CN102344685B - Method for preparing nano cellulose microfibril reinforced polymer composite material - Google Patents
Method for preparing nano cellulose microfibril reinforced polymer composite material Download PDFInfo
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Abstract
The invention discloses a method for in situ generating a nano cellulose microfibril reinforced polymer composite material, comprising the following steps: using ionic liquid as a primary solvent, dissolving cellulose, or mixing cellulose with other polymers via solution mixing, and controlling the solubility of the cellulosic material in the solvent to maintain naturally occurring nano cellulose microfibril in the cellulosic material, so as to in situ obtain the nano cellulose microfibril reinforced polymer composite material. The nano microfibril can be observed under a transmission microscope obviously, which is different from the completely dissolved cellulose solution. In the preparing process, the dissolving temperature is controlled within 30-150 DEG C, and stirring and vacuum deaeration are used as auxiliary. By controlling the dissolving time, solution concentration and ratio of mixing, a polymer solution containing cellulose microfibril with dimension of 5-300 nanometers can be obtained. The polymer solution can be used for preparing composite material fiber, hollow fibrous membrane, diaphragm, film, gel, porous material and other known applications of enhanced material.
Description
Technical field
The present invention relates to a kind of method of preparing nano cellulose microfibril reinforced polymer composite material.
Background technology
Along with increasingly sharpening of global problem of environmental pollution sharply exhausted with petroleum-based energy, natural resources, and the raising of Public environmental attitude, sustainable development, industrial ecology and Green Chemistry are being dominated the direction of material, industrialization product and process later.The biocompatibility matrix material being obtained by renewable biological source can replace synthetic polymer, and reduces the dependence of the whole world to fossil fuel energy, is a kind of brand-new material with great potential.And the Mierocrystalline cellulose the abundantest a kind of natural polymer that is content (only Mierocrystalline cellulose regeneration amount every year just reaches 1.0 * 10
10ton), and because the feature (higher degree of crystallinity, intermolecular and intramolecular hydrogen bond) of aggregated structure makes it have excellent mechanical property, so the preparation of cellulose composite material has caused a large amount of investigators' concern.
The preparation method of cellulose composite material mainly comprises extrudes Mierocrystalline cellulose together with closing the hydrophilic plastic substrate of inclusive NAND with hydrophilic polymer blending.Be exactly to utilize the method for dissolving cellulos to prepare matrix material in addition.This method can generate cellulose chain and the interlaced reticulated structure of polymer chain in regenerative process.
Visibly different with the polymkeric substance that great majority are artificial synthetic, the Mierocrystalline cellulose that nature exists is that the macroscopic fiber shape form to be comprised of a large amount of Mierocrystalline cellulose fentos exists, and complicated, inhomogeneous multiplet structure is a key character of cellulose materials.Cellulosic fibre structurally can divide 3 levels, that is: (1) dust
the cellulosic molecule layer of level; (2) the cellulose crystals oversubscription sublayer of nanometer (nm) level; (3) fibril supramolecular structure layer, this layer is the further larger fiber of various size of self-assembly such as the primitive fibril dressed up by cellulose crystals and noncrystalline cellulose group of molecules, is exactly the macroscopic fiber cellulose fiber that people see at ordinary times.This multilayered structure is plant cellulose self-assembling formation in nature biotechnology building-up process, i.e. so-called generation from bottom to top.But natural Mierocrystalline cellulose is difficult to melt, make it be difficult to machine-shaping, generally all by the method for dissolving, process.And there is the transformation to crystal form of cellulose II by cellulose I crystal formation in consoluet Mierocrystalline cellulose in dissolution process.This transformation makes the mechanical property of itself that change also occur, and generally in dissolving regenerative process, can produce a large amount of non-crystal structures, therefore can make the mechanical property variation of the finished product.Compare with common material of regenerated cellulose, without nano-cellulose fento self-assembling formation, structure improvement in the Mierocrystalline cellulose of solution processing, there are many premium propertiess, as high purity, high-polymerization degree, high-crystallinity, high-hydrophilic, high Young's modulus, high strength, hyperfine structure and high transparent etc.And the cellulose solution working method that we adopt is conventionally that Mierocrystalline cellulose is dissolved in solvent completely, then carry out moulding.In cellulose solution before forming process, the nano-cellulose microfibrillar structure in cellulosic material is destroyed completely like this.If select suitable dissolution conditions, control the dissolution degree of cellulosic material in solvent, only the cellulosic component of lower molecular weight and amorphous and low-crystallinity is dissolved, retain naturally occurring high-polymerization degree in those Mierocrystalline celluloses, high-crystallinity, high Young's modulus, high-intensity nano-cellulose microfiber component, retain cellulose I crystal formation, can make easily the polymer composites strengthening with nano-cellulose fento.
When preparing the polymer composites of nano-cellulose fento enhancing, also there are a lot of methods can be used for differentiating Mierocrystalline cellulose dissolving situation in solvent.Due to the high-crystallinity of natural cellulose I crystal formation, it observes and has obvious anisotropy under polarisation.In cellulosic dissolution process, destruction due to intermolecular and intramolecular hydrogen bond, cellulosic mineral crystal structure is disintegrated gradually, can find can to fade away in the fiber clear zone of the inside at polarized light microscopy Microscopic observation cellulose solution, until the whole visual field presents as dark as a stack of black cats while dissolving completely.Consoluet Mierocrystalline cellulose can be transformed into a large amount of non-crystalline regions and take cellulose II as main crystallizing field after precipitation bath regeneration, can make its mechanical property and thermostability etc. be greatly affected.If control the dissolving process of Mierocrystalline cellulose in solvent, its cellulose I crystal formation can be retained, retain nano level Mierocrystalline cellulose fento.This nanostructure is difficult to observe with polarisation, can also directly observe by transmission electron microscope.In addition, cellulose I and crystal form of cellulose II have obvious difference in the position of nucleus magnetic resonance, infrared absorption and XRD diffractogram, therefore utilize these analysis means can differentiate cellulosic crystal conversion degree, thereby observe the degree that its dissolving is carried out.
Although bibliographical information adopts LiCl/DMAc solvent can make cellulose composite material, but cellulosic material must carry out the loaded down with trivial details activation consuming time of process in advance, and the size of the Fiber In Composite Material obtaining element fento is larger, diameter is at micron order, do not fully demonstrate reinforced effects (Takashi Nishino, Noriko Arimoto.Biomacromolecules 2007,8,2712-2716).Also having bibliographical information to take 5-12wt% sodium hydroxide/8-20wt% urea mixed aqueous solution is solvent, can prepare nano-cellulose matrix material, but need to prepare in advance nano-cellulose fento (Haisong Qi et al.Biomacromolecules 2009,10,1597-1602), the degree of scatter of its nanometer fento in matrix determined the performance of final material.And nano level Mierocrystalline cellulose fento is because its specific surface is very big and mechanical property is excellent, its reinforcing effect is very obvious.But can only extract nanometer fento or crystallite (M.M.de Souza Lima et al.Macromol.Rapid Commun.2004,25,771-787 with the way of chemistry or physics at present;
et al.Biomacromolecules 2007,8,1934-1941), then with polymer blending (Zimmermann et al.AdvancedEngineering Materials 2005,7,1156-1161).This preparation method is not only loaded down with trivial details, and the nano-cellulose fento generally making or crystallite be all to take the suspension that water is medium, is difficult to realize dispersed in most non-soluble polymers especially cellulosic matrix, has greatly limited its range of application.Therefore, develop a kind of can obtain stable Mierocrystalline cellulose nanometer fento and make its in polymeric matrix homodisperse simple effective ways for preparation this kind of matrix material be very important.
Ionic liquid is the environment-friendly solvent that a class of rising in recent years has application prospect, prepares etc. the application of numerous areas day by day by common people, paid close attention at chemosynthesis, electrochemistry, extracting and separating, material.Those skilled in the art have invented a kind ofly take ionic liquid and (referring to Chinese patent: CN1491974A), Mierocrystalline cellulose can dissolve without any activation in some ionic liquid, does not have obvious cellulose degradation to occur as solvent carrys out the method for dissolving cellulos simultaneously.
Summary of the invention
The object of this invention is to provide a kind of method that original position generates the polymer matrix composite of nano-cellulose fento enhancing.
Original position provided by the present invention generates the method for the polymer matrix composite of nano-cellulose fento enhancing, comprises the steps:
1) polymeric matrix of the described polymer matrix composite of preparation is added in solvent, obtain aqueous premix; Wherein, described polymeric matrix is Mierocrystalline cellulose, or the mixture of Mierocrystalline cellulose and other polymkeric substance; Described solvent is ionic liquid, or the mixed solvent of ionic liquid and following at least one solvent formation: water, N, N-dimethyl sulfoxide (DMSO), DMF, N,N-dimethylacetamide and N-Methyl pyrrolidone;
2) by described aqueous premix stirring and dissolving 0.5-10 hour at the temperature of 30-150 ℃, then through deaeration, process, obtain the cellulose solution of homogeneous transparent or the mixing solutions of Mierocrystalline cellulose and polymkeric substance;
3) mixing solutions of described cellulose solution or Mierocrystalline cellulose and polymkeric substance is carried out to plastic film mulch or spinning processing, then the film obtaining or fiber are solidified to regeneration in solidification liquid, clean and be dried the polymer matrix composite that makes the enhancing of nano-cellulose fento.
Mierocrystalline cellulose described in the present invention is from least one in following cellulosic material: Cotton Pulp, linters, cotton, wood pulp cellulose, wood pulps, bamboo pulp, Mierocrystalline cellulose filter paper, absorbent cotton, Microcrystalline Cellulose, bagasse, timber, straw and the Mierocrystalline cellulose making from stalk.The described cellulosic polymerization degree is between 150 to 2000.
Described in the present invention, other polymkeric substance is selected from least one in following polymkeric substance: polyacrylonitrile, polymeric amide, aromatic polyamides, polymethylmethacrylate, polyacrylic acid, poly-p styrene sulfonic acid, poly (sodium 4-styrenesulfonate), polyoxyethylene, polyaniline, Polythiophene, poly-3-butyl thiophene, poly-3-hexyl thiophene, poly-(3, 4-ethylenedioxy thiophene), PA 66 (nylon 66), polycaprolactam (nylon 6), polypyrrole, cellulose acetate, cellulose acetate propionic ester, cellulose acetate-butyrate, hairless protein, collagen protein, chitosan, chitin, starch, dextran, silk fibroin, soybean protein and Keratin sulfate.
Described ionic liquid is the melting salt lower than 100 ℃ by imidazoles or pyridylium and the formed fusing point of negatively charged ion.This ionic liquid specifically can be selected from least one in following substances: 1-ethyl, 3-methylene diacetate imidazole salts ionic liquid (EMIMAC), 1-allyl group, 3-methyl chloride imidazole salts ionic liquid (AMIMCl), 1-allyl group, 3-monobromomethane imidazole salts ionic liquid (AMIMBr), 1-butyl, 3-methyl chloride imidazole salts ionic liquid (BMIMCl), 1-butyl, 3-monobromomethane imidazole salts ionic liquid (BMIMBr), 1-ethyl, 3-methyl chloride imidazole salts ionic liquid (EMIMCl), 1-ethyl, 3-monobromomethane imidazole salts ionic liquid (EMIMBr), 1-allyl group, 3-methylene diacetate imidazole salts ionic liquid (AMIMAC), 1-butyl, 3-methylene diacetate imidazole salts ionic liquid (BMIMAC), N-normal-butyl pyridinium tetrafluoroborate salt ion liquid ([BPy] BF
4), normal-butyl pyridine hexafluorophosphate ionic liquid ([BPy] PF
4), N-n-hexyl pyridine hexafluorophosphate ionic liquid ([[HPy] PF
6]), N-monobromoethane pyridinium salt ionic liquid ([EPy] Br), 1,3-dimethylformamide dimethyl base phosphoric acid ester imidazole salts ionic liquid ([MMIM] [Me
2pO
4]), 1-ethyl, 3-methyl diethyl phosphoric acid ester imidazole salts ionic liquid ([EMIM] [Et
2pO
4]), 3-toluic acid imidazole salts ionic liquid (MIMMA), N-picoline formate ionic liquid ([MPy] MA), 1-ethyl, 3-toluic acid imidazole salts ionic liquid (EMIMMA), 1-butyl, 3-toluic acid imidazole salts ionic liquid (BMIMMA), pyridine carboxylic acid salt ion liquid (PyMA), N-butyl, N-Methyl pyrrolidone Dyhard RU 100 salt ion liquid (BMPDCA), 1-butyl, 3-methyl Dyhard RU 100 imidazole salts ionic liquid (BMIMDCA) and 1-ethyl, 3-tolyl acid imidazole salts ionic liquid (EMIMBA).
Step 1) described solvent is mixed solvent, the mass ratio of described mixed solvent intermediate ion liquid and following at least one solvent is 1: 0.001-1, described solvent is water, N, N-dimethyl sulfoxide (DMSO) (DMSO), N, dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-Methyl pyrrolidone (NMP).
Step 1) in described aqueous premix, the mass concentration of polymeric matrix can be 1% to 40%, is preferably 1-30%.When described polymeric matrix is the mixture of Mierocrystalline cellulose and other polymkeric substance, described cellulosic material accounts for 1% to 50% of polymeric matrix total mass.
Step 2) the Mierocrystalline cellulose fento that is 5-300nm containing diameter in the mixing solutions of described cellulose solution or described Mierocrystalline cellulose and polymkeric substance.
Step 3) described in, solidification liquid is selected from least one in following substances: water, aqueous sulfuric acid, ethanol, methyl alcohol, dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAC) and ionic liquid.
The invention provides and a kind ofly take ionic liquid as primary solvent, by controlling the dissolution degree of cellulosic material in ion liquid solvent, retain the nano-cellulose fento in cellulosic material, thereby prepare the method for nano cellulose microfibril reinforced polymer composite material.The generated in-situ Mierocrystalline cellulose fento of the method diameter is in 5 to 300nm scopes, and in prepared matrix material, nano-cellulose fento content accounts for the 0.3%-30% of matrix material.
Due to cellulosic multilevel hierarchy, its dissolving in ionic liquid is progressively carried out: be first non-crystalline region and degree of crystallinity compared with the dissolving of lower part, secondly just progressively carry out the dissolving of high crystalline cellulose nanometer fento part.Therefore, can, by regulating dissolution conditions (cellulose concentration, solvent temperature and dissolution time) to control the dissolution degree of Mierocrystalline cellulose in ionic liquid, thereby realize, in preparing the process of matrix material, synchronously obtain nano-cellulose fento.In addition, the purity of ionic liquid also directly affects the dissolution degree of Mierocrystalline cellulose in ionic liquid, therefore also can control cellulosic dissolution degree by controlling the water-content in ionic liquid or the method that adds other solvents to dilute ionic liquid, can realize equally with a kind of simple method and generate nanometer fento wild phase at the process situ of preparing matrix material.This method is simply controlled, has overcome the scattering problem of wild phase in nanometer fento matrix material, thereby can greatly improve the reinforced effects of Mierocrystalline cellulose nanometer fento.
The invention has the beneficial effects as follows:
(1) Mierocrystalline cellulose and polymkeric substance are directly added in ionic liquid or mixed solvent, in dissolution process, retained naturally occurring nano-cellulose fento wild phase in Mierocrystalline cellulose sample.The composite structure of gained is even, even transparent.
(2) can select different polymeric matrixs, and different Mierocrystalline celluloses is as matrix, prepares the matrix material that performance is different and meets actual needs.
(3) simple, controlled, the safety of preparation process.
Accompanying drawing explanation
Fig. 1 is the optical photograph of the cellulose ionic liquid solution after deaeration in embodiment 18.
Fig. 2 is transmission electron microscope (TEM) photo of Microcrystalline Cellulose/ionic liquid solution in embodiment 18; (a) be not consoluet cellulose solution; (b) be consoluet cellulose solution.
Fig. 3 is the composite material film of the Mierocrystalline cellulose nanometer fento fortifying fibre element of embodiment 18 preparations.
Embodiment
Below by specific embodiment, method of the present invention is described, but the present invention is not limited thereto.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Taken through vacuum-drying at 80 ℃ the dry Microcrystalline Cellulose of 12 hours (polymerization degree 220) and Keratin sulfate (dry Microcrystalline Cellulose is 1: 3 with Keratin sulfate quality ratio), joined in [HPy] PF6, preparing total concentration of polymer solution is 20%.After dispersed with stirring is even, put into oil bath, control solvent temperature at 60 ℃, and carry out mechanical stirring.Control dissolution time at 4h, after vacuum defoamation, obtain transparent settled solution.Make thus Mierocrystalline cellulose/keratic ionic liquid solution.Plastic film mulch on 40-60 ℃ of hot-plate, puts into water precipitation bath cooling forming.With distilled water, wash away ionic liquid again, dryly in vacuum drying oven obtain transparent nano-cellulose fento and strengthen keratic composite material film.The tensile strength of gained composite material film is 40MPa, and tensile modulus is 1.2GPa, and elongation at break is 10%.
Embodiment 2, prepare the composite fiber that nano-cellulose fento strengthens poly-p styrene sulfonic acid
Take through vacuum-drying at 80 ℃ the absorbent cotton of 12 hours (polymerization degree 1600) and poly-p styrene sulfonic acid (absorbent cotton and poly-p styrene sulfonic acid mass ratio are 1: 1), joined in BMIMCl, prepared total strength of solution 40%.After dispersed with stirring is even, put into oil bath, control solvent temperature at 90 ℃.And carry out mechanical stirring.Control dissolution time at 1h, after vacuum defoamation, obtain transparent settled solution.Make thus the ionic liquid solution of Mierocrystalline cellulose/poly-p styrene sulfonic acid.On small-sized spinning equipment by the mode spinning of wet spinning.Orifice diameter is 80-100 μ m, and precipitation bath is the mixing solutions of BMIMCl and water, and temperature is 20-40 ℃.Through drawing-off, washing, drawing-off, oven dry, obtain the composite fiber that nano-cellulose fento strengthens poly-p styrene sulfonic acid.The intensity of gained conjugated fibre is 3.0cN/dtex.
Embodiment 3, nanofiber fento strengthen the composite fiber of cellulose acetate
Take through vacuum-drying at 80 ℃ the bamboo pulp of 12 hours (polymerization degree 800) and cellulose acetate (bamboo pulp and cellulose acetate mass ratio are 2: 3), joined in [MPy] MA, prepared total strength of solution 25%.After dispersed with stirring is even, put into oil bath, control solution temperature at 100 ℃, and carry out mechanical stirring.Control dissolution time at 0.5h, after vacuum defoamation, obtain transparent settled solution.Make thus bamboo pulp/cellulose acetate/ionic liquid solution.On small-sized spinning equipment by the mode spinning of wet spinning.Orifice diameter is 80-100 μ m, and precipitation bath is water liquid, and temperature is 20-40 ℃.Through drawing-off, washing, drawing-off, oven dry, obtain the composite fiber that nanofiber fento strengthens cellulose acetate.The intensity of gained conjugated fibre is 3.5cN/dtex.
Embodiment 4, nano-cellulose fento strengthen the composite material film of chitosan
Take through vacuum-drying at 80 ℃ the Cotton Pulp of 12 hours (polymerization degree 2000) and chitosan (Cotton Pulp is 1: 99 with chitosan mass ratio), joined in EMIMAC, prepared total strength of solution 10%.After dispersed with stirring is even, put into oil bath, control solution temperature at 30 ℃, and carry out mechanical stirring.Control dissolution time at 8h, after vacuum defoamation, obtain the mixing solutions of clear.Make thus the ionic liquid solution of Cellulose/Chitosan.Plastic film mulch on 40-60 ℃ of hot-plate, puts into 20% aqueous sulfuric acid precipitation bath cooling forming.With distilled water, wash away ionic liquid again, the dry composite material film that obtains transparent nano-cellulose fento enhancing chitosan in vacuum drying oven.The tensile strength of composite material film reaches 100MPa, and tensile modulus reaches 4.GPa.
Embodiment 5, prepare the composite fiber that nano-cellulose fento strengthens maize straw
Taken at the 80 ℃ vacuum-drying Microcrystalline Cellulose of 12 hours (polymerization degree 220) and maize straw (content of cellulose is at 25-32%) (Microcrystalline Cellulose and maize straw mass ratio are 1: 4), join in AMIMCl/DMSO (mass ratio 1: 1), prepare total strength of solution 40%.After dispersed with stirring is even, put into oil bath, control solution temperature at 120 ℃, and carry out mechanical stirring.Control dissolution time at 4h, after vacuum defoamation, obtain the mixing solutions of clear.Make thus the ionic liquid solution of Mierocrystalline cellulose/maize straw.On small-sized spinning equipment by the mode spinning of wet spinning.Orifice diameter is 80-100 μ m, and precipitation bath is the mixing solutions (mass ratio 1: 9) of water and AMIMCl, and temperature is 20-40 ℃.Through drawing-off, washing, drawing-off, oven dry, obtain the composite fiber that nano-cellulose fento strengthens maize straw.The intensity of composite fiber is 3.0cN/dtex.
Embodiment 6, prepare the composite fiber of nano-cellulose fento Reinforced Nylon
Take through vacuum-drying at 80 ℃ the wood pulps of 12 hours (polymerization degree 650) and dry nylon 66 (wood pulps and nylon 66 mass ratioes are 1: 10), joined in EMIMBA, prepared total strength of solution 25%.After dispersed with stirring is even, put into oil bath, control solution temperature at 70 ℃, and carry out mechanical stirring.Control dissolution time at 5h, after vacuum defoamation, obtain the mixing solutions of clear.Make thus the ionic liquid solution of Mierocrystalline cellulose/nylon.On small-sized spinning equipment by the mode spinning of wet spinning.Orifice diameter is 100 μ m, and precipitation bath is the mixing solutions (mass ratio 1: 9) of water and EMIMBA, and temperature is 20-40 ℃.Through drawing-off, washing, drawing-off, oven dry, obtain the composite fiber of nano-cellulose fento Reinforced Nylon.The intensity of composite fiber is 5.0cN/dtex.
Embodiment 7, preparation nanometer fento strengthen the composite material film of polyaniline
Take through vacuum-drying at 80 ℃ drying bagasse (content of cellulose is at 32-48%) and the polyaniline (bagasse and polyaniline mass ratio are 3: 7) of 12 hours, joined in BMPDCA, prepared total strength of solution 8%.After dispersed with stirring is even, put into oil bath, control solution temperature at 120 ℃, and carry out mechanical stirring.Control dissolution time at 6h, after vacuum defoamation, obtain transparent settled solution.Make thus bagasse/polyaniline ionic liquid solution.Plastic film mulch on 40-60 ℃ of hot-plate, puts into water/ethanol (mass ratio 1: 8) precipitation bath cooling forming.With distilled water, wash away ionic liquid again, the dry composite material film that obtains transparent nanometer fento enhancing polyaniline in vacuum drying oven.The tensile strength of gained matrix material is 80MPa, and Young's modulus is 2.0GPa.
Embodiment 8, prepare the composite material film that nano-cellulose fento strengthens timber
The wood shavings (content of cellulose is at 40-50%) (Cotton Pulp is 2: 5 with lumber quality ratio) that has taken through vacuum-drying at 80 ℃ the dry Cotton Pulp of 12 hours (polymerization degree 1000) and pulverized, join in EMIMCl, prepare total strength of solution 5%.After dispersed with stirring is even, put into oil bath, control solution temperature at 130 ℃, and carry out mechanical stirring.Control dissolution time at 6h, after vacuum defoamation, obtain transparent settled solution.Make thus Cotton Pulp/timber ionic liquid solution.Plastic film mulch on 50 ℃ of hot-plates, puts into water precipitation bath cooling forming.With distilled water, wash away ionic liquid again, the dry composite material film that obtains transparent nanometer fento enhancing timber in vacuum drying oven.The tensile strength of gained matrix material can reach 160MPa, and Young's modulus can reach 3.5GPa.
Embodiment 9, prepare the composite fiber that nano-cellulose fento strengthens poly-(3,4-ethylene dioxythiophene)
Take through vacuum-drying at 80 ℃ the linters of 12 hours (polymerization degree 1200) and dry poly-(3,4-ethylene dioxythiophene) (linters is 1: 12.5 with the mass ratio of poly-(3,4-ethylene dioxythiophene)), joined [EPy] Br/H
2in O (mass ratio 1: 0.008), prepare total strength of solution 35%.After dispersed with stirring is even, put into oil bath, control solution temperature at 90 ℃, and carry out mechanical stirring.Control dissolution time at 3h, after vacuum defoamation, obtain the mixing solutions of clear.Make thus Mierocrystalline cellulose/polymers soln.On small-sized spinning equipment by the mode spinning of wet spinning.Orifice diameter is 80-100 μ m, and precipitation bath is the mixing solutions (mass ratio 1: 6) of water and [EPy] Br, and temperature is 20-40 ℃.Through drawing-off, washing, drawing-off, oven dry, obtain the composite fiber that nano-cellulose fento strengthens poly-(3,4-ethylene dioxythiophene).The intensity of conjugated fibre is 1.8cN/dtex.
Embodiment 10, prepare the composite material film of nano-cellulose fento fortifying fibre element
Taken through vacuum-drying at 80 ℃ the dry Microcrystalline Cellulose of 12 hours (polymerization degree 260), joined in EMIMCl/DMAc (mass ratio 1: 0.005), prepared total strength of solution 15%.After dispersed with stirring is even, put into oil bath, control solution temperature at 40 ℃, and carry out mechanical stirring.Control dissolution time at 8h, after vacuum defoamation, obtain transparent settled solution.Make thus cellulose ionic liquid solution.Plastic film mulch on 30-40 ℃ of hot-plate, puts into water precipitation bath cooling forming.With distilled water, wash away ionic liquid again, the dry composite material film that obtains transparent nano-cellulose fento fortifying fibre element in vacuum drying oven.The tensile strength of gained composite material film is 165MPa, and Young's modulus reaches 4.1GPa.
Embodiment 11, prepare the composite fiber of nano-cellulose fento Reinforced Polypropylene nitrile
Take through vacuum-drying at 80 ℃ the cotton of 12 hours (content of cellulose 95%) and dry polyacrylonitrile (cotton and polypropylene mass ratio 2: 3), joined [BPy] BF
4/ H
2in O (1: 0.001), prepare total strength of solution 30%.After dispersed with stirring is even, put into oil bath, control solution temperature at 80 ℃, and carry out mechanical stirring.Control dissolution time at 2h, after vacuum defoamation, obtain the mixing solutions of clear.Make thus Mierocrystalline cellulose/polymers soln.On small-sized spinning equipment by the mode spinning of wet spinning.Orifice diameter is 80-100 μ m, and precipitation bath is water and [BPy] BF
4mixing solutions (mass ratio 1: 9), temperature is 20-40 ℃.Through drawing-off, washing, drawing-off, oven dry, obtain the composite fiber of nano-cellulose fento Reinforced Polypropylene nitrile.The intensity of conjugated fibre is 2.4cN/dtex.
Embodiment 12, preparation contain the holocellulose composite material film of nano-cellulose fento
Taken through vacuum-drying at 80 ℃ the Mierocrystalline cellulose filter paper (Microcrystalline Cellulose and filter paper mass ratio are 1: 10) after the Microcrystalline Cellulose of 12 hours (polymerization degree 200) and fragmentation, join in [EPy] Br/DMF (1: 0.01), prepare total strength of solution 1%.After dispersed with stirring is even, put into oil bath, control solution temperature at 70 ℃, and carry out mechanical stirring.Control dissolution time at 6h, after vacuum defoamation, obtain the mixing solutions of clear.Make thus cellulose ionic liquid solution.Plastic film mulch on 30-40 ℃ of hot-plate, puts into water/DMF (mass ratio 9: 1) precipitation bath cooling forming.With distilled water, wash away ionic liquid again, dry in vacuum drying oven, obtain the transparent holocellulose composite material film containing nano-cellulose fento.Gained composite material film be 150MPa, Young's modulus is 3.2GPa.
Embodiment 13, prepare the composite fiber of nano-cellulose fento Reinforced Nylon
Take through vacuum-drying at 80 ℃ the wood pulps of 12 hours (polymerization degree 500) and nylon 6 (mass ratio of wood pulps and nylon 6 is 1: 5), joined in AMIMAC, prepared total strength of solution 45%.Under room temperature dispersed with stirring evenly after, put into oil bath, control solution temperature at 80 ℃, and carry out mechanical stirring.Control dissolution time at 3h, after vacuum is de-, obtain the mixing solutions of clear.Make thus the ionic liquid solution of Mierocrystalline cellulose/nylon.On small-sized spinning equipment by the mode spinning of wet spinning.Orifice diameter is 100 μ m, and precipitation bath is water, and temperature is 40 ℃.Through drawing-off, washing, drawing-off, oven dry, obtain the composite fiber of nano-cellulose fento Reinforced Nylon.The intensity of conjugated fibre is 4.5cN/dtex.
Embodiment 14, nano-cellulose fento strengthen the composite material film of dextran
Taken at the 80 ℃ vacuum-drying Microcrystalline Cellulose of 12 hours (polymerization degree 220) and dextran (Microcrystalline Cellulose and dextran mass ratio are 1: 2), joins [MMIM] [Me
2pO
4] in, prepare total strength of solution 10%.After dispersed with stirring is even, put into oil bath, control solution temperature at 60 ℃, and carry out mechanical stirring.Control dissolution time at 1h, after vacuum defoamation, obtain the mixing solutions of clear.Make thus the ionic liquid solution of Mierocrystalline cellulose/dextran.Plastic film mulch on 40-60 ℃ of hot-plate, puts into water/[MMIM] [Me
2pO
4] cooling forming in (mass ratio 9: 1) precipitation bath.With distilled water, wash away ionic liquid again, the dry composite material film that obtains transparent nano-cellulose fento enhancing dextran in vacuum drying oven.The tensile strength of gained composite material film is 60MPa, and Young's modulus is 1.3GPa.
Embodiment 15, prepare the composite material film that nano-cellulose fento strengthens starch
Take through vacuum-drying at 80 ℃ the wood pulps of 12 hours (polymerization degree 600) and starch (mass ratio of wood pulps and starch is 1: 1), joined in BMIMBr, prepared total strength of solution 30%.Under room temperature dispersed with stirring evenly after, put into oil bath, control solution temperature at 80 ℃, and carry out mechanical stirring.Control dissolution time at 1h, after vacuum defoamation, obtain the mixing solutions of clear.Make thus Mierocrystalline cellulose/starch/ionic liquid solution.Plastic film mulch on 60 ℃ of hot-plates, puts into water precipitation bath cooling forming.With distilled water, wash away ionic liquid again, the dry composite material film that obtains nano-cellulose fento enhancing starch in vacuum drying oven.The tensile strength of gained composite material film is 18MPa, and Young's modulus is 1.2GPa.
Embodiment 16, prepare the composite fiber that nano-cellulose fento strengthens silk fibroin
Taken vacuum-drying at 80 ℃ broken fiber element filter paper and the silk fibroin (mass ratio of filter paper and silk fibroin is 2: 5) of 12 hours, joins BMIMCl/H
2in O (mass ratio 1: 0.05), prepare total strength of solution 40%.After dispersed with stirring is even, put into oil bath, control solution temperature at 50 ℃, and carry out mechanical stirring.Control dissolution time at 3h, after vacuum defoamation, obtain the mixing solutions of clear.The ionic liquid solution that makes thus Mierocrystalline cellulose/silk fibroin on small-sized spinning equipment by the mode spinning of wet spinning.Orifice diameter is 100 μ m, and precipitation bath is water, and temperature is 30 ℃.Through drawing-off, washing, drawing-off, oven dry, obtain the composite fiber that nano-cellulose fento strengthens silk fibroin.The intensity of conjugated fibre is 2.5cN/dtex.
Embodiment 17, prepare the composite material film of nano-cellulose fento fortifying fibre element
Taken at the 80 ℃ vacuum-drying wood pulps of 12 hours (polymerization degree 1000) and bagasse (content of cellulose is 40%) (mass ratio of wood pulps and bagasse is 1: 3), join in EMIMCl/NMP (mass ratio 1: 1), prepare total strength of solution 15%.After dispersed with stirring is even, put into oil bath, control solution temperature at 130 ℃, and carry out mechanical stirring.Control dissolution time at 4h, after vacuum defoamation, obtain the mixing solutions of clear.Make thus the ionic liquid solution of Mierocrystalline cellulose/stalk.Plastic film mulch on 40-60 ℃ of hot-plate, puts into water/DMSO (mass ratio 9: 1) precipitation bath cooling forming.With distilled water, wash away ionic liquid again, in vacuum drying oven, be dried and obtain transparent composite material film.The tensile strength of gained composite material film can reach 150MPa, and Young's modulus reaches 3.5GPa.
Embodiment 18, prepare the composite material film of nano-cellulose fento fortifying fibre element
Take at 80 ℃ vacuum-drying the Microcrystalline Cellulose of 12 hours (polymerization degree 220), joined in AMIMCl, prepared total strength of solution scope 4%.After dispersed with stirring is even, put into oil bath, control solution temperature at 50 ℃, and carry out mechanical stirring.Control dissolution time at 4h, after vacuum defoamation, obtain the cellulosic ionic liquid solution (seeing Fig. 1) of clear.
Under transmission electron microscope, can see exist (the seeing that Fig. 2 is left) of obvious Mierocrystalline cellulose nanometer fento, completely different from consoluet cellulose solution (seeing that Fig. 2 is right).By this cellulose ionic liquid solution plastic film mulch on 40-60 ℃ of hot-plate, put into water precipitation bath cooling forming.With distilled water, wash away ionic liquid again, the dry composite material film that obtains transparent nano-cellulose fento fortifying fibre element in vacuum drying oven.Take English alphabet as substrate, see through this composite material film and can see clearly the letter on substrate, show that this composite material film has heigh clarity (seeing Fig. 3).The tensile strength of composite material film is 140MPa, and tensile modulus is 4GPa.
Embodiment 19, prepare the composite material film of nano-cellulose fento fortifying fibre element acetate butyrate
Taken at the 80 ℃ vacuum-drying Cotton Pulp of 12 hours (polymerization degree 1500) and cellulose acetate-butyrate (mass ratio of Cotton Pulp and cellulose acetate-butyrate is 3: 10), joins in AMIMCl, prepares total strength of solution 35%.After dispersed with stirring is even, put into IKA vacuum kneader, control solution temperature at 70 ℃, control kneading time at 3h.Make thus the ionic liquid solution of Mierocrystalline cellulose/cellulose acetate-butyrate.Plastic film mulch on 40-60 ℃ of hot-plate, puts into water/DMSO (mass ratio 9: 1) precipitation bath cooling forming.With distilled water, wash away ionic liquid again, the dry composite material film that obtains transparent nano-cellulose fento fortifying fibre element acetate butyrate in vacuum drying oven.The tensile strength of composite material film is 80MPa, and tensile modulus reaches 2.4GPa.
At this, it should be noted that: those skilled in the art under the guidance of above-mentioned description, make apparently such as the variation of each cited macromolecular material add-on of the present invention, the variation of different assembly each other etc., and introduce apparently other suitable macromolecular material etc., should fall into equally appended claims limited range of the present invention.
Claims (1)
1. an original position generates the method for the polymer matrix composite that nano-cellulose fento strengthens, for as follows: taken vacuum-drying at the 80 ℃ wood pulps of the polymerization degree 1000 of 12 hours and content of cellulose is at 40% bagasse, the mass ratio of wood pulps and bagasse is 1:3, join in the EMIMCl/NMP of mass ratio 1:1, prepare total strength of solution 15%; After dispersed with stirring is even, put into oil bath, control solution temperature at 130 ℃, and carry out mechanical stirring, control dissolution time at 4h, after vacuum defoamation, obtain the mixing solutions of clear, make thus cellulosic ionic liquid solution; Plastic film mulch on 40-60 ℃ of hot-plate, puts into water/DMSO precipitation bath cooling forming of mass ratio 9:1, then washes away ionic liquid with distilled water, in vacuum drying oven, is dried and obtains transparent composite material film.
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