CN103396571A - Cellulose nano-fiber/polymethyl methacrylate composite film preparation method - Google Patents
Cellulose nano-fiber/polymethyl methacrylate composite film preparation method Download PDFInfo
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Abstract
The present invention relates to a cellulose nano-fiber/polymethyl methacrylate composite film preparation method, which is characterized by comprising the following steps: 1) a raw material treatment, 2) a chemical treatment, 3) a mechanical treatment, 4) cellulose nano-fiber film preparation, and 5) cellulose nano-fiber/polymethyl methacrylate nanometer composite material preparation. According to the present invention, an average diameter of the prepared cellulose nano-fibers is less than 100 nm, the cellulose nano-fiber film has a tensile elastic modulus of 6.06 GPa, a tensile strength of 148.8 MPa, a thermal expansion coefficient of 16.72*10<-6>/K, and light transmittance of 82.1%, and the nanometer composite material film after compounding with the polymethyl methacrylate has a tensile elastic modulus of 3.61 GPa, a tensile strength of 92 MPa, a thermal expansion coefficient of 21.58*10<-6>/K, and light transmittance of 86.3%.
Description
Technical field
The present invention relates to be a kind of cellulose nano-fibrous/preparation method of polymethylmethacrylate composite membrane, belong to technical field of composite materials.
Background technology
Mierocrystalline cellulose is a kind of natural organic polymer material, it and hemicellulose, and xylogen forms the main component of vegetable cell together jointly.In addition, Mierocrystalline cellulose also is present in the body of some bacterium and knapsack class animal.Mierocrystalline cellulose is a kind of polysaccharide that the occurring in nature distribution is the widest, content is maximum, accounts for more than 50% of vegitabilia's carbon content.The content of cellulose of cotton is near 100%, is natural pure cellulose source.In general timber, Mierocrystalline cellulose accounts for 40 ~ 50%, in addition 10 ~ 30% hemicellulose and 20 ~ 30% xylogen.Fiber crops, straw, straw, bagasse etc. are all cellulosic abundant sources.Mierocrystalline cellulose is important paper making raw material.
In vegetable cell, Mierocrystalline cellulose is not Individual existence, and tens of cellulose molecular chains by hydrogen bonded together, form the primitive protofibril.Between primitive protofibril and primitive protofibril, the hemicellulose unimolecular layer is arranged, they flock together and form the protofibril of diameter between 10～20nm.Be the thick molecular layer of several hemicellulose molecules between protofibril and protofibril, also have xylogen on every side.Protofibril has formed micro-fibril together with hemicellulose and xylogen on every side, and diameter is about 30nm.The diameter of here primitive protofibril, protofibril and micro-fibril all below 100nm, all belongs to cellulose nano-fibrous.When preparation was cellulose nano-fibrous, owing to adopting diverse ways, resulting cellulose nano-fibrous form was different,, according to the difference of form, mainly can be divided into Mierocrystalline cellulose nanocrystal, Mierocrystalline cellulose nano whisker and Mierocrystalline cellulose nanofibrils.
Polymethylmethacrylate, be commonly called as synthetic glass, is a kind of extremely important organic polymer material, belongs to thermoplastics.Polymethylmethacrylate is typical amorphous polymer, the molecular chain irregular arrangement, and its molecular weight distribution is wider, and from several ten thousand to millions of, its density is less, greatly about 1.15～1.19g/cm
3Between, be equivalent to 1/2nd of simple glass.In addition, the fusing point of polymethylmethacrylate is lower, only has 130～140 ℃, and is more much lower than more than 1000 degree centigrade of simple glass.
Due to cellulose nano-fibrous be not to separately exist in vegetable cell, but by hemicellulose, xylogen, wrapped up, and form robust fibre by hydrogen bonded between inner fiber and fiber together.Therefore, when preparation is cellulose nano-fibrous, more rational method is divided into two steps, namely first remove hemicellulose and xylogen, thereby isolate the micron order cellulosic fibre, then through further processing cellulosic fibre be dispersed into nano level cellulosic fibre, namely nano-cellulose fiber.Remove hemicellulose and xylogen the time, can adopt two kinds of diverse ways: a kind of is to add certain chemical reagent under certain condition hemicellulose and lignin reaction to be fallen, and will guarantee that simultaneously Mierocrystalline cellulose can not reacted away; Another kind is that mechanical force is directly acted on vegetable cell, and Mierocrystalline cellulose hemicellulose and xylogen on every side peeled off under the effect of mechanical force.The micron order cellulosic fibre is being dispersed into when cellulose nano-fibrous, can adopting equally two kinds of methods: a kind of is to adopt chemical process that the hydrogen bond between fiber is weakened even and eliminates by chemical force; Another kind is to adopt mechanical means that the hydrogen bond between fiber is eliminated by mechanical force.As seen, two cellulose nano-fibrous steps of preparation all can be selected chemical method or mechanical process.In sum, prepare at present cellulose nano-fibrous method and mainly contain three kinds: chemical method, mechanical process and chemistry-mechanical process.
Chemical method: chemical method refers to that mainly the cell walls that utilizes acid-alkali treatment to make biological material is broken, and makes Mierocrystalline cellulose pars amorpha wherein that chemical reaction occur, and isolates cellulosic crystallizing field, thereby obtains cellulose crystallite.Chemical method prepares cellulose nano-fibrous, due to stronger hydrolytic action, cellulosic noncrystalline domain and a part of crystallizing field also is hydrolyzed simultaneously when acid-alkali treatment.Thereby resulting cellulose nano-fibrous length is too short, and major diameter is smaller, thus cause with the lifting DeGrain of organic polymer material compound tense to material property.In addition, adopt vitriolization easily to cause atmospheric pollution and water to pollute, be unfavorable for suitability for industrialized production.
Mechanical phonograph recorder separation: mechanical phonograph recorder separation refers to utilize the equipment such as shredder, high pressure homogenisers directly the biomass starting material to be carried out Mechanical Crushing and processes, thereby remove the coarse-fibred outer wrap layer of cell walls inner cellulose, and inner Mierocrystalline cellulose robust fibre is separated from each other obtain cellulose nano-fibrous.Mechanical processing method has the advantages such as convenience, environmental protection, but the method by mechanical treatment easily causes fiber to be interrupted because of excessively strong shearing force, causes equally resulting cellulose nano-fibrous length-to-diameter ratio not high and impact and the lifting of organic polymer material compound tense properties.In addition, simple mechanical means can consume the more energy, is unfavorable for equally suitability for industrialized production.
Chemistry-mechanical process: the cellulose nano-fibrous diameter Distribution that obtains by simple chemical process or mechanical phonograph recorder separation is wide, and length is shorter, so length-to-diameter ratio is not very large, and effect is not fine when strengthening superpolymer.Chemistry-mechanical process combines both advantages, and synergy is to prepare at present the maximum method of cellulose nano-fibrous use.Chemistry-mechanical process mainly comprise Chemical Pretreatment in conjunction with mechanical treatment, enzymic hydrolysis in conjunction with mechanical treatment and TEMPO catalyzed oxidation in conjunction with mechanical treatment.
Summary of the invention
The present invention proposes be a kind of cellulose nano-fibrous/preparation method of polymethylmethacrylate composite membrane, its purpose is to overcome the deficiency that prior art exists, the method for utilizing chemical treatment to combine with mechanical treatment, prepare cellulose nano-fibrous; Method by vacuum filtration, take cellulose nano-fibrous aqeous suspension as raw material, prepare cellulose nano-fibrous film, and, by with thin film dipped method in polymethyl methacrylate solution, prepare cellulose nano-fibrous/polymethyl methacrylate nano composite material film.
Technical solution of the present invention: a kind of cellulose nano-fibrous/preparation method of polymethylmethacrylate composite membrane, comprise the following steps: 1) raw material disposal; 2) chemical treatment; 3) mechanical treatment;
4) preparation of cellulose nano-fibrous film; 5) preparation of cellulose nano-fibrous/polymethyl methacrylate nano matrix material.
Advantage of the present invention: the method for 1) utilizing chemical treatment to combine with mechanical treatment has prepared cellulose nano-fibrous; Method by vacuum filtration, take cellulose nano-fibrous aqeous suspension as raw material, prepare cellulose nano-fibrous film, and, by with thin film dipped method in polymethyl methacrylate solution, prepared cellulose nano-fibrous/polymethyl methacrylate nano composite material film.The cellulose nano-fibrous mean diameter that the present invention prepares is below 100nm, and the modulus in tension of cellulose nano-fibrous film is 6.06GPa, and tensile strength is 148.8MPa, and thermal expansivity is 16.72 * 10
-6/ K, transmittance are 82.1%; The modulus in tension of the nanocomposite films after compound with polymethylmethacrylate is 3.61GPa, and tensile strength is 92MPa, and thermal expansivity is 21.58 * 10
-6/ K, transmittance are 86.3%;
2) to be that raw material prepares cellulose nano-fibrous for vegetable fibre of the present invention, because raw material sources are abundant, with low cost, and renewable, biodegradable, therefore belong to typical biological environmental production material.The present invention preparation cellulose nano-fibrous has nanoscale, high length-diameter ratio, and mechanical property is excellent especially, and owing to having removed xylogen and most of hemicellulose, its thermal characteristics also increases.Therefore, cellulose nano-fibrous is ideal chose as composite material reinforcement body.On the other hand, the present invention has also strengthened the application of polymethylmethacrylate on high value added product, such as photovoltaic, and flexible Organic Light Emitting Diode base material particularly.Therefore, the modification of polymethylmethacrylate being carried out above-mentioned several respects has great significance;
3) embodiment take poplar wood powder and medical absorbent cotton as raw material,, by the mechanical treatment of chemical treatment in conjunction with different methods, prepared the cellulose nano-fibrous and cotton cellulose nanofiber of the wood powder of different fibre shapies.Find by Fourier's infrared analysis, utilize Textone to carry out repeatedly the processing xylogen in can removing wood powder under slightly acidic, temperature are the condition of 75 ℃; Utilize potassium hydroxide to carry out repeatedly the processing hemicellulose in can removing wood powder under temperature is the condition of 90 ℃; Can weaken the effect of even removing hydrogen bonded power between fiber and carry out the salt acid treatment under the condition of 80 ℃, thereby good condition can be provided for follow-up mechanical treatment; The variation that Textone processing under similarity condition and potassium hydroxide treatment can not cause the cotton chemical composition.By the comparative analysis discovery of the fiber water suspension to different chemical and mechanical treatment stage, the nanometer degree of fiber is higher, and its aqeous suspension is more uniform and stable, and presents certain transparency.Carry out supersound process or high-pressure homogeneous processing and can significantly improve the nanometer degree of fiber on the basis of milled processed, thereby make the proportion of fibers that really reaches Nano grade in prepare cellulose nano-fibrous increase.Find by contrast, take the poplar wood powder as raw material with respect to more easily prepare the cellulose nano-fibrous of high length-diameter ratio take absorbent cotton as raw material.
Description of drawings
Fig. 1 is cellulose nano-fibrous preparation process schematic diagram.
Fig. 2-a is the cotton cellulose nanofiber scanning electron microscope diagram through 7 milled processed preparations.
Fig. 2-b is the cotton wood cellulose nanofiber scanning electron microscope diagram through 3 milled processed preparations.
Fig. 2-c grinds through 7 times the cotton cellulose nanofiber scanning electron microscope diagram that adds the supersound process preparation.
Fig. 2-d grinds through 3 times the cotton wood cellulose nanofiber scanning electron microscope diagram that adds the supersound process preparation.
Fig. 2-e grinds the cotton cellulose nanofiber scanning electron microscope diagram of the homogenization treatment preparation that adds high pressure 7 times.
Fig. 2-f grinds the cotton wood cellulose nanofiber scanning electron microscope diagram of the homogenization treatment that adds high pressure through 3 times.
Fig. 3 is the cellulose nano-fibrous film that obtains through different mechanical treatments and the thermal expansivity comparison diagram of nanocomposite films thereof.
Fig. 4 is the light transmittance curve figure of cotton cellulose nanofiber/polymethylmethacrylate composite membrane.
Fig. 5 be wood powder cellulose nano-fibrous/the light transmittance curve figure of polymethylmethacrylate composite membrane.
Embodiment
Embodiment 1
prepare cellulose nano-fibrous/polymethylmethacrylate composite membrane: the step 1) raw material disposal, get the poplar wood powder, be 60 orders and 70 purpose sieve combined sortings with aperture, obtained fineness at 60～70 purpose wood powders, then the 15g that takes wherein is standby, measure the toluene of 220ml and the ethanol of 110ml with graduated cylinder, both are mixed and pour in the flask of Soxhlet extractor, the 15g wood powder is put into Soxhlet extractor, carrying out Benzene-ethanol extraction processes, temperature is controlled at 120 ℃, time is 6 h, after extracting, wood powder is taken out, be positioned in culture dish, seasoning 24h in stink cupboard.
Step 2) chemical treatment: take wood powder 10 g that process through extracting, add appropriate distilled water filtered several times, then put it in beaker and add 500 ml distilled water, 3 ml Glacial acetic acid and 3 g Textones; Be placed on heating in water bath in heat collecting type magnetic force heating stirrer and process 1h, temperature is 75 ℃, after completing, reaction adds 3 ml Glacial acetic acid and 3g Textone, continue reaction 1h, repeat operation 5 times, react completely after end, utilize distilled water repeatedly to filter cleaning, until the pH value of its aqeous suspension is near 7.
The step 3) mechanical treatment: adopt three kinds of diverse ways, i.e. milled processed, grinding-supersound process and grinding-high-pressure homogeneous processing, concrete ultrasonic power and time, the rotating speed of grinding and number of times and high-pressure homogeneous pressure and time are distinguished as follows:
1) ultrasonic power is 1000W and time 60min;
2) rotating speed that grinds is that 1500rpm and number of times are 3 times;
3) high-pressure homogeneous pressure is that 1000bar and time are 90min.
The preparation of the cellulose nano-fibrous film of step 4): comprise
1) get that to prepare six kinds of differences cellulose nano-fibrous, namely pass through respectively the cotton wood cellulose nanofiber of milled processed, grinding-high-pressure homogeneous processing and grinding-ultrasonication and pass through respectively the cotton cellulose nanofiber of milled processed, grinding-high-pressure homogeneous processing and grinding-ultrasonication, all being mixed with cellulose nano-fibrous massfraction with distilled water is 0.1% suspension, respectively get 400 ml wherein, be positioned over respectively in six beakers, fully stir, stand-by;
2) connect the suction filtration device, get a qualitative filter paper and be tiled in the Büchner funnel the inside, with a small amount of distilled water, that filter paper is moistening, get a filtering membrane, its tiling is covered on filter paper, open vacuum pump, make filter paper and Büchner funnel, closely, filtering membrane is also moistening because of the moisture on filter paper simultaneously for filtering membrane and filter paper laminating, ready one glass of cellulose nano-fibrous suspension is slowly poured Büchner funnel into before, carries out suction filtration;
3) after suction filtration is completed, close vacuum pump, take off Büchner funnel and together with filter paper, take gently filtering membrane off, then carefully take filter paper off, just only has so the moistening cellulose nano-fibrous membrane of very thin one deck on filtering membrane, this layer nano fibrous membrane taken off from filtering membrane lightly, guarantee that it is not damaged, then cover on two faces of nano fibrous membrane with the filtering membrane of two dryings, form " sandwich " structure, place it in the middle of two iron plates and put into vacuum drying oven, drying temperature is set in 60 ℃, take out after successive drying 48h, so just successfully prepared cellulose nano-fibrous film, other five kinds of cellulose nano-fibrous films are adopted the preparation that uses the same method.
Step 5) is cellulose nano-fibrous/preparation of polymethyl methacrylate nano matrix material:
take the polymethylmethacrylapellets pellets of 5g, be heated to 50 ℃, stirring and dissolving is in the dimethyl formamide of 100ml, be mixed with polymethyl methacrylate solution, pour into after mixing in the culture dish of diameter more than 100mm, get a cellulose nano-fibrous film, be immersed in 10min in solution, taking-up is placed on dry 30min in electric heating constant-temperature blowing drying box, drying temperature is 50 ℃, so just successfully prepared cellulose nano-fibrous/polymethyl methacrylate nano-composite membrane, other five kinds of cellulose nano-fibrous/polymethyl methacrylate nano-composite membranes are adopted the preparation that uses the same method.
Take wood powder 10 g that process through extracting, add appropriate distilled water filtered several times.After last is completed all over filtration, put it in beaker and add 500 ml distilled water, 3 ml Glacial acetic acid and 3 g Textones.Then heating in water bath is processed 1h in heat collecting type magnetic force heating stirrer, and temperature is 75 ℃.Add 3 ml Glacial acetic acid and 3g Textone after reaction is completed, continue with identical conditioned response 1 h, this step has repetitive operation altogether 5 times.React completely after end, utilize distilled water repeatedly to filter cleaning, until the pH value of its aqeous suspension is near 7.
Prepare potassium hydroxide solution 500 ml of 3% mass concentration, the sample of embodiment 1 preparation is put into beaker and poured the solution for preparing into, then heating in water bath is processed 2h, and temperature is 90 ℃.Reaction utilizes distilled water repeatedly to filter cleaning, until the pH value of its aqeous suspension is near 7 after finishing.
Embodiment 4
The sample of embodiment 3 preparations is put into beaker and again added the distilled water of 500ml, the Glacial acetic acid of 3ml and the Textone of 3g.Then heating in water bath is processed 1h, and temperature is 75 ℃.Add 3ml Glacial acetic acid and 3g Textone after reaction is completed, continue with identical conditioned response 1h, react completely after end, utilize distilled water repeatedly to filter cleaning, until the pH value of its aqeous suspension is near 7.
Prepare the potassium hydroxide solution 500ml of 5% mass concentration, the sample of embodiment 3 preparations is put into beaker and poured the solution for preparing into, then heating in water bath is processed 2h, and temperature is 90 ℃.Reaction utilizes distilled water repeatedly to filter cleaning, until the pH value of its aqeous suspension is near 7 after finishing.
Embodiment 6
Prepare the hydrochloric acid soln 500ml of 1% mass concentration, the sample of embodiment 4 preparations is put into beaker and poured the solution for preparing into, then heating in water bath is processed 2h, and temperature is 80 ℃.Reaction utilizes distilled water repeatedly to filter cleaning, until the pH value of its aqeous suspension is near 7 after finishing.
Embodiment 7
The preparation of cotton cellulose nanofiber: because content of cellulose in cotton is high, and hemicellulose and xylogen are seldom, so fairly simple during chemical treatment.Here only adopted a step Textone to process and potassium hydroxide treatment is removed wherein xylogen and hemicellulose, the condition of processing is the same with the chemically treated condition of wood powder.In addition, carry out the fiber separation processing of 2h under 80 ℃ with the hydrochloric acid of 1% mass concentration.There is any should be noted that before chemical treatment, to be torn into very little strip to cotton exactly, be conducive to so on the one hand fully carrying out of chemical reaction, on the other hand after milled processed the time can not twist because of long excessively thick cotton the damage that causes machine in rotating shaft at mill.Three kinds of methods have been selected equally for the mechanical treatment of cotton, i.e. milled processed, grinding-supersound process and grinding-high-pressure homogeneous processing.Consider the form of cotton, first carried out coarse grinding treatment and make its fragmentation before fine grinding is processed.Aspect the mechanical treatment operating parameter, the number of times of processing except fine grinding is that 7 times, remaining operating parameter is the same with the parameter of wood powder mechanical treatment.
Embodiment 8
supersound process and the high-pressure homogeneous processing impact on cellulose nano-fibrous/polymethyl methacrylate nano composite property: again prepare cellulose nano-fibrous take aspen fibers by using silicon as raw material, concrete operations are as follows: being configured to equally later three parts of cellulosic fibre massfractions in chemical treatment is 0.1% aqeous suspension, then to wherein two parts of milled processed of carrying out 7 times, then carry out respectively supersound process and high-pressure homogeneous processing on the basis of 7 grindings, ultrasonic power is 1000 W, time is 60 min, high-pressure homogeneous pressure is 1000 bar, time is 90 min.So just prepared different cellulose nano-fibrously, then carried out suction filtration and operate to prepare cellulose nano-fibrous film, afterwards nanocomposite films corresponding to method preparation by dipping again.
Embodiment 9
Grind the impact of number of times on cellulose nano-fibrous/polymethyl methacrylate nano composite property: take aspen fibers by using silicon as raw material, prepare different cellulose nano-fibrous, after chemical treatment is completed, it is 0.4% aqeous suspension that cellulose fiber Wesy distilled water is mixed with the cellulosic fibre massfraction, totally 500 ml, be divided into five parts after fully stirring, namely the volume of every part is 100ml.Then pour 300ml distilled water into again in every portion of cellulosic fibre aqeous suspension, and fully stir, so just obtained five parts of cellulosic fibre massfractions and be 0.1% aqeous suspension, every part of volume is 400ml.Finally with these five portions of cellulosic fibre aqeous suspensioies respectively through the milled processed of 1,3,7,15 and 30 time, the rotating speed of mill is 1500rpm.Thereby prepared the cellulose nano-fibrous of five kinds of different sizes, respectively called after cellulose nano-fibrous 1, cellulose nano-fibrous 3, cellulose nano-fibrous 7, cellulose nano-fibrous 15 and cellulose nano-fibrous 30.Five kinds of different cellulose nano-fibrous employing suction methods and pickling process are prepared cellulose nano-fibrous membrane and corresponding nanocomposite films.
The impact of cellulose nano-fibrous content on cellulose nano-fibrous/polymethyl methacrylate nano composite property: adopt seven grindings to add the high-pressure homogeneous mechanical processing method of 90min later in chemical treatment and again prepare the cotton wood cellulose nanofiber.With distilled water will finally obtain cellulose nano-fibrous to be mixed with cellulose nano-fibrous massfraction be 0.1% aqeous suspension.Cellulose nano-fibrous aqeous suspension is divided into three parts, and volume is respectively 300 ml, 400 ml and 500 ml, then carries out the vacuum filtration masking under identical condition.Be placed in vacuum drying oven three moistening cellulose nano-fibrous films dry; After three cellulose nano-fibrous films are successfully prepared fully,, with electronic balance weighing respectively, by the rising of their quality, be designated as respectively cellulose nano-fibrous (A), cellulose nano-fibrous (B) and cellulose nano-fibrous (C).Take the polymethylmethacrylapellets pellets that three parts of quality are 5g, 4g and 3g, be positioned in three clean beakers, then pour respectively the dimethyl formamide of equal volume (50ml) into.Polymethylmethacrylate is dissolved in dimethyl formamide gradually under the condition of 50 ℃ of heating in water bath and constantly stirring in, finally obtain the polymethyl methacrylate solution of three kinds of different concns, by the decline of their concentration, be designated as respectively polymethylmethacrylate (A), polymethylmethacrylate (B) and polymethylmethacrylate (C).
Embodiment 11
, take aspen fibers by using silicon as raw material, prepare different cellulose nano-fibrous.After chemical treatment was completed, it was 0.4% aqeous suspension that cellulose fiber Wesy distilled water is mixed with the cellulosic fibre massfraction, and totally 500 ml, be divided into five parts after fully stirring, and namely the volume of every part is 100ml.Then pour 300ml distilled water into again in every portion of cellulosic fibre aqeous suspension, and fully stir, so just obtained five parts of cellulosic fibre massfractions and be 0.1% aqeous suspension, every part of volume is 400ml.Finally with these five portions of cellulosic fibre aqeous suspensioies respectively through the milled processed of 1,3,7,15 and 30 time, the rotating speed of mill is 1500rpm.Thereby prepared the cellulose nano-fibrous of five kinds of different sizes, respectively called after CNF 1, CNF 3, CNF 7, CNF 15 and CNF 30.The detailed step of above-mentioned preparation process is listed in Fig. 1.
Embodiment 12: fiber water suspension form in cellulose nano-fibrous preparation process:
Above not floating on owing to also fully not absorbing water without chemically treated cotton, and the chemically treated cotton of process has fully absorbed moisture owing to being immersed in for a long time in chemical treating process in the aqueous solution, thereby can sink to below.And on form, difference of them is little, and this explanation chemical treatment could not enough change the form of cotton on macroscopic view, and can only remove some composition wherein.After through the corase grind break process, cotton fiber becomes white pulpous state solution, and is standing once being sunken to after the meeting below, and supernatant liquid still is white in color, just color slightly have subtract light.This is just to play because corase grind is broken the effect that the cotton macrofiber is cut off, and can not be with its nanometer.But after processing through fine grinding, cotton fiber has formed suspension comparatively uniformly, and this may be because the fine grinding processing makes the cotton cellulose Fibre diameter obviously reduce, and even reaches micro-nano rank.But after time of repose surpassed 2h, suspension started down to precipitate uniformly before, and 7 times simple milled processed of this explanation are with the cotton fiber nanometer of a part, also leave the larger fiber of a lot of diameters, thereby cause being long placed in the phenomenon of precipitation.And after 7 milled processed are carried out supersound process and high-pressure homogeneous processing respectively later again, present well-proportioned suspension state, and with respect to the cotton fiber suspension of 7 milled processed only, become more transparent.In addition, deposited phenomenon does not still appear after being long placed in, supersound process is carried out in this explanation on the basis of milled processed and high-pressure homogeneous processing all can further make fiber separation, makes its diameter at nanoscale, thereby makes cellulose nano-fibrous diameter Distribution in less scope.
Embodiment 13: cellulose nano-fibrous scanning electron microscope diagram sheet:
Fig. 2-a ~ Fig. 2-f is respectively through the cotton cellulose nanofiber of 7 milled processed preparation (Fig. 2-a), the cotton wood cellulose nanofiber of 3 milled processed preparations (Fig. 2-b), grind the cotton cellulose nanofiber add the supersound process preparation (Fig. 2-c) for 7 times, 3 milled processed add cotton wood cellulose nanofiber (Fig. 2-d) of supersound process preparation, add high pressure cotton cellulose nanofiber (add high pressure cotton wood cellulose nanofiber (the scanning electron microscope diagram sheet of Fig. 2-f) of homogenization treatment of Fig. 2-e) He 3 time milled processed of homogenization treatment preparation of 7 milled processed.By Fig. 2-a and 2-b as can be known, only through the cotton fiber of 7 milled processed and through the aspen fibers by using silicon dispersion effect of 3 milled processed, be not only fine, the nanometer degree is also lower, can see in figure and many fibril aggregations be arranged together in addition.That is to say, although be herein referred to as cellulose nano-fibrously, the proportion of fibers that in fact really reaches Nano grade is very little, therefore strictly says, they should be called cotton cellulose micro-nano fiber and wood powder Mierocrystalline cellulose micro-nano fiber.This mechanical force that has illustrated that also the milled processed of few number of times provides also is not enough to overcome the hydrogen bonded power between fiber, and fiber is separated from each other, and finally reaches the effect of fiber nanometer.But, after carrying out again supersound process or high-pressure homogeneous processing on the basis in few number of times milled processed, can find that resulting Fibre diameter obviously diminishes, the ratio that in fiber, diameter really reaches Nano grade obviously increases, and almost can't see the existing of large fiber aggregate (Fig. 2-c ~ Fig. 2-f).This explanation supersound process and high-pressure homogeneous processing can improve larger mechanical force, thereby hydrogen bonded power between fiber are weakened even eliminate and reach the effect of nanometer fiber.Although and the ratio that the cellulosic fibre Fibre diameter of this moment reaches Nano grade rises to some extent, on the whole, the diameter of fiber also is on micro-nano rank.In addition, carefully contrast can be found, the latter's distribution of fiber diameters scope is less than the former distribution of fiber diameters scope.Cotton fiber is difficult to nanometer more with respect to aspen fibers by using silicon, and this may be that hydrogen bonded power is larger because content of cellulose in cotton is high, therefore more difficult fiber is separated.And in poplar except Mierocrystalline cellulose is arranged, also have more xylogen and half fiber, may cause the destruction of hydrogen bond between fiber when removing them with chemical process again, thereby between the fiber after causing, hydrogen bonded power is less, therefore more easily fiber is separated.
Embodiment 14
Utilize the hot expansibility of the thermomechanical analyzer cellulose nano-fibrous film of test and nano composite material.Before carrying out test experiments, to equipment carry out repeatedly vacuumize and pass into nitrogen treatment, to guarantee the cleaning of sample bin.Sample is cut into 20mm long, the sample that 3mm is wide, use spiral micrometer detect thickness and record equally.Change quartzy stretching support, the sample that cuts is contained on special-purpose ceramic fixture, then hang over gently on support the hot expansibility of test sample under stretch mode.The temperature range of selecting during test is 20～160 ℃ (consider the melt temperature that it is lower when the pure polymethyl methacrylate film of test, select the temperature range of 20～100 ℃), and heat-up rate is 5 ℃/min.When test, pass into nitrogen as sweep gas and protection gas, make sample bin not contaminated.When the needs fast cooling, can utilize the liquid nitrogen operation of lowering the temperature.
The hot expansibility of cellulose nano-fibrous film and nano composite material: Fig. 3 has listed the cellulose nano-fibrous film that obtains through different mechanical treatments and has reached the thermal expansivity contrast of the nanocomposite films corresponding with it the temperature range of 20～100 ℃.As seen from the figure, after 7 milled processed, then carry out supersound process or high-pressure homogeneous processing and can significantly reduce the thermal expansivity of cellulose nano-fibrous film and nano composite membrane thereof.As carry out again later 7 milled processed cellulose nano-fibrous film that supersound process or high-pressure homogeneous processing obtain at the thermal expansivity of the temperature range of 20～100 ℃ from original 21.58 * 10
-6/ K has dropped to respectively 16.76 * 100
-6/ K and 16.72 * 10
-6The thermal expansivity of the nano composite membrane that/K answers in same temperature ranges stated is from original 29.64 * 100
-6/ K has dropped to respectively 21.84 * 100
-6/ K and 21.58 * 10
-6/ K.This is because supersound process or high-pressure homogeneous processing all are conducive to further nanometer fiber, the proportion of fibers that makes it possible to reach Nano grade further increases, thereby can reduce the thermal expansivity of cellulose nano-fibrous film and nanocomposite films thereof.
Embodiment 15
(1) utilize the compound preparation of hot pressing cellulose nano-fibrous/the polymethyl methacrylate nano matrix material: prepare four cellulose nano-fibrous films that specification is identical, method still adopts later to grind for seven times in chemical treatment and adds the high-pressure homogeneous mechanical treatment of 90 min, and then the vacuum filtration masking is also dry under the same conditions.The quality of every film of weighing and record.
(2) seven pure polymethyl methacrylate films that diameter is the same with cellulose nano-fibrous film of preparation, concrete method is: the polymethylmethacrylapellets pellets of 7g is dissolved in the 200ml methylene dichloride, then pouring fifty-fifty 7 diameters into is in the culture dish of 100mm, place until solvent evaporates is complete in air, take polymethyl methacrylate film off, the quality of every film of weighing and record.
The preparation method of (3) first nanocomposite films (being designated as film A) is as follows: be 130 ℃ with the Temperature Setting of thermocompressor, get two 20 * 20cm
2Iron plate, a nano-cellulose film is clipped in the middle of two polymethyl methacrylate films, form " glued board " structure, two sides covers the tetrafluoroethylene release paper and also is placed in the middle of two iron plates.When temperature is raised to 130 ℃, iron plate is placed in the middle of press, and applies pressure to the gauge pressure of 2Mpa.After keeping this temperature and pressure 30 min, turn off heat button and make its cooling, pressure release when temperature drops to 80 ℃, then take off iron plate and take composite material film off.
The preparation method of (4) second nanocomposite films (being designated as film B) is similar to the preparation method of film A.Just film B is five-layer structure, namely first, the 3rd and layer 5 be polymethyl methacrylate film, the second layer and the 4th layer are cellulose nano-fibrous films.
(5) pure polymethyl methacrylate film through hot pressing of preparation in contrast, concrete grammar is as follows: remaining two pure polymethyl methacrylate films are stacked, two tetrafluoroethylene release papers of same covering, stick on iron plate to prevent film.Then be 130 ℃ in temperature, pressure is to carry out hot pressing under the condition of 2MPa, and concrete control method is identical with film A's.
Embodiment 16
Tension test: pure polymethyl methacrylate film to be tested, cotton cellulose and cotton wood cellulose nano fibrous membrane and nano compound film separately thereof are cut into width at 4～5 mm, the sample of length between 30～40 mm.Measure thickness and the record of sample with the spiral micrometer, sample holder between two fixtures, is guaranteed that its span is between 20～30mm, in addition, the load of setting trier is that 50N(is set as 100N when the pure polymethyl methacrylate film of test), loading velocity is 1 mm/min.The nano compound film sample of leaving and taking after breaking is used for doing section microanalysis afterwards.
The tensile property index of table 1 has been listed wood powder cellulose nano-fibrous film, wood powder cellulose nano-fibrous/polymethyl methacrylate nano composite material film and pure polymethyl methacrylate film.As can be known, after compound with polymethylmethacrylate, Young's modulus and the tensile strength of film all significantly decrease by data in table.After compound with polymethylmethacrylate, its Young's modulus and tensile strength have descended respectively 35.2% and 26.1% as the cellulose nano-fibrous film through the preparation of 3 milled processed.But even now, than pure polymethyl methacrylate film, the Young's modulus of cellulose nano-fibrous laminated film and tensile strength all have significantly raising.Improved respectively 143.3% and 80% as the nanofiber laminated film through 3 milled processed preparations than the Young's modulus of pure polymethyl methacrylate film and tensile strength.And the nanofiber laminated film through grinding high-pressure homogeneous processing preparation after 3 times improves manyly than the Young's modulus of pure polymethyl methacrylate film and tensile strength, has improved respectively 243.1% and 115%.This illustrates the cellulose nano-fibrous mechanical property that can significantly strengthen polymethylmethacrylate.
The tensile property of the cellulose nano-fibrous film of table 1 wood powder and composite material film thereof
Embodiment 17
Light transmission is analyzed: the light transmission of utilizing UV, visible light near infrared spectrometer test pure polymethyl methacrylate film, cotton cellulose and cotton wood cellulose nano fibrous membrane and nano compound film separately thereof.Film slitting to be measured is become the sample of 30mm * 20mm size, after opening instrument and testing software, preheating 30min.Before test sample, first parameters, as to be arranged on wavelength be 340nm switching tungsten lamp and deuterium lamp, at wavelength, is the 850nm switch detector.Then in the situation that not setting-out product first carry out baseline scan, the wavelength region of scanning is 200～1000nm, and the speed of scanning is 300nm/min.After baseline scan finishes, put into sample to be tested, adopt equally identical sweep limit and sweep velocity to carry out test experiments.
The light transmission of cellulose nano-fibrous/polymethyl methacrylate nano matrix material: Fig. 54 is light transmittance curve figure of cotton cellulose nanofiber/polymethylmethacrylate laminated film and pure polymethyl methacrylate film.As seen from the figure, the transmittance of pure polymethyl methacrylate film is the highest, and it has reached 92.6% at the transmittance at wavelength 600 nm places.After the cotton cellulose nano-fiber film was compound with it, transmittance descended to some extent, and declines by a big margin.Only have 73% as the transmittance of cotton cellulose nanofiber laminated film at wavelength 600 nm places through the preparation of 7 milled processed, this transmittance also is not suitable for applying the base material with indicating meter obviously.Causing the lower major cause of this laminated film transmittance is that wherein cotton cellulose Fibre diameter is larger, has the diameter of fiber greatly to surpass 100 nanometers, has even reached the hundreds of nanometer.There is research verified, if Fibre diameter so just can be avoided scattering of light less than 1/10th of visible wavelength (380～780 nm), thereby help to improve the light transmission of matrix material.And at this, three grow cotton in cellulose nano-fibrous laminated film, which kind of no matter by method, prepare, all the diameter of some fiber does not reach Nano grade, therefore can cause the loose look of light more or less, thereby causes their laminated film transmittance that in various degree decline is arranged.In addition, correlation curve b and c or curve b and d can find, the transmittance of c and d curve will be higher than the transmittance of b curve, this has also illustrated 3 milled processed and has carried out supersound process later or high-pressure homogeneous processing helps further nanometer cotton fiber, make wherein diameter less than 100 nm, even the proportion of fibers less than 50 nm improves, thereby causes the raising of transmittance.
Fig. 5 be wood powder cellulose nano-fibrous/the light transmittance curve figure of polymethylmethacrylate laminated film and pure polymethyl methacrylate film.as seen from the figure, transmittance than cotton cellulose nanofiber laminated film, the transmittance of the cellulose nano-fibrous laminated film of wood powder is higher, the transmittance that is cotton cellulose nanofiber laminated film corresponding to 81%(as the transmittance of the cellulose nano-fibrous laminated film of wood powder at wavelength 600nm place by 3 milled processed preparations is only 73%), be that the transmittance of cotton cellulose nanofiber laminated film corresponding to 82.1%(is only 77.6% by grinding after 3 times the transmittance of the cellulose nano-fibrous laminated film of wood powder at wavelength 600nm place that carries out supersound process preparation), and by the transmittance that the transmittance of the cellulose nano-fibrous laminated film of wood powder at the 600nm place that grind 3 laggard horizontal high voltage homogenization treatment preparations reached cotton cellulose nanofiber laminated film corresponding to 83.6%(, be only 79.2%).Therefore, proved again the fiber nanometer effect that fiber nanometer effect that 7 milled processed for cotton reach reaches not as 3 milled processed for wood powder here.
Those skilled in the art will recognize that; above-mentioned embodiment is exemplary; in order to make those skilled in the art can better understand content of the present invention; should not be understood as limiting the scope of the invention; so long as the improvement of doing according to technical solution of the present invention all falls into protection scope of the present invention.
Claims (6)
1. the preparation method of cellulose nano-fibrous/polymethylmethacrylate composite membrane is characterized in that the method comprises the following steps:
1) raw material disposal;
2) chemical treatment;
3) mechanical treatment;
4) preparation of cellulose nano-fibrous film;
5) preparation of cellulose nano-fibrous/polymethyl methacrylate nano matrix material.
according to claim 1 a kind of cellulose nano-fibrous/preparation method of polymethylmethacrylate composite membrane, it is characterized in that described step 1) raw material disposal, get the poplar wood powder, be 60 orders and 70 purpose sieve combined sortings with aperture, obtained fineness at 60 ~ 70 purpose wood powders, then the 15g that takes wherein is standby, measure the toluene of 220ml and the ethanol of 110 ml with graduated cylinder, both are mixed and pour in the flask of Soxhlet extractor, the 15g wood powder is put into Soxhlet extractor, carrying out Benzene-ethanol extraction processes, temperature is controlled at 120 ℃, time is 6 h, after extracting, wood powder is taken out, be positioned in culture dish, seasoning 24h in stink cupboard.
According to claim 1 a kind of cellulose nano-fibrous/preparation method of polymethylmethacrylate composite membrane, it is characterized in that described step 2) chemical treatment: take wood powder 10 g that process through extracting, add appropriate distilled water filtered several times, then put it in beaker and add 500 ml distilled water, 3 ml Glacial acetic acid and 3g Textone; Be placed on heating in water bath in heat collecting type magnetic force heating stirrer and process 1h, temperature is 75 ℃, after completing, reaction adds 3ml Glacial acetic acid and 3g Textone, continue reaction 1h, repeat operation 5 times, react completely after end, utilize distilled water repeatedly to filter cleaning, until the pH value of its aqeous suspension is near 7.
According to claim 1 a kind of cellulose nano-fibrous/preparation method of polymethylmethacrylate composite membrane, it is characterized in that described step 3) mechanical treatment: adopt three kinds of diverse ways, it is milled processed, grinding-supersound process and grinding-high-pressure homogeneous processing, concrete ultrasonic power and time, the rotating speed of grinding and number of times and high-pressure homogeneous pressure and time are distinguished as follows:
1) ultrasonic power is 1000W and time 60min;
2) rotating speed that grinds is that 1500rpm and number of times are 3 times;
3) high-pressure homogeneous pressure is that 1000bar and time are 90min.
According to claim 1 a kind of cellulose nano-fibrous/preparation method of polymethylmethacrylate composite membrane, it is characterized in that the preparation of the cellulose nano-fibrous film of described step 4): comprise
1) get that to prepare six kinds of differences cellulose nano-fibrous, namely pass through respectively the cotton wood cellulose nanofiber of milled processed, grinding-high-pressure homogeneous processing and grinding-ultrasonication and pass through respectively the cotton cellulose nanofiber of milled processed, grinding-high-pressure homogeneous processing and grinding-ultrasonication, all being mixed with cellulose nano-fibrous massfraction with distilled water is 0.1% suspension, respectively get 400 ml wherein, be positioned over respectively in six beakers, fully stir, stand-by;
2) connect the suction filtration device, get a qualitative filter paper and be tiled in the Büchner funnel the inside, with a small amount of distilled water, that filter paper is moistening, get a filtering membrane, its tiling is covered on filter paper, open vacuum pump, make filter paper and Büchner funnel, closely, filtering membrane is also moistening because of the moisture on filter paper simultaneously for filtering membrane and filter paper laminating, ready one glass of cellulose nano-fibrous suspension is slowly poured Büchner funnel into before, carries out suction filtration;
3) after suction filtration is completed, close vacuum pump, take off Büchner funnel and together with filter paper, take gently filtering membrane off, then carefully take filter paper off, just only has so the moistening cellulose nano-fibrous membrane of very thin one deck on filtering membrane, this layer nano fibrous membrane taken off from filtering membrane lightly, guarantee that it is not damaged, then cover on two faces of nano fibrous membrane with the filtering membrane of two dryings, form " sandwich " structure, place it in the middle of two iron plates and put into vacuum drying oven, drying temperature is set in 60 ℃, take out after successive drying 48h, so just successfully prepared cellulose nano-fibrous film.
According to claim 1 a kind of cellulose nano-fibrous/preparation method of polymethylmethacrylate composite membrane, it is characterized in that described step 5) cellulose nano-fibrous/preparation of polymethyl methacrylate nano matrix material:
take the polymethylmethacrylapellets pellets of 5g, be heated to 50 ℃, stirring and dissolving is in the dimethyl formamide of 100ml, be mixed with polymethyl methacrylate solution, pour into after mixing in the culture dish of diameter more than 100mm, get a cellulose nano-fibrous film, be immersed in 10min in solution, taking-up is placed on dry 30min in electric heating constant-temperature blowing drying box, drying temperature is 50 ℃, so just successfully prepared cellulose nano-fibrous/polymethyl methacrylate nano-composite membrane, other five kinds of cellulose nano-fibrous/polymethyl methacrylate nano-composite membranes are adopted the preparation that uses the same method.
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