CN101270205A - Method for preparing organic or inorganic composite fiber material with supercritical carbonic anhydride - Google Patents
Method for preparing organic or inorganic composite fiber material with supercritical carbonic anhydride Download PDFInfo
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- CN101270205A CN101270205A CNA200810036565XA CN200810036565A CN101270205A CN 101270205 A CN101270205 A CN 101270205A CN A200810036565X A CNA200810036565X A CN A200810036565XA CN 200810036565 A CN200810036565 A CN 200810036565A CN 101270205 A CN101270205 A CN 101270205A
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Abstract
The invention belongs to the technical field of organic and inorganic composite materials, in particular to a preparation method of organic and inorganic composite fibrous materials with supercritical carbon dioxide. The method includes pre-treatment and activation treatment of cellulose, doping of inorganic sol to the cellulose, etc. The invention makes use of the strong permeability of the carbon dioxide under supercritical conditions, can activate the cellulose with cosolvent, or lead nano particles in the inorganic sol to be absorbed and settled on the surface of the cellulose to form an even, continuous and stable coating layer; meanwhile, some sol particles penetrate into the fiber, so as to dope plenty of cellulose. The supercritical carbon dioxide adopted by the invention is safe, reliable, non-toxic, no pollutant and recyclable, and is environment friendly green solvent. The method of the invention is simple and easy to be operated, and the hybrid material has broad application prospect.
Description
Technical field
The invention belongs to the organic/inorganic composite material technical field, be specifically related to a kind of method for preparing under the supercritical co environment based on Mierocrystalline cellulose and inorganic oxide composites of utilizing.
Background technology
Mierocrystalline cellulose is the abundantest renewable resources of content on the earth, and annual occurring in nature is about 1 * 10 by photosynthesis synthetic Mierocrystalline cellulose
12Ton.Mierocrystalline cellulose is of many uses, has characteristics such as excellent biodegradability, biocompatibility and easy derivatize.In Mierocrystalline cellulose inside, intramolecularly that great amount of hydroxy group forms and intermolecular hydrogen bonding network have been given the fabulous hydrophilic nmature of Mierocrystalline cellulose and have been made its indissoluble, infusibility also, and this has greatly limited cellulosic processing and application (Angew.Chem., Int.Ed., 2005,44,3358.).For this reason, cellulosic regeneration and hybrid modification research thereof are the focuses that people explore always, particularly Mierocrystalline cellulose is carried out the inorganic doping modification, thereby preparation hybrid inorganic-organic materials expansion fiber element and the application of derivative in fields such as weaving, catalysis, pharmacy and functional membranes thereof extensively cause investigator's interest (Prog.Polym.Sci., 1995,20,889; Macromol.Rapid Commun., 2004,25,1632; Adv.Mater, 2005,17,2365.).
In various cellulose-derived methods, emerging in large numbers and being applied as of supercritical fluid technology handled and modified-cellulose provides a kind of new way.Particularly supercritical co nontoxic because of it, do not burn, pollution-free, easily reclaim and advantage such as low price, be the supercutical fluid that is most widely used.In addition, carbonic acid gas has the performance of many excellences under supercritical state, big as spread coefficient, viscosity is low and do not have surface tension, character such as mass transfer and dissolving power, specific inductivity can change rapidly with the adjusting of pressure, natural polymer and synthetic polymer had very strong infiltration and swelling ability (Ind.Eng.Chem.Res., 2003,42,367.).Therefore, can utilize the collaborative osmosis of supercritical co, realize the infiltration of additive, thereby material structure is changed, finish the preparation of organic-inorganic hybrid material polymer matrix to modified materials.After the step-down, carbonic acid gas is overflowed from matrix, and is recyclable, and whole process is simple and easy to operate, and good reproducibility is a kind of method of processing modified polymkeric substance of environmental protection.
In the various matrix materials that with the Mierocrystalline cellulose are matrix, the research of Mierocrystalline cellulose/inorganic oxide composites is especially noticeable.Utilize the synergy between organic phase (Mierocrystalline cellulose) and inorganic (metal or nonmetal oxide) mutually component, Mierocrystalline cellulose/inorganic oxide composites all has widely in a lot of fields to be used, the for example degraded of catalytic environment dirt and harmful chemical, the functional film material that preparation has ultraviolet protection and excellent mechanical property, and (J.Photochem.Photobiol., A-Chemistry., 2007 such as anti-biotic material and transition metal carbide material, 189,286; J.Sol-Gel Sci.Technol., 2007,44,111; Surf.Sci., 2005,599,69; Adv.Mater., 2004,16,1212.).
With Mierocrystalline cellulose/composite titania material is example, at present, surperficial sol-gel method, chemical Vapor deposition process and atomic shell decomposition method etc. is arranged on the synthetic method of matrix material.Investigator such as Huang and Kunitake utilizes filter paper to be template, introduces coating of titanium dioxide on its surface, has accurately duplicated cellulosic hierarchical structure (J.Am.Chem.Soc., 2003,125,11834.) under nanoscale.Because the colloidal sol body has higher viscosity and surface tension, under the effect of capillary effect, this method can't make colloidal sol cover narrower positions such as gap in the template fiber.People such as Zhang and Ikushima utilizes sodium hydroxide/urea and 1-butyl-3-Methylimidazole chloro ion liquid dissolving Mierocrystalline cellulose respectively, and by adding titania powder or its presoma, thereby preparation Mierocrystalline cellulose/composite titania material (J.Appl.Polym.Sci., 2006,101,3600; GreenChem., 2007,9,18.).These methods can't be avoided the dissolving and the regenerative process of natural cellulose, and change has all taken place its crystal formation.Scholar such as Liu and Han utilizes supercritical co that the sol precursor isopropyl titanate is permeated and is adsorbed on the cotton fibre surface, water and active group reaction with fiber surface absorption, thereby introducing coating of titanium dioxide, prepare Mierocrystalline cellulose/composite titania material (Chem.Commun., 2005,23,2948.).But employed presoma isopropyl titanate price is more expensive relatively in this method, and the water generation hydrolysis of itself and fiber surface absorption and the ratio and the speed of condensation reaction should not be controlled.
Summary of the invention
The preparation method who the purpose of this invention is to provide the organic or inorganic composite fiber material that a kind of cost is lower, reaction conditions is easily controlled.
Organic or inorganic composite fiber material among the present invention is Mierocrystalline cellulose and inorganic oxide composites, and wherein Mierocrystalline cellulose is macrofiber, Powdered fiber or staple fibre shape coacervate.The surfaces externally and internally of fiber all is coated with inorganic oxide, and the thickness of coating layer is in 3～10 nanometers.The fibrous inside infiltration has inorganic oxide particle.In the matrix material, cellulosic content is 35～99.5%, and the content of inorganic oxide is 0.5～65%, and described per-cent is weight percentage.
The Mierocrystalline cellulose that the present invention proposes and the preparation method of inorganic oxide composites comprise the steps:
(1) cellulosic pre-treatment.Can and need carry out pre-treatment or not carry out pre-treatment according to cellulosic kind.Have impurity such as wax or grease in Mierocrystalline cellulose, need carry out pre-treatment, method is as follows: use solvent with Mierocrystalline cellulose extracting 0.5-48 hour, impurity such as wax in the removal Mierocrystalline cellulose and grease.Here solvent for use is acetone, toluene or ethanol etc., perhaps other solubilized wax and greasy solvent.
(2) cellulosic activation treatment.Mierocrystalline cellulose and cosolvent that step (1) is handled are put in the high pressure vessel, by the pump pressure injecting carbon dioxide, controlled temperature is 15-200 ℃, pressure is the 4-40 megapascal (MPa), and kept reaction times 0.5-24 hour, cool the temperature to room temperature then, take out sample after the container release emptying, promptly obtain after the vacuum-drying through the activated cellulose after supercritical co and the cosolvent processing.Perhaps:
(3) inorganic sol is to cellulosic doping.Mierocrystalline cellulose and cosolvent that the inorganic sol for preparing in advance or its presoma and step (1) are handled join in the high pressure vessel, by the pump pressure injecting carbon dioxide, controlled temperature is 15-200 ℃, pressure is the 4-40 megapascal (MPa), kept reaction times 0.5-24 hour, cool the temperature to room temperature, take out sample after the container release emptying; Obtain the hybrid material of Mierocrystalline cellulose and inorganic oxide, with Mierocrystalline cellulose and the inorganic oxide hybridized material that solvent wash makes, preserve dry back.
Mierocrystalline cellulose described in the step (1) is the natural cellulose or derivatives thereof, and wherein natural cellulose comprises recyclability plant by-products such as linters, cotton fabric, bagasse, stalk, various paper product, bamboo, flax and non-sawn timber; The natural cellulose derivative is mainly products such as cellulose ester that natural cellulose produced by direct physical dissolving and the dissolving of part non-derivative and ether of cellulose, but does not get rid of the natural cellulose derived product by other method production.
Solvent load described in the step (1) is 10
1～10
3Milliliter.
Activated cellulose described in the step (2) is characterized in that fiber surface has distinctive groove shape crackle, crackle orientation or the direction shape extension in the shape of a spiral of stretching along fiber, the visible tiny primitive fiber (protofibril) of inside crack.
Cosolvent described in step (2) and (3) is one or more in the following solvent: methyl alcohol, ethanol, propyl carbinol, isopropylcarbinol, acetone, tetrahydrofuran (THF), formaldehyde, butyraldehyde-n, isobutyric aldehyde.
Preferred range is 40～160 ℃ in step (2) and (3).
Preferred pressure range is 7～25 megapascal (MPa)s in step (2) and (3).
The preferred reaction times of mixing is 1～14 hour in step (2) and (3).
The time range that release was overflowed carbonic acid gas after reaction described in step (2) and (3) finished is 1-30 minute, and preferred time range is 1-5 minute.
Inorganic sol described in the step (3) comprises following one or more oxide compounds, comprises that silicon oxide, titanium oxide, zinc oxide, stannic oxide, ferric oxide, aluminum oxide and zirconium white etc. are any by the inorganics of its presoma by sol-gel method or non-aqueous sol-gel method preparation.
Presoma described in the step (3) is to contain the metal in the described oxide compound or the alkoxide or the halogenide of non-metallic element.
Mierocrystalline cellulose described in the step (3), inorganic sol or its presoma consumption are:
Mierocrystalline cellulose: 35～99.5%;
Inorganic sol or its presoma: 0.5～65%.
Cosolvent is inorganic sol or presoma and Mierocrystalline cellulose total amount: 0.5～50%;
Described per-cent is weight percentage.
Cleaning solvent described in the step (3) is one or more in the following solvent: alcohols such as ethers such as water, toluene, acetone, normal hexane, tetrahydrofuran (THF) and ether, sherwood oil and methyl alcohol, ethanol, propyl carbinol, isopropylcarbinol.
Mierocrystalline cellulose of the present invention and inorganic oxide composites can be used for fields such as chemical industry, catalysis, weaving, medical, packing to be made and has materials with function such as photochemical catalysis, uv-absorbing and germ resistance, also can be used for making have toughness reinforcing, uvioresistant, the additive and the filler of functional plastics such as ageing resistance.
The present invention utilizes supercritical carbon dioxide fluid to be carrier, add the inorganic sol and the cosolvent that prepare in advance, under suitable temperature and pressure, utilize the strong penetrating power of carbonic acid gas under supercritical state, but activated cellulose changes cellulosic molecular structure on the one hand, and the hydrogen bond of cellulosic molecule interchain is by partial destruction, descending appears in degree of crystallinity, and cellulosic reactive behavior improves; On the other hand, the activatory cellulose surface helps the absorption and the coating of the inorganic nano-particle in the colloidal sol, thus form at cellulose surface have continuously, the inorganic oxide coating layer of homogeneous and stabilising characteristic; Simultaneously; Carbonic acid gas also helps the inorganic nano-particle infiltration in the colloidal sol and inserts imbedding between the cellulosic molecule to the destruction of cellulosic infiltration and crystalline texture, the great amount of hydroxy group that is rich in by the inorganic nano-particle sub-surface can form hydrogen bond network with the activation hydroxyl in the cellulose molecular chain, thereby realizes that inorganic oxide is to cellulosic a large amount of doping.
The Mierocrystalline cellulose among the present invention and the preparation method of inorganic oxide hybridized material are simple to operation.The supercritical co that adopts is safe and reliable, does not burn, and is pollution-free, the toxicological harmless effect, and it is convenient to reclaim, can be recycled, be a kind of eco-friendly green solvent.The doping content height of inorganic oxide in the hybrid material, and can simply regulate and control by changing factors such as feed ratio, temperature of reaction, reaction pressure.The easily separated purifying of product, the character stable homogeneous has broad application prospects in each fields such as catalysis, chemical industry, packing, weavings.
Description of drawings
Fig. 1 utilizes supercritical co to prepare the device synoptic diagram of Mierocrystalline cellulose and inorganic oxide hybridized material among the embodiment 1.Wherein the component names of symbol of numeral representative is as follows:
Fig. 2 is for utilizing the electron scanning micrograph of the activated cellulose of supercritical co and cosolvent ethanol preparation among the embodiment 1.
Fig. 3 utilizes the Mierocrystalline cellulose of supercritical co and cosolvent ethanol preparation and the electron scanning micrograph of titanium dioxide hybrid material among the embodiment 3.
Fig. 4 utilizes the Mierocrystalline cellulose of supercritical co and cosolvent ethanol preparation and the transmission electron microscope photo of titanium dioxide hybrid material among the embodiment 3.
Number in the figure: 1, dioxide bottle; 2,3,4, valve; 5, whipping appts; 6, stainless steel high pressure vessel; 7, pressure transmitter; 8, thermometer; 9, electroheat pair; 10, oil bath.
Embodiment
Following examples are that the present invention is further elaborated, are used for showing use known for inventor preferred forms of the present invention to the technician of association area and industry, but do not limit content of the present invention and scope.Can make amendment and do not exceed scope of the present invention following embodiment, for the technician of this area and relevant industries, be conspicuous by following examples for implementing the inventive method.Therefore, in the scope of claims and equivalent thereof, can by with the following specifically describes different modes and implement the present invention.
Embodiment 1:
In fatty extractor, put into 4 gram linterss,, remove wax and lubricant component in the linters, insert dried for standby in the vacuum drying oven afterwards with 50 milliliters of acetone extractings 4 hours.
Utilize device shown in Figure 1.0.3 gram is handled linters and 3 milliliters of ethanol later through above-mentioned extracting to join in the stainless steel autoclave, the temperature of oil bath is 40 ℃ in the control thermostatic bath, feed amounts of carbon dioxide with the air emptying in the reaction unit after, by the high-pressure pump injecting carbon dioxide, the control device internal pressure is 15 megapascal (MPa)s.Close intake valve, reactor constant temperature in oil bath was placed 2 hours.Remove thermostatic bath then, treat in 5 minutes, the carbonic acid gas in the reactor to be discharged after temperature is reduced to room temperature, treat that pressure unloads to normal pressure, take out sample, obtain the linters sample of supercritical co and Ethanol Treatment after the vacuum-drying.Observe under scanning electronic microscope, obtain electromicroscopic photograph as shown in Figure 2, the surface of its activated fiber has distinctive groove shape crack.
Embodiment 2:
Utilize device shown in Figure 1.1 gram ashless filter paper and 10 milliliters of ethanol are joined in the stainless steel autoclave, the temperature of oil bath is 50 ℃ in the control thermostatic bath, feed amounts of carbon dioxide with the air emptying in the reaction unit after, by the high-pressure pump injecting carbon dioxide, the control device internal pressure is 20 megapascal (MPa)s.Close intake valve, reactor constant temperature in oil bath was placed 5 hours.Remove thermostatic bath then, treat in 3 minutes, the carbonic acid gas in the reactor to be discharged after temperature is reduced to room temperature, treat that pressure unloads to normal pressure, take out sample, obtain the ashless filter paper activated fiber sample of supercritical co and Ethanol Treatment after the vacuum-drying.
Embodiment 3:
In fatty extractor, put into 10 gram cottons,, remove the impurity component in the cotton, insert dried for standby in the vacuum drying oven afterwards with 100 milliliters of toluene extractings 8 hours.
Utilize device shown in Figure 1.3 grams are handled cotton later through above-mentioned extracting, 10 milliliters of TiO 2 sols and 3 milliliters of ethanol join in the stainless steel autoclave, the temperature of oil bath is 60 ℃ in the control thermostatic bath, feed amounts of carbon dioxide with the air emptying in the reaction unit after, by the high-pressure pump injecting carbon dioxide, the control device internal pressure is 18 megapascal (MPa)s.Close intake valve, reactor constant temperature in oil bath was placed 4 hours.Remove thermostatic bath then, treat in 5 minutes, the carbonic acid gas in the reactor to be discharged after temperature is reduced to room temperature, treat that pressure unloads to normal pressure, take out sample, with washing with alcohol final vacuum drying, obtain the Mierocrystalline cellulose and the titanium dioxide hybrid material of preparation under the supercritical co environment.Under scanning electronic microscope, observe, obtain electromicroscopic photograph as shown in Figure 3.Under transmission electron microscope, observe, obtain electromicroscopic photograph as shown in Figure 4.The fiber surfaces externally and internally of hybrid material all is coated with titanium dioxide, and the thickness of coating layer is about 5nm, and the fibrous inside infiltration has titanium dioxide nano-particle.It is Powdered that hybridized fiber is, and staple length is 30～1000 microns, and diameter is 8～30 microns.
Embodiment 4:
Utilize device shown in Figure 1.With 10 gram ashless filter papers, 20 milliliters of TiO 2 sols and 6 ml methanol join in the stainless steel autoclave, the temperature of oil bath is 50 ℃ in the control thermostatic bath, feed amounts of carbon dioxide with the air emptying in the reaction unit after, by the high-pressure pump injecting carbon dioxide, the control device internal pressure is 25 megapascal (MPa)s.Close intake valve, reactor constant temperature in oil bath was placed 5 hours.Remove thermostatic bath then, treat in 3 minutes, the carbonic acid gas in the reactor to be discharged after temperature is reduced to room temperature, treat that pressure unloads to normal pressure, take out sample, with methanol wash final vacuum drying, obtain the Mierocrystalline cellulose and the titanium dioxide hybrid material of preparation under the supercritical co environment.
Claims (4)
1, a kind of method of utilizing supercritical co to prepare organic or inorganic composite fiber material is characterized in that concrete steps are as follows:
(1) cellulosic pre-treatment is according to cellulosic kind and need carry out pre-treatment or not carry out pre-treatment; Have impurity such as wax or grease in Mierocrystalline cellulose, need carry out pre-treatment, method is as follows: use solvent with Mierocrystalline cellulose extracting 0.5-48 hour, impurity such as wax in the removal Mierocrystalline cellulose and grease; Here solvent for use is acetone, toluene or ethanol, perhaps other solubilized wax and greasy solvent;
(2) cellulosic activation treatment, Mierocrystalline cellulose and cosolvent that step (1) is handled are put in the high pressure vessel, by the pump pressure injecting carbon dioxide, controlled temperature is 15-200 ℃, pressure is the 4-40 megapascal (MPa), and keeps reaction times 0.5-24 hour, cools the temperature to room temperature then, take out sample after the container release emptying, promptly obtain after the vacuum-drying through the activated cellulose after supercritical co and the cosolvent processing; Perhaps:
(3) inorganic sol is to cellulosic doping, Mierocrystalline cellulose and cosolvent that the inorganic sol for preparing in advance or its presoma and step (1) are handled join in the high pressure vessel, by the pump pressure injecting carbon dioxide, controlled temperature is 15-200 ℃, pressure is the 4-40 megapascal (MPa), kept reaction times 0.5-24 hour, and cooled the temperature to room temperature, take out sample after the container release emptying; Obtain the hybrid material of Mierocrystalline cellulose and inorganic oxide, with Mierocrystalline cellulose and the inorganic oxide hybridized material that solvent wash makes, preserve dry back.
2, method according to claim 1 is characterized in that described cosolvent is one or more in the following solvent: methyl alcohol, ethanol, propyl carbinol, isopropylcarbinol, acetone, tetrahydrofuran (THF), formaldehyde, butyraldehyde-n, isobutyric aldehyde.
3, method according to claim 1, it is characterized in that described inorganic sol comprises following one or more oxide compounds: silicon oxide, titanium oxide, zinc oxide, stannic oxide, ferric oxide, aluminum oxide, zirconium white, by the inorganics of its presoma by sol-gel method or non-aqueous sol-gel method preparation; Described presoma is to contain the metal in the described oxide compound or the alkoxide or the halogenide of non-metallic element.
4, method according to claim 1, the consumption that it is characterized in that the Mierocrystalline cellulose described in the step (3), inorganic sol or its presoma, cosolvent is by mass percentage: Mierocrystalline cellulose: 35～99.5%, and inorganic sol or its presoma: 0.5～65%; Cosolvent is inorganic sol or presoma and Mierocrystalline cellulose total amount: 0.5～50%.
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| CN109174072A (en) * | 2018-10-13 | 2019-01-11 | 吴亚良 | A kind of supercritical preparation process of the uniform nano-titanium dioxide of particle diameter distribution |
| US20210371604A1 (en) * | 2020-05-28 | 2021-12-02 | Ford Global Technologies, Llc | Post-harvest method for natural fiber nanoparticle reinforcement using supercritical fluids |
| US11623978B2 (en) * | 2020-05-28 | 2023-04-11 | Ford Global Technologies, Llc | Post-harvest method for natural fiber nanoparticle reinforcement using supercritical fluids |
| CN112919967A (en) * | 2021-03-02 | 2021-06-08 | 青海高原地沣肥业有限公司 | Method for preparing organic fertilizer from municipal sludge |
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