CN105440141B - A kind of preparation method of acetyl group bytyry cellulose - Google Patents
A kind of preparation method of acetyl group bytyry cellulose Download PDFInfo
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- CN105440141B CN105440141B CN201510771050.4A CN201510771050A CN105440141B CN 105440141 B CN105440141 B CN 105440141B CN 201510771050 A CN201510771050 A CN 201510771050A CN 105440141 B CN105440141 B CN 105440141B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
- C08B3/18—Aceto-butyrates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/02—Catalysts used for the esterification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/22—Post-esterification treatments, including purification
- C08B3/26—Isolation of the cellulose ester
- C08B3/28—Isolation of the cellulose ester by precipitation
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Abstract
The invention belongs to technical field of polymer chemistry, specifically discloses a kind of preparation method of acetyl group bytyry cellulose.Specifically：Cellulose is soaked with acetic acid and activated; then by the cellulose of activation, butyric anhydride and catalyst heating response; then catalyst and acetic anhydride are added; it is subsequently added into catalyst; reaction is cooled to room temperature after terminating; add the step such as hexane, filtered, sodium bicarbonate solution immersion, deionized water washing, drying, crushing and obtain acetyl group bytyry cellulose.The acetyl group bytyry cellulose of high butyl content is can obtain using the inventive method, for bytyry content up to more than 55%, product quality is stable；Catalyst adds by several times, effectively reduces the degree of degradation of cellulose, and the mean molecule quantity of product is high；The recyclable protection and the sustainable development of economy used again, be advantageous to environment of acetic anhydride, butyric anhydride, acetic acid and butyric acid being excessively used.
Description
Technical field
The invention belongs to technical field of polymer chemistry, and in particular to a kind of preparation side of acetyl group bytyry cellulose
Method.
Background technology
With the development of the society, synthesis high polymer material usage amount in daily life is more and more, due to they
Biodegradable or degraded do not need long time, and very important bear is caused to natural environment for the survival of mankind
Face rings, and there is an urgent need to find new high polymer material by people.Natural macromolecular material has renewable feature, the exploitation to it
Research and production focus is increasingly becoming with application.The hydrophily of cellulose causes them incompatible with oil loving resin, reduces
The mechanical performance of composite.Therefore, the modification to cellulose is particularly important, and acetyl group bytyry cellulose is wherein
One kind.
Acetyl group bytyry cellulose is that hydroxyl is esterified generated one kind by acetyl group and bytyry in cellulosic molecule
Modified cellulose, have excellent moisture-resistant, ultraviolet resistance, it is cold-resistant, flexible, transparent, be electrically insulated etc. performance, and can with synthetic resin and
Higher boiling plasticizer has preferable compatibility, available for the making high grade of transparency, the plastic base of good weatherability, film and various paintings
The levelling agent of material, film forming matter etc..Film chip base such as processed, aerophotography chip base, film, Oilfield Natural Gas Plant conveyance conduit, work
Have handle, automobile, the Glass lamp of aircraft, underground telephone wire and cable tube, steering wheel, label face, glint reflection device etc., additionally
Stripping lacquer, insulated paint, weather-proof high-grade paint and staple fibre can be done.Acetyl group bytyry fiber is known as many types, including not
Same bytyry, acetyl group and hydroxy radical content, different product viscosities etc.；Therefore, their performance difference is very big.Acetyl group fourth
Atriacetyl cellulose is compatible with many resins, also is soluble in a variety of plasticizer, suitable for many coating, including woodcare paint, vapour
Car finish paint, rubber and plastic paint, textile coating, glass coating, flexible board, intaglio plate, screen printing ink, PUR and bonding
Agent.Acetyl group bytyry cellulose does not react ultraviolet light stabilized with dyestuff, fluorescent pigment or metallic pigments.
In the acetyl group bytyry cellulose of country's research and development, the content of bytyry is low and unstable, it is big to consumption of raw materials, into
This height, the reaction time is long, reaction temperature is high, poor controllability, and waste material caused by reaction is more, is not easily recycled, does not meet greenization
Theory, it is difficult to realize industrialization.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the acetyl group bytyry cellulose with high bytyry content.
To reach above-mentioned purpose, the present invention uses following technical scheme：
A kind of preparation method of acetyl group bytyry cellulose, comprises the following steps：
（1）Cellulose is placed in acid-resistant container, acetic acid immersion is added, filters out excess acetic acid；
（2）Cellulose after immersion, butyric anhydride, catalyst are placed in acid-resistant container, reacted；
（3）Catalyst and acetic anhydride are added, continues to react；
（4）Catalyst is added, continues to react；
（5）Room temperature is cooled to, hexane is added and stirs, obtain suspension；
（6）Suspension is filtered, gained solid powder is soaked with sodium bicarbonate solution, filtered again, is washed with deionized
Product is finally dried, crushes and produce to neutrality.
Further, the cellulose is at least one of wood pulps, Cotton Pulp, bamboo pulp and purified cotton.
Further, step（1）In, the mass ratio of cellulose and acetic acid is 1：5 ~ 10, soak time is 0.5 ~ 7 day.
Further, step（2）In, cellulose, butyric anhydride, the mass ratio of catalyst are 1：2~6：0.1~0.2.
Further, step（2）In, reaction temperature is 50 ~ 70 DEG C, and the time is 0.5 ~ 1h.
Further, step（2）、（3）、（4）In, catalyst is acetic acid and the concentrated sulfuric acid by 9：1 mass ratio prepare and
Into mixture.
Further, the concentration of the concentrated sulfuric acid is 98wt%.
Further, step（3）In, catalyst be cellulose quality 5 ~ 10%, acetic anhydride for cellulose quality 1.5 ~
3 times.
Further, step（3）In, reaction temperature is 50 ~ 70 DEG C, and the time is 0.5 ~ 1h.
Further, step（4）In, catalyst is the 5 ~ 10% of cellulose quality.
Further, step（4）In, reaction temperature is 50 ~ 70 DEG C, and the time is 0.5 ~ 1h.
Further, step（5）In, hexane is 5 ~ 10 times of cellulose quality, 0.5 ~ 1h of mixing time.
Further, step（6）In, the concentration of sodium bicarbonate solution is 0.5 ~ 1wt%, and sodium bicarbonate aqueous solution is fiber
10 ~ 20 times of quality amount.
Further, the preparation method also includes：Step（6）The filtrate obtained after filtering suspension, air-distillation filtrate
Hexane is reclaimed, remaining liq rectifying obtains acetic anhydride, butyric anhydride, acetic acid, butyric acid.
The invention has the advantages that：
1 the present invention by cellulose first with butyric acid anhydride reactant, then with acetic anhydride, can obtain the acetyl of high butyl content
Base bytyry cellulose, for bytyry content up to more than 55%, product quality is stable.
2 present invention add by the use of acetic acid dilute sulphuric acid as catalyst, effectively reduce the degree of degradation of cellulose in three times,
Strand hydrolytic cleavage is few, obtains the high acetyl group bytyry cellulose of mean molecule quantity.
3 present invention avoid using water, a large amount of unreacted acid anhydrides and acid can using hexane sedimentation acetyl group bytyry cellulose
To recycle, production cost is saved, is advantageous to the protection of environment and economic sustainable development.
4 present invention reaction time is short, reaction temperature is relatively low, the energy can be saved；Simple to operate, controllability is strong, raw material
It is cheap and easy to get, can be with industrialized production；Avoid using the larger solvent of toxicity, safe operating environment is environmentally friendly.
Embodiment
With reference to specific embodiment, the present invention is described further：
Used catalyst is acetic acid and the 98wt% concentrated sulfuric acids by 9 in embodiment 1 ~ 4：The mixing that 1 mass ratio is formulated
Thing.
Embodiment 1
Acetyl group bytyry cellulose is prepared according to following steps：
（1）10g Cotton Pulps are placed in beaker, 50g acetic acid is added, sealing, soaks 0.5 day at room temperature, filter out excess acetic acid；
（2）Cotton Pulp after immersion and 40g butyric anhydrides, 1g catalyst are placed in equipped with condenser pipe and churned mechanically three neck
Flask, in 70 DEG C of stirring reaction 0.5h；
（3）0.5g catalyst is added, is subsequently added into 20g acetic anhydrides, continues stirring reaction 0.5h at 70 DEG C；
（4）0.5g catalyst is added, continues stirring reaction 0.5h at 70 DEG C；
（5）By step（4）Obtained product is cooled to room temperature, and 50g hexanes are added in flask under quick stirring, stirred
0.5h, obtain suspension；
（6）Suspension is filtered, gained solid powder soaks 1h with 100g 1wt% sodium bicarbonate solutions, filtered again, uses
Deionized water washed product is finally dried, crushed, packing and produce acetyl group bytyry cellulose to neutrality；
（7）Step（6）The filtrate obtained after filtering suspension, 80 DEG C of air-distillation filtrates reclaim hexane, remaining liq essence
Evaporate to obtain acetic anhydride, butyric anhydride, acetic acid, butyric acid.
The acetyl group bytyry cellulose bytyry content that the present embodiment obtains is 58%, and number-average molecular weight is more than 20000.
Embodiment 2
Acetyl group bytyry cellulose is prepared according to following steps：
（1）10g wood pulps are placed in beaker, 100g acetic acid is added, sealing, soaks 2 days at room temperature, filter out excess acetic acid；
（2）Wood pulps after immersion and 20g butyric anhydrides, 2g catalyst are placed in equipped with condenser pipe and churned mechanically three neck
Flask, in 50 DEG C of stirring reaction 1h；
（3）1g catalyst is added, is subsequently added into 15g acetic anhydrides, continues stirring reaction 1h at 50 DEG C；
（4）1g catalyst is added, continues stirring reaction 1h at 50 DEG C；
（5）By step（4）Obtained product is cooled to room temperature, and 100g hexanes are added in flask under quick stirring, stirred
1h is mixed, obtains suspension；
（6）Suspension is filtered, gained solid powder soaks 0.5h with 200g 0.5wt% sodium bicarbonate solutions, again mistake
Filter, product is washed with deionized to neutrality, finally dries, crush, packing and produce acetyl group bytyry cellulose；
（7）Step（6）The filtrate obtained after filtering suspension, 80 DEG C of air-distillation filtrates reclaim hexane, remaining liq essence
Evaporate to obtain acetic anhydride, butyric anhydride, acetic acid, butyric acid.
The acetyl group bytyry cellulose bytyry content that embodiment obtains is 55%, and number-average molecular weight is more than 20000.
Embodiment 3
Acetyl group bytyry cellulose is prepared according to following steps：
（1）10g bamboo pulps are placed in beaker, 60g acetic acid is added, sealing, soaks 7 days at room temperature, filter out excess acetic acid；
（2）Bamboo pulp after immersion and 60g butyric anhydrides, 1.5g catalyst are placed in equipped with condenser pipe and churned mechanically three
Neck flask, in 60 DEG C of stirring reaction 0.8h；
（3）0.8g catalyst is added, is subsequently added into 30g acetic anhydrides, continues stirring reaction 1h at 60 DEG C；
（4）0.7g catalyst is added, continues stirring reaction 0.5h at 60 DEG C；
（5）By step（4）Obtained product is cooled to room temperature, and 80g hexanes are added in flask under quick stirring, stirred
1h, obtain suspension；
（6）Suspension is filtered, gained solid powder soaks 0.5h with 150g 1wt% sodium bicarbonate solutions, filtered again,
Product is washed with deionized to neutrality, finally dries, crush, packing and produce acetyl group bytyry cellulose；
（7）Step（6）The filtrate obtained after filtering suspension, 80 DEG C of air-distillation filtrates reclaim hexane, remaining liq essence
Evaporate to obtain acetic anhydride, butyric anhydride, acetic acid, butyric acid.
The acetyl group bytyry cellulose bytyry content that the present embodiment obtains is 60%, and number-average molecular weight is more than 20000.
Embodiment 4
Acetyl group bytyry cellulose is prepared according to following steps：
（1）10g purified cottons are placed in beaker, 80g acetic acid is added, sealing, soaks 5 days at room temperature, filter out excess acetic acid；
（2）Purified cotton after immersion and 50g butyric anhydrides, 2g catalyst are placed in equipped with condenser pipe and churned mechanically three neck
Flask, in 60 DEG C of stirring reaction 0.5h；
（3）0.5g catalyst is added, is subsequently added into 20g acetic anhydrides, continues stirring reaction 1h at 70 DEG C；
（4）1g catalyst is added, continues stirring reaction 0.5h at 50 DEG C；
（5）By step（4）Obtained product is cooled to room temperature, and 100g hexanes are added in flask under quick stirring, stirred
0.5h is mixed, obtains suspension；
（6）Suspension is filtered, gained solid powder soaks 1h with 100g 1wt% sodium bicarbonate solutions, filtered again, uses
Deionized water washed product is finally dried, crushed, packing and produce acetyl group bytyry cellulose to neutrality；
（7）Step（6）The filtrate obtained after filtering suspension, 80 DEG C of air-distillation filtrates reclaim hexane, remaining liq essence
Evaporate to obtain acetic anhydride, butyric anhydride, acetic acid, butyric acid.
The acetyl group bytyry cellulose bytyry content that the present embodiment obtains is 57%, and number-average molecular weight is more than 20000.
Comparative example 1
Acetyl group bytyry cellulose is prepared according to following steps：
（1）10g purified cottons are placed in beaker, 80g acetic acid is added, sealing, soaks 5 days at room temperature, filter out excess acetic acid；
（2）By the purified cotton after immersion and 50g butyric anhydrides, 0.2g catalyst（The 98wt% concentrated sulfuric acids）It is placed in and is furnished with condenser pipe
With churned mechanically three-neck flask, in 60 DEG C of stirring reaction 0.5h；
（3）Add 0.15g catalyst（The 98wt% concentrated sulfuric acids）, 20g acetic anhydrides are subsequently added into, continue stirring reaction at 70 DEG C
1h；
（4）By step（3）Obtained product is cooled to room temperature, and 100g hexanes are added in flask under quick stirring, stirred
0.5h is mixed, obtains suspension；
（5）Suspension is filtered, gained solid powder soaks 1h with 100g 1wt% sodium bicarbonate solutions, filtered again, uses
Deionized water washed product is finally dried, crushed, packing and produce acetyl group bytyry cellulose to neutrality；
（6）Step（5）The filtrate obtained after filtering suspension, 80 DEG C of air-distillation filtrates reclaim hexane, remaining liq essence
Evaporate to obtain acetic anhydride, butyric anhydride, acetic acid, butyric acid.
The acetyl group bytyry cellulose number-average molecular weight that the present embodiment obtains is less than 10000.
Although the used catalyst concentrated sulfuric acid dosage of comparative example 1 and embodiment 4 are identical, do not diluted with acetic acid, and
Do not add in three times, gained acetyl group bytyry molecular weight cellulose is far from the height of embodiment 4.Prove using the present invention's
Method, the higher acetyl group bytyry cellulose of mean molecule quantity can be obtained.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any
Belong to those skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in, all should
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be defined by scope of the claims.
Claims (7)
1. a kind of preparation method of acetyl group bytyry cellulose, it is characterised in that comprise the following steps：
(1) cellulose is placed in acid-resistant container, adds acetic acid immersion, filter out excess acetic acid；
(2) cellulose after immersion, butyric anhydride, catalyst are placed in acid-resistant container, reacted, cellulose, butyric anhydride, catalysis
The mass ratio of agent is 1：2~6：0.1~0.2, reaction temperature is 50~70 DEG C, and the time is 0.5~1h；
(3) catalyst and acetic anhydride are added, continues to react, catalyst is the 5~10% of cellulose quality, and acetic anhydride is cellulose
1.5~3 times of quality, reaction temperature are 50~70 DEG C, and the time is 0.5~1h；
(4) catalyst is added, continues to react, catalyst is the 5~10% of cellulose quality, and reaction temperature is 50~70 DEG C, when
Between be 0.5~1h；
(5) room temperature is cooled to, hexane is added and stirs, obtain suspension；
(6) suspension is filtered, gained solid powder is soaked with sodium bicarbonate solution, filtered again, and product is washed with deionized
To neutrality, finally dry, crush and produce, in step (2), (3), (4), catalyst be acetic acid with the concentrated sulfuric acid by 9：1 quality
Than the mixture being formulated.
2. preparation method according to claim 1, it is characterised in that the cellulose is wood pulps, Cotton Pulp, bamboo pulp
At least one of.
3. preparation method according to claim 1, it is characterised in that the cellulose is wood pulp cypress, bamboo pulp cypress, purified cotton
At least one of.
4. preparation method according to claim 1, it is characterised in that in step (1), the mass ratio of cellulose and acetic acid is
1：5~10, soak time is 0.5~7 day.
5. preparation method according to claim 1, it is characterised in that in step (5), hexane for cellulose quality 5~
10 times, 0.5~1h of mixing time.
6. preparation method according to claim 1, it is characterised in that in step (6), the concentration of sodium bicarbonate solution is
0.5~1wt%, sodium bicarbonate aqueous solution are 10~20 times of cellulose quality.
7. preparation method according to claim 1, it is characterised in that also include：Obtained after step (6) filtering suspension
Filtrate, air-distillation filtrate recovery hexane, remaining liq rectifying obtain acetic anhydride, butyric anhydride, acetic acid, butyric acid.
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| CN102898530A (en) * | 2012-09-13 | 2013-01-30 | 无锡市凯利药业有限公司 | Preparation method for cellulose acetate-butyrate |
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| US7893138B2 (en) * | 2003-03-14 | 2011-02-22 | Eastman Chemical Company | Low molecular weight carboxyalkylcellulose esters and their use as low viscosity binders and modifiers in coating compositions |
| US20060004192A1 (en) * | 2004-07-02 | 2006-01-05 | Fuji Photo Film Co., Ltd. | Method of preparing a cellulose acylate, cellulose acylate film, polarizing plate, and liquid crystal display device |
| JP2008056819A (en) * | 2006-08-31 | 2008-03-13 | Daicel Chem Ind Ltd | Mixed fatty acid cellulose ester, and method for producing the same |
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2015
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| CN102898530A (en) * | 2012-09-13 | 2013-01-30 | 无锡市凯利药业有限公司 | Preparation method for cellulose acetate-butyrate |
| CN103709254A (en) * | 2013-12-20 | 2014-04-09 | 江苏瑞晨化学有限公司 | Preparation method of medium-viscosity cellulose acetate butyrate |
| CN104371026A (en) * | 2014-11-17 | 2015-02-25 | 江苏瑞晨化学有限公司 | Cellulose acetate butyrate mixed ester with high butyryl content, and preparation method thereof |
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| Conversion of cotton byproducts to mixed cellulose esters;H.N. Cheng et al.;《Carbohydrate Polymers》;20110612;第86卷(第3期);第1130-1136页 * |
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