CN104371026A - Cellulose acetate butyrate mixed ester with high butyryl content, and preparation method thereof - Google Patents
Cellulose acetate butyrate mixed ester with high butyryl content, and preparation method thereof Download PDFInfo
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- CN104371026A CN104371026A CN201410651086.4A CN201410651086A CN104371026A CN 104371026 A CN104371026 A CN 104371026A CN 201410651086 A CN201410651086 A CN 201410651086A CN 104371026 A CN104371026 A CN 104371026A
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Abstract
The invention discloses cellulose acetate butyrate mixed ester with high butyryl content, and a preparation method thereof. The cellulose ester is prepared from the following components in parts by weight: 600 parts of wood pulp, 800-1200 parts of butyric acid, 2500-3500 parts of butyric anhydride, 20-40 parts of acetic anhydride, and concentrated sulfuric acid catalyst accounting for 5-10% of total weight parts of wood pulp. The preparation method comprises the following steps: activating, performing esterification reaction, mixing, adding magnesium acetate solution, hydrolyzing, performing chromatography, and then sequentially conventionally filtering, washing and drying to obtain a finished product. According to cellulose acetate butyrate mixed ester with high butyryl content, cellulose acetate butyrate with the butyryl content of 48-53% and acetyl content of less than or equal to 4% can be obtained after the combination according to specific formula and proportion, and the product is stable in performances. The preparation method is simple in steps, the preparation period is short, the preparation conditions are not strict and easily achieved, and especially, the activated solid is fed into a cooling liquid within 2-5min, so that the quality of products can be guaranteed while the fast follow-up reaction is guaranteed.
Description
Technical field
The present invention relates to a kind of cellulose acetate butyrate mixed ester of high butyryl radicals content, the invention still further relates to a kind of preparation method of cellulose acetate butyrate mixed ester of high butyryl radicals content, belong to cellulose ester analog derivative field.
Background technology
Cellulose acetate butyrate (being called for short CAB) is a kind of cellulose organic ester obtained through esterification by Mierocrystalline cellulose, acetic anhydride and butyryl oxide.CAB can be compatible with multiple synthetic resins, and snappiness, winter hardiness, levelling property, color and luster retentivity are good, and anti-aging, not yellowing, be the important auxiliary agent of the industry technology development such as contemporary automotive paint, motorcycle paints, furniture paint, ink, pen processed.
In the cellulose acetate butyrate of current domestic production, butyryl radicals content is lower and unstable.Chinese Patent Application No. is: 200810106426.X patent discloses a kind of method preparing cellulose acetate propionate or cellulose acetate butyrate, the method comprises the following steps: a. by Mierocrystalline cellulose with can the ionic liquid of dissolving cellulos mix, obtain containing cellulosic ionic liquid solution; B. by 1) acetylize and propionating reagent or 2) acetylize and Butyrylation reagent adds containing in cellulosic ionic liquid solution, and at 40-120 DEG C of reaction 1-24 hour, preferred 1-12 hour, obtains reaction mixture; C. in described reaction mixture, C is added
1-C
3lower aliphatic alcohols, filter containing the reaction mixture of lower aliphatic alcohols; D., after solid drying filtration obtained, cellulose acetate propionate or cellulose acetate butyrate is obtained.The method uses ionic liquid to be solvent, without any need for catalyzer, has simple, the free of contamination advantage of technique.But the Mierocrystalline cellulose efficiency of producing is low, butyryl radicals content is low, and temperature of reaction is high, and the reaction times is longer.
Summary of the invention
The object of the invention is to for deficiency of the prior art; cellulose acetate butyrate mixed ester of a kind of high butyryl radicals content and preparation method thereof is provided; can obtain the cellulose acetate butyrate of butyryl radicals content 48 ~ 53%, acetyl content≤4%, product performance are stablized.
For solving the problems of the technologies described above; the technical solution used in the present invention is: a kind of cellulose acetate butyrate mixed ester of high butyryl radicals content; its innovative point is: comprise following composition: wood pulp 600 weight part, butyric acid 800 ~ 1200 weight part, butanoic anhydride 2500 ~ 3500 weight part, aceticanhydride 20 ~ 40 weight part, account for the concentrated sulfuric acid catalyst of wood pulp total weight parts 5 ~ 10%.
Another object of the present invention is to provide a kind of cellulose acetate butyrate mixed ester preparation method of high butyryl radicals content, and its innovative point is: specifically comprise the following steps:
(1) wood pulp of dosage part is first with 370 weight part butyric acid sprays, activates 12 ~ 15h under being then placed on 25 DEG C ~ 30 DEG C temperature;
(2) butanoic anhydride of the butyric acid of residual content and proportional quantity, aceticanhydride, concentrated sulfuric acid catalyst are mixed, and mixed solution is cooled to-15 DEG C ~ 20 DEG C stand-by;
(3) solid after activation in step (1) is put into the cooling fluid of step (2) in 2 ~ 5min, abundant stirring, regulate the amount of cooling water of cooling fluid to control reaction temperature rise rate, make the temperature in final esterification system be no more than 55 DEG C, the reaction times is set to 60min ~ 180min;
(4) in the reaction system of step (3), add magnesium acetate solution, neutralize 40% ~ 60% concentrated sulfuric acid catalyst of proportional quantity; And then to add 1250 weight part concentration be that 60% ~ 70% acetum is hydrolyzed, hydrolysis temperature 60 ~ 70 DEG C, hydrolysis time 4 ~ 6h;
(5), after hydrolysis reaction terminates, continue to add magnesium acetate solution until neutralize the concentrated sulfuric acid catalyst of residual content;
(6) material in step (5) mixture and water are carried out chromatography under abundant stirring state, then carry out conventional filtration successively, washing, baking step obtain finished product.
Further, the solid-liquid feed ratio in described step (3) controls in 1:5.5 ~ 7.5.
Further, described wood pulp is the wood pulp pulverized, the short flannel length≤1mm after pulverizing.
Further, liquid component butyryl radicals ratio >=99% in described step (3) reaction system.
Further, before the hydrolysis reaction of described step (3) starts, control the initial moisture content of reaction system 5% ~ 10%.
Further, gained cellulose acetate butyrate finished product butyryl radicals content >=48% in described step (6).
Beneficial effect of the present invention is as follows:
(1) the cellulose acetate butyrate mixed ester of high butyryl radicals content of the present invention, after the combination according to special formulation dosage, can obtain the cellulose acetate butyrate of butyryl radicals content >=48%, acetyl content≤4%, and product performance are stablized.
(2) the cellulose acetate butyrate mixed ester of high butyryl radicals content of the present invention, liquid acid catalyst selects the vitriol oil, has reaction fast, effective, the advantage that consumption is few.
(3) the cellulose acetate butyrate mixed ester preparation method of high butyryl radicals content of the present invention; step is simple, preparation cycle is short; preparation condition is not harsh easily to be reached; be applicable to suitability for industrialized production; especially, solid after activation is put into cooling fluid in 2 ~ 5min, while ensure that the carrying out fast of subsequent reactions; ensure that the quality of product, butyryl radicals content 48% ~ 53% can be obtained.
(4) the cellulose acetate butyrate mixed ester preparation method of high butyryl radicals content of the present invention, is arranged on 25 DEG C ~ 30 DEG C by activation temperature, and temperature of reaction system is arranged on and is not more than 55 DEG C, ensures that subsequent reactions process is carried out at optimum conditions, accelerates reaction efficiency.
(5), in method of the present invention, the wood pulp selected is the wood pulp pulverized, the short flannel length≤1mm after pulverizing, and ensure that sufficient reacting carries out, cellulose conversion rate reaches 98%, solution clear after reaction.
(6) in method of the present invention, control the initial moisture content of reaction system between 5% ~ 10%, make hydrolysis reaction gentle, controlled, desirable substitution value can be reached.
(7), in method of the present invention, liquid component butyryl radicals ratio >=99% in reaction system, ensures that butyryl radicals content is 48% ~ 53%.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is elaborated.
Embodiment 1
A cellulose acetate butyrate mixed ester for high butyryl radicals content, comprises following composition: wood pulp 600kg, butyric acid 980kg, butanoic anhydride 2745kg, aceticanhydride 24kg, 30kg concentrated sulfuric acid catalyst.
The cellulose acetate butyrate mixed ester preparation method of this high butyryl radicals content above, its innovative point is: specifically comprise the following steps:
(1) wood pulp of dosage part is first with 370kg butyric acid spray, activates 12h and become solid under being then placed on 25 DEG C of temperature;
(2) butanoic anhydride of the butyric acid of residual content and proportional quantity, aceticanhydride, concentrated sulfuric acid catalyst are mixed, and mixed solution is cooled to 3 DEG C stand-by;
(3) solid after activation in step (1) is put into the cooling fluid of step (2) in 5min, abundant stirring, regulate the amount of cooling water of cooling fluid to control reaction temperature rise rate, make the temperature in final esterification system be no more than 55 DEG C, the reaction times is set to 90min;
(4) in the reaction system of step (3), add magnesium acetate solution, neutralize 40% concentrated sulfuric acid catalyst of proportional quantity; And then to add 1250kg concentration be that 60% acetum is hydrolyzed, hydrolysis temperature 60 DEG C, hydrolysis time 4h;
(5), after hydrolysis reaction terminates, continue to add magnesium acetate solution until neutralize the concentrated sulfuric acid catalyst of residual content;
(6) material in step (5) mixture and water are carried out chromatography under abundant stirring state, then carry out conventional filtration successively, washing, baking step obtain finished product.
The present embodiment obtains the cellulose acetate butyrate of butyryl radicals content 50%, acetyl content 3%, and product performance are stablized.
Embodiment 2
On the basis of embodiment 1, change the content of concentrated sulfuric acid catalyst in composition, specific as follows: wood pulp 600kg, butyric acid 980kg, butanoic anhydride 2745kg, aceticanhydride 24kg, 60kg concentrated sulfuric acid catalyst.Adopt the preparation method of embodiment 1 to be prepared, obtain product.
The present embodiment obtains the cellulose acetate butyrate of butyryl radicals content 52%, acetyl content 2.5%, and product performance are stablized.
Embodiment 3
On the basis of embodiment 1 or 2, proportional quantity between the raw material adopting embodiment 1 or 2, pulverizes the wood pulp in raw material, ensures the short flannel length≤1mm after pulverizing, and before controlled hydrolysis reaction process starts, control the initial moisture content of reaction system 5% ~ 10%.Adopt the preparation method of embodiment 1 to be prepared, obtain product.
The present embodiment obtains the cellulose acetate butyrate of butyryl radicals content 52%, acetyl content 3%, and product performance are stablized.
Embodiment 4
On the basis of embodiment 3, change the content of concentrated sulfuric acid catalyst in composition, specific as follows: wood pulp 600kg, butyric acid 980kg, butanoic anhydride 2745kg, aceticanhydride 24kg, 45kg concentrated sulfuric acid catalyst.Control in reaction system after liquid component butyryl radicals ratio >=99%, then adopt the preparation method of embodiment 3 to be prepared, obtain product.
The present embodiment obtains the cellulose acetate butyrate of butyryl radicals content 51%, acetyl content 2.8%, and product performance are stablized.
Embodiment 5
On the basis of embodiment 3, change each component concentration in composition, specific as follows: wood pulp 600kg, butyric acid 1200kg, butanoic anhydride 2700kg, aceticanhydride 30kg, 33kg concentrated sulfuric acid catalyst.Adopt the preparation method of embodiment 3 to be prepared, obtain product.
The present embodiment obtains the cellulose acetate butyrate of butyryl radicals content 51%, acetyl content 3.4%, and product performance are stablized.
More than show and describe ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (7)
1. the cellulose acetate butyrate mixed ester of one kind high butyryl radicals content; it is characterized in that: comprise following composition: wood pulp 600 weight part, butyric acid 800 ~ 1200 weight part, butanoic anhydride 2500 ~ 3500 weight part, aceticanhydride 20 ~ 40 weight part, account for the concentrated sulfuric acid catalyst of wood pulp total weight parts 5 ~ 10%.
2. a cellulose acetate butyrate mixed ester preparation method for high butyryl radicals content according to claim 1, is characterized in that: specifically comprise the following steps:
(1) wood pulp of dosage part is first with 370 weight part butyric acid sprays, activates 12 ~ 15h under being then placed on 25 DEG C ~ 30 DEG C temperature;
(2) butanoic anhydride of the butyric acid of residual content and proportional quantity, aceticanhydride, concentrated sulfuric acid catalyst are mixed, and mixed solution is cooled to-15 DEG C ~ 20 DEG C stand-by;
(3) wood pulp after activation in step (1) is put into the cooling fluid of step (2) in 2 ~ 5min, abundant stirring, regulate the amount of cooling water of cooling fluid to control reaction temperature rise rate, make the temperature in final esterification system be no more than 55 DEG C, the reaction times is set to 60min ~ 180min;
(4) in the reaction system of step (3), add magnesium acetate solution, neutralize 40% ~ 60% concentrated sulfuric acid catalyst of proportional quantity; And then to add 1250 weight part concentration be that 60% ~ 70% acetum is hydrolyzed, hydrolysis temperature 60 ~ 70 DEG C, hydrolysis time 4 ~ 6h;
(5), after hydrolysis reaction terminates, continue to add excessive magnesium acetate solution until neutralize the concentrated sulfuric acid catalyst of residual content;
(6) material in step (5) mixture and water are carried out chromatography under abundant stirring state, then carry out conventional filtration successively, washing, baking step obtain finished product.
3. the cellulose acetate butyrate mixed ester preparation method of high butyryl radicals content according to claim 2, is characterized in that: the solid-liquid feed ratio in described step (3) controls in 1:5.5 ~ 7.5.
4. the cellulose acetate butyrate mixed ester preparation method of high butyryl radicals content according to claim 2, is characterized in that: described wood pulp is the wood pulp pulverized, the short flannel length≤1mm after pulverizing.
5. the cellulose acetate butyrate mixed ester preparation method of high butyryl radicals content according to claim 2, is characterized in that: liquid component butyryl radicals ratio >=99% in described step (3) reaction system.
6. the cellulose acetate butyrate mixed ester preparation method of high butyryl radicals content according to claim 2, is characterized in that: before the hydrolysis reaction of described step (3) starts, and controls the initial moisture content of reaction system 5% ~ 10%.
7. the cellulose acetate butyrate mixed ester preparation method of high butyryl radicals content according to claim 2, is characterized in that: gained cellulose acetate butyrate finished product butyryl radicals content 48% ~ 53% in described step (6).
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199002A (en) * | 2015-11-12 | 2015-12-30 | 江苏瑞晨化学有限公司 | Preparation method of cellulose acetate propionate mixed ester with high propionyl content |
| CN105254768A (en) * | 2015-11-12 | 2016-01-20 | 江苏瑞晨化学有限公司 | Preparation method of low-propionyl-content cellulose acetate propionate mixed ester |
| CN105440141A (en) * | 2015-11-12 | 2016-03-30 | 中山大桥化工集团有限公司 | Method for preparing acetyl butyryl cellulose |
| CN106632697A (en) * | 2016-12-16 | 2017-05-10 | 万华化学集团股份有限公司 | Preparation method of cellulose acetate butyrate with high butyryl content |
| CN106977610A (en) * | 2017-05-09 | 2017-07-25 | 江苏瑞晨化学有限公司 | A kind of method that dichloromethane solvent method prepares acetylbutyrylcellulose |
| CN107011448A (en) * | 2017-05-09 | 2017-08-04 | 江苏瑞晨化学有限公司 | A kind of preparation method of high viscosity cellulose acetate propionate |
| CN113788899A (en) * | 2021-09-07 | 2021-12-14 | 万华化学集团股份有限公司 | Method for removing sulfate radical in cellulose acetate butyrate reaction solution through ultrasonic crystallization and application of method |
| CN113956364A (en) * | 2021-11-05 | 2022-01-21 | 江苏瑞佳新材料有限公司 | Preparation method of cellulose acetate butyrate |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199002A (en) * | 2015-11-12 | 2015-12-30 | 江苏瑞晨化学有限公司 | Preparation method of cellulose acetate propionate mixed ester with high propionyl content |
| CN105254768A (en) * | 2015-11-12 | 2016-01-20 | 江苏瑞晨化学有限公司 | Preparation method of low-propionyl-content cellulose acetate propionate mixed ester |
| CN105440141A (en) * | 2015-11-12 | 2016-03-30 | 中山大桥化工集团有限公司 | Method for preparing acetyl butyryl cellulose |
| CN105440141B (en) * | 2015-11-12 | 2018-01-09 | 中山大桥化工集团有限公司 | A kind of preparation method of acetyl group bytyry cellulose |
| CN106632697A (en) * | 2016-12-16 | 2017-05-10 | 万华化学集团股份有限公司 | Preparation method of cellulose acetate butyrate with high butyryl content |
| CN106632697B (en) * | 2016-12-16 | 2019-01-29 | 万华化学集团股份有限公司 | A method of preparing the acetylbutyrylcellulose of high bytyry content |
| CN106977610A (en) * | 2017-05-09 | 2017-07-25 | 江苏瑞晨化学有限公司 | A kind of method that dichloromethane solvent method prepares acetylbutyrylcellulose |
| CN107011448A (en) * | 2017-05-09 | 2017-08-04 | 江苏瑞晨化学有限公司 | A kind of preparation method of high viscosity cellulose acetate propionate |
| CN113788899A (en) * | 2021-09-07 | 2021-12-14 | 万华化学集团股份有限公司 | Method for removing sulfate radical in cellulose acetate butyrate reaction solution through ultrasonic crystallization and application of method |
| CN113956364A (en) * | 2021-11-05 | 2022-01-21 | 江苏瑞佳新材料有限公司 | Preparation method of cellulose acetate butyrate |
| CN113956364B (en) * | 2021-11-05 | 2022-08-09 | 江苏瑞佳新材料有限公司 | Preparation method of cellulose acetate butyrate |
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Application publication date: 20150225 |