CN105254768A - Preparation method of low-propionyl-content cellulose acetate propionate mixed ester - Google Patents
Preparation method of low-propionyl-content cellulose acetate propionate mixed ester Download PDFInfo
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- CN105254768A CN105254768A CN201510768983.8A CN201510768983A CN105254768A CN 105254768 A CN105254768 A CN 105254768A CN 201510768983 A CN201510768983 A CN 201510768983A CN 105254768 A CN105254768 A CN 105254768A
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- cellulose acetate
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- acetate propionate
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- mixed ester
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Abstract
The invention relates to a preparation method of low-propionyl-content cellulose acetate propionate mixed ester. Cellulose is prepared from, by weight, 650 g of wood pulp, 296 g of propionic acid, 2250 g of acetic acid, 118 g of acetic anhydride, 2070 g of propionic anhydride and 19.5-52 g of catalysts. The ratio of liquid acid catalysts to heteropolyacid catalyst is between 4 to 6 and 6 to 4. The preparation method includes the steps of conducting activating, the esterification reaction, mixing, magnesium acetate solution adding, hydrolysis and chromatography, sequentially conducting conventional filtering, washing and drying, and obtaining the finished product. The method has the advantages that the propionyl content of the obtained cellulose acetate propionate finished product is 15-20%, and the acetyl content is smaller than 22-30%; the mixture of liquid acid and heteropolyacid is selected for the catalysts, and therefore the sulfuric acid consumption is lowered, the corrosion to a technological device and the pollution to the environment can be reduced, and technological safety is improved; meanwhile, by adding heteropolyacid, the esterification reaction is accelerated, and the hydrolysis reaction is more precise and controllable.
Description
Technical field
The invention belongs to cellulose ester analog derivative field, particularly the high propionyl content of one
The preparation method of cellulose acetate propionate mixed ester.
Background technology
Cellulose acetate propionate (being called for short CAP) is a kind of cellulose organic ester obtained through esterification by Mierocrystalline cellulose, aceticanhydride and propionic anhydride.CAP has excellent toughness, thermostability and consistency, is widely used in the industry such as auto parts, tool holder, receiving set and television components, bearing circle, film, filter membrane, wireless transistor, toy, Wall or floor tile, coating, spinning.
In current domestic production cellulose acetate propionate, propionyl content is relatively unstable; Chinese Patent Application No. is: the preparation method that patent discloses a kind of cellulose acetate propionate of 201110009701.8; the method take Mierocrystalline cellulose as raw material; after diacetyl oxide and the activation of propionic anhydride mixed solution; add acetic acid and propionic acid solvent, solid super acid catalyst carry out esterification; esterification terminates rear Filtration of catalyst; add waste acid water to be hydrolyzed; carry out precipitating with waste acid water again, obtain cellulose acetate propionate finally by filtration, washing, drying and other steps.This simple in production process operation, but the Mierocrystalline cellulose efficiency of producing is low, and temperature of reaction is high, and the reaction times is longer.
Chinese Patent Application No. is: the preparation method that patent discloses a kind of allied fiber element organic acid acetic cellulose acetate butyrate of 201410651086.4, this preparation method comprises activation, esterification, mixes, adds magnesium acetate solution, hydrolysis, chromatography, then carries out conventional filtration successively, washing, baking step obtain finished product.The cellulose acetate butyrate butyryl radicals content that the method is prepared into is higher, but there is following problem: 1. use the vitriol oil for catalyzer in this preparation method, have very strong corrodibility, and use the vitriol oil in a large number, pollute the environment to processing unit; 2. reaction time of esterification is longer, and hydrolysis reaction controls accurate not; 3. step of reaction need be cooled by external jacket, makes production cost higher.
In addition, some specific chemical fields can use low propionyl content cellulose acetate propionate mixed ester at present, but it is rarely found to produce low propionyl content cellulose acetate propionate mixed ester at present.
Summary of the invention
The technical problem to be solved in the present invention is to provide one can reduce environmental pollution, increases process safety and the system of the low propionyl content cellulose acetate propionate mixed ester of acceleration esterification
Preparation Method.
For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of preparation method of low propionyl content cellulose acetate propionate mixed ester, and its innovative point is: specifically comprise the following steps:
(1) wood pulp 650g, propionic acid 296g, acetic acid 2250g, aceticanhydride 118g, propionic anhydride 2070g, catalyzer 19.5g ~ 52g is weighed, described catalyzer is the mixture of liquid acid catalyst and heteropolyacid catalyst, and wherein the ratio of liquid acid catalyst and heteropolyacid catalyst is 4:6 ~ 6:4;
(2) wood pulp of 650g is first sprayed with the acetic acid of 325g ~ 1300g, under being then placed on 25 DEG C ~ 35 DEG C temperature, activate 0.5h ~ 3h;
(3) propionic acid of remaining acetic acid and proportional quantity, propionic anhydride, aceticanhydride, catalyzer are mixed, and mixed solution is cooled to-10 DEG C ~ 15 DEG C stand-by;
(4) the solid wood pulp after step (2) being activated puts into step in 5min ~ 8min
Suddenly the cooling fluid of (3), fully stirs, and without the need to exterior cooling, reaction nature heats up, and make the temperature in final esterification system be no more than 50 DEG C, the reaction times is set to 90min ~ 120min;
(5) in the reaction system of step (4), add 45g ~ 50g magnesium acetate solution, neutralize the catalyzer that proportional quantity is 40% ~ 60%; And then to add 2kg concentration be that 60% ~ 70% acetum is hydrolyzed, hydrolysis temperature 70 DEG C ~ 85 DEG C, hydrolysis time 2h ~ 6h;
(6), after hydrolysis reaction terminates, continue to add magnesium acetate solution until neutralize the catalyzer of residual content;
(7) material in mixture in step (6) and water are carried out chromatography under abundant stirring state, then carry out conventional filtration, washing, baking step obtain finished product.
Further, described liquid acid catalyst is any one in sulfuric acid or phosphoric acid, and heteropolyacid catalyst is H
3pW
12o
40or H
4siW
12o
40in any one.
Further, the wood pulp in described step (4) and the feed ratio of cooling fluid control in 1:7 ~ 13.
Further, described step (4) esterification system controls liquid component propionyl ratio between 50% ~ 60%.
Further, the temperature of described step (7) chromatography is 30 DEG C ~ 50 DEG C, and to control after chromatography in final liquid phase acetic acid amount between 15% ~ 35%.
Further, described step (7) is washed, and controls the pH of washing water between 6 ~ 7.
The invention has the advantages that:
(1) by the preparation side of the present invention's low propionyl content cellulose acetate propionate mixed ester
Method, gained cellulose acetate propionate finished product propionyl content is 15% ~ 20%, and acetyl content is less than 22% ~ 30%, and product performance are stablized.
(2) preparation method of the present invention's low propionyl content cellulose acetate propionate mixed ester, the mixture of what catalyzer was selected is liquid acid and heteropolyacid, like this, decreases the consumption of sulfuric acid, and then the corrosion that can reduce processing unit and environmental pollution, increase process safety; Meanwhile, increase the application of heteropolyacid, thus accelerate esterification, make hydrolysis reaction more accurate, controlled.
(3) preparation method of the present invention's low propionyl content cellulose acetate propionate mixed ester, step of reaction is without the need to exterior cooling, and reaction nature heats up, thus reduces production cost.
(4) preparation method of height propionyl content cellulose acetate propionate mixed ester of the present invention, activation temperature is arranged on 25 DEG C ~ 35 DEG C, temperature of reaction system is arranged on and is not more than 50 DEG C, ensures that reaction is carried out at optimum conditions, thus accelerates reaction efficiency.
(5) in method of the present invention, esterification system controls liquid component propionyl ratio between 50% ~ 60%, ensures that propionyl content is between 15% ~ 20%.
(6), in method of the present invention, after controlling chromatography, in final liquid phase, acetic acid amount, between 15% ~ 35%, is to make product easily separate out shaping.
Embodiment
The following examples can make the present invention of professional and technical personnel's comprehend, but therefore do not limit the present invention among described scope of embodiments.
embodiment 1
The preparation method of the present embodiment low propionyl content cellulose acetate propionate mixed ester, specifically comprises the following steps:
(1) weigh wood pulp 650g, propionic acid 296g, acetic acid 2250g, aceticanhydride 118g, propionic anhydride 2070g, catalyzer 19.5g, catalyzer is the mixture of liquid acid catalyst and heteropolyacid catalyst, wherein liquid acid catalyst sulfuric acid 3.8g, heteropolyacid catalyst H
3pW
12o
4011.7g;
(2) wood pulp of 650g is first sprayed with the acetic acid of 325g, under being then placed on 25 DEG C of temperature, activate 0.5h;
(3) propionic acid of remaining acetic acid and proportional quantity, propionic anhydride, aceticanhydride, catalyzer are mixed, and mixed solution is cooled to-10 DEG C stand-by;
(4) cooling fluid of step (3) put into by the solid wood pulp after step (2) being activated in 5min, fully stirs, and without the need to exterior cooling, reaction nature heats up, and make the temperature in final esterification system be no more than 50 DEG C, the reaction times is set to 90min;
(5) in the reaction system of step (4), add 45g magnesium acetate solution, neutralize the catalyzer that proportional quantity is 40%; And then to add 2kg concentration be that 60% acetum is hydrolyzed, hydrolysis temperature 70 DEG C, hydrolysis time 2h;
(6), after hydrolysis reaction terminates, continue to add magnesium acetate solution until neutralize the catalyzer of residual content;
(7) material in mixture in step (6) and water are carried out chromatography under abundant stirring state, then carry out conventional filtration, washing, baking step obtain finished product.
embodiment 2
The preparation method of the present embodiment low propionyl content cellulose acetate propionate mixed ester, specifically comprises the following steps:
(1) weigh wood pulp 650g, propionic acid 296g, acetic acid 2250g, aceticanhydride 118g, propionic anhydride 2070g, catalyzer 52g, catalyzer is the mixture of liquid acid catalyst and heteropolyacid catalyst, wherein liquid acid catalyst phosphoric acid 31.2g, heteropolyacid catalyst H
3pW
12o
4020.8g;
(2) wood pulp of 650g is first sprayed with the acetic acid of 1300g, under being then placed on 35 DEG C of temperature, activate 3h;
(3) propionic acid of remaining acetic acid and proportional quantity, propionic anhydride, aceticanhydride, catalyzer are mixed, and mixed solution is cooled to 5 DEG C stand-by;
(4) cooling fluid of step (3) put into by the solid wood pulp after step (2) being activated in 8min, fully stirs, and without the need to exterior cooling, reaction nature heats up, and make the temperature in final esterification system be no more than 50 DEG C, the reaction times is set to 120min;
(5) in the reaction system of step (4), add 50g magnesium acetate solution, neutralize the catalyzer that proportional quantity is 60%; And then to add 2kg concentration be that 70% acetum is hydrolyzed, hydrolysis temperature 85 DEG C, hydrolysis time 6h;
(6), after hydrolysis reaction terminates, continue to add magnesium acetate solution until neutralize the catalyzer of residual content;
(7) material in mixture in step (6) and water are carried out chromatography under abundant stirring state, then carry out conventional filtration, washing, baking step obtain finished product.
embodiment 3
The preparation method of the present embodiment low propionyl content cellulose acetate propionate mixed ester, specifically comprises the following steps:
(1) weigh wood pulp 650g, propionic acid 296g, acetic acid 2250g, aceticanhydride 118g, propionic anhydride 2070g, catalyzer 36g, catalyzer is the mixture of liquid acid catalyst and heteropolyacid catalyst, wherein liquid acid catalyst sulfuric acid 18g, heteropolyacid catalyst H
3pW
12o
4018g;
(2) wood pulp of 650g is first sprayed with the acetic acid of 650g, under being then placed on 30 DEG C of temperature, activate 2h;
(3) propionic acid of remaining acetic acid and proportional quantity, propionic anhydride, aceticanhydride, catalyzer are mixed, and mixed solution is cooled to 5 DEG C stand-by;
(4) cooling fluid of step (3) put into by the solid wood pulp after step (2) being activated in 6min, fully stirs, and without the need to exterior cooling, reaction nature heats up, and make the temperature in final esterification system be no more than 50 DEG C, the reaction times is set to 105min;
(5) in the reaction system of step (4), add 48g magnesium acetate solution, neutralize the catalyzer that proportional quantity is 50%; And then to add 2kg concentration be that 65% acetum is hydrolyzed, hydrolysis temperature 80 DEG C, hydrolysis time 4h;
(6), after hydrolysis reaction terminates, continue to add magnesium acetate solution until neutralize the catalyzer of residual content;
(7) material in mixture in step (6) and water are carried out chromatography under abundant stirring state, then carry out conventional filtration, washing, baking step obtain finished product.
Following table is the contrast of the product that embodiment 1 ~ 3 low propionyl content cellulose acetate propionate mixed ester preparation method and traditional cellulose acetate propionate preparation method obtain:
| Product | Embodiment 1 | Embodiment 2 | Embodiment 3 | Traditional method |
| Propionyl content | 16.7% | 16.3% | 17.2% | 24.6% |
| Acetyl content | 24% | 24.2% | 23.8% | 28.9% |
Conclusion: traditional preparation method, when gained cellulose acetate propionate finished product propionyl content is minimum, is also greater than 20%, and the present invention to obtain cellulose acetate propionate finished product propionyl content be 15% ~ 20%, acetyl content is less than 22% ~ 30%, and product performance are stablized.
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 (6)
1. a preparation method for high propionyl content cellulose acetate propionate mixed ester, is characterized in that: specifically comprise the following steps:
(1) wood pulp 650g, propionic acid 296g, acetic acid 2250g, aceticanhydride 118g, propionic anhydride 2070g, catalyzer 19.5g ~ 52g is weighed, described catalyzer is the mixture of liquid acid catalyst and heteropolyacid catalyst, and wherein the ratio of liquid acid catalyst and heteropolyacid catalyst is 4:6 ~ 6:4;
(2) wood pulp of 650g is first sprayed with the acetic acid of 325g ~ 1300g, under being then placed on 25 DEG C ~ 35 DEG C temperature, activate 0.5h ~ 3h;
(3) propionic acid of remaining acetic acid and proportional quantity, propionic anhydride, aceticanhydride, catalyzer are mixed, and mixed solution is cooled to-10 DEG C ~ 15 DEG C stand-by;
Solid wood pulp after step (2) being activated puts into step in 5min ~ 8min
Suddenly the cooling fluid of (3), fully stirs, and without the need to exterior cooling, reaction nature heats up, and make the temperature in final esterification system be no more than 50 DEG C, the reaction times is set to 90min ~ 120min;
(5) in the reaction system of step (4), add 45g ~ 50g magnesium acetate solution, neutralize the catalyzer that proportional quantity is 40% ~ 60%; And then to add 2kg concentration be that 60% ~ 70% acetum is hydrolyzed, hydrolysis temperature 70 DEG C ~ 85 DEG C, hydrolysis time 2h ~ 6h;
(6), after hydrolysis reaction terminates, continue to add magnesium acetate solution until neutralize the catalyzer of residual content;
(7) material in mixture in step (6) and water are carried out chromatography under abundant stirring state, then carry out conventional filtration, washing, baking step obtain finished product.
2. the preparation method of low propionyl content cellulose acetate propionate mixed ester according to claim 1, is characterized in that: described liquid acid catalyst is any one in sulfuric acid or phosphoric acid, and heteropolyacid catalyst is H
3pW
12o
40or H
4siW
12o
40in any one.
3. the preparation method of low propionyl content cellulose acetate propionate mixed ester according to claim 1, is characterized in that: the wood pulp in described step (4) and the feed ratio of cooling fluid control in 1:7 ~ 13.
4. the preparation method of high propionyl content cellulose acetate propionate mixed ester according to claim 1, is characterized in that: described step (4) esterification system controls liquid component propionyl ratio between 50% ~ 60%.
5. the preparation method of high propionyl content cellulose acetate propionate mixed ester according to claim 1, is characterized in that: the temperature of described step (7) chromatography is 30 DEG C ~ 50 DEG C, and to control after chromatography in final liquid phase acetic acid amount between 15% ~ 35%.
6. the preparation method of high propionyl content cellulose acetate propionate mixed ester according to claim 1, is characterized in that: described step (7) is washed, and controls the pH of washing water between 6 ~ 7.
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| CN109400719A (en) * | 2018-09-28 | 2019-03-01 | 江苏瑞佳新材料有限公司 | The preparation method of cellulose acetate propionate |
| CN111205372A (en) * | 2020-03-18 | 2020-05-29 | 北京化工大学 | Preparation method of cellulose acetate propionate |
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Application publication date: 20160120 |