CN103626879A - Mechanical activation and enhancement method for preparing cellulose acetate-butyrate or cellulose acetate-propionate - Google Patents
Mechanical activation and enhancement method for preparing cellulose acetate-butyrate or cellulose acetate-propionate Download PDFInfo
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Abstract
The invention relates to the field of cellulose processing, and in particularly relates to a mechanical activation and enhancement method for preparing cellulose acetate-butyrate or cellulose acetate-propionate. The method comprises the following steps: weighing reactants including cellulose, butyric acid, acetic anhydride and a catalyst in a ratio of 10g:(30-100g):(10-30g):(0.1-0.5g), putting all the reactants into a ball mill, controlling the ratio of the reactants to pellets at 100g:(100-300ml), controlling the temperature of a circulating water bath at 50-80 DEG C, stirring at a low speed to perform an acylation reaction for 1-4 hours to obtain a crude product, separating the crude product and the pellets, standing the crude product in 50% ethanol water to separate out a solid, separating the separated solid, and washing the separated solid with deionized water until the solid is neutral, thereby obtaining a cellulose acetate-butyrate or cellulose acetate-propionate product. Compared with the existing method for producing cellulose acetate-butyrate or cellulose acetate-propionate, the method disclosed by the invention has the characteristics of simple process, high efficiency, no pollution, high product quality and the like.
Description
Technical field
The present invention relates to the method for acetate butyrate/cellulose acetate propionate, particularly a kind of method that adopts mechanical activation reinforcement to prepare cellulose acetate butyrate/cellulose acetate propionate.
Background technology
The exploitation of derivatived cellulose is long-standing, especially since 20 century 70s, understanding along with the energy and oil data finiteness, and fiber material material products itself has the not available characteristic of other synthesized polymer materials, in the research and utilization of polymeric material field, derivatived cellulose more and more comes into one's own.Cellulose ester is a kind of important derivatived cellulose wherein.
Cellulose acetate butyrate (cellulose acetate-butyrate, CAB) is part of hydroxyl in the Mierocrystalline cellulose product after by acetic acid and butyric acid esterification.In the molecule of CAB, hydroxyl-removal, ethanoyl also contain butyryl radicals outward, and its performance is relevant with the content of three kinds of groups.Fusing point and tensile strength increase with acetyl content and become large, reduce and increase within the specific limits with the consistency of softening agent and the flexibility of film with acetyl content.Hydroxy radical content increases and promotes its solubleness in polar solvent.The increase of butyryl radicals content makes its density reduce, and soluble end expands.It has good moisture-resistant, the performances such as ultraviolet resistance, cold-resistant, pliable and tough, transparent, electrical isolation, and can there is good consistency with resin and high boiling point softening agent, can movie film base processed, transport pipe, handle for tool, automobile, the Glass lamp of aircraft, underground telephone wire and cable tube, bearing circle, label face, the flash of light reverberator etc. such as aerophotography sheet base, film, Oilfield Natural Gas Plant, can also do in addition stripping lacquer, insullac, weather-proof high-grade paint and regenerated fiber.
Cellulose acetate propionate (CAP) is the derivatived cellulose through esterification gained by natural cellulose, belongs to cellulose organic ester.After Mierocrystalline cellulose is processed with propionic acid, then with propionic acid, propionic anhydride and acetic acid, acetic oxide mixed solution under sulfuric acid exists, carry out esterification, and then through hydrolysis, precipitating, washing, the operation such as be dried and just can obtain the cellulose acetate propionate of a certain substitution value.Cellulose organic ester is owing to being subject to the restriction in esterifying agent (organic acid and acid anhydrides thereof) source, has practical value and become cellulose acetate (CA), cellulose acetate propionate, the cellulose acetate butyrate of industrial-scale production.CAP has than the better shock strength of CA, water tolerance, dimensional stability with than the better ventilation property of CAB, and has good solubility, consistency and mechanical property, is therefore widely used in the fields such as coating, film, artwork manufacture.
The preparation method that CAB, CAP are traditional: acetic acid is made aceticanhydride through high-temperature cracking method.Aceticanhydride and butyric acid are made butanoic anhydride with acid anhydrides exchange process.Utilize refined cotton linter to take sulfuric acid as catalyst, acetic acid, butyric acid are that solvent and vinegar butanoic anhydride carry out homogeneous phase esterification and obtain raw product, then through hydrolysis, neutralization, precipitating, washing, boiling, the dry final finished cellulose acetate butyrate that to obtain.Traditional method intermediate ion liquid dissolving cellulos method needs preprocessing process (liquid phase method needs preactivated Mierocrystalline cellulose: Glacial acetic acid, acetic anhydride soak more than 12 hours) and hydrolytic process (liquid phase method all needs the equal time of hydrolysis and reaction times), preparation process is consuming time, and efficiency is low.
CN200810106426.X, a kind of method of preparing cellulose acetate propionate or cellulose acetate butyrate, this disclosure of the invention method comprise the following steps: a. mixes Mierocrystalline cellulose with ionic liquid that can dissolving cellulos, obtain containing cellulosic ionic liquid solution; B. by 1) acetylize and the third acylating reagent or 2) acetylize and Butyrylation reagent adds and contains in cellulosic ionic liquid solution, and at 40-120 ℃ of reaction 1-24 hour, preferably 1-12 hour, obtains reaction mixture; C. to the lower aliphatic alcohols that adds C1-C3 in described reaction mixture, filter the reaction mixture that contains lower aliphatic alcohols; D., after solid drying filtration being obtained, obtain cellulose acetate propionate or cellulose acetate butyrate.
Ask the wayward cost that causes of preparation process length consuming time, complex procedures of the above prior art CAB of matter foot degree a and CAP high; and Mierocrystalline cellulose has high-crystallinity; accessibility is low; be difficult to occur chemical reaction; crude product purification process requires strict; the not high product physicochemical property that causes of acidylate degree of product is poor, is difficult to meet the demand of environmental protection, high-quality coating.
Summary of the invention
The object of the invention is to overcome cellulose acetate butyrate/cellulose acetate propionate preparation method exists preparation process length consuming time, the wayward cost that causes of complex procedures high; and Mierocrystalline cellulose has high-crystallinity; accessibility is low; be difficult to occur chemical reaction; crude product purification process requires strict; the not high product physicochemical property that causes of acidylate degree of product is poor; be difficult to meet the problems such as demand of environmental protection, high-quality coating, a kind of method that adopts mechanical activation reinforcement to prepare cellulose acetate butyrate/cellulose acetate propionate is provided.
Cellulose acetate butyrate of the present invention is prepared scheme by such realization: the method for cellulose acetate butyrate is prepared in a kind of mechanical activation strengthening, it is characterized in that, according to Mierocrystalline cellulose: the ratio of butyric acid: acetic anhydride: catalyzer=10g: 30 ~ 100g:10 ~ 30g:0.1 ~ 0.5g weighs gets reaction mass, reaction mass is all placed in ball mill, control reaction mass and pellet (heap volume) ratio=100g:100 ~ 300ml, 50 ~ 90 ℃ of controlled circulation bath temperatures, stirring at low speed is carried out acylation reaction 1 ~ 4h, after finishing, reaction obtains product crude product, product crude product is separated with pellet, product crude product is the standing solid of separating out in aqueous ethanolic solution, isolate and separate out solid, washing is separated out solid to neutral, obtain cellulose acetate butyrate product.This programme utilizes this emerging interleaving techniques of mechanical activation to carry out solid state reaction; in reaction process, mechanical energy being converted into can in material; material chemical energy is improved; promote efficiently carrying out of acylation reaction; shorten preparation time; improve the content of ethanoyl, butyryl radicals in product, compare with traditional method without preprocessing process (liquid phase method needs preactivated Mierocrystalline cellulose: Glacial acetic acid, acetic anhydride soak more than 12 hours) and hydrolytic process (liquid phase method all needs the equal time of hydrolysis and reaction times).
As a further improvement on the present invention, described Mierocrystalline cellulose is any or their composition in gossypin, wood cellulose; Described catalyzer is any in acids, bases, salt; Described acids is sulfuric acid, hydrochloric acid, phosphoric acid, cross any or their composition in chloric acid, methylsulfonic acid, p-methyl benzenesulfonic acid; Described bases is any or their composition in sodium hydroxide, aluminium hydroxide; Described salt is any or their composition in sodium carbonate, sodium-acetate, calcium acetate, p-methyl benzenesulfonic acid sodium, zinc chloride.
As a further improvement on the present invention, described pellet is zirconia balls, and the diameter of zirconia balls is 0.5 ~ 6mm.
As a further improvement on the present invention, described stirring at low speed is that stirring velocity is controlled at 100 ~ 500r/min.
As a further improvement on the present invention, the aqueous ethanolic solution that described aqueous ethanolic solution is 40 ~ 60%.
Cellulose acetate propionate of the present invention is prepared scheme by such realization: the method for cellulose acetate propionate is prepared in a kind of mechanical activation strengthening, it is characterized in that, according to Mierocrystalline cellulose: the ratio of propionic acid: acetic anhydride: catalyzer=10g: 30 ~ 100g:10 ~ 30g:0.1 ~ 0.5g weighs gets reaction mass, reaction mass is all placed in ball mill, control reaction mass and pellet (heap volume) ratio=100g:100 ~ 300ml, 50 ~ 90 ℃ of controlled circulation bath temperatures, stirring at low speed is carried out acylation reaction 1 ~ 4h, after finishing, reaction obtains product crude product, product crude product is separated with pellet, product crude product is the standing solid of separating out in aqueous ethanolic solution, isolate and separate out solid, washing is separated out solid to neutral, obtain cellulose acetate propionate product.This programme utilizes this emerging interleaving techniques of mechanical activation to carry out solid state reaction; in reaction process, mechanical energy being converted into can in material; material chemical energy is improved; promote efficiently carrying out of acylation reaction; shorten preparation time; improve the content of ethanoyl, propionyl in product, compare with traditional method without preprocessing process (liquid phase method needs preactivated Mierocrystalline cellulose: Glacial acetic acid, acetic anhydride soak more than 12 hours) and hydrolytic process (liquid phase method all needs the equal time of hydrolysis and reaction times).
As a further improvement on the present invention, described Mierocrystalline cellulose is any or their composition in gossypin, wood cellulose; Described catalyzer is any in acids, bases, salt; Described acids is sulfuric acid, hydrochloric acid, phosphoric acid, cross any or their composition in chloric acid, methylsulfonic acid, p-methyl benzenesulfonic acid; Described bases is any or their composition in sodium hydroxide, aluminium hydroxide; Described salt is any or their composition in sodium carbonate, sodium-acetate, calcium acetate, p-methyl benzenesulfonic acid sodium, zinc chloride.
As a further improvement on the present invention, described pellet is zirconia balls, and the diameter of zirconia balls is 0.5 ~ 6mm.
As a further improvement on the present invention, described stirring at low speed is that stirring velocity is controlled at 100 ~ 500r/min.
As a further improvement on the present invention, the aqueous ethanolic solution that described aqueous ethanolic solution is 40 ~ 60%.
The present invention possesses following good result:
(1) the present invention be take ball mill as reactor, adopt the method for mechanical activation strengthening to prepare cellulose acetate butyrate/cellulose acetate propionate, compare with the method for existing production cellulose acetate butyrate/cellulose acetate propionate, there is simple, the free of contamination feature of technique.
(2) cellulosic two kinds of esterifications, the cellulose mixed esters that obtains wanting of completing in 1 ~ 4h of the present invention.And without preprocessing process (liquid phase method needs preactivated Mierocrystalline cellulose: Glacial acetic acid, acetic anhydride/the third acid anhydride soak more than 12 hours) and hydrolytic process (liquid phase method all needs the equal time of hydrolysis and reaction times), and present method adopts mechanical activation strengthening reaction modifying technology, technique is simple, easy to operate, cost, production process is discharged without " three wastes ".
(3) the present invention adopts the inventive method, and in CAB, acetyl content is 0-40%, and butyryl radicals content is 0-40%; In CAP, acetyl content is 0-40%, and propionyl content is 0-40%.Meanwhile, by the control to the amount of reaction conditions and acylating agent, the hydroxyl on ethanoyl and butyryl radicals/propionyl substituted cellulose more controlled, thus obtain the CAB/CAP of required physicochemical property.
Embodiment
Below in conjunction with embodiment with describe the method that a kind of mechanical activation reinforcement of the present invention is prepared cellulose acetate butyrate/cellulose acetate propionate, these descriptions are not that content of the present invention is further limited.
Embodiment 1 cellulose acetate butyrate preparation
The Mierocrystalline cellulose that the present embodiment is used is gossypin; Catalyzer is the sulfuric acid in acids.
According to Mierocrystalline cellulose: the ratio of butyric acid: acetic anhydride: catalyzer=10g: 43g:250g:0.1g weighs gets reaction mass, reaction mass is all placed in ball mill, control reaction mass and pellet (heap volume) ratio=100g:150ml, pellet is that diameter is the zirconia balls of 6mm, 80 ℃ of controlled circulation bath temperatures, stirring velocity is controlled at 450r/min and carries out acylation reaction 3h, after finishing, reaction obtains product crude product, product crude product is separated with pellet, product crude product is the standing solid of separating out in 50% aqueous ethanolic solution, isolate and separate out solid, washing is separated out solid to neutral, obtain cellulose acetate butyrate product.
The present embodiment gained CAB product after testing acetyl content is 23.87%; Butyryl radicals content is 19.92%.
Embodiment 2 cellulose acetate butyrate preparations
The Mierocrystalline cellulose that the present embodiment is used is lignocellulose; Catalyzer is the methylsulfonic acid in acids.
According to Mierocrystalline cellulose: the ratio of butyric acid: acetic anhydride: catalyzer=10g: 66g:20g:0.5g weighs gets reaction mass, reaction mass is all placed in ball mill, control reaction mass and pellet (heap volume) ratio=100g:100ml, pellet is that diameter is the zirconia balls of 2mm, 50 ℃ of controlled circulation bath temperatures, stirring velocity is controlled at 100r/min and carries out acylation reaction 4h, after finishing, reaction obtains product crude product, product crude product is separated with pellet, product crude product is the standing solid of separating out in 40% aqueous ethanolic solution, isolate and separate out solid, washing is separated out solid to neutral, obtain cellulose acetate butyrate product.
The present embodiment gained CAB product after testing acetyl content is 35.21%; Butyryl radicals content is 16.92%.
Embodiment 3 cellulose acetate butyrate preparations
The Mierocrystalline cellulose that the present embodiment is used is the composition that gossypin mixes according to the part by weight of 1:1 with lignocellulose; Catalyzer is sodium hydroxide in bases.
According to Mierocrystalline cellulose: the ratio of butyric acid: acetic anhydride: catalyzer=10g: 95g:25g:0.3g weighs gets reaction mass, reaction mass is all placed in ball mill, control reaction mass and pellet (heap volume) ratio=100g:200ml, pellet is that diameter is the zirconia balls of 3.5mm, 60 ℃ of controlled circulation bath temperatures, stirring velocity is controlled at 200r/min and carries out acylation reaction 1.5h, after finishing, reaction obtains product crude product, product crude product is separated with pellet, product crude product is the standing solid of separating out in 60% aqueous ethanolic solution, isolate and separate out solid, washing is separated out solid to neutral, obtain cellulose acetate butyrate product.
The present embodiment gained CAB product after testing acetyl content is 40.00%; Butyryl radicals content is 22.24%.
Embodiment 4 cellulose acetate butyrate preparations
In the present embodiment, Mierocrystalline cellulose is lignocellulose; Catalyzer is the composition that sodium carbonate, sodium-acetate mix according to weight ratio 1:1.
According to Mierocrystalline cellulose: the ratio of butyric acid: acetic anhydride: catalyzer=10g: 100g:25g:0.45g weighs gets reaction mass, reaction mass is all placed in ball mill, control reaction mass and pellet (heap volume) ratio=100g:300ml, pellet is that diameter is the zirconia balls of 5.5mm, 90 ℃ of controlled circulation bath temperatures, stirring velocity is controlled at 200r/min and carries out acylation reaction 1h, after finishing, reaction obtains product crude product, product crude product is separated with pellet, product crude product is the standing solid of separating out in 50% aqueous ethanolic solution, isolate and separate out solid, washing is separated out solid to neutral, obtain cellulose acetate butyrate product.
The present embodiment gained CAB product after testing acetyl content is 25.68%; Butyryl radicals content is 20.52%.
Embodiment 5 cellulose acetate butyrate preparations
In the present embodiment, Mierocrystalline cellulose is gossypin; Catalyzer is the composition that calcium acetate, p-methyl benzenesulfonic acid sodium mix according to weight ratio 1:1.
According to Mierocrystalline cellulose: the ratio of butyric acid: acetic anhydride: catalyzer=10g: 30g:10g:0.1g weighs gets reaction mass, reaction mass is all placed in ball mill, control reaction mass and pellet (heap volume) ratio=100g:300ml, pellet is that diameter is the zirconia balls of 3.5mm, 80 ℃ of controlled circulation bath temperatures, stirring velocity is controlled at 500r/min and carries out acylation reaction 3h, after finishing, reaction obtains product crude product, product crude product is separated with pellet, product crude product is the standing solid of separating out in 50% aqueous ethanolic solution, isolate and separate out solid, washing is separated out solid to neutral, obtain cellulose acetate butyrate product.
The present embodiment gained CAB product after testing acetyl content is 22.3%; Butyryl radicals content is 18.00%.
Embodiment 6 cellulose acetate propionate preparations
In the present embodiment, Mierocrystalline cellulose is lignocellulose; Catalyzer is hydrochloric acid.
According to Mierocrystalline cellulose: butyric acid: the ratio of the third acid anhydride: catalyzer=10g: 30g:30g:0.25g weighs gets reaction mass, reaction mass is all placed in ball mill, control reaction mass and pellet (heap volume) ratio=100g:300ml, pellet is that diameter is the zirconia balls of 1.5mm, 90 ℃ of controlled circulation bath temperatures, stirring velocity is controlled at 500r/min and carries out acylation reaction 3h, after finishing, reaction obtains product crude product, product crude product is separated with pellet, product crude product is the standing solid of separating out in 50% aqueous ethanolic solution, isolate and separate out solid, washing is separated out solid to neutral, obtain cellulose acetate propionate product.
The present embodiment gained CAP product after testing acetyl content is 26.87%; Propionyl content is 25.72%.
Embodiment 7 cellulose acetate propionate preparations
In the present embodiment, Mierocrystalline cellulose is gossypin; Catalyzer is aluminium hydroxide;
According to Mierocrystalline cellulose: butyric acid: the ratio of the third acid anhydride: catalyzer=10g: 100g:30g:0.1g weighs gets reaction mass, reaction mass is all placed in ball mill, control reaction mass and pellet (heap volume) ratio=100g:100ml, pellet is that diameter is the zirconia balls of 5mm, 90 ℃ of controlled circulation bath temperatures, stirring velocity is controlled at 500r/min and carries out acylation reaction 4h, after finishing, reaction obtains product crude product, product crude product is separated with pellet, product crude product is the standing solid of separating out in 40% aqueous ethanolic solution, isolate and separate out solid, washing is separated out solid to neutral, obtain cellulose acetate propionate product.
The present embodiment gained CAP product after testing acetyl content is 25.24%; Propionyl content is 24.92%.
Embodiment 8 cellulose acetate propionate preparations
In the present embodiment, Mierocrystalline cellulose is gossypin; Catalyzer is calcium acetate.
According to Mierocrystalline cellulose: butyric acid: the ratio of the third acid anhydride: catalyzer=10g: 80g:10g:0.15g weighs gets reaction mass, reaction mass is all placed in ball mill, control reaction mass and pellet (heap volume) ratio=100g:200ml, pellet is that diameter is the zirconia balls of 3.5mm, 60 ℃ of controlled circulation bath temperatures, stirring velocity is controlled at 100r/min and carries out acylation reaction 4h, after finishing, reaction obtains product crude product, product crude product is separated with pellet, product crude product is the standing solid of separating out in 40% aqueous ethanolic solution, isolate and separate out solid, washing is separated out solid to neutral, obtain cellulose acetate propionate product.
The present embodiment gained CAP product after testing acetyl content is 40.00%; Propionyl content is 36.75%.
Embodiment 9 cellulose acetate propionate preparations
In the present embodiment, Mierocrystalline cellulose is the composition that gossypin mixes according to the part by weight of 1:1 with lignocellulose; Catalyzer is zinc chloride.
According to Mierocrystalline cellulose: butyric acid: the ratio of the third acid anhydride: catalyzer=10g: 50g:10g:0.25g weighs gets reaction mass, reaction mass is all placed in ball mill, control reaction mass and pellet (heap volume) ratio=100g:150ml, pellet is that diameter is the zirconia balls of 5.5mm, 70 ℃ of controlled circulation bath temperatures, stirring velocity is controlled at 400r/min and carries out acylation reaction 1.0h, after finishing, reaction obtains product crude product, product crude product is separated with pellet, product crude product is the standing solid of separating out in 55% aqueous ethanolic solution, isolate and separate out solid, washing is separated out solid to neutral, obtain cellulose acetate propionate product.
The present embodiment gained CAP product after testing acetyl content is 28.24%; Propionyl content is 25.42%.
Embodiment 10 cellulose acetate propionate preparations
In the present embodiment, Mierocrystalline cellulose is lignocellulose; Catalyzer is the composition that sodium-acetate and calcium acetate mix according to the part by weight of 1:1.
According to Mierocrystalline cellulose: butyric acid: the ratio of the third acid anhydride: catalyzer=10g: 90g:20g:0.35ml weighs gets reaction mass, reaction mass is all placed in ball mill, control reaction mass and pellet (heap volume) ratio=100g:100ml, pellet is that diameter is the zirconia balls of 3.5mm, 50 ℃ of controlled circulation bath temperatures, stirring velocity is controlled at 500r/min and carries out acylation reaction 4h, after finishing, reaction obtains product crude product, product crude product is separated with pellet, product crude product is the standing solid of separating out in 55% aqueous ethanolic solution, isolate and separate out solid, washing is separated out solid to neutral, obtain cellulose acetate propionate product.
The present embodiment gained CAP product after testing acetyl content is 34.52%; Propionyl content is 28.24%.
Embodiment 11 cellulose acetate propionate preparations
In the present embodiment, Mierocrystalline cellulose is gossypin; Catalyzer is methylsulfonic acid.
According to Mierocrystalline cellulose: butyric acid: the ratio of the third acid anhydride: catalyzer=10g: 45g:20g:0.35g weighs gets reaction mass, reaction mass is all placed in ball mill, control reaction mass and pellet (heap volume) ratio=100g:150ml, pellet is that diameter is the zirconia balls of 4mm, 60 ℃ of controlled circulation bath temperatures, stirring velocity is controlled at 300r/min and carries out acylation reaction 3h, after finishing, reaction obtains product crude product, product crude product is separated with pellet, product crude product is the standing solid of separating out in 55% aqueous ethanolic solution, isolate and separate out solid, washing is separated out solid to neutral, obtain cellulose acetate propionate product.
The present embodiment gained CAP product after testing acetyl content is 32.24%; Propionyl content is 29.52%.
Claims (10)
1. a mechanical activation is strengthened the method for preparing cellulose acetate butyrate, it is characterized in that, according to Mierocrystalline cellulose: the ratio of butyric acid: acetic anhydride: catalyzer=10g: 30 ~ 100g:10 ~ 30g:0.1 ~ 0.5g weighs gets reaction mass, reaction mass is all placed in ball mill, control reaction mass and pellet (heap volume) ratio=100g:100 ~ 300ml, 50 ~ 90 ℃ of controlled circulation bath temperatures, stirring at low speed is carried out acylation reaction 1 ~ 4h, after finishing, reaction obtains product crude product, product crude product is separated with pellet, product crude product is the standing solid of separating out in aqueous ethanolic solution, isolate and separate out solid, washing is separated out solid to neutral, obtain cellulose acetate butyrate product.
2. the method for cellulose acetate butyrate is prepared in mechanical activation according to claim 1 strengthening, it is characterized in that, described Mierocrystalline cellulose is any or their composition in gossypin, wood cellulose; Described catalyzer is any in acids, bases, salt; Described acids is any in sulfuric acid, hydrochloric acid, phosphoric acid, mistake chloric acid, methylsulfonic acid, p-methyl benzenesulfonic acid; Described bases is any in sodium hydroxide, aluminium hydroxide; Described salt is any in sodium carbonate, sodium-acetate, calcium acetate, p-methyl benzenesulfonic acid sodium, zinc chloride.
3. the method for cellulose acetate butyrate is prepared in mechanical activation strengthening according to claim 2, it is characterized in that, described pellet is zirconia balls, and the diameter of zirconia balls is 0.5 ~ 6mm.
4. the method for cellulose acetate butyrate is prepared in mechanical activation strengthening according to claim 2, it is characterized in that, described stirring at low speed is that stirring velocity is controlled at 100 ~ 500r/min.
5. according to the mechanical activation strengthening described in claim 2 or 3 any one, prepare the method for cellulose acetate butyrate, it is characterized in that the aqueous ethanolic solution that described aqueous ethanolic solution is 40 ~ 60%.
6. a mechanical activation is strengthened the method for preparing cellulose acetate propionate, it is characterized in that, according to Mierocrystalline cellulose: the ratio of propionic acid: acetic anhydride: catalyzer=10g: 30 ~ 100g:10 ~ 30g:0.1 ~ 0.5g weighs gets reaction mass, reaction mass is all placed in ball mill, control reaction mass and pellet (heap volume) ratio=100g:100 ~ 300ml, 50 ~ 90 ℃ of controlled circulation bath temperatures, stirring at low speed is carried out acylation reaction 1 ~ 4h, after finishing, reaction obtains product crude product, product crude product is separated with pellet, product crude product is the standing solid of separating out in aqueous ethanolic solution, isolate and separate out solid, washing is separated out solid to neutral, obtain cellulose acetate propionate product.
7. the method for cellulose acetate propionate is prepared in mechanical activation according to claim 6 strengthening, it is characterized in that, described Mierocrystalline cellulose is any or their composition in gossypin, wood cellulose; Described catalyzer is any in acids, bases, salt; Described acids is any in sulfuric acid, hydrochloric acid, phosphoric acid, mistake chloric acid, methylsulfonic acid, p-methyl benzenesulfonic acid; Described bases is any in sodium hydroxide, aluminium hydroxide; Described salt is any in sodium carbonate, sodium-acetate, calcium acetate, p-methyl benzenesulfonic acid sodium, zinc chloride.
8. the method for cellulose acetate propionate is prepared in mechanical activation strengthening according to claim 7, it is characterized in that, described pellet is zirconia balls, and the diameter of zirconia balls is 0.5 ~ 6mm.
9. according to the mechanical activation strengthening described in claim 7 or 8 any one, prepare the method for cellulose acetate propionate, it is characterized in that, described stirring at low speed is that stirring velocity is controlled at 100 ~ 500r/min.
10. the method for cellulose acetate propionate is prepared in mechanical activation strengthening according to claim 9, it is characterized in that the aqueous ethanolic solution that described aqueous ethanolic solution is 40 ~ 60%.
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Effective date of registration: 20170106 Address after: Jishan Industrial Park 350001 Sanming City Jiangle County in Fujian Province Economic Development Zone Patentee after: Fujian Hongyan Chemical Co., Ltd. Address before: 530004 College of chemical engineering, Guangxi University, the Guangxi Zhuang Autonomous Region, Nanning Patentee before: Guangxi Univ |