CN110357972A - The manufacturing method of cellulose acetate - Google Patents
The manufacturing method of cellulose acetate Download PDFInfo
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- CN110357972A CN110357972A CN201810310416.1A CN201810310416A CN110357972A CN 110357972 A CN110357972 A CN 110357972A CN 201810310416 A CN201810310416 A CN 201810310416A CN 110357972 A CN110357972 A CN 110357972A
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- cellulose acetate
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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
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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
- C08B3/22—Post-esterification treatments, including purification
- C08B3/24—Hydrolysis or ripening
Abstract
The object of the present invention is to provide a kind of cleaning treatments for not needing to carry out having used organic solvent, the manufacturing method for the cellulose acetate for reducing environmental pressure.The manufacturing method of above-mentioned cellulose acetate is with the following process: by contacting cellulose acetate mixture or solution with storng-acid cation exchange resin, to above-mentioned cellulose acetate be hydrolyzed, the process for reducing the total degree of substitution of its acetyl group；And make the process for the cellulose acetate precipitating that the total degree of substitution of acetyl group is reduced by above-mentioned hydrolysis.
Description
Technical field
The present invention relates to the manufacturing methods of cellulose acetate.
Background technique
The manufacturing method of common cellulose acetate is carried out according to following step.By the paper that will be used as cellulosic material
Slurry, velveteen etc. crush and add the pretreatment procedure of the acetic acid with or without sulfuric acid catalyst, add acetic acid after cooling, second
Acid anhydrides and sulfuric acid catalyst control temperature using outer sleeve in kneader, and carry out acetylation (acetylation process).It is logical
After acetylation has obtained complete three substituted acetic acids cellulose (cellulose acetate), a sticky cellulose acetate is thrown
Enter digester, the neutralizers such as addition magnesium acetate solution neutralize (complete neutralization or part neutralize) sulfuric acid using magnesium, while utilizing second
The moisture contained in sour magnesium inactivates acetic anhydride, makes its hydrolysis, obtains cellulose acetate (the curing work of desired degree of acetylation
Sequence).The a large amount of moisture of addition in the cellulose acetate (secondary cellulose acetate), makes cellulose acetate precipitate (precipitator
Sequence).The cellulose acetate of precipitating is separated by solid-liquid separation and is cleaned (purification procedures), makes it dry and obtains cellulose acetate
(drying process).
It is 2.8~3.0 that the manufacturing method of above-mentioned common cellulose acetate, which can be applied to the total degree of substitution of acetyl group,
So-called cellulose triacetate (Cellulose triacetate), the so-called diethyl that the total degree of substitution of acetyl group is 2.2~2.7
The manufacture of acid cellulose (Cellulose diacetate).However, the acetic acid that degree of substitution total for acetyl group is 0.6~1.4
For cellulose (Cellulose monoacetate), due to cellulose acetate itself generate it is water-soluble, to the swellability of water,
Therefore a large amount of moisture cannot be added into secondary cellulose acetate precipitate cellulose acetate, cannot use above-mentioned precipitating
Process, purification procedures and drying process.Strictly speaking greater than 1.4 and 1.6 cellulose acetates below the total degree of substitution of acetyl group is
Be not belonging to the classification of a cellulose acetate, but have with similar in a cellulose acetate to the swellability of water, with an acetate fiber
Element similarly cannot add a large amount of moisture precipitate cellulose acetate as cellulose triacetate, cellulose diacetate.
The manufacture of cellulose acetate as low degree of substitution (low degree of acetylation) (the total degree of substitution of acetyl group is 0.4~1.1)
Method, it is known that following method.By hydrolyzing process (curing step), (B) of degree of substitution in (A) to high substituted degree cellulose acetate
Precipitation process and (C) that carries out as needed cleaning and neutralization step and obtain cellulose acetate method (patent document 1,
Patent document 2).
In (A) hydrolyzing process, in organic solvent, in the presence of catalyst (curing catalyst), make raw acetic acid fiber
Element reacts with water.As the catalyst of the reaction, sulfuric acid is mainly used.If it is the acid other than sulfuric acid, then at least water
The acid of dissolubility, does not otherwise show catalytic action.(B) in precipitation process, acetone etc. is added into reaction system and is mixed with water
Organic solvent or precipitate cellulose acetate the big organic solvent of the solubility of water.
Additionally, it is known that with the organic solvents such as the ketone such as the alcohol such as methanol, acetone (poor solvent) in (C) cleaning and neutralization step
Cleaning precipitating after cellulose acetate, in addition with the organic solvent (poor solvent) containing alkaline matter clean and neutralization precipitation after
Cellulose acetate.As the catalyst in (A) hydrolyzing process, sulfuric acid is mainly used, but in finally obtained cellulose acetate
Sulfuric acid residual quantity it is more when, the bad stability of the product as cellulose acetate.Therefore, in order to obtain as cellulose acetate
The stability of product, needs to clean by (C) and neutralization step removes sulfuric acid.
Existing technical literature
Patent document
Patent document 1: International Publication No. 2014/142166
Patent document 2: International Publication No. 2015/146853
Summary of the invention
Subject to be solved by the invention
However, need a large amount of organic solvent to remove sulfuric acid, there are recovery and rinsing, treated that organic solvent carries out
The hidden danger for recycling processing and causing environmental pressure big.In addition, the second due to carrying out the recycling and recycling processing, as product
The manufacturing cost of acid cellulose also increases.
The object of the present invention is to provide a kind of cleaning treatment for not needing to carry out having used organic solvent, reduce ring
The manufacturing method of the cellulose acetate of border burden.
The method to solve the problem
The present invention relates to the manufacturing method of cellulose acetate, this method is with the following process: by keeping cellulose acetate mixed
It closes object or solution is contacted with storng-acid cation exchange resin, so that above-mentioned cellulose acetate be hydrolyzed, make its acetyl group
The process that total degree of substitution reduces；And make the cellulose acetate precipitating that the total degree of substitution of acetyl group is reduced by above-mentioned hydrolysis
Process.
In the manufacturing method of above-mentioned cellulose acetate, above-mentioned cellulose acetate mixture or solution can be by by conducts
The cellulose acetate of raw material mixes or is dissolved in acetic acid or solution containing acetic acid and prepares.
In the manufacturing method of above-mentioned cellulose acetate, above-mentioned cellulose acetate mixture or solution can be by by conducts
The cellulose acetate of raw material mixes or is dissolved in the mixed solution containing acetic acid and water and prepares.
In the manufacturing method of above-mentioned cellulose acetate, make above-mentioned cellulose acetate mixture or solution and highly acid sun from
The method of sub-exchange resin contact, which can be, adds above-mentioned highly acidic cation in above-mentioned cellulose acetate mixture or solution
Exchanger resin and the method being stirred.
In the manufacturing method of above-mentioned cellulose acetate, make above-mentioned cellulose acetate solution and strongly acidic cation exchange tree
The method of rouge contact can be the column for flowing through above-mentioned cellulose acetate solution filled with above-mentioned storng-acid cation exchange resin
Method.
Above-mentioned storng-acid cation exchange resin is added in above-mentioned cellulose acetate mixture or solution and is stirred
Method in, the cellulose acetate concentration of above-mentioned cellulose acetate mixture or solution is preferably 1 weight/volume % or more and 15
Weight/volume % is hereinafter, above-mentioned weight/volume % is with the unit of the value of the % weight/volume indicated, above-mentioned weight and volume
Respectively g and mL.
Above-mentioned storng-acid cation exchange resin is added in above-mentioned cellulose acetate mixture or solution and is stirred
Method in, relative to 100 parts by weight of above-mentioned cellulose acetate in above-mentioned cellulose acetate mixture or solution, preferably add
More than 5 parts by weight and 500 parts by weight above-mentioned storng-acid cation exchange resin below.
In the method for making above-mentioned cellulose acetate solution flow through the column filled with above-mentioned storng-acid cation exchange resin,
The cellulose acetate concentration of above-mentioned cellulose acetate solution be preferably 1 weight/volume % or more and 10 weight/volume % hereinafter,
Above-mentioned weight/volume % is with the value of the % weight/volume indicated, and the unit of above-mentioned weight and volume is respectively g and mL.
Cellulose acetate in the manufacturing method of above-mentioned cellulose acetate, in above-mentioned cellulose acetate mixture or solution
The total degree of substitution of acetyl group can be 1.7 or more and 2.9 or less.
In the manufacturing method of above-mentioned cellulose acetate, the acetyl group of cellulose acetate can be made always to take by above-mentioned hydrolysis
Dai Du is 0.3 or more and 1.6 or less.
The effect of invention
According to the present invention it is possible to provide a kind of cleaning treatment for not needing to carry out having used organic solvent, reduce environment
The manufacturing method of the cellulose acetate of burden.
Detailed description of the invention
Fig. 1 is the chart for showing an example of relationship of hydrolysis time and the total degree of substitution of acetyl group.
Specific embodiment
Hereinafter, an example to preferred embodiment is specifically described.
The manufacturing method of cellulose acetate of the invention is with the following process: by making cellulose acetate mixture or solution
It is contacted with storng-acid cation exchange resin, so that above-mentioned cellulose acetate be hydrolyzed, makes the total degree of substitution drop of its acetyl group
Low process；And make the process for the cellulose acetate precipitating that the total degree of substitution of acetyl group is reduced by above-mentioned hydrolysis.
(cellulose acetate mixture or solution)
Cellulose acetate mixture or solution used in manufacturing method to cellulose acetate of the invention are illustrated.
It is swelling body (also referred to as starching) that cellulose acetate mixture, which is primarily referred to as cellulose acetate,.In addition, swelling refers to second
The acid cellulose state that volume increases due to absorbing liquid.Cellulose acetate mixture is distinguished with cellulose acetate solution.
Cellulose acetate mixture or solution can be by will be used as the cellulose acetate of raw material to mix or be dissolved in acetic acid
Or solution containing acetic acid and prepare.
In addition, above-mentioned cellulose acetate mixture or solution can be mixed or molten by that will be used as the cellulose acetate of raw material
Mixed solution that Xie Yu contains acetic acid and water and prepare.
Cellulose acetate solution can be made for example, by increasing the acetic acid concentration of mixed liquor in cellulose acetate mixture.
The cellulose acetate of middle degree of substitution to high substituted degree can be used for example in cellulose acetate as raw material.Here,
The cellulose acetate of middle degree of substitution to high substituted degree refers to that the total degree of substitution of acetyl group is that such as 1.7 or more and 3 acetic acid below are fine
Dimension element, preferably 2 or more and 3 cellulose acetates below.
Acetyl group as the cellulose acetate in the cellulose acetate and cellulose acetate mixture or solution of raw material is total
Degree of substitution can be 1.7 or more and 3 hereinafter, preferably 1.7 or more and 2.9 hereinafter, more preferably 2.2 or more and 2.9 hereinafter, into
One step is preferably 2.2 or more and 2.7 or less.When being lower than 1.7, its own is difficult to manufacture, when more than 2.7, to the molten of solvent
Solution property is deteriorated, in addition, process the time it takes of hydrolysis increases when more than 2.9.
It is, for example, the situation for being greater than 2.56 and 2.9 or less in the total degree of substitution of the acetyl group of the cellulose acetate as raw material
Down, it is preferable to use acetic acid or the solution containing acetic acid are mixed or dissolved.The situation can also add moisture.
In the cellulose acetate that the total degree of substitution of the acetyl group of the cellulose acetate as raw material is, for example, 0.6~1.4
In the case of, it is preferable to use the mixed solution containing acetic acid and water.It is fine that the total degree of substitution of acetyl group is greater than 1.4 and 1.6 acetic acid below
The gelation with the additive amount of moisture when dimension is known as, in such a case it is possible to by being contacted with storng-acid cation exchange resin
And it hydrolyzes.
In addition, cellulose acetate mixture of the invention or solution can be and dissolving or dispersing acetyl cellulose sheet
It obtains.In this case, the cellulose acetate mixture that solution is still slurried is made and depends on the acetic acid solution added
Concentration and amount.Even acetyl cellulose sheet is also dissolvable in water the high acetic acid solvent of acetic acid concentration, when acetic acid concentration reduces,
It can be made into the cellulose acetate mixture for being separated into pulpous state.
The shape of cellulose acetate as raw material can be enumerated: graininess, threadiness or flake do not limit especially
It is fixed.It should be noted that it includes flakey, granular, powdery laminar shape that flake refers to extensively.
In addition, the cellulose acetate as raw material can be to be dissolved in the form of the solution (also referred to as coating) of acetic acid solution
Supply.In such a case it is possible to be make cellulose and acetic anhydride in the presence of a catalyst, be esterified obtained from react
Solution.In addition, above-mentioned reaction solution can be the solution of a cellulose acetate.Alternatively, it is also possible to being to above-mentioned reaction solution
The water or acetic acid diluted of excessive addition and inactivate acetic anhydride, on this basis hydrolyze a cellulose acetate and be adjusted to given
Degree of substitution obtained from secondary cellulose acetate.
In the case where the total degree of substitution of the acetyl group of the cellulose acetate as raw material is high (for example, the total degree of substitution of acetyl group
In the case where 2.56), the cellulose acetate as raw material can be mixed or to be dissolved in the mixing containing acetic acid and water molten
Liquid, but under the mixing or the prolonged situation of dissolution needs in acetic acid and water, it can be in advance by the acetate fiber as raw material
Element is dissolved in acetic acid to prepare the solution of cellulose acetate.
Relative to 100 parts by weight of cellulose acetate as raw material, the amount of acetic acid is, for example, 50 parts by weight or more and 5000
Parts by weight hereinafter, it is more than preferably 100 parts by weight and 2000 parts by weight hereinafter, it is more than further preferably 300 parts by weight and
Below 1000 parts by weight.The acetic acid that acetic acid concentration is 99 weight % or more can be used.
Relative to 100 parts by weight of cellulose acetate as raw material, the amount of water is, for example, 50 parts by weight or more and 2000 weights
Part is measured hereinafter, more than preferably 100 parts by weight and 1000 parts by weight are hereinafter, more than further preferably 200 parts by weight and 700 weights
Measure part or less.
Cellulose acetate mixture or solution can for example pass through the acetyl of cellulose by being diluted with water or acetic acid diluted etc.
Change and generate cellulose acetate reaction solution and by the reaction solution hydrolysis obtained from hydrolysis (de- ester) reaction it is molten
Liquid and obtain.In this case, be made cellulose acetate mixture, be also formed into cellulose acetate solution according to acetic acid in solvent with
The degree of substitution of the ratio of components of water and cellulose acetate determines.For example, the reaction solution (one of the cellulose acetate due to acetylation
Secondary cellulose acetate) degree of substitution be about 3, therefore, can by keep the acetic acid concentration of acetic acid solution to be added sufficiently high from
And to keep the form of solution state (cellulose acetate solution) for hydrolyzing process of the invention.On the other hand, to be added
Acetic acid solution amount is few, in highly concentrated situation of cellulose acetate, cellulose acetate solution cannot keep solution state, second
Acid cellulose is settled into pulpous state.Such substance also can be for hydrolyzing process of the invention.
By contacting the reaction solution of a cellulose acetate with storng-acid cation exchange resin to above-mentioned
In the case that cellulose acetate is hydrolyzed, reduces the total degree of substitution of its acetyl group, it is convenient to omit by the thin slice of cellulose acetate
The process for mixing or being dissolved in acetic acid or the solution containing acetic acid.
In order to be hydrolyzed, the reaction solution of cellulose acetate or the reaction solution of secondary cellulose acetate are required to
Water.Therefore, the feelings of acetic acid have been used in the reaction solution of the reaction solution of cellulose acetate or secondary cellulose acetate
Under condition, in order to be hydrolyzed to desired degree of substitution, need to add required moisture.
Reaction solution is sticky liquid phase, can add acetic acid to be adjusted to concentration appropriate.Water or dilute second can be passed through
Acid adds moisture to the solution.When adding moisture according to the concentration of the cellulose acetate in amount of moisture and liquid phase to be added, deposit
The case where keeping solution state, there is also generate cellulose acetate precipitating the case where.These systems can be used in the present invention
Any one of.For example, having been carried out at storng-acid cation exchange resin in the system to the precipitating for generating cellulose acetate
In the case where reason, its hydrolysis can also be made.
It should be noted that the reaction in the reaction solution or secondary cellulose acetate of an above-mentioned cellulose acetate is molten
In liquid, remain the acid catalysts such as sulfuric acid catalyst used in acetylation process and hydrolyzing process sometimes, but in this case
It also can be using the present invention.
In addition, in the manufacturing process of existing cellulose acetate of the invention, also can be used after precipitation process and
The sediment of cellulose acetate before purification procedures.In this case, in precipitation process, the reaction solution of cellulose acetate
It generates sediment (cellulose acetate), if it is common process, then cleans (purifying) sediment with water, acetic acid diluted etc., into
Row drying, obtains acetyl cellulose sheet.It in the present invention, can be by being dissolved or dispersed in the sediment in precipitation process
Acetic acid solvent (solution of acetic acid and water) obtains cellulose acetate mixture, cellulose acetate solution.
Under the either case of acetic acid or the solution containing acetic acid or the mixed solution containing acetic acid and water, mixing or
Dissolution can be carried out by merging each solution with the cellulose acetate as raw material to be stirred.In system when stirring
Temperature be, for example, 40 DEG C or more and 97 DEG C hereinafter, preferably 70 DEG C or more and 97 DEG C hereinafter, more preferably 90 DEG C or more and 97
DEG C or more.When temperature is too low, hydrolyzing process needs for a long time, when the temperature is excessively high, the molecular weight of the cellulose acetate of generation
Reduction becomes significantly, to need for reaction system to be set as pressurized systems, in other words, needs to make its reaction in pressure vessel.
In addition, as its mixing time, for example, 5 hours or more and 32 hours hereinafter, for 5 hours or more and 32 hours with
Under, further preferably 24 hours or more and 32 hours or less.When time is too short, dissolution or swelling (mixing) are become inadequate,
When overlong time, the molecular weight reduction of cellulose acetate becomes significant.
The cellulose acetate for being used as raw material is being mixed or be dissolved in acetic acid or solution containing acetic acid or is containing acetic acid
And water mixed solution when, from the aspect of safety measure, be preferably set to the non-active gas atmosphere such as rare gas, nitrogen.
In middle degree of substitution into high substituted degree cellulose acetate, in the second for the use of the total degree of substitution of acetyl group being 2.27~2.56
When the cellulose acetate of acid cellulose or the total degree of substitution of range acetyl group below, be easy to be dissolved completely in containing acetic acid and
The mixed solution of water.On the other hand, the total degree of substitution of acetyl group is greater than 2.56 and can not be complete for the cellulose acetate of 3 ranges below
Fully dissolved easily becomes the pulpous state cellulose acetate mixture being swollen in the mixed solution containing acetic acid and water.
(hydrolyzing process)
In hydrolyzing process, by contacting cellulose acetate mixture or solution with storng-acid cation exchange resin,
To which above-mentioned cellulose acetate be hydrolyzed, reduce the total degree of substitution of its acetyl group.
It by using storng-acid cation exchange resin, does not need to add sulfuric acid in hydrolyzing process, not need to remove
It removes sulfuric acid and used the cleaning treatment of organic solvent, the processing after not only precipitating cellulose acetate becomes simply, and
And storng-acid cation exchange resin can be regenerated and be reused, therefore environmental pressure can be reduced.
As storng-acid cation exchange resin, preferably cation exchange groups are sulfonic resin.It can specifically enumerate for example:
Dow Chemical company manufactures AMBERLITE (registered trademark) IR-120B, IR-124, the 200CT of (ORGANO (strain) sale)
And DOWEX (registered trademark) 50WX2 and 50WX8 etc. of 252 and Dow Chemical company manufacture.Wherein, from crosslink density
From the viewpoint of high, excellent heat stability, preferably 50WX8.If the degree of cross linking is identical, the small person of preferable particle size.In addition, as upper
Partial size is stated, the resin that mesh size specified in JIS Z 8815:1994 is 100-200 can be used for example.
As the method for contacting cellulose acetate mixture or solution with storng-acid cation exchange resin, can enumerate
Such as: in cellulose acetate mixture or solution add storng-acid cation exchange resin and the method that is stirred and
Cellulose acetate solution is set to flow through method of the column filled with storng-acid cation exchange resin etc..
To the method adding storng-acid cation exchange resin in cellulose acetate mixture or solution and being stirred
It is described in detail.
In the method, as long as the cellulose acetate concentration in cellulose acetate mixture or solution can stir acetic acid fibre
Tie up plain mixture or solution and storng-acid cation exchange resin, be not particularly limited, preferably 1 weight/volume % with
Upper and 15 weight/volume % are hereinafter, more preferably 5 weight/volume % or more and 10 weight/volume % or less.When excessive concentration,
Stirring becomes difficult.
For the cellulose acetate concentration in cellulose acetate mixture, will comprising cellulose acetate mixture (
Referred to as swelling body or slurry) contained by the volume of solid component cellulose acetate concentration is found out as the volume of solution.
It should be noted that for the cellulose acetate concentration of cellulose acetate mixture, by the acetic acid of solid
Cellulose (such as flake) is mixed with solvent prepared in the case where, it is fine that the acetic acid used in preparation can be found out in advance
The weight of dimension element (such as flake) and the weight of mixture totality, with the cellulose acetate of solid/mixture totality weight
The form of × 100 (weight %) is calculated.In addition, cellulose and acetic anhydride is made to carry out ester in the presence of using catalyst
In the case where reaction solution obtained from change etc., budgetary estimate can be carried out according to used cellulose amount is reacted.
In addition, relative to 100 parts by weight of cellulose acetate in cellulose acetate mixture or solution, highly acidic cation
The additive amount of exchanger resin is preferably 5 parts by weight or more and 500 parts by weight hereinafter, more than more preferably 10 parts by weight and 350 weights
Part is measured hereinafter, more than further preferably 10 parts by weight and 300 parts by weight are hereinafter, more than most preferably 250 parts by weight and 320 weights
Measure part or less.When additive amount is very few, hydrolysis is difficult to carry out, when additive amount is excessive, it is difficult to the strong acid after filtering off hydrolysis
Property cation exchange resin.
The temperature in system when stirring for example can be for 40 DEG C or more and 100 DEG C hereinafter, preferably 70 DEG C or more and 100
DEG C hereinafter, further preferably 90 DEG C or more and 99 DEG C or less.When temperature is too low, reaction becomes without when the temperature is excessively high, dividing
Son amount is easily reduced.It can be cited for example that adding storng-acid cation exchange resin in cellulose acetate mixture or solution
And it is stirred, while with oil bath heating reaction vessel, being maintained at the temperature range.
Hydrolysis time for example can be for 8 hours or more and 32 hours hereinafter, can be 16 hours or more and 24 hours
Hereinafter, can be 24 hours or so.It can be according to the total degree of substitution of desired acetyl group come appropriate adjustment hydrolysis time.This
In, hydrolysis time refers to, contact cellulose acetate mixture or solution with storng-acid cation exchange resin and will be anti-
The time that cellulose acetate precipitates will extremely be started by answering system to be set as given temperature.
The case where cellulose acetate is dissolved completely in the mixed solution containing acetic acid and water before hydrolysis and acetic acid
Under the either case for the case where cellulose is not completely dissolved and forms the paste mixture being swollen, can it be preferably used in anti-
Answer the method adding storng-acid cation exchange resin in system and being stirred.
Next, being carried out to the method for making cellulose acetate solution flow through the column filled with storng-acid cation exchange resin
It is described in detail.As long as contacting cellulose acetate solution with the column filled with storng-acid cation exchange resin.For example, can
So that cellulose acetate solution recycles in the column filled with storng-acid cation exchange resin.If with hydrolysis into
It goes, the water in reaction system is reduced, then hydrolysis becomes difficult to carry out.In addition, can not be hydrolyzed if water is finished.
Therefore, water can be added into reaction system to be supplemented.
In the method, as long as the cellulose acetate concentration in cellulose acetate solution can flow through column, without spy
It does not limit, preferably 1 weight/volume % or more and 10 weight/volume % are hereinafter, more preferably 3 weight/volume % or more and 9
Weight/volume % is hereinafter, further preferably 5 weight/volume % or more and 8 weight/volume % or less.It is raw when concentration is too low
Deterioration of efficiency is produced, when excessive concentration, it is difficult to be swollen, be dissolved.
Relative to 100 parts by weight of cellulose acetate in cellulose acetate solution, the highly acidic cation added in column is handed over
The amount for changing resin be preferably 1 parts by weight or more and 500 parts by weight hereinafter, it is more than more preferably 5 parts by weight and 400 parts by weight with
Under, more than further preferably 10 parts by weight and below 300 parts by weight.When the amount of storng-acid cation exchange resin is very few, instead
Deterioration of efficiency is answered, the total degree of substitution of desired acetyl group can not be obtained, on the other hand, the amount of storng-acid cation exchange resin is excessive
When, the production cost increases.
Cellulose acetate solution when cellulose acetate solution being made to flow through the column filled with storng-acid cation exchange resin
And the temperature of the column for example can be for 40 DEG C or more and 100 DEG C hereinafter, preferably 70 DEG C or more and 100 DEG C hereinafter, further excellent
It is selected as 90 DEG C or more and 99 DEG C or less.When temperature is too low, hydrolysis becomes without when the temperature is excessively high, molecular weight is easy drop
It is low.For example, the temperature range can be kept by making the oily circulation etc. in the column with casing for having adjusted temperature.
The case where making cellulose acetate solution flow through the method for the column filled with storng-acid cation exchange resin
Under, cellulose acetate solution is preferably completely dissolved in the mixed solution containing acetic acid and water.This is in order to avoid column blocking.
(precipitation process)
In precipitation process, make the cellulose acetate precipitating that the total degree of substitution of acetyl group is reduced by above-mentioned hydrolysis.For example,
The poor solvents such as water, acetone are added in the mixture or solution of cellulose acetate for reducing the total degree of substitution of acetyl group, make second
Acid cellulose precipitating.Generally, when the total degree of substitution of the acetyl group of cellulose acetate is 1.4 or less, it is preferable to use acetone, is surpassing
, it is preferable to use water when 1.4.
(any process)
It is preferred that being cleaned to cellulose acetate obtained in (B) precipitation process.Water can be used to carry out in cleaning.Separately
Outside, the organic solvents such as the ketone such as the alcohol such as methanol, acetone (poor solvent) Lai Qingxi can also be used.Especially show it is water-soluble
In the case where the cellulose acetate of the low total degree of substitution of acetyl group, preferably cleaned with organic solvent (poor solvent).Then, may be used
To be cleaned, be neutralized with the organic solvent (for example, ketone such as the alcohol such as methanol, acetone etc.) containing alkaline matter.By cleaning, in
With, though in cellulose acetate containing the impurity such as sulfate, also it can expeditiously be removed.It can be to precipitating
Cellulose acetate be dehydrated and dried.
(cellulose acetate of the total degree of substitution of acetyl group is reduced by hydrolyzing)
The manufacturing method of cellulose acetate according to the present invention, the acetate fiber of the available low total degree of substitution of acetyl group
Element.The total degree of substitution of the acetyl group of cellulose acetate (DS) for example be preferably 0.3 or more and 1.6 hereinafter, more preferably 0.4 or more and
1.5 hereinafter, further preferably 0.6 or more and 1.4 or less.
It should be noted that the total degree of substitution of acetyl group is the 2 of the glucose ring of cellulose acetate, 3,6 each acetyl group
The sum of average substitution degree.
Especially as described in the following record in patent document 2, the high serviceability of the cellulose acetate of low degree of substitution is expected,
Therefore it is very useful that realizing, which reduces the manufacturing method of environmental pressure,.To be 0.4~1.1 containing the total degree of substitution of acetyl group
It alimentation composition that cellulose acetate is characterized, feed stripped, lipid-metabolism-improving agent, inflammatory bowel disease and/or is immunized different
The prevention of normal prevention and/or therapeutic agent, cancer and/or therapeutic agent, the prevention of nonalcoholic fatty liver disease and/or therapeutic agent,
Prevention and/or the therapeutic agent (patent document of fat and/or diabetes preventions and/or therapeutic agent and hypercholesterolemia
2)。
The total degree of substitution of the acetyl group of cellulose acetate can be by being dissolved in fit corresponding with degree of substitution for cellulose acetate
It is measured when solvent finds out the well known titration of the degree of substitution of cellulose acetate.The total degree of substitution of acetyl group can be according to Asklsl
The complete derivatization of the hydroxyl of cellulose acetate is formed second by the method for (Tezuka, Carbonydr.Res.273,83 (1995))
After sour cellulose propionate (CAP), be dissolved in deuterated chloroform, by NMR (13C-NMR or1H-NMR it) is measured.
In addition, the total degree of substitution of acetyl group can be with following formula to according to (the test side of cellulose acetate etc. ASTM:D-817-91
Method) in the degree of acetylation that finds out of degree of acetylation measuring method converted and found out.This is the second of cellulose acetate most typically
The total degree of substitution of acyl group finds out method.
DS=162.14 × AV × 0.01/ (60.052-42.037 × AV × 0.01)
DS: the total degree of substitution of acetyl group
AV: degree of acetylation (%)
Firstly, cellulose acetate (sample) 500mg that accurate weighing is dry, is dissolved in the mixed solution of ultrapure water and acetone
Then (capacity ratio 4:1) 50ml adds the sodium hydrate aqueous solution 50ml of 0.2N, carry out being saponified for 2 hours at 25 DEG C.Then,
The hydrochloric acid 50ml for adding 0.2N, using phenolphthalein as indicator, with sodium hydrate aqueous solution (the sodium hydroxide equivalent of 0.2N of 0.2N
Solution) titrate the acetic acid amount being detached from.In addition, carrying out blank test (test of sample is not used) by the same method.Then,
It is calculate by the following formula out AV (degree of acetylation) (%).
AV (the %)=sample weight (g) of (A-B) × F × 1.201/
The titer (ml) of the sodium hydroxide normal solution of A:0.2N
B: the titer (ml) of the sodium hydroxide normal solution of the 0.2N in blank test
The factor of the sodium hydroxide normal solution of F:0.2N
Embodiment
Hereinafter, the present invention is concretely demonstrated by embodiment, but technical scope of the invention is not by these realities
Apply the restriction of example.
(embodiment 1)
Magnetic stirring apparatus (band heater), condenser and thermometer are installed on reaction vessel (capacity 300mL).In order into
Nitrogen displacement in row reaction vessel, imports reaction vessel for nitrogen, also persistently imports nitrogen later.Hold in nitrogen to the reaction
Device adds glacial acetic acid 90mL, water 40mL (when being calculated in the form of the concentration of the acetic acid solution to be formed by acetic acid and water: second
Acid be 69.2 volume %) and cellulose triacetate (manufacture of Co., Ltd.'s Daicel, the total degree of substitution 2.87 of acetyl group, in conjunction with sulfuric acid
Measure 190ppm) 10g, mixture is made.Stir the mixture.Stirring continue for 5 hours at 70 DEG C.Then, stirring is terminated
Mixture afterwards stands an evening at room temperature, is prepared for the mixture (swelling object) of cellulose acetate.The mixing of cellulose acetate
Cellulose acetate concentration (CA concentration) in object (swelling object) is 7.7 weight/volume %.
Then, cellulose acetate is hydrolyzed.Details is as described below.By 1g (relative to 100 parts by weight of cellulose acetate
For 10 parts by weight) the cellulose acetate that makes an addition to of AMBERLITE (registered trademark) IR-120B mixture (swelling object)
It as storng-acid cation exchange resin, is stirred, reaction mixture has been made.Then, it is mixed with the oil bath heating reaction
Object is kept for 24 hours at 70 ± 1 DEG C.
It is small 0 hour (before addition storng-acid cation exchange resin), 8 hours, 16 hours and 24 in this 24 hours
When each stage sample reaction mixture 1g, make an addition in 25mL water, precipitate cellulose acetate.
The cellulose acetate for filtering precipitating, is cleaned with pure water, is recycled in the form of wet cake.
4 times the water of 25mL (use every time) wet wet cakes are washed with water, obtain the wet product of white, 80 DEG C in a vacuum
Under be dried, obtained cellulose acetate.Pass through above-mentioned use1The method of H-NMR measures obtained cellulose acetate
Acetyl group total degree of substitution.Show the result in table 1.
(embodiment 2)
2g is added to (relative to 100 weight of cellulose acetate into the mixture (swelling object) of obtained cellulose acetate
Part be 20 parts by weight) AMBERLITE (registered trademark) IR-120B as storng-acid cation exchange resin, in addition to this, with
Embodiment 1 gets similarly cellulose acetate, determines the total degree of substitution of acetyl group.Show the result in table 1.
(embodiment 3)
5g is added to (relative to 100 weight of cellulose acetate into the mixture (swelling object) of obtained cellulose acetate
Part be 50 parts by weight) AMBERLITE (registered trademark) IR-120B as storng-acid cation exchange resin, in addition to this, with
Embodiment 1 gets similarly cellulose acetate, determines the total degree of substitution of acetyl group.Show the result in table 1.
(embodiment 4)
Magnetic stirring apparatus (band heater), condenser and thermometer are installed on reaction vessel (capacity 300mL).In order into
Nitrogen displacement in row reaction vessel, imports reaction vessel for nitrogen, also persistently imports nitrogen later.Hold in nitrogen to the reaction
Device adds glacial acetic acid 45mL, water 20mL (when being calculated in the form of the concentration of the acetic acid solution to be formed by acetic acid and water: second
Acid be 69.2 volume %) and cellulose triacetate (manufacture of Co., Ltd.'s Daicel, the total degree of substitution 2.87 of acetyl group, in conjunction with sulfuric acid
Measure 190ppm) 5g, mixture is made.Stir the mixture.Stirring continue for 5 hours at 70 DEG C.It then, will be after stirring
Mixture stand an evening at room temperature, be prepared for the mixture (swelling object) of cellulose acetate.The mixture of cellulose acetate
Cellulose acetate concentration (CA concentration) in (swelling object) is 7.7 weight/volume %.
Then, cellulose acetate is hydrolyzed.Details is as described below.Mixture to obtained cellulose acetate is (molten
Swollen object) in addition 15g (relative to 100 parts by weight of cellulose acetate be 300 parts by weight) AMBERLITE (registered trademark) IR-
120B is stirred as storng-acid cation exchange resin, and reaction mixture has been made.Then, with the oil bath heating reaction
Mixture is kept for 24 hours at 40 ± 1 DEG C.
It is small 0 hour (before addition storng-acid cation exchange resin), 8 hours, 16 hours and 24 in this 24 hours
When each stage sample reaction mixture 1g, make an addition in 25mL water, precipitate cellulose acetate.
The cellulose acetate for filtering precipitating, is cleaned with pure water, is recycled in the form of wet cake.
4 times the water of 25mL (use every time) wet wet cakes are washed with water, obtain the wet product of white, 80 DEG C in a vacuum
Under be dried, obtained cellulose acetate.Pass through above-mentioned use1The method of H-NMR measures obtained cellulose acetate
Acetyl group total degree of substitution.Show the result in table 1.
(embodiment 5)
Other than temperature when by hydrolyzing is set as 70 ± 1 DEG C, cellulose acetate is obtained similarly to Example 4, is measured
Acetyl group total degree of substitution.Show the result in table 1.
(embodiment 6)
Temperature when hydrolyzing is kept for 24 hours at 90 ± 1 DEG C, in this 24 hours, in 8 hours and 16 hours each ranks
Section sampling reaction mixture 1g, makes an addition in 25mL water, precipitates cellulose acetate, and 24 hours stages, sampling reaction was mixed
Object 1g is closed, makes an addition in 25mL acetone, precipitates cellulose acetate.In addition, to precipitating in 8 hours and 16 hours each stages
Cellulose acetate is filtered, and is cleaned with pure water, is filtered to the cellulose acetate precipitated in 24 hour stage, clear with acetone
It washes.Other than changing conditions above, cellulose acetate is obtained similarly to Example 4, determines the total degree of substitution of acetyl group.It will
As a result shown in table 1.
(embodiment 7)
Magnetic stirring apparatus (band heater), condenser and thermometer are installed on reaction vessel (capacity 300mL).In order into
Nitrogen displacement in row reaction vessel, imports reaction vessel for nitrogen, also persistently imports nitrogen later.Hold in nitrogen to the reaction
Device adds glacial acetic acid 90mL, water 40mL (when being calculated in the form of the concentration of the acetic acid solution to be formed by acetic acid and water: second
Acid be 69.2 volume %) and cellulose triacetate (manufacture of Co., Ltd.'s Daicel, the total degree of substitution 2.87 of acetyl group, in conjunction with sulfuric acid
Measure 190ppm) 10g, mixture is made.Stir the mixture.Stirring continue for 5 hours at 70 DEG C.Then, stirring is terminated
Mixture afterwards stands an evening at room temperature, is prepared for the mixture (swelling object) of cellulose acetate.The mixing of cellulose acetate
Cellulose acetate concentration (CA concentration) in object (swelling object) is 7.7 weight/volume %.
Then, cellulose acetate is hydrolyzed.Details is as described below.Mixture to obtained cellulose acetate is (molten
Swollen object) in addition 30g (relative to 100 parts by weight of cellulose acetate be 300 parts by weight) Dowex (registered trademark) 50WX2 make
It for storng-acid cation exchange resin, is stirred, reaction mixture has been made.Then, with the oil bath heating reaction mixture,
It is kept for 32 hours at 97 ± 1 DEG C.
In this 32 hours, reaction mixture 1g was sampled 8 hours stages, makes an addition in 25mL water, makes acetate fiber
Element precipitating sampled reaction mixture 1g 16 hours, 24 hours and 32 hours each stages, makes an addition in 25mL acetone, make second
Acid cellulose precipitating.
In addition, being filtered to the cellulose acetate precipitated in 8 hour stage, cleaned with pure water, in the form of wet cake
Recycling.The cellulose acetate precipitated in 16 hours, 24 hours and 32 hours each stages is filtered, is cleaned with acetone, with
The form of wet cake recycles.
4 times the water of 25mL (use every time) wet wet cakes are washed with water, obtain the wet product of white, 80 DEG C in a vacuum
Under be dried, obtained cellulose acetate.Pass through above-mentioned use1The method of H-NMR measures obtained cellulose acetate
Acetyl group total degree of substitution.Show the result in table 1 and Fig. 1.
(embodiment 8)
Reaction mixture 1g is sampled, is added using Dowex (registered trademark) 50WX8 as storng-acid cation exchange resin
It is added in 25mL acetone, precipitates cellulose acetate, the cellulose acetate precipitated in whole stages is filtered, it is clear with acetone
It washes, is recycled in the form of wet cake, in addition to this, obtain cellulose acetate similarly to Example 7, determine acetyl group and always take
Dai Du.Show the result in table 1.
(embodiment 9)
Magnetic stirring apparatus (band heater), condenser and thermometer are installed on reaction vessel (capacity 300mL).In order into
Nitrogen displacement in row reaction vessel, imports reaction vessel for nitrogen, also persistently imports nitrogen later.Hold in nitrogen to the reaction
Device adds glacial acetic acid 90mL, water 40mL (when being calculated in the form of the concentration of the acetic acid solution to be formed by acetic acid and water: second
Acid be 69.2 volume %) and cellulose diacetate (manufacture of Co., Ltd.'s Daicel, the total degree of substitution 2.44 of acetyl group, in conjunction with sulfuric acid
Measure 190ppm) 10g, mixture is made.Stir the mixture.Stirring continue for 5 hours at 70 DEG C.Then, stirring is terminated
Mixture afterwards stands an evening at room temperature, is prepared for the mixture (swelling object) of cellulose acetate.The mixing of cellulose acetate
Cellulose acetate concentration (CA concentration) in object (swelling object) is 7.7 weight/volume %.
Then, cellulose acetate is hydrolyzed.Details is as described below.Mixture to obtained cellulose acetate is (molten
Swollen object) in addition 30g (relative to 100 parts by weight of cellulose acetate be 300 parts by weight) Dowex (registered trademark) 50WX2 make
It for storng-acid cation exchange resin, is stirred, reaction mixture is made.Then, with the oil bath heating reaction mixture,
97 ± 1 DEG C are kept for 32 hours.
In this 32 hours, 0 hour (before addition storng-acid cation exchange resin), 8 hours, 16 hours, 24 hours
And 32 hours each stages sampled reaction mixture 1g, made an addition in 25mL acetone, precipitated cellulose acetate.
The cellulose acetate of precipitating is filtered, is cleaned with acetone, is recycled in the form of wet cake.
4 (using the acetone of 25mL every time) wet wet cakes are cleaned with acetone, obtain the wet product of white, in a vacuum
It is dried at 80 DEG C, has obtained cellulose acetate.Pass through above-mentioned use1The method of H-NMR is to obtained cellulose acetate
Determine the total degree of substitution of acetyl group.Show the result in table 1 and Fig. 1.
(comparative example 1)
Magnetic stirring apparatus (band heater), condenser and thermometer are installed on reaction vessel (capacity 300mL).In order into
Nitrogen displacement in row reaction vessel, imports reaction vessel for nitrogen, also persistently imports nitrogen later.Hold in nitrogen to the reaction
Device adds glacial acetic acid 90mL, water 40mL (when being calculated in the form of the concentration of the acetic acid solution to be formed by acetic acid and water: second
Acid be 69.2 volume %) and cellulose diacetate (manufacture of Co., Ltd.'s Daicel, the total degree of substitution 2.44 of acetyl group, in conjunction with sulfuric acid
Measure 190ppm) 10g, mixture is made.Stir the mixture.Stirring continue for 5 hours at 70 DEG C.Then, stirring is terminated
Mixture afterwards stands an evening at room temperature, is prepared for the mixture (swelling object) of cellulose acetate.The mixing of cellulose acetate
Cellulose acetate concentration (CA concentration) in object (swelling object) is 7.7 weight/volume %.
Then, the mixture (swelling object) of the cellulose acetate obtained with oil bath heating, is kept for 32 hours at 97 ± 1 DEG C.
In this 32 hours, 0 hour (before addition storng-acid cation exchange resin), 8 hours, 16 hours, 24 hours
And 32 hours each stages sampled reaction mixture 1g, made an addition in 25mL water, precipitated cellulose acetate.
The cellulose acetate of precipitating is filtered, is washed with water, is recycled in the form of wet cake.
4 times the water of 25mL (use every time) wet wet cakes are washed with water, obtain the wet product of white, 80 DEG C in a vacuum
Under be dried, obtained cellulose acetate.Pass through above-mentioned use1The method of H-NMR determines obtained cellulose acetate
The total degree of substitution of acetyl group.Show the result in table 1.
[table 1]
As shown in table 1, cellulose acetate can be made abundant without adding sulfuric acid by using storng-acid cation exchange resin
Hydrolysis, can reduce the total degree of substitution of acetyl group.It is possible thereby to confirm, do not need used organic molten to remove sulfuric acid
The cleaning treatment of agent, the processing after not only precipitating cellulose acetate becomes simply, but also highly acidic cation can be exchanged
Resin regeneration and reused, therefore environmental pressure can be reduced.
Claims (10)
1. a kind of manufacturing method of cellulose acetate, this method are with the following process:
By contacting cellulose acetate mixture or solution with storng-acid cation exchange resin, thus to the acetate fiber
Element is hydrolyzed, the process for reducing the total degree of substitution of its acetyl group；And
Make to hydrolyze the process for reducing the cellulose acetate precipitating of the total degree of substitution of acetyl group by described.
2. the manufacturing method of cellulose acetate according to claim 1, wherein the cellulose acetate mixture or solution
By will be used as, the cellulose acetate of raw material mixes or is dissolved in acetic acid or prepared by solution containing acetic acid.
3. the manufacturing method of cellulose acetate according to claim 1, wherein the cellulose acetate mixture or solution
It is prepared by the cellulose acetate of raw material will be used as to mix or be dissolved in the mixed solution containing acetic acid and water.
4. the manufacturing method of cellulose acetate described in any one of claim 1 to 3, wherein make the acetate fiber
The method that plain mixture or solution are contacted with storng-acid cation exchange resin is in the cellulose acetate mixture or solution
The middle method adding the storng-acid cation exchange resin and being stirred.
5. the manufacturing method of cellulose acetate described in any one of claim 1 to 3, wherein make the acetate fiber
The method that plain solution is contacted with storng-acid cation exchange resin is to flow through the cellulose acetate solution filled with described strong
The method of the column of acid cation exchange resin.
6. the manufacturing method of cellulose acetate according to claim 4, wherein the cellulose acetate mixture or solution
Cellulose acetate concentration be 1 weight/volume % or more and 15 weight/volume % hereinafter, the weight/volume % is with % table
The unit of the value for the weight/volume shown, the weight and volume is respectively g and mL.
7. the manufacturing method of cellulose acetate according to claim 4, wherein relative to the cellulose acetate mixture
Or 100 parts by weight of the cellulose acetate in solution, add 5 parts by weight or more and the 500 parts by weight highly acid below
Cation exchange resin.
8. the manufacturing method of cellulose acetate according to claim 5, wherein the acetic acid of the cellulose acetate solution is fine
Plain concentration is tieed up as 1 weight/volume % or more and 10 weight/volume % are hereinafter, the weight/volume % is the weight indicated with %
The unit of amount/volume value, the weight and volume is respectively g and mL.
9. the manufacturing method of cellulose acetate described according to claim 1~any one of 8, wherein the cellulose acetate
The total degree of substitution of the acetyl group of cellulose acetate in mixture or solution is 1.7 or more and 2.9 or less.
10. the manufacturing method of cellulose acetate described according to claim 1~any one of 9, wherein made by the hydrolysis
The total degree of substitution of the acetyl group of cellulose acetate is 0.3 or more and 1.6 or less.
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