CN100400579C - Method for preparing functional material of regenerated cellulose - Google Patents
Method for preparing functional material of regenerated cellulose Download PDFInfo
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- CN100400579C CN100400579C CNB2004101018009A CN200410101800A CN100400579C CN 100400579 C CN100400579 C CN 100400579C CN B2004101018009 A CNB2004101018009 A CN B2004101018009A CN 200410101800 A CN200410101800 A CN 200410101800A CN 100400579 C CN100400579 C CN 100400579C
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Abstract
The present invention discloses a method for preparing functionalized regenerated cellulose materials. Natural cellulose raw materials are dried and mixed with cellulose solvents, the mixture is heated and stirred or mechanically kneaded until the cellulose is completely dissolved, and uniform and transparent cellulose homogeneous phase solution is obtained. Functionalized stuffing is added into the cellulose homogeneous phase solution and continuously stirred until the mixture is uniform. The obtained solution is defoamed in vacuum, regenerated in coagulation bath, washed in water and dried or spun to obtain the functionalized regenerated cellulose materials. Compared with a traditional viscose process, the preparation method of the present invention has the advantages of simple manufacturing process, no pollution, little power consumption, etc.
Description
Technical field
The present invention relates to the preparation method of functional material of regenerated cellulose.
Background technology
Along with increasingly sharpening and petroleum-based energy, the rapid threat of exhausting of natural resources of global problem of environmental pollution to Sustainable development, and the raising of public's environmental consciousness, impelling with the natural reproducible resource is that the research of the macromolecular material of raw material is developed rapidly.Mierocrystalline cellulose is a natural polymer the abundantest on the earth, and existing availability has recyclability again, has cheapness, degradable simultaneously and ecotope is not produced advantage such as pollution.Be widely used in traditional industries such as plastics, textile and paper at present based on cellulosic material, and obtained important application at food chemical industry, daily-use chemical industry, medicine, building, oilfield chemistry and biochemical field.People estimate that in the future days, cellulose materials will be played an important role at aspects such as improving the ecological environment, improve human life quality, the increase energy, development type material.
But well-known, natural cellulose has the characteristics of self aggregated structure, and its intramolecularly and intermolecularly exist a large amount of hydrogen bonds has higher degree of crystallinity simultaneously, makes natural cellulose have not melt, undissolved characteristics in most of solvents.This is the major limitation of present natural cellulose in application, also makes the exploitation of various regenerated fibre cellulose products be subjected to very big restriction.Viscose fiber technology occupies dominant position always in the regenerated cellulose fibre production field, but the shortcoming of this technology also clearly, that is: technology is extremely complicated, energy consumption is big, particularly very serious to the pollution of environment.At present a lot of in the world developed countries or close the manufacturing enterprise of its domestic viscose fiber perhaps transfer to developing country with its manufacturing enterprise.Use cellulosic active solvent, be equipped with the important channel that cellulosic fibre is the exploitation material of regenerated cellulose by the direct solvent legal system, this also is the important directions of regenerated cellulose industry Future Development.
N, N '-N,N-DIMETHYLACETAMIDE (DMAC)/lithium chloride (LiCl) (referring to U.S.'s patent of invention, US4278790) and N-methylmorpholine oxide compound (NMMO) be the representative of comparatively successful Mierocrystalline cellulose direct solvent.Wherein but the NMMO dissolving cellulos has advantages such as dissolving power is strong, the low efficient recovery of toxicity, is that the preparation material of regenerated cellulose technology of solvent has realized industrialization with NMMO, also is the Mierocrystalline cellulose direct solvent of unique in the world realization industrialization.(referring to China and U.S.'s patent of invention: ZL97107819.X, CN1151194A, CN1238016A, US5919412, US6153003).
Ionic liquid is a kind of emerging natural cellulose solvent.One of green solvent of very praising highly as Green Chemistry, itself has lot of advantages ionic liquid, as: (1) comprises that to a lot of chemical substances organism and inorganics have the good solubility energy; (2) has higher ionic conductivity; (3) higher thermostability; (4) the liquid temperature scope of broad; (5) higher polarity, solvation performance.(6) volatilization, not oxidation hardly, do not burn; (7) viscosity is low, thermal capacitance is big; (8) all stable to water and air; (9) easily reclaim, can be recycled; (10) synthesis device is simple, synthesis condition is gentle.The ionic liquid that has been found that some ad hoc structure at present has excellent solubility property to Mierocrystalline cellulose.(CN1491974A CN1417407A) has all reported the content of this respect to the patent in world patent (WO03/029329 A2) and we early stage.
Specific filler is joined in the macromolecular material, to realize enhancing, toughness reinforcing and other functionalization effect, is method very commonly used in the macromolecular material research and development field.For example carbon nanotube, nanometer are covered holder soil as in the filler absorption macromolecule matrix material, can play the mechanical property that improves material, thermostability, barrier property and effect such as antistatic, relevant report has had a lot.And in viscose fiber, add the functionalization filler, can make fiber have some specific function equally.As in patent CN1102682C and CN 1123637, having described the method that adopts the adhering process preparation to contain the viscose fiber cellulose fiber of medical stone, nano ceramics, can give cellulosic fibre with functions such as body-care, antibiotic, uvioresistant and anti-visible-lights.But as previously mentioned, it is very complicated to adopt traditional viscose process to prepare the technology of material of regenerated cellulose, and the environmental pollution of adhering process own is extremely serious, energy consumption is big.In today that environmental consciousness improves day by day, this technology is being faced with restriction greatly.
Summary of the invention
The invention provides and a kind ofly prepare the method for functional material of regenerated cellulose with the Mierocrystalline cellulose direct solvent, can prepare the material of regenerated cellulose of functionalization easily and effectively, the problem of having avoided adhering process to exist has remarkable advantages.Up to the present, these solvents also of no use prepare the relevant report of functional material of regenerated cellulose.
The preparation method of functional material of regenerated cellulose of the present invention will mix with cellosolve after the natural cellulosic feedstocks drying, imposes to stir or the machinery kneading in heating, dissolves fully up to Mierocrystalline cellulose, obtains the homogeneous transparent homogeneous cellulose solution; Add functional filler again, continue to stir, mix; With the deaeration under vacuum of gained solution, handle through precipitation bath regeneration, washing, drying or spinning, obtain the material of regenerated cellulose of functionalization.Solvent can recycling.
Described natural cellulosic feedstocks is one or more in the Mierocrystalline cellulose that makes in Microcrystalline Cellulose, the cotton pulp dregs of rice, linters, cotton, wood pulp cellulose, wood pulps, bamboo pulp, Mierocrystalline cellulose filter paper or all kinds of straw.
Described natural cellulosic feedstocks shreds the back and uses, better effects if.
The polymerization degree of described natural cellulosic feedstocks is preferably 200～700 in 150～1500 scopes, and more excellent is 300～600.
Described cellosolve is N-methylmorpholine oxide compound (NMMO) aqueous solution, N-ethyl-N '-Methylimidazole villaumite ionic liquid (EMIMCl), N-propyl group-N '-Methylimidazole villaumite ionic liquid (PMIMCl), N-butyl-N '-Methylimidazole villaumite ionic liquid (BMIMCl), N-allyl group-N '-Methylimidazole villaumite ionic liquid (AMIMCl), N-methacrylic-N '-Methylimidazole villaumite ionic liquid (mAMIMCl), N-ethyl-N '-Methylimidazole acetate ionic liquid (EMIMAc), N-propyl group-N '-Methylimidazole acetate ionic liquid (PMIMAc), N-butyl-N '-Methylimidazole acetate ionic liquid (BMIMAc), in N-allyl group-N '-Methylimidazole acetate ionic liquid (AMIMAc) or N-methacrylic-N '-Methylimidazole acetate ionic liquid (mAMIMAc) one or more.Wherein remove the NMMO aqueous solution for buying, other cellosolves all can be referring to patent and document: CN1417407A, Inorg.Chem.1996, and 35,1168-1178 is synthetic.
The weight concentration of described cellulosic material in cellosolve can be 5～30%, is preferably 8～15%.
In described method,,, therefore preferably carry out the thorough drying processing to desiring the dissolved natural cellulose because free moisture can reduce the dissolving power of ionic liquid to natural cellulose in the system for ion liquid solvent.
Described functional filler is that nanometer is covered holder soil, carbon nanotube, chitin, chitosan, Lalgine, medical stone, carbon black, carbon nano fiber, polypyrrole micro mist, nano titanium oxide (TiO
2), nano zine oxide (ZnO), nano silicon (SiO
2), nano-aluminium oxide (Al
2O
3) or nanometer metallic silver (Ag) in one or more.
The weight of described functional filler is 0.1%～10% of natural cellulose weight.
Functional filler size is that nano level is to micron order.
Among the preparation method of described functional material of regenerated cellulose, described Heating temperature is 50～120 ℃ of scopes, is preferably 70～120 ℃.
Among the preparation method of described functional material of regenerated cellulose, before the regeneration of functional fiber cellulosic material, must carry out vacuum defoamation to cellulose solution and handle.
The precipitation bath that described cellulose regenerated process is used is the mixture of water or water and cellosolve.If making the mixture of water and cellosolve is precipitation bath, the weight ratio of water and cellosolve is 95: 5～50: 50 in the mixture, and preferred weight ratio is 95: 5～70: 30.The temperature of described precipitation bath is controlled at 10～80 ℃ of scopes, and preferred temperature range is 20～50 ℃.
Material of regenerated cellulose by described method preparation can be regenerated cellulose mould material, functionalization regenerated cellulose fibre or other forms of functional material of regenerated cellulose (as gel, separatory membrane etc.).
Described solvent recuperation, the moisture in can bathing by the direct evaporation or the back evaporation coagulation of saltouing is realized.Also can make solvent enrichment to be recycled in the production by multistage washing or the way of saltouing.
The direct solvent legal system is equipped with cellulose materials to be compared with traditional adhering process, has advantages such as technology is simple, pollution-free, energy consumption is little.Under the situation of using ionic liquid as cellosolve, used ion liquid solvent synthetic method is simple, low price, nontoxic, harmless, and solvent recuperation is easy, safe simultaneously.By adding functional filler, be easy to realize the functionalization of material of regenerated cellulose, as barrier properties for gases, electroconductibility, static resistance, uvioresistant, antibiotic, body-care etc., thereby greatly expanded the use range of Mierocrystalline cellulose this " ancient " natural macromolecular material.
Embodiment
Providing some embodiment below and just further specify the present invention, is not to have a mind to limit scope involved in the present invention.
Embodiment 1
Take by weighing the dry wood pulps of 17.0g exsiccant EMIMCl ionic liquid and 3.0g, under 100 ℃, mix.After about 40 minutes, form the brown yellow solution of clear,, illustrate that Mierocrystalline cellulose dissolves fully, make the cellulose solution that concentration is 15.0wt% thus with being black in the polarized light microscope observing visual field.Multi-walled carbon nano-tubes (MWNT) is through behind the purifying, 50 ℃ with a certain proportion of vitriol oil and concentrated nitric acid acidifying, water repetitive scrubbing to acidity-basicity ph value is 6 again, obtains acidated multi-walled carbon nano-tubes.With 50mg acidifying carbon nanotube, mix in the cellulose solution that adding has made.The mixing solutions deaeration of Mierocrystalline cellulose that makes and carbon nanotube after 120 minutes, is added the mode spinning of small-sized spinning equipment by dry-jet wet-spinning.Orifice diameter is 100 μ m, and solidification liquid is a water, and temperature is 25 ℃, through drawing-off, washing, drawing-off, oven dry, obtains carbon nanotube enhanced conjugated fibre cellulose fiber.Evaporate the water in the precipitation bath, the EMIMCl ionic liquid that obtains reclaiming.
Embodiment 2
Take by weighing the NMMO/H of 18.5g
2The O solvent adds the 50mg nanometer and covers holder soil, mixes 120 minutes 90 ℃ of following mechanical stirring.Add the dry cotton pulp dregs of rice of 1.5g again, continue to stir at 90 ℃.After about 50 minutes, form the brown yellow solution of clear, make thus and contain the homogeneous cellulose solution that nanometer is covered holder soil.After 120 minutes, evenly be layered on the solution deaeration that makes in the tetrafluoroethylene mould this moment, adds entry as solidification liquid.Through washing, drying obtains containing and peels off or the native regenerated cellulose film of intercal type nano illiteracy holder, can improve mechanical property, thermostability and the barrier property etc. of cellulose membrane.Evaporate water most in the precipitation bath, the NMMO/H that obtains reclaiming
2The O solvent.
Embodiment 3
Take by weighing 19.0g PMIMCl solvent, add the dry wood pulps of 1.0g, add 50mg chitosan fine powder again and implement mechanical stirring at 110 ℃.After about 40 minutes, form the brown yellow solution of clear, make the homogeneous cellulose solution that contains chitosan thus.The solution deaeration that makes after 120 minutes, is added the mode spinning of small-sized spinning equipment by dry-jet wet-spinning.Orifice diameter is 100 μ m, and solidification liquid is a water, and temperature is 25 ℃, through drawing-off, washing, drawing-off, oven dry, the regenerated cellulose conjugated fibre that obtains having germ resistance.Evaporate the water in the precipitation bath, the PMIMCl solvent that obtains reclaiming.
Embodiment 4
Take by weighing 18.6g exsiccant BMIMCl ionic liquid, add the dry cotton pulp dregs of rice of 1.4g, under 80 ℃, carry out mechanical stirring.After about 80 minutes, form the brown yellow solution of clear,, illustrate that Mierocrystalline cellulose dissolves fully, make the cellulose solution that concentration is 7.0wt% thus with being black in the polarized light microscope observing visual field.Again with the 10mg nano-TiO
2Add in the cellulose solution that has made and mix.Make thus and contain nano-TiO
2Homogeneous cellulose solution.The solution deaeration that makes after 120 minutes, is added the mode spinning of small-sized spinning equipment by dry-jet wet-spinning.Orifice diameter is 100 μ m, and solidification liquid is the mixing solutions of water and BMIMCl, and temperature is 25 ℃, through drawing-off, washing, drawing-off, oven dry, obtains having cellulose composite fiber antibiotic, uvioresistant function.Evaporate the water in the precipitation bath, the BMIMCl ionic liquid that obtains reclaiming.
Embodiment 5
Take by weighing 19.0g exsiccant BMIMAc ionic liquid, add the dry good cotton pulp dregs of rice of 1.0g, under 70 ℃, carry out mechanical stirring.After about 70 minutes, form the brown yellow solution of clear,, illustrate that Mierocrystalline cellulose dissolves fully, make the cellulose solution that concentration is 5.0wt% thus with being black in the polarized light microscope observing visual field.Again the 20mg nano-ZnO is added in the cellulose solution that has made and mix.Make the homogeneous cellulose solution that contains nano-ZnO thus.The solution deaeration that makes after 120 minutes, is added the mode spinning of small-sized spinning equipment by dry-jet wet-spinning.Orifice diameter is 100 μ m, and solidification liquid is the mixing solutions of water and BMIMAc, and temperature is 25 ℃, through drawing-off, washing, drawing-off, oven dry, obtains having cellulose composite fiber antibiotic, uvioresistant function.Evaporate the water in the precipitation bath, the BMIMAc ionic liquid that obtains reclaiming.
Embodiment 6
Take by weighing 18.4g exsiccant AMIMAc ionic liquid, add the dry cotton pulp dregs of rice of 1.6g, under 70 ℃, carry out mechanical stirring.After about 70 minutes, form the brown yellow solution of clear,, illustrate that Mierocrystalline cellulose dissolves fully, make the cellulose solution that concentration is 8.0wt% thus with being black in the polarized light microscope observing visual field.Again with 10mg nanometer SiO
2Add in the cellulose solution that has made and mix.Make thus and contain nanometer SiO
2Homogeneous cellulose solution.Again with this solution deaeration after 120 minutes, the mode spinning by wet spinning on small-sized spinning equipment.Orifice diameter is 100 μ m, and precipitation bath is the mixing solutions of water and AMIMAc, and temperature is 25 ℃, through drawing-off, washing, drawing-off, oven dry, obtains having cellulose composite fiber antibiotic, uvioresistant function.Evaporate the water in the precipitation bath, the AMIMAc ionic liquid that obtains reclaiming.
Embodiment 7
Take by weighing 18.0g exsiccant mAMIMAc ionic liquid, add the dry wood pulps of 2.0g, under 70 ℃, carry out mechanical stirring.After about 70 minutes, form the brown yellow solution of clear,, illustrate that Mierocrystalline cellulose dissolves fully, make the cellulose solution that concentration is 10.0wt% thus with being black in the polarized light microscope observing visual field.Again with 30mg nanometer Al
2O
3Add in the cellulose solution that has made and mix.Make thus and contain nanometer Al
2O
3Homogeneous cellulose solution.Again with this solution deaeration after 120 minutes, the mode spinning by wet spinning on small-sized spinning equipment.Orifice diameter is 100 μ m, and precipitation bath is the mixing solutions of water and mAMIMAc, and temperature is 40 ℃, through drawing-off, washing, drawing-off, oven dry, obtains having cellulose composite fiber antibiotic, uvioresistant function.Evaporate the water in the precipitation bath, the mAMIMAc ionic liquid that obtains reclaiming.
Embodiment 8
Take by weighing 18.2g exsiccant mAMIMCl ionic liquid, add the dry wood pulps of 1.8g, under 80 ℃, carry out mechanical stirring.After about 60 minutes, form the brown yellow solution of clear,, illustrate that Mierocrystalline cellulose dissolves fully, make the cellulose solution that concentration is 9.0wt% thus with being black in the polarized light microscope observing visual field.10mg is added in the cellulose solution that makes and mixes through being crushed to 300-500 purpose maifanite powder after the washing, dedusting, removal of impurities.The Mierocrystalline cellulose medical stone mixing solutions deaeration that makes after 120 minutes, is added the mode spinning of small-sized spinning equipment by dry-jet wet-spinning.Orifice diameter is 100 μ m, and solidification liquid is a water, and temperature is 30 ℃, through drawing-off, washing, drawing-off, oven dry, obtains having the cellulose composite fiber of ir radiation.Evaporate the water in the precipitation bath, the mAMIMCl ionic liquid that obtains reclaiming.
Embodiment 9
Take by weighing 18.0g exsiccant AMIMAc ionic liquid, add the dry wood pulps of 2.0g, under 80 ℃, carry out mechanical stirring.After about 60 minutes, form the brown yellow solution of clear,, illustrate that Mierocrystalline cellulose dissolves fully, make the cellulose solution that concentration is 10.0wt% thus with being black in the polarized light microscope observing visual field.To mix in 10mg carbon black and the 10mg polypyrrole adding cellulose solution again.The cellulose solution deaeration that contains carbon black and polypyrrole that makes after 120 minutes, is added the mode spinning of small-sized spinning equipment by dry-jet wet-spinning.Orifice diameter is 100 μ m, and solidification liquid is a water, and temperature is 40 ℃, through drawing-off, washing, drawing-off, oven dry, obtains anlistatig cellulose composite fiber.Evaporate the water in the precipitation bath, the AMIMAc ionic liquid that obtains reclaiming.
Embodiment 10
Take by weighing the vacuum drying AMIMCl ionic liquid of 18.0g, add the dry wood pulps of 2.0g, under 80 ℃, carry out mechanical stirring.After about 80 minutes, form the brown yellow solution of clear,, illustrate that Mierocrystalline cellulose dissolves fully, make the cellulose solution that concentration is 10.0wt% thus with being black in the polarized light microscope observing visual field.Again 10mg nano-ZnO and 10mg nanometer Ag are added in the cellulose solution that has made and mix.The cellulose solution deaeration that contains nano-ZnO and nanometer Ag that makes after 120 minutes, is added the mode spinning of small-sized spinning equipment by dry-jet wet-spinning.Orifice diameter is 100 μ m, and solidification liquid is a water, and temperature is 25 ℃, through drawing-off, washing, drawing-off, oven dry, obtains antibiotic, uvioresistant cellulose composite fiber.Evaporate the water in the precipitation bath, the AMIMCl ionic liquid that obtains reclaiming.
Embodiment 11
Take by weighing the vacuum drying PMIMAc ionic liquid of 18.0g, add the dry wood pulps of 2.0g, under 80 ℃, carry out mechanical stirring.After about 80 minutes, form the brown yellow solution of clear,, illustrate that Mierocrystalline cellulose dissolves fully, make the cellulose solution that concentration is 10.0wt% thus with being black in the polarized light microscope observing visual field.Again the 30mg carbon nano fiber is added in the cellulose solution that has made and mix.The cellulose solution deaeration that contains carbon nano fiber that makes after 120 minutes, is added the mode spinning of small-sized spinning equipment by dry-jet wet-spinning.Orifice diameter is 100 μ m, and solidification liquid is a water, and temperature is 25 ℃, through drawing-off, washing, drawing-off, oven dry, obtains having enhancing, anlistatig cellulose composite fiber.Evaporate the water in the precipitation bath, the PMIMAc ionic liquid that obtains reclaiming.
Embodiment 12
Take by weighing the vacuum drying AMIMAc ionic liquid of 19.0g, add the dry wood pulps of 1.0g, under 80 ℃, carry out mechanical stirring.After about 60 minutes, form the brown yellow solution of clear,, illustrate that Mierocrystalline cellulose dissolves fully, make the cellulose solution that concentration is 5.0wt% thus with being black in the polarized light microscope observing visual field.Again the 20mg nano-ZnO is added in the cellulose solution that has made and mix.The cellulose solution deaeration that contains nano-ZnO that makes after 120 minutes, is scraped mould with small-sized knifing machine, be immersed in temperature again and be in 30 ℃ the water precipitation bath,, obtain cellulose composite membrane material antibiotic, uvioresistant performance through washing, oven dry.Evaporate the water in the precipitation bath, the AMIMAc ionic liquid that obtains reclaiming.
Claims (6)
1. the preparation method of functional material of regenerated cellulose will mix with cellosolve after the natural cellulosic feedstocks drying, imposes to stir or the machinery kneading in heating, dissolves fully up to Mierocrystalline cellulose, obtains the homogeneous transparent homogeneous cellulose solution; Add functional filler again, continue to stir, mix; With the deaeration under vacuum of gained solution, handle through precipitation bath regeneration, washing, drying or spinning, obtain the material of regenerated cellulose of functionalization;
Described cellosolve is the N-methylmorpholine oxide water solution, N-ethyl-N '-Methylimidazole villaumite ionic liquid, N-propyl group-N '-Methylimidazole villaumite ionic liquid, N-butyl-N '-Methylimidazole villaumite ionic liquid, N-allyl group-N '-Methylimidazole villaumite ionic liquid, N-methacrylic-N '-Methylimidazole villaumite ionic liquid, N-ethyl-N '-Methylimidazole acetate ionic liquid, N-propyl group-N '-Methylimidazole acetate ionic liquid, N-butyl-N '-Methylimidazole acetate ionic liquid, in N-allyl group-N '-Methylimidazole acetate ionic liquid or N-methacrylic-N '-Methylimidazole acetate ionic liquid one or more;
Described functional filler is that nanometer is covered one or more in holder soil, carbon nanotube, chitin, chitosan, Lalgine, medical stone, carbon black, carbon nano fiber, polypyrrole micro mist, nano titanium oxide, nano zine oxide, nano silicon, nano-aluminium oxide or the nanometer metallic silver;
Described functional filler is of a size of nano level to micron order.
2. according to the preparation method of claim 1, it is characterized in that: described natural cellulosic feedstocks is one or more in the Mierocrystalline cellulose that makes in Microcrystalline Cellulose, the cotton pulp dregs of rice, linters, cotton, wood pulp cellulose, wood pulps, bamboo pulp, Mierocrystalline cellulose filter paper or all kinds of straw.
3. according to the preparation method of claim 1 or 2, it is characterized in that: the polymerization degree of described natural cellulosic feedstocks is in 150～1500 scopes.
4. according to the preparation method of claim 1, it is characterized in that: the weight concentration of described cellulosic material in cellosolve is 5～30%.
5. according to the preparation method of claim 1, it is characterized in that: the weight of described functional filler is 0.1%～10% of natural cellulose weight.
6. according to the preparation method of claim 1, it is characterized in that: described Heating temperature is 50～120 ℃ of scopes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9834652B2 (en) | 2013-11-01 | 2017-12-05 | Institute Of Chemistry, Chinese Academic Of Sciences | Regenerated cellulose film, functional film and preparation method therefor |
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Assignee: Weifang Henglian Cellophane Co., Ltd. Assignor: Institute of Chemistry, Chinese Academy of Sciences Contract record no.: 2011370000336 Denomination of invention: Method for preparing functional material of regenerated cellulose Granted publication date: 20080709 License type: Exclusive License Open date: 20060705 Record date: 20110715 |
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