a large amount of hydroxyls is contained on the surface of the nanofibrils after grinding-supersound process, make fibril easily reunite in drying process, the feature that can not keep individual filaments, needing that for this reason the gained nanofibrils is carried out high pressure homogenization processes, to avoid fibril to produce clustering phenomena in drying process, and then the chitosan nano fibril that obtains nanoscale, high length-diameter ratio, is separated from each other and is woven into a mesh structure.
The diameter Distribution of the chitin fiber after Fig. 6 grinding+supersound process.The chitin fiber that carries out supersound process after grinding has further obtained refinement, the diameter of fiber mainly is distributed in the scope of 20 ~ 60nm, and quantity accounts for 72%, and wherein 49% Fibre diameter is in 40 ~ 60nm, robust fibre is less, and sample reaches being uniformly distributed of Nano grade substantially.
Chitin fiber after Fig. 7 grinding+ultrasonic+high-pressure homogeneous processing.As seen from the figure, after utilizing high pressure homogenization to process chitosan nano fibril 30min, obtained having high length-diameter ratio, the uniform Mierocrystalline cellulose nanofibrils of diameter size distribution.Only amplify in the situation of 20000 quilts, with the sample after grinding-supersound process, carry out step by step the fibril of gained after high-pressure homogeneous processing and have the very good fine effect of machinery solution, fibril is separated from each other each other, can observe clearly the feature of individual filaments, almost not observe the existence of a large amount of bunches of shape fibril aggregates, but be interweaved again between fibril, be overlapped into netted tangled structure, can when improving polymer strength, improve its toughness.
The diameter Distribution of the chitin fiber after Fig. 8 grinding+ultrasonic+high-pressure homogeneous processing.Be the diameter Distribution figure through the chitin fiber of grinding-ultrasonic-continuous mechanical treatment of homogeneous shown in figure.55% Fibre diameter is in the scope of 20 ~ 40nm as we know from the figure, and only 4% Fibre diameter has surpassed 80nm, and fabric integer is evenly distributed.And in the zone of whole Electronic Speculum picture of Fig. 7, almost do not observe the two ends of individual filaments, show that the length of gained fibril at least will be higher than 10um, its length-to-diameter ratio mean values is higher than 500.And when carrying out electron microscopy observation, need to carry out metal spraying to sample to process, the gold layer covers fiber surface,, because the gold layer self has certain thickness, makes like this result of electron microscopy observation bigger than normal than the diameter value of actual fibril.Therefore, the actual length-to-diameter ratio of the chitin fiber after homogenization treatment should be higher than 500.This high length-diameter ratio, netted entanglement, the uniform chitosan nano fibril of diameter size distribution, have very good enhancing by polymer structure.
Embodiment 4
The preparation of chitosan nano fiber film: accurately measure 500ml with graduated cylinder, massfraction is 0.1% suspension, pours in Büchner funnel, opens vacuum pump and carries out extracting, can obtain a wet chitosan nano fiber film.Film is taken out, two-sided covering release paper, then with sheet glass, suppress post-drying, and can obtain smooth, dry chitosan nano fiber film, store to be measured.
Embodiment 5
The preparation of chitosan/polymethylmethacrylate laminated film: with a chitosan nano fiber film sample, after weighing, being designated as W1. impregnated in polymethyl methacrylate solution, be placed in the vacuum drying oven impregnating by pressure 24h of 60 ℃, after solvent evaporates, can obtain chitosan/polymethyl methacrylate nano-composite membrane.Weigh this moment, is designated as W2.Calculate chitosan nano fiber in laminated film content and with the sample drying of final gained, store to be measured.
Embodiment 6
The preparation method of chitosan nano fiber/polyethersulfone resin laminated film:
(1) use electronics sky chessboard to take the pulverous polyethersulfone resin of 5g, in order to prepare the polyethersulfone resin solution of 5% concentration, use N, N-dimethylacetamide solution is as the solvent of polyethersulfone resin and take 95g N, N-dimethylacetamide solution joins in the beaker that the polyethers powder is housed, and beaker is put into heat collecting type magnetic force heating stirrer stir 60min.
(2) the chitosan nano fiber film of mechanical treatment preparation is placed in the glass culture dish that diameter is 6cm, then add the 20g polyethersulfone resin in culture dish, nano-fiber film is fully flooded 12h in resin solution, the culture dish that then will contain film and polyethersulfone solution is placed on dry 12h in vacuum drying oven, takes out afterwards the chitin nanofiber just can obtain our preparation/polyethersulfone resin matrix material.Simultaneously, the polyethersulfone resin of getting after a certain amount of dissolving is poured in culture dish, puts into equally loft drier and carries out drying, prepares the polyethersulfone resin film, is used for experiment in contrast.
Specific embodiment is further to set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention for explanation the present 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 limited range equally.
Claims (10)
1. the preparation method of a chitosan nano fiber resin compounded mould material, is characterized in that the method comprises the steps:
(1) the pure chitin of business being bought is prepared into chitosan by deacetylated chemical treatment with chitin;
(2) to chitosan grind, ultrasonic, high-pressure homogeneous, centrifugal machine processes and prepares chitosan nano fiber;
(3) chitosan nano fiber is prepared the chitosan nano fiber film;
(4) chitosan nano fiber film and resin compounded are prepared chitosan nano fiber resin compounded mould material.
2. the preparation method of a kind of chitosan nano fiber resin compounded mould material according to claim 1, is characterized in that the described chitin chitosan for preparing, and specifically comprises 1) acid treatment of learning from else's experience removes inorganic salt; 2) alkaline purification deproteination matter and ethanolic soln remove the chitin powder of pigment, pour in sodium hydroxide solution, put into heat collecting type magnetic force heating stirrer and stir; Heated and stirred in water-bath, keep, and changes alkaline solution one time; 3) the chitin powder after deacetylated is washed to neutrality, then to its drying, drying temperature is 60 ℃, and times 24 ~ 48 h, just obtained chitosan; The hot alkaline solution that 4) will contain chitosan fully washs through vacuumfilter, namely obtains the chitosan sample.
3. the preparation method of a kind of chitosan nano fiber resin compounded mould material according to claim 2, is characterized in that described acquisition chitosan, specifically comprises 1) get chitin powder 10g; 2) preparation 300 ~ 400ml mass concentration is 45% ~ 50% sodium hydroxide alkaline solution 300 ml; 3) pour in the beaker that the chitin powder is housed, 65 ~ 90 ℃ of heated and stirred 12h in water-bath, kept every 4 ~ 8 hours, change alkaline solution one time, finally with the hot alkaline solution of chitosan-containing through vacuumfilter fully wash to pH be 7, can obtain the chitosan sample,, then to its drying, just obtain chitosan.
4. the preparation method of a kind of chitosan nano fiber resin compounded mould material according to claim 1, it is characterized in that described to chitosan grind, ultrasonic, high-pressure homogeneous, centrifugal machine processes, specifically: (1) first milled processed 20 times or 30min, then with diluted sample and carry out supersound process, each 250ml, ultrasonic time is each 30min, get the sample after ultrasonic, carry out high-pressure homogeneous processing, time is 30min, pressure on average can reach 1500bar, and final gained sample is nano level chitin fiber suspension; (2) chitosan solution after ultrasonic is carried out centrifugal treating, the centrifugal speed of sedimentator is set to 8000r/min, and centrifugation time is 10min, and gets centrifugal supernatant liquid.
5. the preparation method of a kind of chitosan nano fiber resin compounded mould material according to claim 4, it is characterized in that described final gained nano level chitin fiber suspension, specifically 1) take the chitosan sample of 3g oven dry, add 300ml distilled water, be mixed with mass concentration and be 1% suspension; 2) after milled processed 20 times with diluted sample, to mass concentration, be 0.1% suspension; 3) carry out supersound process, each 250ml, ultrasonic time is each 30min; 4) get sample after ultrasonic, carry out high-pressure homogeneous processing, the time is 30min, and pressure on average reaches 1500bar.
6. the preparation method of a kind of chitosan nano fiber resin compounded mould material according to claim 1, it is characterized in that the described chitosan nano fiber for preparing is 1) the chitosan powder that will prepare takes 5g, is mixed with weight concentration and is 1% chitosan solution; 2) use speed lapping to carry out 30min and grind pre-treatment, make chitosan reach the rank of nanometer; 3) in process of lapping, mill is slowly contacted, then pour chitosan solution into, rotating speed is 1500r/min, obtains chitosan nano fiber.
7. the preparation method of a kind of chitosan nano fiber resin compounded mould material according to claim 1, is characterized in that the described chitosan nano fiber film for preparing; To add through grinding specifically that ultrasonic to add prepared mass concentration after centrifugal treating be 0.4% chitosan nano fiber solution 450ml, filter at vacuum apparatus, the filter membrane aperture of using is 0.2 μ m, diameter is 9mm, the diameter of Büchner funnel is 12mm, first pad the filter paper of two-layer 12mm diameter in Büchner funnel, again filter membrane fully is attached to the filter paper surface, use the wetting filter membrane of distilled water, and open vacuum pump make filter membrane fully with the Büchner funnel laminating, pour chitin nanofiber solution in Büchner funnel filtering coating at this moment; After to be filmed, filter membrane is taken out, on the filter membrane surface with chitosan film, paste a filter membrane again, be clipped in the middle of two layers of filter paper, put into vacuum drying oven, 60 ℃ of drying temperatures, just obtained the chitosan nano fiber film after dry 24 ~ 48 hours.
8. the preparation method of a kind of chitosan nano fiber resin compounded mould material according to claim 1, it is characterized in that the described chitosan nano fiber film for preparing, can also adopt graduated cylinder accurately to measure the 500ml mass concentration is 0.1% suspension, pour in Büchner funnel, open vacuum pump and carry out extracting, obtain a wet chitosan nano fiber film; Film is taken out, two-sided covering release paper, then with sheet glass, suppress post-drying, can obtain smooth, dry chitosan nano fiber film.
9. the preparation method of a kind of chitosan nano fiber resin compounded mould material according to claim 1, it is characterized in that the described chitosan nano fiber resin compounded mould material for preparing, comprise 1) use electronics sky chessboard to take the pulverous polyethersulfone resin of 5g, the preparation mass concentration is 5% polyethersulfone resin solution, 2) use N, N-dimethylacetamide solution is as the solvent of polyethersulfone resin and take 95gN, N-dimethylacetamide solution joins in the beaker that the polyethers powder is housed, 3) beaker is put into heat collecting type magnetic force heating stirrer stirs 60min; 4) the chitosan nano fiber film of mechanical treatment preparation is placed in the glass culture dish that diameter is 6cm, then add the 20g polyethersulfone resin in culture dish, 5) nano-fiber film is fully flooded 12h in resin solution, the culture dish that then will contain film and polyethersulfone solution is placed on dry 12h in vacuum drying oven, 6) take out and just can obtain chitin nanofiber/polyethersulfone resin matrix material.
10. the preparation method of according to claim 7 or 8 described a kind of chitosan nano fiber resin compounded mould materials, it is characterized in that described chitosan nano fiber is thin film dipped in PMMA or polyethersulfone resin solution, be placed in the vacuum drying oven impregnating by pressure 24h of 60 ℃, after solvent evaporates, obtain chitosan nano fiber thin with resin compounded prepare the optical clear mould material.
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| CN105111477A (en) * | 2015-09-29 | 2015-12-02 | 浙江工业大学 | Method for preparing antibacterial edible films |
| CN105111477B (en) * | 2015-09-29 | 2018-05-08 | 浙江工业大学 | A kind of preparation method of antibiotic property edible film |
| CN106478840A (en) * | 2016-09-13 | 2017-03-08 | 浙江大学 | A kind of preparation method of cross-linked chitosan |
| CN107511898A (en) * | 2017-07-21 | 2017-12-26 | 阜南县大自然工艺品有限公司 | A kind of preparation method of bamboo wood resin integrated material for bamboo weaving |
| CN108896540A (en) * | 2018-05-02 | 2018-11-27 | 武汉职业技术学院 | A kind of aquatic products formaldehyde examination card |
| CN108896540B (en) * | 2018-05-02 | 2021-08-24 | 武汉职业技术学院 | Aquatic product formaldehyde detection card |
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| CN113736147A (en) * | 2021-09-14 | 2021-12-03 | 南京大学 | Waterproof and antibacterial chitosan transparent film and preparation method thereof |
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