WO2019198307A1 - Procédé de production d'acétate de cellulose - Google Patents

Procédé de production d'acétate de cellulose Download PDF

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WO2019198307A1
WO2019198307A1 PCT/JP2019/003063 JP2019003063W WO2019198307A1 WO 2019198307 A1 WO2019198307 A1 WO 2019198307A1 JP 2019003063 W JP2019003063 W JP 2019003063W WO 2019198307 A1 WO2019198307 A1 WO 2019198307A1
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cellulose acetate
solution
weight
mixture
acetic acid
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PCT/JP2019/003063
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Japanese (ja)
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修二 吉岡
周 島本
立瑞 潘
小健 劉
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株式会社ダイセル
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/22—Post-esterification treatments, including purification
    • C08B3/24—Hydrolysis or ripening

Definitions

  • the present invention relates to a method for producing cellulose acetate.
  • a general method for producing cellulose acetate is performed according to the following procedure. Pulp, linter, etc., which are cellulosic materials, are crushed, acetic acid with or without sulfuric acid catalyst is added, and cooled acetic acid, acetic anhydride, and sulfuric acid catalyst are added, and the temperature is measured by an external jacket with a kneader. While controlling, acetylation is performed (acetylation process).
  • cellulose acetate After obtaining fully trisubstituted cellulose acetate (primary cellulose acetate) by acetylation, drop the viscous primary cellulose acetate into the aging tank, add neutralizing agent such as magnesium acetate solution, and neutralize sulfuric acid with magnesium (Complete neutralization or partial neutralization)
  • neutralizing agent such as magnesium acetate solution
  • acetic anhydride is deactivated by moisture contained in magnesium acetate and hydrolyzed to obtain cellulose acetate having a desired degree of acetylation (aging step).
  • a large amount of water is added to the cellulose acetate (secondary cellulose acetate) to precipitate the cellulose acetate (precipitation step).
  • the precipitated cellulose acetate is separated into solid and liquid, washed (purification step), and dried to obtain cellulose acetate (drying step).
  • the above-mentioned general methods for producing cellulose acetate include so-called cellulose triacetate having a total degree of acetyl substitution of 2.8 to 3.0 and so-called diacetic acid having a total degree of acetyl substitution of 2.2 to 2.7. It can be applied to the production of cellulose (Cellulose diacetate). However, in cellulose monoacetate with a total degree of acetyl substitution of 0.6 to 1.4, cellulose acetate itself is water-soluble and swellable with water. Cannot be added to precipitate cellulose acetate, and the above precipitation, purification and drying steps cannot be employed.
  • cellulose monoacetate Those having a total degree of acetyl substitution of more than 1.4 and less than or equal to 1.6 are not strictly classified as cellulose monoacetate, but have a swellability to water similar to cellulose monoacetate, and are similar to cellulose monoacetate. Like cellulose acetate or cellulose diacetate, cellulose acetate cannot be precipitated by adding a large amount of water.
  • the following method is known as a method for producing cellulose acetate having a low substitution degree (low acetylation degree) (acetyl substitution degree of 0.4 to 1.1).
  • Patent Document 1 Patent Document 2.
  • (C) In the washing and neutralization step, the precipitated cellulose acetate is washed with an organic solvent (poor solvent) such as an alcohol such as methanol or a ketone such as acetone, or an organic solvent containing a basic substance. It is known to wash and neutralize with (poor solvent).
  • an organic solvent such as an alcohol such as methanol or a ketone such as acetone, or an organic solvent containing a basic substance. It is known to wash and neutralize with (poor solvent).
  • A As a catalyst in the hydrolysis step, sulfuric acid is mainly used. However, when the residual amount of sulfuric acid in the finally obtained cellulose acetate is large, the stability of the cellulose acetate as a product is inferior. Therefore, in order to obtain stability as a product of cellulose acetate, it is necessary to remove sulfuric acid by this (C) washing and neutralization step.
  • An object of the present invention is to provide a method for producing cellulose acetate that does not require cleaning treatment using an organic solvent and has reduced environmental burden.
  • the present invention includes a step of contacting the cellulose acetate mixture or solution with a strongly acidic cation exchange resin to hydrolyze the cellulose acetate to reduce the total degree of acetyl substitution, and the degree of acetyl total substitution by the hydrolysis.
  • the present invention relates to a method for producing cellulose acetate, which comprises a step of precipitating cellulose acetate having a reduced content.
  • the cellulose acetate mixture or solution may be prepared by mixing or dissolving cellulose acetate as a raw material in acetic acid or a solution containing acetic acid.
  • the cellulose acetate mixture or solution may be prepared by mixing or dissolving cellulose acetate as a raw material in a mixed solution containing acetic acid and water.
  • the method of bringing the cellulose acetate mixture or solution into contact with a strong acid cation exchange resin is a method in which the strong acid cation exchange resin is added to the cellulose acetate mixture or solution and stirred. It may be.
  • the method in which the cellulose acetate solution is brought into contact with a strong acid cation exchange resin may be a method in which the cellulose acetate solution is passed through a column packed with the strong acid cation exchange resin.
  • the cellulose acetate concentration of the cellulose acetate mixture or solution is 1% by weight or more and 15% by weight or less. Is preferred.
  • the weight / volume% is a value of weight / volume expressed in%, and the units of the weight and volume are g and mL, respectively.
  • the strong acid cation exchange resin is added to 100 parts by weight of the cellulose acetate in the cellulose acetate mixture or solution. It is preferable to add at least 500 parts by weight.
  • the cellulose acetate concentration of the cellulose acetate solution is preferably 1% by weight or more and 10% by weight or less.
  • the weight / volume% is a value of weight / volume expressed in%, and the units of the weight and volume are g and mL, respectively.
  • the total acetyl substitution degree of cellulose acetate in the cellulose acetate mixture or solution may be 1.7 or more and 2.9 or less.
  • the total acetyl substitution degree of cellulose acetate may be 0.3 or more and 1.6 or less by the hydrolysis.
  • the method for producing cellulose acetate of the present disclosure includes a step of hydrolyzing the cellulose acetate to reduce the total degree of acetyl substitution by bringing the cellulose acetate mixture or solution into contact with a strongly acidic cation exchange resin, and the hydrolysis It has the process of precipitating the cellulose acetate which reduced the acetyl total substitution degree by decomposition
  • Cellulose acetate mixture or solution The cellulose acetate mixture or solution used in the method for producing cellulose acetate of the present disclosure will be described.
  • the cellulose acetate mixture mainly refers to a swelling body (also referred to as slurry) of cellulose acetate. Swelling refers to a state in which cellulose acetate has increased in volume by absorbing liquid. Cellulose acetate mixtures are distinguished from cellulose acetate solutions.
  • the cellulose acetate mixture or solution may be prepared by mixing or dissolving cellulose acetate as a raw material in acetic acid or a solution containing acetic acid.
  • the cellulose acetate mixture or solution may be prepared by mixing or dissolving cellulose acetate as a raw material in a mixed solution containing acetic acid and water.
  • the cellulose acetate mixture can be made into a cellulose acetate solution, for example, by increasing the acetic acid concentration of the mixed solution.
  • the raw material cellulose acetate for example, medium to high-substituted cellulose acetate can be used.
  • the medium to high-substituted cellulose acetate refers to cellulose acetate having an acetyl total substitution degree of, for example, 1.7 to 3, preferably 2 to 3.
  • the total acetyl substitution degree of cellulose acetate in cellulose acetate as a raw material and cellulose acetate mixture or solution may be 1.7 or more and 3 or less, preferably 1.7 or more and 2.9 or less, preferably 2.2 or more and 2. 9 or less is more preferable, and 2.2 or more and 2.7 or less are more preferable. If it is less than 1.7, the production itself is difficult. If it exceeds 2.7, the solubility in a solvent becomes poor, and if it exceeds 2.9, the time required for the hydrolysis process becomes long.
  • the total acetyl substitution degree of cellulose acetate as a raw material is, for example, more than 2.56 and up to 2.9, it is preferable to mix or dissolve using acetic acid or a solution containing acetic acid. In this case as well, moisture can be added.
  • the total acetyl substitution degree of cellulose acetate as a raw material is, for example, 0.6 to 1.4 monoacetate, it is preferable to use a mixed solution containing acetic acid and water. If the total degree of acetyl substitution exceeds 1.4 and is 1.6 or less, gelation may occur depending on the amount of water added, but even in this case, hydrolysis may be caused by contacting a strongly acidic cation exchange resin. it can.
  • the cellulose acetate mixture or solution of the present disclosure can also be obtained by dissolving or dispersing cellulose acetate flakes.
  • whether it becomes a solution or a slurry cellulose acetate mixture depends on the concentration and amount of the acetic acid solution to be added.
  • Even cellulose acetate flakes dissolve in an acetic acid solvent having a high acetic acid concentration, and when the acetic acid concentration is lowered, a cellulose acetate mixture dispersed in a slurry is obtained.
  • the shape of cellulose acetate used as a raw material includes pellets, fibers, or flakes, but is not particularly limited.
  • the flake shape refers to a flaky shape that widely includes scaly, granular, and powdery shapes.
  • cellulose acetate as a raw material may be supplied as a solution (also referred to as a dope) dissolved in an acetic acid solution.
  • the reaction solution may be esterified by reacting cellulose with acetic anhydride in the presence of a catalyst.
  • the reaction solution may be a primary cellulose acetate solution.
  • secondary cellulose acetate prepared by adding an excessive amount of water or dilute acetic acid to the reaction solution to deactivate acetic anhydride and then hydrolyzing the primary cellulose acetate to a predetermined substitution degree. Good.
  • the raw cellulose acetate When the total acetyl substitution degree of the raw material cellulose acetate is high (for example, when the total acetyl substitution degree exceeds 2.56), the raw cellulose acetate is mixed or dissolved in a mixed solution containing acetic acid and water. However, when it takes a long time to mix or dissolve in acetic acid and water, cellulose acetate as a raw material may be dissolved in acetic acid in advance to prepare a cellulose acetate solution.
  • the amount of acetic acid is, for example, 50 parts by weight or more and 5000 parts by weight or less, preferably 100 parts by weight or more and 2000 parts by weight or less, more preferably 300 parts by weight or more and 1000 parts by weight or less with respect to 100 parts by weight of cellulose acetate as a raw material. It is. A concentration of acetic acid of 99% by weight or more can be used.
  • the amount of water is, for example, from 50 parts by weight to 2000 parts by weight, preferably from 100 parts by weight to 1000 parts by weight, and more preferably from 200 parts by weight to 700 parts by weight with respect to 100 parts by weight of cellulose acetate as a raw material. It is.
  • the cellulose acetate mixture or solution is prepared by, for example, diluting a reaction solution of cellulose acetate generated by acetylation of cellulose or a hydrolysis (deesterification) reaction solution obtained by hydrolyzing this reaction solution with water or dilute acetic acid. Can be obtained at In this case, whether it becomes a cellulose acetate mixture or a cellulose acetate solution is determined by the composition ratio of acetic acid and water as a solvent and the substitution degree of cellulose acetate.
  • a reaction solution of acetylated cellulose acetate (primary cellulose acetate) has a substitution degree of about 3, the acetic acid concentration of the added acetic acid solution is sufficiently high so that the solution state is maintained (cellulose acetate solution). It can also use for the hydrolysis process of this indication.
  • the amount of the acetic acid solution to be added is small and the concentration of the cellulose acetate is high, the cellulose acetate solution does not maintain the solution state and the cellulose acetate is precipitated in a slurry state. Even such a thing can use for the hydrolysis process of this indication.
  • the cellulose acetate flakes are mixed with acetic acid or acetic acid.
  • the step of mixing or dissolving can be omitted.
  • the reaction solution is a viscous liquid phase, but it can be adjusted to an appropriate concentration by adding acetic acid.
  • Water can be added to this solution with water or dilute acetic acid.
  • the solution state may be maintained, or precipitation of cellulose acetate may occur.
  • the present invention can be used in any of these systems. For example, it can be hydrolyzed even when a strongly acidic cation exchange resin is formed on a cellulose acetate precipitate.
  • an acid catalyst such as a sulfuric acid catalyst used in the acetylation step and hydrolysis step may remain. Even so, the present invention is applicable.
  • a cellulose acetate precipitate after the precipitation process and before the purification process can also be used.
  • the cellulose acetate reaction solution produces a precipitate (cellulose acetate).
  • this precipitate is washed (purified) with water, dilute acetic acid, etc., and dried to obtain cellulose acetate flakes. obtain.
  • a cellulose acetate mixture or a cellulose acetate solution can be obtained by dissolving or dispersing the precipitate in the precipitation step in an acetic acid solvent (a solution of acetic acid and water).
  • Mixing or dissolution is performed by combining and stirring each solution and cellulose acetate as a raw material in any case of acetic acid, a solution containing acetic acid, or a mixed solution containing acetic acid and water.
  • the temperature in the system at the time of stirring is, for example, 40 ° C. or higher and 97 ° C. or lower, preferably 70 ° C. or higher and 97 ° C. or lower, more preferably 90 ° C. or higher and 97 ° C. or higher. If the temperature is too low, it will take a long time in the hydrolysis process. If it is too high, the molecular weight of the produced cellulose acetate will be significantly reduced, and the reaction system must be a pressurized system, in other words, it must be reacted in a pressure vessel. There is.
  • the stirring time is, for example, 5 hours or more and 32 hours or less, 5 hours or more and 32 hours or less, and more preferably 24 hours or more and 32 hours or less. If the time is too short, dissolution or swelling (mixing) will be insufficient, and if it is too long, the molecular weight of cellulose acetate will decrease significantly.
  • an inert gas atmosphere such as a rare gas or nitrogen gas is used as a safety measure. It is preferable.
  • cellulose acetate having an acetyl total substitution degree of 2.27 to 2.56 or cellulose acetate having an acetyl total substitution degree below this range when cellulose acetate having an acetyl total substitution degree of 2.27 to 2.56 or cellulose acetate having an acetyl total substitution degree below this range is used, acetic acid and water are contained. It is easy to dissolve completely in the mixed solution. On the other hand, cellulose acetate having a total degree of acetyl substitution exceeding 2.56 and up to 3 cannot be completely dissolved in a mixed solution containing acetic acid and water, and tends to be a swollen slurry cellulose acetate mixture. .
  • Hydrolysis step In the hydrolysis step, the cellulose acetate mixture or solution is brought into contact with a strongly acidic cation exchange resin to hydrolyze the cellulose acetate and reduce its total acetyl substitution degree.
  • the strongly acidic cation exchange resin By using a strongly acidic cation exchange resin, there is no need to add sulfuric acid in the hydrolysis step, and there is no need to perform washing treatment using an organic solvent to remove the sulfuric acid. Besides simplifying the treatment, the strongly acidic cation exchange resin can be regenerated and reused, so that the environmental load can be reduced.
  • the strong acid cation exchange resin a resin in which the exchange group is a sulfone group is preferable.
  • a resin in which the exchange group is a sulfone group is preferable.
  • Amberlite (registered trademark) IR-120B, IR-124, 200CT, and 252 manufactured by Dow Chemical Company (sold by Organo Corporation) and DOWEX (registered by DOW Chemical Company) are registered. Trademarks) 50WX2 and 50WX8.
  • 50WX8 is preferable because of its high crosslink density and excellent thermal stability. If the degree of cross-linking is the same, a small particle size is preferable. Further, as the particle size, for example, a mesh size defined by JIS Z 8815: 1994 having a size of 100-200 can be used.
  • Examples of the method of bringing the cellulose acetate mixture or solution into contact with the strong acid cation exchange resin include, for example, a method of adding a strong acid cation exchange resin to the cellulose acetate mixture or solution and stirring, and a cellulose acetate solution containing a strong acid cation exchange resin. And flowing through a column packed with a cationic cation exchange resin.
  • the concentration of cellulose acetate in the cellulose acetate mixture or solution is not particularly limited as long as the cellulose acetate mixture or solution and the strong acid cation exchange resin can be stirred. Volume% or less is preferable and 5 weight / volume% or more and 10 weight / volume% or less are more preferable. If it is too high, stirring becomes difficult.
  • the cellulose acetate concentration in the cellulose acetate mixture may be determined by taking the volume containing the solid component contained in the cellulose acetate mixture (also referred to as swollen body or slurry) as the volume of the solution.
  • the cellulose acetate concentration of the cellulose acetate mixture is prepared by mixing solid cellulose acetate (for example, flakes) with a solvent
  • the weight of cellulose acetate (for example, flakes) used for preparation in advance and The total weight of the mixture can be determined and calculated as solid cellulose acetate / total weight of the mixture ⁇ 100 (% by weight).
  • the addition amount of the strongly acidic cation exchange resin is preferably 5 parts by weight or more and 500 parts by weight or less, more preferably 10 parts by weight or more and 350 parts by weight or less with respect to 100 parts by weight of cellulose acetate in the cellulose acetate mixture or solution. 10 to 300 parts by weight is more preferable, and 250 to 320 parts by weight is most preferable. If the addition amount is too small, the hydrolysis reaction is difficult to proceed. If the addition amount is too large, it is difficult to separate the strongly acidic cation exchange resin after the hydrolysis reaction.
  • the temperature in the system at the time of stirring may be, for example, 40 ° C. or more and 100 ° C. or less, preferably 70 ° C. or more and 100 ° C. or less, and more preferably 90 ° C. or more and 99 ° C. or less. If the temperature is too low, the reaction does not proceed, and if it is too high, the molecular weight tends to decrease. For example, adding a strongly acidic cation exchange resin to a cellulose acetate mixture or solution and stirring, the reaction vessel is heated in an oil bath and maintained in this temperature range.
  • the hydrolysis reaction time may be, for example, 8 hours to 32 hours, 16 hours to 24 hours, or about 24 hours. What is necessary is just to adjust a hydrolysis reaction time suitably with the desired acetyl total substitution degree.
  • the hydrolysis reaction time refers to the time from when the cellulose acetate mixture or solution is brought into contact with the strongly acidic cation exchange resin to set the reaction system to a predetermined temperature and immediately before the precipitation of cellulose acetate is started.
  • a method in which a strong acidic cation exchange resin is added and stirred can be preferably used.
  • the cellulose acetate solution may be brought into contact with a column packed with a strongly acidic cation exchange resin.
  • the cellulose acetate solution may be circulated through a column packed with a strongly acidic cation exchange resin. If the water in the reaction system decreases as the hydrolysis reaction proceeds, the hydrolysis reaction does not proceed easily. Moreover, when water runs out, it cannot hydrolyze. For this reason, water may be additionally replenished in the reaction system.
  • the concentration of cellulose acetate in the cellulose acetate solution is not particularly limited as long as it can be passed through the column, but is preferably 1% by weight to 10% by volume and preferably 3% by weight to 9% by volume. The following is more preferable, and 5% by weight to 8% by volume is more preferable. If the concentration is too low, the production efficiency becomes poor, and if it is too high, swelling and dissolution become difficult.
  • the amount of the strongly acidic cation exchange resin added to the column is preferably 1 part by weight or more and 500 parts by weight or less, more preferably 5 parts by weight or more and 400 parts by weight or less, with respect to 100 parts by weight of cellulose acetate in the cellulose acetate solution.
  • the amount is more preferably 10 parts by weight or more and 300 parts by weight or less. If the amount of the strongly acidic cation exchange resin is too small, the reaction efficiency becomes poor and the desired total degree of acetyl substitution cannot be obtained. On the other hand, if the amount is too large, the production cost increases.
  • the temperature of the cellulose acetate solution and the column when flowing the cellulose acetate solution through the column packed with the strongly acidic cation exchange resin may be, for example, 40 ° C. or more and 100 ° C. or less, and preferably 70 ° C. or more and 100 ° C. or less. 90 ° C. or higher and 99 ° C. or lower is more preferable. If the temperature is too low, the hydrolysis reaction will not proceed, and if it is too high, the molecular weight tends to decrease. For example, this temperature range can be maintained by circulating temperature-controlled oil through a jacketed column.
  • cellulose acetate solution When using a method in which a cellulose acetate solution is passed through a column packed with a strongly acidic cation exchange resin, it is preferable that the cellulose acetate solution is completely dissolved in a mixed solution containing acetic acid and water. This is to avoid clogging the column.
  • cellulose acetate having a reduced degree of acetyl total substitution by the hydrolysis is precipitated.
  • a cellulose acetate is precipitated by adding a poor solvent such as water or acetone to a mixture or solution of cellulose acetate having a reduced degree of total acetyl substitution.
  • a poor solvent such as water or acetone
  • acetone is preferable if the total acetyl substitution degree of cellulose acetate is 1.4 or less, and if it exceeds 1.4, it is preferable to use water.
  • cellulose acetate with reduced total acetyl substitution by hydrolysis According to the method for producing cellulose acetate of the present disclosure, cellulose acetate having a low degree of total acetyl substitution can be obtained.
  • the total degree of acetyl substitution (DS) of cellulose acetate is, for example, preferably from 0.3 to 1.6, more preferably from 0.4 to 1.5, and even more preferably from 0.6 to 1.4.
  • the total acetyl substitution degree is the sum of the respective acetyl average substitution degrees at the 2, 3, and 6 positions of the glucose ring of cellulose acetate.
  • Nutritional composition, livestock feed, lipid metabolism improving agent, prevention of inflammatory bowel disease and / or immune abnormality characterized by containing cellulose acetate having a total degree of acetyl substitution of 0.4 to 1.1 and / or Therapeutic agent, preventive and / or therapeutic agent for cancer, preventive and / or therapeutic agent for nonalcoholic steatohepatitis, prophylactic and / or therapeutic agent for obesity and / or diabetes, and preventive and / or hypercholesterolemia Therapeutic agent (Patent Document 2).
  • the total acetyl substitution degree of cellulose acetate can be measured by a known titration method in which cellulose acetate is dissolved in a suitable solvent according to the substitution degree and the substitution degree of cellulose acetate is obtained.
  • the total degree of acetyl substitution was determined by dissolving the hydroxyl group of cellulose acetate into fully derivatized cellulose acetate propionate (CAP) according to the method of Tezuka (Tetsuka, Carbondr. Res. 273, 83 (1995)), and then dissolving it in deuterated chloroform. , NMR ( 13 C-NMR or 1 H-NMR).
  • the total degree of acetyl substitution can be obtained by converting the degree of acetylation determined according to the measurement method of the degree of acetylation in ASTM: D-817-91 (testing method for cellulose acetate, etc.) by the following formula. This is the most common way of determining the total acetyl substitution degree of cellulose acetate.
  • DS 162.14 ⁇ AV ⁇ 0.01 / (60.052-42.037 ⁇ AV ⁇ 0.01)
  • DS Degree of total acetyl substitution AV: Degree of acetylation (%)
  • AV (degree of acetylation) (%) is calculated according to the following formula.
  • AV (%) (AB) ⁇ F ⁇ 1.201 / sample weight (g)
  • Example 1 A reaction vessel (capacity 300 mL) was equipped with a magnetic stirrer (with a heater), a condenser, and a thermometer. Nitrogen was introduced into the reaction vessel in order to perform nitrogen replacement in the reaction vessel, and nitrogen introduction was continued thereafter. Under nitrogen, 90 mL of glacial acetic acid, 40 mL of water (when calculated as the concentration of an acetic acid solution consisting of acetic acid and water: 69.2% by volume of acetic acid), and cellulose triacetate (produced by Daicel Corporation, acetyl total 10 g of substitution degree 2.87 and bound sulfuric acid amount 190 ppm) was added to obtain a mixture. The mixture was stirred. Stirring was continued at 70 ° C. for 5 hours.
  • the cellulose acetate concentration (CA concentration) in the cellulose acetate mixture (swelled product) is 7.7% by weight / volume.
  • cellulose acetate was hydrolyzed. Details are as follows. 1 g of Amberlite (registered trademark) IR-120B as a strongly acidic cation exchange resin (10 parts by weight with respect to 100 parts by weight of cellulose acetate) was added to the resulting mixture (swelled product) of cellulose acetate and stirred. A reaction mixture was obtained. The reaction mixture was then heated in an oil bath and maintained at 70 ⁇ 1 ° C. for 24 hours.
  • Amberlite registered trademark
  • IR-120B as a strongly acidic cation exchange resin
  • the precipitated cellulose acetate was filtered, washed with pure water, and collected as a wet cake.
  • Example 2 Except for adding 2 g (20 parts by weight to 100 parts by weight of cellulose acetate) of Amberlite (registered trademark) IR-120B as a strongly acidic cation exchange resin to the obtained mixture (swelled product) of cellulose acetate. In the same manner as in Example 1, cellulose acetate was obtained, and the total degree of acetyl substitution was measured. The results are shown in Table 1.
  • Example 3 Except for adding 5 g (50 parts by weight to 100 parts by weight of cellulose acetate) of Amberlite (registered trademark) IR-120B as a strongly acidic cation exchange resin to the obtained mixture (swelled product) of cellulose acetate. In the same manner as in Example 1, cellulose acetate was obtained, and the total degree of acetyl substitution was measured. The results are shown in Table 1.
  • Example 4 A reaction vessel (capacity 300 mL) was equipped with a magnetic stirrer (with a heater), a condenser, and a thermometer. Nitrogen was introduced into the reaction vessel in order to perform nitrogen replacement in the reaction vessel, and nitrogen introduction was continued thereafter. Under nitrogen, this reaction vessel was charged with 45 mL of glacial acetic acid, 20 mL of water (when calculated as the concentration of an acetic acid solution consisting of acetic acid and water: 69.2% by volume of acetic acid), and cellulose triacetate (produced by Daicel Corporation, acetyl total 5 g) was added to obtain a mixture. The mixture was stirred. Stirring was continued at 70 ° C. for 5 hours.
  • the cellulose acetate concentration (CA concentration) in the cellulose acetate mixture (swelled product) is 7.7% by weight / volume.
  • cellulose acetate was hydrolyzed. Details are as follows. 15 g of Amberlite (registered trademark) IR-120B as a strongly acidic cation exchange resin (300 parts by weight with respect to 100 parts by weight of cellulose acetate) was added to the mixture (swelled material) of cellulose acetate obtained, and the mixture was stirred. A reaction mixture was obtained. The reaction mixture was then heated in an oil bath and maintained at 40 ⁇ 1 ° C. for 24 hours.
  • Amberlite registered trademark
  • IR-120B as a strongly acidic cation exchange resin
  • the precipitated cellulose acetate was filtered, washed with pure water, and collected as a wet cake.
  • Example 5 Cellulose acetate was obtained in the same manner as in Example 4 except that the temperature during hydrolysis was 70 ⁇ 1 ° C., and the total degree of acetyl substitution was measured. The results are shown in Table 1.
  • Example 6 The hydrolysis temperature is maintained at 90 ⁇ 1 ° C. for 24 hours, and at each stage of 8 hours and 16 hours, 1 g of the reaction mixture is sampled and added to 25 mL of water to precipitate cellulose acetate. In the 24-hour stage, 1 g of the reaction mixture was sampled and added to 25 mL of acetone to precipitate cellulose acetate. The precipitated cellulose acetate at each stage of 8 hours and 16 hours was filtered and washed with pure water, and the precipitated cellulose acetate at the stage of 24 hours was filtered and washed with acetone. Cellulose acetate was obtained in the same manner as in Example 4 except that the above conditions were changed, and the total degree of acetyl substitution was measured. The results are shown in Table 1.
  • Example 7 A reaction vessel (capacity 300 mL) was equipped with a magnetic stirrer (with a heater), a condenser, and a thermometer. Nitrogen was introduced into the reaction vessel in order to perform nitrogen replacement in the reaction vessel, and nitrogen introduction was continued thereafter. Under nitrogen, 90 mL of glacial acetic acid, 40 mL of water (when calculated as the concentration of an acetic acid solution consisting of acetic acid and water: 69.2% by volume of acetic acid), and cellulose triacetate (produced by Daicel Corporation, acetyl total 10 g of substitution degree 2.87 and bound sulfuric acid amount 190 ppm) was added to obtain a mixture. The mixture was stirred. Stirring was continued at 70 ° C.
  • the cellulose acetate concentration (CA concentration) in the cellulose acetate mixture (swelled product) is 7.7% by weight / volume.
  • cellulose acetate was hydrolyzed. Details are as follows. 30 g of Dowex (registered trademark) 50WX2 as a strongly acidic cation exchange resin (300 parts by weight with respect to 100 parts by weight of cellulose acetate) was added to the resulting mixture (swelled product) of cellulose acetate, and the reaction mixture was stirred. did. The reaction mixture was then heated in an oil bath and maintained at 97 ⁇ 1 ° C. for 32 hours.
  • Dowex registered trademark
  • 50WX2 as a strongly acidic cation exchange resin
  • the precipitated cellulose acetate at the stage of 8 hours was filtered, washed with pure water, and recovered as a wet cake.
  • the precipitated cellulose acetate at each stage of 16 hours, 24 hours and 32 hours was filtered, washed with acetone and collected as a wet cake.
  • Example 8 Dowex® 50WX8 as a strongly acidic cation exchange resin, 1 g of reaction mixture is sampled and added to 25 mL of acetone to precipitate cellulose acetate, and the precipitated cellulose acetate in all stages is filtered and washed with acetone Then, cellulose acetate was obtained in the same manner as in Example 7 except that it was recovered as a wet cake, and the total degree of acetyl substitution was measured. The results are shown in Table 1.
  • Example 9 A reaction vessel (capacity 300 mL) was equipped with a magnetic stirrer (with a heater), a condenser, and a thermometer. Nitrogen was introduced into the reaction vessel in order to perform nitrogen replacement in the reaction vessel, and nitrogen introduction was continued thereafter. Under nitrogen, in this reaction vessel, 90 mL of glacial acetic acid, 40 mL of water (when calculated as the concentration of an acetic acid solution consisting of acetic acid and water: acetic acid is 69.2% by volume), and cellulose diacetate (produced by Daicel Corporation, acetyl total 10 g of a substitution degree of 2.44 and a combined sulfuric acid amount of 190 ppm were added to obtain a mixture. The mixture was stirred.
  • cellulose acetate was hydrolyzed. Details are as follows. 30 g of Dowex (registered trademark) 50WX2 as a strongly acidic cation exchange resin (300 parts by weight with respect to 100 parts by weight of cellulose acetate) was added to the resulting mixture (swelled product) of cellulose acetate, and the reaction mixture was stirred. did. The reaction mixture was then heated in an oil bath and maintained at 97 ⁇ 1 ° C. for 32 hours.
  • Dowex registered trademark
  • 50WX2 as a strongly acidic cation exchange resin
  • the precipitated cellulose acetate was filtered, washed with acetone, and collected as a wet cake.
  • a reaction vessel (capacity 300 mL) was equipped with a magnetic stirrer (with a heater), a condenser, and a thermometer. Nitrogen was introduced into the reaction vessel in order to perform nitrogen replacement in the reaction vessel, and nitrogen introduction was continued thereafter. Under nitrogen, in this reaction vessel, 90 mL of glacial acetic acid, 40 mL of water (when calculated as the concentration of an acetic acid solution consisting of acetic acid and water: acetic acid is 69.2% by volume), and cellulose diacetate (produced by Daicel Corporation, acetyl total 10 g of a substitution degree of 2.44 and a combined sulfuric acid amount of 190 ppm were added to obtain a mixture. The mixture was stirred.
  • reaction mixture was sampled at each stage of 0 hour (before addition of strong acid cation exchange resin), 8 hours, 16 hours, 24 hours, and 32 hours, and added to 25 mL of water to add acetic acid. Cellulose was precipitated.
  • the precipitated cellulose acetate was filtered, washed with water, and collected as a wet cake.

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  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

L'objectif de la présente invention est de fournir un procédé de production d'acétate de cellulose, ledit procédé supprimant la nécessité d'effectuer un processus de nettoyage à l'aide d'un solvant organique et réduisant l'impact environnemental. Le procédé de production d'acétate de cellulose comprend une étape d'hydrolyse d'acétate de cellulose et de réduction du degré total de substitution d'acétyle par la mise en contact d'un mélange ou d'une solution d'acétate de cellulose avec une résine échangeuse de cations fortement acide, et une étape de précipitation de l'acétate de cellulose dans laquelle le degré total de substitution d'acétyle a été réduit au moyen de l'hydrolyse.
PCT/JP2019/003063 2018-04-09 2019-01-30 Procédé de production d'acétate de cellulose WO2019198307A1 (fr)

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JPH07206773A (ja) * 1994-01-26 1995-08-08 Mitsubishi Chem Corp 乳酸エステルの製造方法
WO2014142166A1 (fr) * 2013-03-13 2014-09-18 株式会社ダイセル Acétocellulose faiblement substituée

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ATA43094A (de) * 1994-03-01 1995-04-15 Chemiefaser Lenzing Ag Verfahren zur herstellung cellulosischer formkörper, lösung eines tert. aminoxids und ihre aufarbeitung
CN100484960C (zh) * 2006-11-16 2009-05-06 泸州北方化学工业有限公司 高温酯化低温水解制备液晶用纤维素醋酸酯的方法
KR101048645B1 (ko) * 2008-05-19 2011-07-12 한국과학기술연구원 고체 산 촉매 및 이온성 액체를 이용한 셀룰로오스가수분해 방법
CN106832005A (zh) * 2017-03-07 2017-06-13 北京理工大学 低酯化度的醋酸纤维素酯的制备方法

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JPS51119088A (en) * 1975-04-11 1976-10-19 Asahi Chem Ind Co Ltd Method for preparing a low molecular weight cellulose ester
JPH07206773A (ja) * 1994-01-26 1995-08-08 Mitsubishi Chem Corp 乳酸エステルの製造方法
WO2014142166A1 (fr) * 2013-03-13 2014-09-18 株式会社ダイセル Acétocellulose faiblement substituée

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022085119A1 (fr) * 2020-10-21 2022-04-28 株式会社ダイセル Acétate de cellulose et composition d'acétate de cellulose
US11572457B2 (en) 2020-10-21 2023-02-07 Daicel Corporation Cellulose acetate and cellulose acetate composition

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