CN102504285A - Regenerated cellulose microspheres and preparation method thereof - Google Patents
Regenerated cellulose microspheres and preparation method thereof Download PDFInfo
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- CN102504285A CN102504285A CN2011103419047A CN201110341904A CN102504285A CN 102504285 A CN102504285 A CN 102504285A CN 2011103419047 A CN2011103419047 A CN 2011103419047A CN 201110341904 A CN201110341904 A CN 201110341904A CN 102504285 A CN102504285 A CN 102504285A
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Abstract
The invention relates to a preparation method for preparing regenerated cellulose microspheres by taking an ionic liquid as a solvent. The preparation method comprises the following steps of: dissolving cellulose into an ionic liquid for preparing a cellulose solution; adding the cellulose solution into an oil phase; condensing the cellulose solution into liquid drops through inverse phase suspension and programmed cooling; adding a curing agent to cure the cellulose solution liquid drops into cellulose microspheres; and washing with distilled water and soaking the cellulose microspheres till the ionic liquid is completely soaked into a soaking liquid to obtain oyster white regenerated cellulose microspheres. In the invention, the ionic liquid is taken as a solvent for preparing the cellulose microspheres, a process is simple, the used solvent can be used circularly, a cellulose raw material has a wide source and low cost, and high-valued utilization of natural plant cellulose can be realized. The cellulose microspheres prepared with the method are spherical and circular, and have high mechanical performance, high thermal stability and high acid-base tolerance; and the particle sizes of 95 percent of microspheres are distributed between 40 mum and 200 mum.
Description
Technical field
The present invention relates to a kind of preparation method of cellulose microsphere, belong to the high polymer material chemical field.
Background technology
Polymer microsphere be meant particle diameter at nano level to micron order, be shaped as the macromolecular material of sphere or other solids.Microballoon has played special and crucial effect because of its special size and special construction at many key areas, and the microballoon of different-grain diameter and pattern has different functions and purposes.Polymer microsphere mainly contains following function: microstorage, microreactor, tiny segregator and microstructure unit; Their application almost relates to all areas; Be applied to high leading-edge field from general industry, like biochemical field, medical treatment and field of medicaments, electronic information field etc.Polymer microsphere is especially popular in recent years in the applied research in biochemical engineering and pharmaceutical engineering field, like the separation and the purifying of biologically active substance, enzyme immobilization, the embedding of toxicity and biologically active drug, the embedding of cell, protein and DNA etc.
Nineteen fifty-one, O ' Neill reported first the employing gunite cellulose bead that has been feedstock production with the viscose.After about 20 years, numerous research researchers just begin to have made big quantity research at cellulose microsphere aspect preparing, and have prepared various Mierocrystalline celluloses and verivate microspheres product thereof.Recent two decades mainly is to prepare cellulose microsphere through the cellosolve that develops new green, or improves the existing preparation process method or the novel derivatived cellulose of preparation is used to prepare microballoon to satisfy harsh with most advanced and sophisticated more application demand.
Be different from synthetic macromolecule and can prepare various functional microballoons more simply; The cellulose family natural polymer then must be through special method preparation, like inverse suspension method (emulsification-solidification method), single coacervation, complex coacervation, spray-drying process, self-emulsifying-solidification method and laminated assembling technology etc.The ultimate principle of these methods is similar, at first prepares Mierocrystalline cellulose or solution of cellulose derivative, is distributed to then in the specific dispersion liquid, next adopts different curings to solidify balling-up according to cellulosic material character and SOLUTION PROPERTIES.Also can the cellulose solution that prepare be directly injected in inert media or the air and disperse or splash in the solid solution through specific installation.Wherein, the most general method is an inverse suspension method, and it is simple, is fit to suitability for industrialized production.Inverse suspension method specifically can be divided into following step: (1) preparation Mierocrystalline cellulose or derivatives thereof solution; (2) the loosen collagen fibre cellulose solution becomes drop; (3) drop curing makes cellulose regenerated balling-up; (4) aftertreatments such as washing, drying.
The key that inverse suspension method prepares cellulose microsphere is the preparation of cellulose solution; Adopt the direct dissolving cellulos of appropriate solvent, the preparation cellulose solution forms cellulose microsphere through suitable renovation process again; Can simplify technology, reduce of the pollution of preparation process environment.The solvent that is used for dissolving cellulos at present mainly contains N-methylmorpholine-N-oxide compound (NMMO), lithium chloride/N,N-DIMETHYLACETAMIDE (LiCl/DMAc), ionic liquid, carbamate system, sodium hydroxide/water (NaOH/H
2O) system, alkali/urea or thiocarbamide/aqueous systems.In the preparation process of traditional cellulose microsphere, can produce salkali waste, spent acid, H
2Pollution substances such as S gas and spent organic solvent, N-methylmorpholine-N-oxide compound (NMMO) has low toxicity, advantage such as recyclable as cellulosic solvent, has obtained extensive studies, and has put in the scale operation Loycell fiber.Yet the technology of NMMO dissolving cellulos is complicated, needs higher temperature, and is prone to oxidizedly, needs nitrogen protection, but also has problems such as byproduct of reaction and the recovery are low, and need further address these problems could heavy industrialization.But ion liquid odorless, tasteless, pollution-free, nonflammable, be prone to separate, be prone to reclaim advantages such as repeated multiple times recycles with product, make it become the ideal substitute of traditional cellosolve.It has avoided with an organic solvent causing the serious environmental pollution problem effectively, becomes eco-friendly green solvent.At present, existing bibliographical information utilizes the ion liquid dissolving Mierocrystalline cellulose, preparation cellulosefilm and cellulose silk.But the ion liquid dissolving legal system is equipped with cellulose microsphere, and difficulty is bigger, and some critical processes are still waiting perfect.
The present invention is solvent with the ionic liquid, adopts inverse suspension method to prepare cellulose microsphere.The preparation process of cellulose solution and cellulose microsphere all is a physical process, and chemical reaction does not take place.Preparation technology is simple, and is lower to equipment requirements, and the recyclable repeated use of used ionic liquid is a kind of eco-friendly novel process.Prepared cellulose microsphere has mechanical property and good thermostability preferably, has suitable particle diameter and size distribution, can be used for the separation and purification of bioprotein, also can be used as the carrier of enzyme or other biological material.
Summary of the invention
The purpose of this invention is to provide the method for preparing cellulose microsphere of a kind of environmental protection, safety non-toxic, it can overcome the shortcoming of the cellulosic prepared cellulose microsphere of traditional dissolution with solvents.
The method that the present invention prepares cellulose microsphere is to be solvent with the ionic liquid, adopts inverse suspension method to realize, specifically may further comprise the steps:
(1) preparation of cellulose solution: under 50～80 ℃ temperature, (g: be 1: 20～50 to join in the ionic liquid mL), stirring at low speed 5～10h dissolves Mierocrystalline cellulose fully, obtains cellulose solution by mass volume ratio with Mierocrystalline cellulose;
(2) anti-phase suspension: under 60～100 ℃ of temperature; Add oil phase and emulsifying agent, the volume ratio of cellulose solution and oil phase is 1: 3～6, and the volume ratio of emulsifying agent and oil phase is 1: 40～100; Under the rotating speed of 300～900r/min, stir 10～30min, form inverse suspension system;
(3) programmed cooling: attemperation, make system be cooled to 25～50 ℃ with the speed of 0.5 ℃/min, cellulose solution condenses into drop;
(4) curing of microballoon: add solidifying agent, the volume ratio of cellulose solution and solidifying agent is 1: 2～3, reduces rotating speed after adding solidifying agent, continues to stir 10～30min, and the cellulose solution drop solidifies, the formation cellulose microsphere;
(5) washing: spinning solid-liquid phase; With distilled water wash cellulose microsphere 3～6 times; Then cellulose microsphere is immersed in 24～48h in 100～500mL zero(ppm) water, ionic liquid is got in the soak solution fully, can obtain milky regenerated cellulose microballoon.
Described ionic liquid is 1-allyl group-3-Methylimidazole villaumite; Mierocrystalline cellulose is paper pulp pulp, gossypin, bamboo cellulose, wood fiber is plain, bagasse fibre is plain or Microcrystalline Cellulose; Oil phase is whiteruss, kerosene, Viscotrol C or peanut oil; Emulsifying agent is the mixture of Span80, Tween80, Tween85 or two or more composition in them; Solidifying agent is the mixture of zero(ppm) water, ethanol, acetone or two or more composition in them.
The inventive method is simple; Safety non-toxic is a kind of novel process of environmental protection, adopts the cellulose microsphere of present method preparation to have good sphericity, suitable particle diameter and distribution thereof; Have mechanical property preferably, good thermostability and acid and alkali-resistance ability; Can widen its Application Areas through surface chemical modification or surface group derivatize, can be used for proteinic separation and purifying, also can be used as the solid support material of enzyme immobilization.
Embodiment
Below be used to further specify the method that the present invention describes through the practical implementation instance, but do not limit the present invention.
Embodiment 1
The bagasse fibre that accurately takes by weighing after 1.0g purifies is plain, joins in the 50mL ionic liquid, in 50 ℃ oil bath, dissolves 10h, obtains cellulose solution.In the 500mL there-necked flask, add 150mL whiteruss and 3mLSpan80, put into oil bath and be heated to 60 ℃, under stirring at low speed, cellulose solution is slowly joined in the there-necked flask then, add the back stirring velocity and be made as 900r/min, pick up counting.Behind the 30min, stop heating and slowly be cooled to 50 ℃, through anti-phase suspension and programmed cooling, the cellulose solution balling-up of condensing.In whipping process, slowly add 100mL zero(ppm) water with dropper and make the cellulose solution drop solidify to form cellulose microsphere, add the zero(ppm) water continued and stir 10min.Stop to stir, after leaving standstill profit is separated, with whizzer cellulose microsphere is separated from the aqueous solution again, from the aqueous solution, reclaim ionic liquid.With distilled water wash cellulose microsphere 3～6 times, at last cellulose microsphere is immersed in 48h in the 200mL zero(ppm) water, ionic liquid is all got in the soak solution, promptly obtain the cellulose microsphere that particle diameter is 40～200 μ m.
Embodiment 2
Accurately take by weighing the 1.5g gossypin, join in the 50mL ionic liquid, in 60 ℃ oil bath, dissolve 9h, obtain cellulose solution.In the 500mL there-necked flask, add 200mL whiteruss and 2mLTween80, put into oil bath and be heated to 70 ℃, under stirring at low speed, cellulose solution is slowly joined in the there-necked flask then, add the back stirring velocity and be made as 800r/min, pick up counting.Behind the 25min, stop heating and slowly be cooled to 40 ℃, through anti-phase suspension and programmed cooling, the cellulose solution balling-up of condensing.In whipping process, slowly add 150mL ethanol with dropper and make the cellulose solution drop solidify to form cellulose microsphere, add the ethanol continued and stir 20min.Stop to stir, after leaving standstill profit is separated, with whizzer cellulose microsphere is separated from the aqueous solution again, from the aqueous solution, reclaim ionic liquid.With distilled water wash cellulose microsphere 3～6 times, at last cellulose microsphere is immersed in 36h in the 300mL zero(ppm) water, ionic liquid is all got in the soak solution, promptly obtain the cellulose microsphere that particle diameter is 40～200 μ m.
Embodiment 3
The wood fiber that accurately takes by weighing after 2.0g purifies is plain, joins in the 50mL ionic liquid, in 70 ℃ oil bath, dissolves 8h, obtains cellulose solution.In the 500mL there-necked flask, add 100mL Viscotrol C and 2.5mLTween85, put into oil bath and be heated to 80 ℃, under stirring at low speed, cellulose solution is slowly joined in the there-necked flask then, add the back stirring velocity and be made as 700r/min, pick up counting.Behind the 20min, stop heating and slowly be cooled to 30 ℃, through anti-phase suspension and programmed cooling, the cellulose solution balling-up of condensing.In whipping process, slowly add 150mL zero(ppm) water with dropper and make the cellulose solution drop solidify to form cellulose microsphere, add the zero(ppm) water continued and stir 30min.Stop to stir, after leaving standstill profit is separated, with whizzer cellulose microsphere is separated from the aqueous solution again, from the aqueous solution, reclaim ionic liquid.With distilled water wash cellulose microsphere 3～6 times, at last cellulose microsphere is immersed in 24h in the 400mL zero(ppm) water, ionic liquid is all got in the soak solution, promptly obtain the cellulose microsphere that particle diameter is 40～200 μ m.
Embodiment 4
Accurately take by weighing the 2.5g Microcrystalline Cellulose, join in the 50mL ionic liquid, in 80 ℃ oil bath, dissolve 5h, obtain cellulose solution.In the 500mL there-necked flask, add 300mL peanut oil and 7.5mLSpan80, put into oil bath and be heated to 100 ℃, under stirring at low speed, cellulose solution is slowly joined in the there-necked flask then, add the back stirring velocity and be made as 500r/min, pick up counting.Behind the 30min, stop heating and slowly be cooled to 25 ℃, through anti-phase suspension and programmed cooling, the cellulose solution balling-up of condensing.In whipping process, slowly add 100mL acetone with dropper and make the cellulose solution drop solidify to form cellulose microsphere, add the acetone continued and stir 30min.Stop to stir, after leaving standstill profit is separated, with whizzer cellulose microsphere is separated from the aqueous solution again, from the aqueous solution, reclaim ionic liquid.With distilled water wash cellulose microsphere 3～6 times, at last cellulose microsphere is immersed in 24h in the 400mL zero(ppm) water, ionic liquid is all got in the soak solution, promptly obtain the cellulose microsphere that particle diameter is 40～200 μ m.
Embodiment 5
Accurately take by weighing the bamboo cellulose after 2.0g purifies, join in the 50mL ionic liquid, in 80 ℃ oil bath, dissolve 5h, obtain cellulose solution.In the 500mL there-necked flask, add 150mL whiteruss and 6mLTween80, put into oil bath and be heated to 80 ℃, under stirring at low speed, cellulose solution is slowly joined in the there-necked flask then, add the back stirring velocity and be made as 300r/min, pick up counting.Behind the 30min, stop heating and slowly be cooled to 50 ℃, through anti-phase suspension and programmed cooling, the cellulose solution balling-up of condensing.In whipping process, slowly add 100mL zero(ppm) water with dropper and make the cellulose solution drop solidify to form cellulose microsphere, add the zero(ppm) water continued and stir 20min.Stop to stir, after leaving standstill profit is separated, with whizzer cellulose microsphere is separated from the aqueous solution again, from the aqueous solution, reclaim ionic liquid.With distilled water wash cellulose microsphere 3～6 times, at last cellulose microsphere is immersed in 24h in the 500mL zero(ppm) water, ionic liquid is all got in the soak solution, promptly obtain the cellulose microsphere that particle diameter is 40～200 μ m.
Claims (7)
1. the preparation method of a regenerated cellulose microballoon is characterized in that, is to be solvent with the ionic liquid, adopts inverse suspension method to realize, specifically may further comprise the steps:
(1) preparation of cellulose solution: under 50～80 ℃ temperature, (g: be 1: 20～50 to join in the ionic liquid mL), stirring at low speed 5～10h dissolves Mierocrystalline cellulose fully, obtains cellulose solution by mass volume ratio with Mierocrystalline cellulose;
(2) anti-phase suspension: under 60～100 ℃ of temperature; Add oil phase and emulsifying agent, the volume ratio of cellulose solution and oil phase is 1: 3～6, and the volume ratio of emulsifying agent and oil phase is 1: 40～100; Under the rotating speed of 300～900r/min, stir 10～30min, form inverse suspension system;
(3) programmed cooling: attemperation, make system be cooled to 25～50 ℃ with the speed of 0.5 ℃/min, cellulose solution condenses into drop;
(4) curing of microballoon: add solidifying agent, the volume ratio of cellulose solution and solidifying agent is 1: 2～3, reduces rotating speed after adding solidifying agent, continues to stir 10～30min, and the cellulose solution drop solidifies, the formation cellulose microsphere;
(5) washing: spinning solid-liquid phase; With distilled water wash cellulose microsphere 3～6 times; Then cellulose microsphere is immersed in 24～48h in the zero(ppm) water of 100～500mL, ionic liquid is got in the soak solution fully, can obtain milky regenerated cellulose microballoon.
2. method according to claim 1 is characterized in that: described ionic liquid is 1-allyl group-3-Methylimidazole villaumite.
3. method according to claim 1 is characterized in that: described Mierocrystalline cellulose is paper pulp pulp, gossypin, bamboo cellulose, wood fiber is plain, bagasse fibre is plain or Microcrystalline Cellulose.
4. method according to claim 1 is characterized in that: described oil phase is whiteruss, kerosene, Viscotrol C or peanut oil.
5. method according to claim 1 is characterized in that: described emulsifying agent is the mixture of Span80, Tween80, Tween85 or two or more composition in them.
6. method according to claim 1 is characterized in that: described solidifying agent is the mixture of zero(ppm) water, ethanol, acetone or two or more composition in them.
7. method according to claim 1 is characterized in that: described cellulose microsphere particle diameter is 40～200 μ m.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103233381A (en) * | 2013-04-12 | 2013-08-07 | 南开大学 | High efficiency composite precipitating agent and method for extracting cellulose |
| CN103497346A (en) * | 2013-10-11 | 2014-01-08 | 中国科学院大学 | Regenerated wood microsphere and preparation method thereof |
| CN103642788A (en) * | 2013-12-11 | 2014-03-19 | 江苏科技大学 | Preparation method of cellulase immobilization carrier |
| CN103667243A (en) * | 2013-12-11 | 2014-03-26 | 江苏科技大学 | Method for preparing cellulase immobilized carrier from straws treated by ionic liquid and modifier |
| CN103992487A (en) * | 2013-08-05 | 2014-08-20 | 广西弘耀祥科技有限公司 | Cellulose acetate propionate microspheres and preparation method thereof |
| CN103990439A (en) * | 2013-08-05 | 2014-08-20 | 中国科技开发院广西分院 | Method for preparing cellulose acetate butyrate microsphere adsorption material |
| CN105001635A (en) * | 2015-07-21 | 2015-10-28 | 上海交通大学 | Ionic liquid and method for preparing aromatic polymer microspheres by adopting ionic liquid as solvent |
| CN106496597A (en) * | 2016-11-22 | 2017-03-15 | 中国科学院过程工程研究所 | A kind of method that utilization ionic liquid prepares polysaccharide microsphere |
| CN107244704A (en) * | 2017-05-26 | 2017-10-13 | 玉灵华科技有限公司 | A kind of advanced water treatment method |
| CN108402540A (en) * | 2017-12-30 | 2018-08-17 | 戴承 | A kind of pure upright cotton is without glue net underwear and preparation method thereof |
| CN108948415A (en) * | 2018-06-29 | 2018-12-07 | 广西大学 | A kind of preparation method that porous cellulose is microsphere supported |
| CN109134944A (en) * | 2018-08-28 | 2019-01-04 | 安徽聚欣新材料科技有限公司 | A kind of porous small ball and its application with different chemical functional groups |
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| CN103233381A (en) * | 2013-04-12 | 2013-08-07 | 南开大学 | High efficiency composite precipitating agent and method for extracting cellulose |
| CN103992487A (en) * | 2013-08-05 | 2014-08-20 | 广西弘耀祥科技有限公司 | Cellulose acetate propionate microspheres and preparation method thereof |
| CN103990439A (en) * | 2013-08-05 | 2014-08-20 | 中国科技开发院广西分院 | Method for preparing cellulose acetate butyrate microsphere adsorption material |
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| CN103642788B (en) * | 2013-12-11 | 2016-03-30 | 江苏科技大学 | A kind of preparation method of cellulase immobilization carrier |
| CN103642788A (en) * | 2013-12-11 | 2014-03-19 | 江苏科技大学 | Preparation method of cellulase immobilization carrier |
| CN103667243A (en) * | 2013-12-11 | 2014-03-26 | 江苏科技大学 | Method for preparing cellulase immobilized carrier from straws treated by ionic liquid and modifier |
| CN105001635A (en) * | 2015-07-21 | 2015-10-28 | 上海交通大学 | Ionic liquid and method for preparing aromatic polymer microspheres by adopting ionic liquid as solvent |
| CN106496597A (en) * | 2016-11-22 | 2017-03-15 | 中国科学院过程工程研究所 | A kind of method that utilization ionic liquid prepares polysaccharide microsphere |
| CN106496597B (en) * | 2016-11-22 | 2019-02-12 | 中国科学院过程工程研究所 | A method of polysaccharide microsphere is prepared using ionic liquid |
| CN107244704A (en) * | 2017-05-26 | 2017-10-13 | 玉灵华科技有限公司 | A kind of advanced water treatment method |
| CN108402540A (en) * | 2017-12-30 | 2018-08-17 | 戴承 | A kind of pure upright cotton is without glue net underwear and preparation method thereof |
| CN108948415A (en) * | 2018-06-29 | 2018-12-07 | 广西大学 | A kind of preparation method that porous cellulose is microsphere supported |
| CN109134944A (en) * | 2018-08-28 | 2019-01-04 | 安徽聚欣新材料科技有限公司 | A kind of porous small ball and its application with different chemical functional groups |
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Application publication date: 20120620 |