CN102153659B - Preparation method of cellulose acetate - Google Patents
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Abstract
The invention belongs to the field of high polymer chemistry, and relates to a preparation method of cellulose acetate. The product obtained by the method provided by the invention has the advantages of high degree of substitution and high viscosity. The method comprises the following steps: A. soaking 1 part by weight of cellulose with 8-20 parts by weight of glacial acetic acid at 20-60 DEG C; B. esterifying at 20-58 DEG C for 3-8 hours by adding 4-6 parts by weight of acetic anhydride and 0.005-0.05 part by weight of catalyst; C. adding 0.5-1.5 parts by weight of 60-80% acetic acid at 15-25 DEG C, and reacting until the content of acetic acid in the cellulose acetate reaches 60.5-62.5%; D. adding 1.1-1.5 parts by weight of 5-15% acetate water solution, and reacting at 20-50 DEG C for 1-3 hours; and E. filtering, settling and granulating. The product obtained according to the invention has the advantages of high degree of substitution (the content of acetic acid in the product is higher than or equal to 60.0%) and high viscosity (the falling ball viscosity is higher than or equal to 70 seconds). The method provided by the invention increases the consumption of acetates for neutralization, effectively removes sulfates and enhances the heat resistance of the cellulose triacetate film.
Description
Technical field
The invention belongs to technical field of polymer chemistry, particularly the preparation method of acetyl cellulose.
Background technology
Acetyl cellulose (Cellulose Acetate is called for short CA) is a kind of cellulose ester that is obtained by the acetylize of natural cellulose process, is extremely important cellulose organic ester.According to its degree of esterification, can be divided into a plurality of ranks.Zhi Huadu between 2～3, bonded acetic acid amount 48.5～58.8% be called the Cellulose diacetate ester; Mierocrystalline cellulose is by esterification fully, and its Zhi Huadu is 3, and bonded acetic acid amount is called cellulose triacetate (Tri-cellulose Acetate is called for short TCA) 60.0～62.5%.
As photographic material, the film of cellulose triacetate finds broad application.And, also applied to manufacturing liquid-crystal display or LCD because cellulose triacetate film has fabulous smoothness and optics anisotropic.On LCD device, cellulose triacetate thin film is as the protective membrane of polaroid or colour filter.This film requires: must need very high transparency and low-birefringence; It can not disturb polarized light like this, and simultaneously, it should have certain ventilation property for water vapour; The tackiness agent that with water is matrix like this is accumulated on the polarizer, and this film can make its evaporation.The thickness requirement of this film is very thin, is prone to film, thus require cellulose triacetate to have HV, and preferably cheap.
The acetyl cellulose industry of China is started late, and acetyl cellulose 85% leans on import in recent years.(application number: 200610138482): the method that high temperature esterification and low temperature hydrolysis prepares cellulose acetate for liquid crystal use is divided into five reactions step and carries out patent; Be Cellulose activation reaction, esterification, hydrolysis reaction, neutralization reaction, washing of precipitate, be specially:
1, with Glacial acetic acid min. 99.5 at 20～60 ℃ of following activation 0.5～3h, the mass ratio of Mierocrystalline cellulose and Glacial acetic acid min. 99.5 is 1: 5～20, Mierocrystalline cellulose refers to wood pulps, the cotton pulp dregs of rice, bamboo pulp, the material that content of cellulose such as purified cotton are abundant.
2, during esterification process, directly utilize acetic acid in the reactivation process as solvent, add catalyzer earlier, consumption is a Mierocrystalline cellulose 0.5%～5.0%, and catalyzer is meant 98% the sulfuric acid and the perchloric acid of high density.Add acetic anhydride again as reaction solution, make the abundant acetylize of Mierocrystalline cellulose, consumption is cellulosic 2～6 times.Esterification temperature is 20～58 ℃, esterification time 3～8h.Adopt lower temperature and less catalyzer to carry out esterification, help in esterification process, obtaining the FM of viscosity higher like this.
3, hydrolysis requires the esterifying liquid temperature to be lower than 25 ℃, and hydrolyzed solution is 60～80% acetic acid, and stir on the limit, and the limit slowly adds.Purpose is that excessive acetic anhydride is reacted away, and guarantees the homogeneity of FM.Mierocrystalline cellulose and hydrolyzed solution mass ratio are 1: 0.5～1.5.Hydrolysis time 0.5～2 hour, the acetic acid content that makes FM between 60.5～62.5%,
4, neutralization, purpose is catalyst sulfuric acid or perchloric acid are reacted away, and increases the thermostability of acetyl cellulose.Neutralizer is an acetate solution, and acetate is sodium-acetate or magnesium acetate.Concentration is 5～15%.The neutralizer add-on is cellulosic 0.3～1 times, requires the hydrolyzed solution limit to stir, and the limit slowly adds.
5, slaking, purpose are to obtain the uniform FM of substitution value.After the hydrolysis neutralization finishes, react 15～45min at normal temperatures.
6, filter precipitating.Purpose is with reacted slurries, cross filter out unreacted intact give birth to fiber and half a lifetime fiber, precipitating is that the acetyl cellulose precipitating that is dissolved in the acetic acid is come out.Method: with the reacting slurry after the slaking, through 60 orders～1000 purpose filtration units.Carry out precipitating with dilute acetic acid then, stir fast down, reacting slurry is joined in the dilute acetic acid solution.The concentration of dilute acetic acid is 5～30%.
7, granulation.Purpose is with the acetyl cellulose that separates out, and manufactures size identical small-particle or small pieces with tablets press and tabletting machine.What tablets press used is the rotation dicing machine of rotary cutter.What tabletting machine used is two roll calender.
The inventive point of this invention is under hot conditions, to carry out esterification can make the product replacement more even, and preparation cycle is short, and catalyzer H
2SO
4Consumption is less, can reduce the palliating degradation degree of product; Hydrolysis under coldcondition simultaneously makes reaction be easy to control, can prevent local hydrolysis, obtains acetylize product more uniformly.Problems such as but this method exists activation inhomogeneous, causes the product Zhi Huadu inhomogeneous, and Zhi Huadu is not high, and viscosity is not high.
Summary of the invention
Technical problem to be solved by this invention provides a kind of easy-operating, and the preparation method of the acetyl cellulose that the product transparency is high, turbidity is low realizes with the usage quantity that has increased neutralization procedure acetate through prolonging the slaking reaction time.
The preparation method of acetyl cellulose of the present invention comprises activation, esterification, hydrolysis, neutralization, slaking, filtration precipitating and granulation, specifically may further comprise the steps:
Under the A, 20～60 ℃, the Mierocrystalline cellulose of 1 weight part soaks with the Glacial acetic acid min. 99.5 of 8～20 weight parts;
B, in the solution that steps A obtains, add the catalyzer esterification of the acetic anhydride and 0.005～0.05 weight part of 4～6 weight parts; Esterification temperature is 20～58 ℃, esterification time 3～8h;
15～25 ℃ of the reaction solution controlled temperature that C, step B obtain add 60～80% (mass percent concentration) acetic acid of 0.5～1.5 weight part, react acetic acid content to FM 60.5～62.5%;
The acetate aqueous solution that adds 1.1～1.5 weight parts in the reaction solution of D, step C, the weight percent concentration of acetate aqueous solution are 5～15%, react 1～3h down at 20～50 ℃;
E, filtration, precipitating, granulation promptly get.
The steps A soak time is 0.5～3h.
The effect of step B acetic anhydride is a reaction solution, and catalyzer is meant the sulfuric acid of mass concentration 98% or 98% perchloric acid.
Step D acetate is sodium-acetate or magnesium acetate.
The said slurries that are filtered into of step e are crossed 60 orders～1000 mesh sieves.Said precipitating is to stir fast down, and slurries are joined in the dilute acetic acid solution, and the concentration of volume percent of dilute acetic acid is 5～30%.
Product acetic acid content >=60.0% that the present invention obtains, falling ball viscosity >=70 second full-bodied acetyl cellulose.Method of the present invention has increased the usage quantity of neutralization procedure acetate, can effectively remove the sulfuric ester in the cellulosetri-acetate, thereby improves the transparency of cellulose triacetate film.Prolonged the reaction times of maturation stage, can guarantee that the turbidity of FM is low.
Embodiment
L, under 20～60 ℃, the Mierocrystalline cellulose of l weight part soaks activation 0.5～3h with the Glacial acetic acid min. 99.5 of 8～20 weight parts, Mierocrystalline cellulose refers to wood pulps, the cotton pulp dregs of rice, bamboo pulp, the material that content of cellulose such as purified cotton are abundant.
2, during esterification process, directly utilize acetic acid in the reactivation process as solvent, add catalyzer earlier, consumption is 0.5～5.0% of a cellulose, and catalyzer is meant 98% sulfuric acid or 98% perchloric acid.Add acetic anhydride again as reaction solution, make the abundant acetylize of Mierocrystalline cellulose, consumption is 4～6 times of cellulose.Esterification temperature is 20～58 ℃, esterification time 3～8h.Adopt lower temperature and less catalyzer to carry out esterification, help in esterification process, obtaining the FM of viscosity higher like this.
3, hydrolysis requires 15～25 ℃ of esterifying liquid temperature, and hydrolyzed solution is 60～80% (mass percent concentration) acetic acid, and stir on the limit, and the limit slowly adds.Purpose is that excessive acetic anhydride is reacted away, and guarantees the homogeneity of FM.Mierocrystalline cellulose and hydrolyzed solution mass ratio are l:1.1～1.5.Hydrolysis time 0.5～2 hour, the acetic acid content that makes FM is between 60.5～62.5%.
4, neutralization, purpose is catalyst reaction is fallen, and increases the thermostability of acetyl cellulose.Neutralizer is an acetate solution, and the weight percent concentration of acetate aqueous solution is 5～15%.The neutralizer add-on is cellulosic 0.5～1.5 times, requires the hydrolyzed solution limit to stir, and the limit slowly adds.In with time 0.5～l hour.
5, slaking, purpose are to obtain the uniform FM of substitution value.After the hydrolysis neutralization finishes, react l～3h down at 20～50 ℃.
6, filter precipitating.Purpose is with reacted slurries, cross filter out unreacted intact give birth to fiber and half a lifetime fiber, precipitating is that the acetyl cellulose precipitating that is dissolved in the acetic acid is come out.Method: with the reacting slurry after the slaking, through 60 orders～1000 purpose filtration units.Carry out precipitating with dilute acetic acid then, stir fast down, reacting slurry is joined in the dilute acetic acid solution.The concentration of dilute acetic acid is 5～30%.
7, granulation.Purpose is with the acetyl cellulose that separates out, and manufactures size identical small-particle or small pieces with tablets press and tabletting machine.What tablets press used is the rotation dicing machine of rotary cutter.What tabletting machine used is two roll calender.
EXAMPLE l
At 40 ℃ of following activation lh, the weight ratio of Mierocrystalline cellulose and Glacial acetic acid min. 99.5 is l to the Mierocrystalline cellulose of l, l weight part with Glacial acetic acid min. 99.5: 10, and Mierocrystalline cellulose refers to wood pulps.
2, during esterification process, directly utilize acetic acid in the reactivation process as solvent, add 98% sulfuric acid earlier, consumption is 0.5% of a cellulose.Add acetic anhydride again as reaction solution, make the abundant acetylize of Mierocrystalline cellulose, consumption is cellulosic 4.5 times.Esterification temperature is 40 ℃, esterification time 3.5h.
3, hydrolysis requires 25 ℃ of esterifying liquid temperature, and hydrolyzed solution is 80% (mass percent concentration) acetic acid, and stir on the limit, and the limit slowly adds.Mierocrystalline cellulose and hydrolyzed solution weight ratio are 1: 1.Hydrolysis time 1.5 hours, the acetic acid content that makes FM when treating that temperature no longer changes, continue to add the sodium acetate aqueous solution of 1.3 weight parts 10% between 60.5-62.5%.After adding finishes, temperature of reaction is controlled at 30 ℃, continues reaction 1.5 hours.Slurries with reaction filter through 500 purpose strainers then, and the slurries after the filtration are passed in 10% the aqueous acetic acid and carry out precipitating, and the material after the precipitating cuts into dices with the rotary cutter tablets press, carries out compressing tablet with two roll calender.Wash at last, oven dry can obtain cellulose triacetate.
Product is detected through nucleus magnetic resonance, and through comparing with cellulosetri-acetate standard nucleus magnetic resonance figure, it is just the same to go out the peak position.Product is detected through ir spectra, prove that the synthetic sample is a cellulosetri-acetate.In infrared spectrum, can see having 1051 cm in the lower wave number scope
-1The characteristic peak of place's Mierocrystalline cellulose ehter bond, 1369cm
-1The place-CH
3Stretching vibration peak, 1235cm
-1C-O-C asymmetrical stretching vibration peak in the acetic ester at place is simultaneously at 1051,11 61cm
-1C-O-C asymmetrical stretching vibration peak in the new ester group has appearred in the place, receives peak position and shape and has proved it is cellulosetri-acetate.
Product is after chemical analysis detects, and it is 61.4% that acetic acid combines content.The falling ball viscosity of 14% triacetate fiber solution 78 seconds, substitution value 2.93, turbidity 11.4NTU, the transparency 98.2%.The solvent that adopts during determination of light transmittance is a methylene dichloride: methyl alcohol=9: 1 (volume ratio).
Embodiment 2:
1, at 35 ℃ of following activation 1.5h, the weight ratio of Mierocrystalline cellulose and Glacial acetic acid min. 99.5 is 1: 15 to the Mierocrystalline cellulose of 1 weight part with Glacial acetic acid min. 99.5, and Mierocrystalline cellulose refers to the cotton pulp dregs of rice.
2, during esterification process, directly utilize acetic acid in the reactivation process as solvent, add catalyzer earlier, consumption is 0.65% of a cellulose, and catalyzer is meant 98% sulfuric acid.Add acetic anhydride again as reaction solution, make the abundant acetylize of Mierocrystalline cellulose, consumption is cellulosic 4 times.Esterification temperature is 35 ℃, esterification time 4h.
3, hydrolysis requires 20 ℃ of esterifying liquid temperature, and hydrolyzed solution is 75% (mass percent concentration) acetic acid, and stir on the limit, and the limit slowly adds.Mierocrystalline cellulose and hydrolyzed solution weight ratio are 1: 1.2.Hydrolysis time 1.2 hours, the acetic acid content that makes FM when treating that temperature no longer changes, continue to add the sodium acetate aqueous solution of 1.2 weight parts 10% (wt%) between 60.5-62.5%.After adding finishes, temperature of reaction is controlled at 30 ℃, continues reaction 1.5 hours.Slurries with reaction filter through 800 purpose strainers then, and the slurries after the filtration are passed in 10% the aqueous acetic acid and carry out precipitating, and the material after the precipitating cuts into dices with the rotary cutter tablets press, carries out compressing tablet with two roll calender.Wash at last, oven dry can obtain cellulose triacetate.
Product is after chemical analysis detects, and it is 60.9% that acetic acid combines content.The falling ball viscosity of 14% triacetate fiber solution 83 seconds, substitution value 2.92, turbidity 11.3NTU, the transparency 98.8%.The solvent that adopts during determination of light transmittance is a methylene dichloride: methyl alcohol=9: 1 (volume ratio).
Embodiment 3:
1, at 55 ℃ of following activation 1.5h, the weight ratio of Mierocrystalline cellulose and Glacial acetic acid min. 99.5 is 1: 8 to the Mierocrystalline cellulose of 1 weight part with Glacial acetic acid min. 99.5, and Mierocrystalline cellulose refers to the cotton pulp dregs of rice.
2, during esterification process, directly utilize acetic acid in the reactivation process as solvent, add catalyzer earlier, consumption is 0.65% of a cellulose, and catalyzer is meant 98% sulfuric acid.Add acetic anhydride again as reaction solution, make the abundant acetylize of Mierocrystalline cellulose, consumption is cellulosic 6 times.Esterification temperature is 55 ℃, esterification time 3h.
3, hydrolysis requires 15 ℃ of esterifying liquid temperature, and hydrolyzed solution is 65% (mass percent concentration) acetic acid, and stir on the limit, and the limit slowly adds.Mierocrystalline cellulose and hydrolyzed solution weight ratio are 1: 1.1.Hydrolysis time 1.2 hours, the acetic acid content that makes FM when treating that temperature no longer changes, continue to add the sodium acetate aqueous solution of 1.1 weight parts 5% (wt%) between 60.5-62.5%.After adding finishes, temperature of reaction is controlled at 45 ℃, continues reaction 3 hours.Slurries with reaction filter through 800 purpose strainers then, and the slurries after the filtration are passed in 5% the aqueous acetic acid and carry out precipitating, and the material after the precipitating cuts into dices with the rotary cutter tablets press, carries out compressing tablet with two roll calender.Wash at last, oven dry can obtain cellulose triacetate.
Product is after chemical analysis detects, and it is 61.0% that acetic acid combines content.The falling ball viscosity of 14% triacetate fiber solution 84 seconds, substitution value 2.91, turbidity 11.5NTU, the transparency 98.7%.The solvent that adopts during determination of light transmittance is a methylene dichloride: methyl alcohol=9: 1 (volume ratio).
Embodiment 4:
1, at 35 ℃ of following activation 1.5h, the weight ratio of Mierocrystalline cellulose and Glacial acetic acid min. 99.5 is 1: 12 to the Mierocrystalline cellulose of 1 weight part with Glacial acetic acid min. 99.5, and Mierocrystalline cellulose refers to the cotton pulp dregs of rice.
2, during esterification process, directly utilize acetic acid in the reactivation process as solvent, add catalyzer earlier, consumption is 5% of a cellulose, and catalyzer is meant 98% sulfuric acid.Add acetic anhydride again as reaction solution, make the abundant acetylize of Mierocrystalline cellulose, consumption is cellulosic 5 times.Esterification temperature is 25 ℃, esterification time 8h.
3, hydrolysis requires 22 ℃ of esterifying liquid temperature, and hydrolyzed solution is 78% (mass percent concentration) acetic acid, and stir on the limit, and the limit slowly adds.Mierocrystalline cellulose and hydrolyzed solution weight ratio are 1: 1.5.Hydrolysis time 1.5 hours, the acetic acid content that makes FM when treating that temperature no longer changes, continue to add the sodium acetate aqueous solution of 1.5 weight parts 15% (wt%) between 60.5-62.5%.After adding finishes, temperature of reaction is controlled at 30 ℃, continues reaction 1.5 hours.Slurries with reaction filter through 800 purpose strainers then, and the slurries after the filtration are passed in 30% the aqueous acetic acid and carry out precipitating, and the material after the precipitating cuts into dices with the rotary cutter tablets press, carries out compressing tablet with two roll calender.Wash at last, oven dry can obtain cellulose triacetate.
Product is after chemical analysis detects, and it is 61.1% that acetic acid combines content.The falling ball viscosity of 14% triacetate fiber solution 85 seconds, substitution value 2.92, turbidity 11.1NTU, the transparency 98.7%.The solvent that adopts during determination of light transmittance is a methylene dichloride: methyl alcohol=9: 1 (volume ratio).
Comparative Examples:
The polymerization degree adds 200 parts in Glacial acetic acid min. 99.5, at 40 ℃ of following activation 1h 100 parts of 705 pulverizing gossypins in 15min.Activation finishes, and reaction system is cooled to 10 ℃, keeps 30min, adds Glacial acetic acid min. 99.5, acetic anhydride, sulfuric acid mixture.Said mixture is 300 parts of Glacial acetic acid min. 99.5,260 parts of acetic anhydride, 3 parts of sulfuric acid mixing back sealings, is cooled to below 10 ℃, keeps 1h to process.The reinforced reaction 15min that finishes is warming up to 75 ℃ of reaction 30min, and the TRT is 1h, is cooled to 50 ℃, keeps 15min.With the mixture heating up to 50 of 3 parts in sulfuric acid, 25 parts in water, 25 parts of compositions of Glacial acetic acid min. 99.5 ℃, add previous reaction liquid simultaneously, reaction 2h adds the magnesium acetate aqueous solution, continues reaction 30min.Stir the acetic acid precipitating of pouring 20 times of volumes down into, filter and obtain throw out, be washed till neutrality, be drying to obtain.It is 59.9% that the acetic acid of product combines content; The falling ball viscosity of 14% triacetate fiber solution 54 seconds, substitution value 2.85, turbidity 30.4NTU, the transparency 96.5%.The solvent that adopts during determination of light transmittance is a methylene dichloride: methyl alcohol=9: 1).
Claims (6)
1. the preparation method of acetyl cellulose is characterized in that: may further comprise the steps:
Under the A, 20～60 ℃, the Mierocrystalline cellulose of 1 weight part soaks with the Glacial acetic acid min. 99.5 of 8～20 weight parts;
B, in the solution that steps A obtains, add the catalyzer esterification of the acetic anhydride and 0.005～0.05 weight part of 4～6 weight parts; Esterification temperature is 20～58 ℃, esterification time 3～8h;
15～25 ℃ of the reaction solution controlled temperature that C, step B obtain add 60～80% acetic acid of 0.5～1.5 weight part, react acetic acid content to FM 60.5～62.5%;
The acetate aqueous solution that adds 1.1～1.5 weight parts in the reaction solution of D, step C, acetate aqueous solution concentration are 5～15%, react 1～3h down at 20～50 ℃;
E, filtration, precipitating, granulation promptly get.
2. the preparation method of acetyl cellulose according to claim 1, it is characterized in that: the steps A soak time is 0.5～3h.
3. the preparation method of acetyl cellulose according to claim 1, it is characterized in that: step B catalyzer is meant the sulfuric acid of mass concentration 98% or 98% perchloric acid.
4. the preparation method of acetyl cellulose according to claim 1, it is characterized in that: step D acetate is sodium-acetate or magnesium acetate.
5. the preparation method of acetyl cellulose according to claim 1, it is characterized in that: the said slurries that are filtered into of step e are crossed 60 orders～1000 mesh sieves.
6. the preparation method of acetyl cellulose according to claim 1 is characterized in that: the said precipitating of step e joins slurries in the dilute acetic acid solution for stirring down fast, and the concentration of volume percent of dilute acetic acid is 5～30%.
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| CN103709254B (en) * | 2013-12-20 | 2014-09-10 | 江苏瑞晨化学有限公司 | Preparation method of medium-viscosity cellulose acetate butyrate |
| CN106317229A (en) * | 2016-08-22 | 2017-01-11 | 四川北方硝化棉股份有限公司 | Production method for preparing low-substituted cellulose acetate |
| CN107286258B (en) * | 2017-07-27 | 2018-08-10 | 四川普什醋酸纤维素有限责任公司 | Triafol T and preparation method thereof |
| CN108383915B (en) * | 2018-01-25 | 2021-02-19 | 南通醋酸纤维有限公司 | Method for preparing cellulose acetate |
| CN109721660B (en) * | 2019-01-22 | 2021-07-30 | 南通醋酸纤维有限公司 | Method for preparing cellulose acetate by high-temperature acetification process |
| CN112795993B (en) * | 2020-12-30 | 2022-05-10 | 温州市四通制笔零件有限公司 | Antibacterial and anti-mildew fiber pen point and preparation method thereof |
| CN114075299B (en) * | 2022-01-04 | 2022-08-09 | 江苏瑞佳新材料有限公司 | Cellulose triacetate and preparation method thereof |
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| JP3974058B2 (en) * | 2003-03-11 | 2007-09-12 | ダイセル化学工業株式会社 | Method for preparing mixed fatty acid ester solution of cellulose and method for producing mixed fatty acid ester film of cellulose |
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