CN103509123B - The preparation method of Cellulose diacetate - Google Patents
The preparation method of Cellulose diacetate Download PDFInfo
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- CN103509123B CN103509123B CN201310441708.6A CN201310441708A CN103509123B CN 103509123 B CN103509123 B CN 103509123B CN 201310441708 A CN201310441708 A CN 201310441708A CN 103509123 B CN103509123 B CN 103509123B
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Abstract
The invention discloses a kind of preparation method of Cellulose diacetate, the method is passed through Mierocrystalline cellulose, acetic acid, ionic liquid, catalyzer, acetylation reagent add in reaction unit simultaneously carry out acetylization reaction generate Cellulose diacetate, reaction times is 2 ~ 12h, temperature of reaction is 60 ~ 120 DEG C, described catalyzer is sulfonation solid acid Amberlyst15, described acetylation reagent is diacetyl oxide or Acetyl Chloride 98Min., the amount ratio of described Mierocrystalline cellulose and ionic liquid is (0.025 ~ 0.05) g/ml, described catalyzer and cellulosic mol ratio are (0.05 ~ 0.1): 1, described acetylation reagent and cellulosic mol ratio are (3 ~ 6): 1, after having reacted, reclaim solid catalyst by solid-liquid separation, supernatant liquor gets final product separated product after treatment and reclaims ionic liquid.This method can the excellent Cellulose diacetate of one-step synthesis solubility property, and catalyzer and reaction medium are all recyclable and reuse, and overcomes the problem of environmental pollution that corrosion caused by traditional strong acid catalyst and volatile organic solvent bring.
Description
Technical field
The invention belongs to cellulosic application technology as the second resource field, particularly the preparation method of Cellulose diacetate.
Background technology
Along with the day by day exhausted of fossil energy and the mankind are to the concern increasingly of environmental problem, finding reproducible clean energy has become the focus paid close attention in the whole world, and the renewable resources that natural wooden fiber's element enriches the most as occurring in nature receives much concern.Lignocellulose is extensively present in various agricultural wastes (rice straw, straw, rice husk, cotton straw, waste of flax and bagasse etc.), and the annual agricultural crop straw growing amount in the whole world is about 2.9 × 1010t.It is estimated, if development energy forestry with recycle waste wood Mierocrystalline cellulose and develop simultaneously, then every year alternative more than 1/3 fuel alcohol.
Acid cellulose is one of compound carrying out merchandized handling the earliest in derivatived cellulose, and global annual production is about 6.8 × 108t.The methylcellulose Acetylated product of substitution value between 2-2.5 is commonly called Cellulose diacetate; because Cellulose diacetate has good thermoplasticity and solubility property; be widely used in and manufacture cigarette filter tip, medical filter material, textiles, plastics, film and liquid crystal material etc., be internationally recognized and not yet find nontoxic, the harmless product of alternative material so far.Cellulose diacetate, not easily by methylcellulose Acetylated direct preparation, is normally obtained through partly-hydrolysed hydrolysis by the complete acetylizad product cellulosetri-acetate of Mierocrystalline cellulose, there is process complexity and the uneven first-class shortcoming of product characteristics.In addition, at present mainly adopt that strong acid catalyst is methylcellulose Acetylated prepares cellulosetri-acetate, corrosive equipment and produce relatively large waste liquid.
Natural cellulose there is higher degree of crystallinity and intermolecular with molecular memory at a large amount of hydrogen bonds, it is made to be difficult to be dissolved in general organic solvent, become the bottleneck that constraints on fiber element large-scale develops and utilizes, developing effective cellosolve system is the key point solving this difficult problem.Ionic liquid is a study hotspot in recent years in Green Chemistry field, has that steam forces down, unique physicochemical property and the distinctive function such as not volatile; The salt that ionic liquid is made up of zwitterion, thus good dissolution characteristics is had, the different substancess such as energy dissolved organic matter, inorganics and polymkeric substance, adopt ionic liquid effectively can reduce the problem of environmental pollution that volatile organic matter (VolatileOrganicCompounds) brings for reaction medium, be the fine solvent of a lot of chemical reaction, demonstrate good application prospect at numerous areas such as organic synthesis, extracting and separating and electrochemistry.
It is still few that current ionic liquid is applied to methylcellulose Acetylated research, and mainly concentrate on cellulosic homogeneous phase reaction aspect, and reaction terminates rear catalyst and is difficult to separate from reaction system, causes all more difficult recovery of solvent and catalyzer and recycles.The present invention adopts ionic liquid and the acid Resin A mberlyst15 of sulfonation to make reaction medium and catalyzer respectively, achieves recovery and the recycling of reaction medium and catalyzer.
Summary of the invention
A kind of Mierocrystalline cellulose is the object of the present invention is to provide to be converted into the method for Cellulose diacetate by acetylization reaction one step.
The object of the invention is to be achieved through the following technical solutions:
1) Mierocrystalline cellulose, ionic liquid, catalyzer, acetic acid and acetylation reagent are added in reaction unit simultaneously carry out acetylization reaction, reaction times is 2 ~ 12h, temperature of reaction is 60 ~ 120 DEG C, described catalyzer is sulfonation solid acid Amberlyst15, described acetylation reagent is diacetyl oxide or Acetyl Chloride 98Min., the amount ratio of described Mierocrystalline cellulose and ionic liquid is (0.025 ~ 0.05) g/ml, described catalyzer and cellulosic mol ratio are (0.05 ~ 0.1): 1, and described acetylation reagent and cellulosic mol ratio are (3 ~ 6): 1;
2) after having reacted, reaction mixture is cooled to room temperature, through solid-liquid separation, obtains the catalyst A mberlyst15 of solid-phase and the ionic liquid phase containing product; To ionic liquid mutually in add deionized water, separate out precipitation; Again through solid-liquid separation, obtain the solid-phase containing product and the ionic liquid phase containing deionized water, ionic liquid removes deionized water and recyclable ionic liquid through rotary evaporation; Add methylene dichloride to containing in the stationary phase of product, partly precipitated dissolves, and filter, steam the solvent in filtrate, add acetone solution, rotary evaporation obtains product.
Further, in described step 1), described ionic liquid is the one in 1-alkyl-3-Methylimidazole villaumite, 1-alkyl-3-Methylimidazole bromine salt, 1-ethylpyridine bromide, 1-ethyl pyridinium chloride, 1-allyl group-3-Methylimidazole villaumite and 1-allyl group-3-Methylimidazole bromine salt.
Further, described step 2) in, described solid-liquid separation is centrifugation or filtering separation.
Mierocrystalline cellulose of the present invention includes but not limited to commercial fibre element market can being purchased available gossypin and so on, also comprises and extracts by rice straw, wheat stalk and maize straw the Mierocrystalline cellulose obtained.
The present invention has following beneficial effect:
1) the present invention is directed to the feature that Mierocrystalline cellulose is comparatively insoluble in ordinary organic solvents, cellulosic heterogeneous acetylization reaction in exploitation ionic liquid, after having reacted, reaction medium and catalyzer all can obtain efficient recovery.
2) inventive process avoids the problem of environmental pollution that corrosion caused by strong acid catalyst and volatile organic solvent bring, safety and environmental protection.
3) the inventive method can prepare Cellulose diacetate by one kettle way, and the Cellulose diacetate substitution value of preparation is between 2.0 ~ 2.4.
Embodiment
Describe the present invention further by the following examples, following examples are the preferred embodiment of the present invention, but are not to further restriction of the present invention.
Embodiment 1
1g Mierocrystalline cellulose (about 6.2mmol), 0.25g acetic acid, 2.5g diacetyl oxide, 30ml chloro 1-butyl-3-Methylimidazole and 0.5mmolAmberlyst15 are joined in there-necked flask, 80 DEG C of reaction 8h, be cooled to room temperature, filter, solid is recovery catalyzer; To ionic liquid mutually in add 120ml deionized water, have Precipitation, centrifugation.Be recycled to by supernatant liquid in flask, revolve steaming and remove deionized water, 100 DEG C of vacuum-dryings, obtain recovery ionic liquid.Proceed in flask by centrifuge tube bottom settlings, add methylene dichloride, dissolve, filter, steam the solvent in clear liquid, can obtain membranaceous product, shift out product with acetone, revolve steaming in flask, dry product, substitution value is 2.03.
Embodiment 2
1g Mierocrystalline cellulose (about 6.2mmol), 0.25g acetic acid, 2.5g diacetyl oxide, 30ml chloro 1-butyl-3-Methylimidazole and 0.5mmolAmberlyst15 are joined in there-necked flask, 80 DEG C of reaction 10h, be cooled to room temperature, filter, solid is recovery catalyzer; In liquid phase, add 120ml deionized water, have Precipitation, centrifugation.Be recycled to by supernatant liquid in flask, revolve steaming and remove deionized water, 100 DEG C of vacuum-dryings, obtain recovery ionic liquid.Proceed in flask by centrifuge tube bottom settlings, add methylene dichloride, dissolve, filter, steam the solvent in clear liquid, can obtain membranaceous product, shift out product with acetone, revolve steaming in flask, dry product, substitution value is 2.16.
Embodiment 3
1g Mierocrystalline cellulose (about 6.2mmol), 0.25g acetic acid, 2.5g diacetyl oxide, 30ml chloro 1-butyl-3-Methylimidazole and 0.5mmolAmberlyst15 are joined in there-necked flask, 100 DEG C of reaction 8h, be cooled to room temperature, centrifugation, solid is recovery catalyzer, in liquid phase, add 120ml deionized water, have Precipitation, centrifugation.Be recycled to by supernatant liquid in flask, revolve steaming and remove deionized water, 100 DEG C of vacuum-dryings, obtain recovery ionic liquid.Proceed in flask by centrifuge tube bottom settlings, add methylene dichloride, dissolve, filter, steam the solvent in clear liquid, can obtain membranaceous product, shift out product with acetone, revolve steaming in flask, dry product, substitution value is 2.38.
Embodiment 4
1g Mierocrystalline cellulose (about 6.2mmol), 0.25g acetic acid, 2.5g diacetyl oxide, 30ml bromo 1-butyl-3-Methylimidazole and 0.5mmolAmberlyst15 are joined in there-necked flask, 60 DEG C of reaction 12h, be cooled to room temperature, centrifugation, solid is recovery catalyzer, in liquid phase, add 120ml deionized water, have Precipitation, centrifugation.Be recycled to by supernatant liquid in flask, revolve steaming and remove deionized water, 100 DEG C of vacuum-dryings, obtain recovery ionic liquid.Proceed in flask by centrifuge tube bottom settlings, add methylene dichloride, dissolve, filter, steam the solvent in clear liquid, can obtain membranaceous product, shift out product with acetone, revolve steaming in flask, dry product, substitution value is 2.25.
Embodiment 5
1g Mierocrystalline cellulose (about 6.2mmol), 0.25g acetic acid, 2.5g diacetyl oxide, 30ml1-allyl group-3-Methylimidazole villaumite and 0.5mmolAmberlyst15 are joined in there-necked flask, 90 DEG C of reaction 5h, be cooled to room temperature, centrifugation, solid is recovery catalyzer, in liquid phase, add 120ml deionized water, have Precipitation, centrifugation.Be recycled to by supernatant liquid in flask, revolve steaming and remove deionized water, 100 DEG C of vacuum-dryings, obtain recovery ionic liquid.Proceed in flask by centrifuge tube bottom settlings, add methylene dichloride, dissolve, filter, steam the solvent in clear liquid, can obtain membranaceous product, shift out product with acetone, revolve steaming in flask, dry product, substitution value is 2.20.
Embodiment 6
1g Mierocrystalline cellulose (about 6.2mmol), 0.25g acetic acid, 2.5g diacetyl oxide, 30ml1-allyl group-3-Methylimidazole bromine salt and 0.5mmolAmberlyst15 are joined in there-necked flask, 100 DEG C of reaction 8h, be cooled to room temperature, centrifugation, solid is recovery catalyzer, in liquid phase, add 120ml deionized water, have Precipitation, centrifugation.Be recycled to by supernatant liquid in flask, revolve steaming and remove deionized water, 100 DEG C of vacuum-dryings, obtain recovery ionic liquid.Proceed in flask by centrifuge tube bottom settlings, add methylene dichloride, dissolve, filter, steam the solvent in clear liquid, can obtain membranaceous product, shift out product with acetone, revolve steaming in flask, dry product, substitution value is 2.23.
Embodiment 7
1g Mierocrystalline cellulose (about 6.2mmol), 0.25g acetic acid, 2.4g Acetyl Chloride 98Min., 30ml chloro 1-butyl-3-Methylimidazole and 0.5mmolAmberlyst15 are joined in there-necked flask, 100 DEG C of reaction 8h, be cooled to room temperature, centrifugation, solid is recovery catalyzer, in liquid phase, add 120ml deionized water, have Precipitation, centrifugation.Be recycled to by supernatant liquid in flask, revolve steaming and remove deionized water, 100 DEG C of vacuum-dryings, obtain recovery ionic liquid.Proceed in flask by centrifuge tube bottom settlings, add methylene dichloride, dissolve, filter, steam the solvent in clear liquid, can obtain membranaceous product, shift out product with acetone, revolve steaming in flask, dry product, substitution value is 2.12.
Embodiment 8
The chloro 1-butyl-3-Methylimidazole reclaim 1g Mierocrystalline cellulose (about 6.2mmol), 0.25g acetic acid, 2.5g diacetyl oxide, 30ml and 0.5mmolAmberlyst15 join in there-necked flask, 100 DEG C of reaction 8h, be cooled to room temperature, filter, solid is recovery catalyzer, in liquid phase, add 120ml deionized water, have Precipitation, centrifugation.Be recycled to by supernatant liquid in flask, revolve steaming and remove deionized water, 100 DEG C of vacuum-dryings, obtain recovery ionic liquid.Proceed in flask by centrifuge tube bottom settlings, add methylene dichloride, dissolve, filter, steam the solvent in clear liquid, can obtain membranaceous product, shift out product with acetone, revolve steaming in flask, dry product, substitution value is 2.35.
Embodiment 9
The Amberlyst15 that 1g Mierocrystalline cellulose (about 6.2mmol), 0.25g acetic acid, 2.5g diacetyl oxide, 30ml chloro 1-butyl-3-Methylimidazole and 0.5mmol reclaim is joined in there-necked flask, 100 DEG C of reaction 8h, be cooled to room temperature, centrifugation, solid is recovery catalyzer, in liquid phase, add 120ml deionized water, have Precipitation, centrifugation.Be recycled to by supernatant liquid in flask, revolve steaming and remove deionized water, 100 DEG C of vacuum-dryings, obtain recovery ionic liquid.Proceed in flask by centrifuge tube bottom settlings, add methylene dichloride, dissolve, filter, steam the solvent in clear liquid, can obtain membranaceous product, shift out product with acetone, revolve steaming in flask, dry product, substitution value is 2.21.
Claims (3)
1. a preparation method for Cellulose diacetate, is characterized in that: comprise the steps:
1) Mierocrystalline cellulose, acetic acid, ionic liquid, catalyzer, acetylation reagent are added in reaction unit simultaneously carry out acetylization reaction, reaction times is 2 ~ 12h, temperature of reaction is 60 ~ 120 DEG C, described catalyzer is sulfonation solid acid Amberlyst15, described acetylation reagent is diacetyl oxide or Acetyl Chloride 98Min., the amount ratio of described Mierocrystalline cellulose and ionic liquid is (0.025 ~ 0.05) g/ml, described catalyzer and cellulosic mol ratio are (0.05 ~ 0.1): 1, and described acetylation reagent and cellulosic mol ratio are (3 ~ 6): 1;
2) after having reacted, reaction mixture is cooled to room temperature, through solid-liquid separation, obtains the catalyst A mberlyst15 of solid-phase and the ionic liquid phase containing product; To ionic liquid mutually in add deionized water, separate out precipitation; Again through solid-liquid separation, obtain the solid-phase containing product and the ionic liquid phase containing deionized water, ionic liquid removes deionized water and recyclable ionic liquid through rotary evaporation; Add methylene dichloride to containing in the stationary phase of product, partly precipitated dissolves, and filter, steam the solvent in filtrate, add acetone solution, rotary evaporation obtains product.
2. the preparation method of Cellulose diacetate according to claim 1, it is characterized in that: in described step 1), described ionic liquid is the one in 1-alkyl-3-Methylimidazole villaumite, 1-alkyl-3-Methylimidazole bromine salt, 1-ethylpyridine bromide, 1-ethyl pyridinium chloride, 1-allyl group-3-Methylimidazole villaumite and 1-allyl group-3-Methylimidazole bromine salt.
3. the preparation method of Cellulose diacetate according to claim 1 and 2, is characterized in that: described step 2) in, described solid-liquid separation is centrifugation or filtering separation.
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| US8980050B2 (en) | 2012-08-20 | 2015-03-17 | Celanese International Corporation | Methods for removing hemicellulose |
| US8986501B2 (en) | 2012-08-20 | 2015-03-24 | Celanese International Corporation | Methods for removing hemicellulose |
| CN105085688B (en) * | 2015-03-19 | 2018-03-16 | 北京林业大学 | The preparation method of water-soluble cellulose and the water-soluble cellulose prepared by this method |
| CN105970594B (en) * | 2016-05-11 | 2018-04-06 | 苏州大学 | A kind of preparation method of water repellent monkey grass suede |
| CN109336985B (en) * | 2018-09-21 | 2021-06-22 | 南通科技职业学院 | Preparation method of acetylated nanocrystalline cellulose |
| CN111320774B (en) * | 2020-04-17 | 2021-11-02 | 武汉轻工大学 | Preparation method of starch composite membrane |
| CN112898438A (en) * | 2021-02-20 | 2021-06-04 | 天津信诚康达药业有限公司 | Preparation method of cellulose acetate particles |
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| CN1958616A (en) * | 2005-11-01 | 2007-05-09 | 中国科学院过程工程研究所 | Method for producing cellulose ester acetate by using plant cellulose |
| CN101668779A (en) * | 2007-02-14 | 2010-03-10 | 伊士曼化工公司 | Cellulose esters and their production in carboxylated ionic liquids |
| CN102504028A (en) * | 2011-10-11 | 2012-06-20 | 常茂生物化学工程股份有限公司 | Method for preparing organic cellulose acid ester by solid acid catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1958616A (en) * | 2005-11-01 | 2007-05-09 | 中国科学院过程工程研究所 | Method for producing cellulose ester acetate by using plant cellulose |
| CN101668779A (en) * | 2007-02-14 | 2010-03-10 | 伊士曼化工公司 | Cellulose esters and their production in carboxylated ionic liquids |
| CN102504028A (en) * | 2011-10-11 | 2012-06-20 | 常茂生物化学工程股份有限公司 | Method for preparing organic cellulose acid ester by solid acid catalysts |
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Inventor after: Fan Guozhi Inventor after: Wang Min Inventor after: Li Jianfen Inventor after: Liao Chongjing Inventor after: Fang Tao Inventor before: Fan Guozhi Inventor before: Wang Min Inventor before: Xu Yuling Inventor before: Liao Chongjing Inventor before: Fang Tao |
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