CN110407946A - A kind of method that carried superstrong solid acid catalysis prepares Triafol T - Google Patents
A kind of method that carried superstrong solid acid catalysis prepares Triafol T Download PDFInfo
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- CN110407946A CN110407946A CN201910729392.8A CN201910729392A CN110407946A CN 110407946 A CN110407946 A CN 110407946A CN 201910729392 A CN201910729392 A CN 201910729392A CN 110407946 A CN110407946 A CN 110407946A
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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
- C08B3/02—Catalysts used for the esterification
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The present invention provides a kind of method for catalyzing and synthesizing cellulose acetate using carried superstrong solid acid, and specifically cellulose and glacial acetic acid are added in reaction unit according to the mass ratio of 1:2 ~ 10, activates 1 ~ 3 hour at 25 ~ 30 DEG C；Catalyst is added, acylating reagent is added dropwise to kettle and insulation reaction 2 ~ 6 hours at 50 ~ 60 DEG C by control system temperature under stirring condition；Reaction system is cooled to room temperature, and is separated by filtration recycling catalyst；To gained filtrate injection deionized water, be precipitated white precipitate through suction filtration, washing, be dried acetic acid conjugation be 59 ~ 61% Triafol T.The catalyst perfluor type sulfonic acid supported solid superacid acid catalyst that the method for the present invention uses is a kind of support type perfluorinated sulfonic resin, there is the perfluorinated sulfonic acid of superacid catalysis performance by porous functional material load, catalytic performance is good, avoids catalytic erosion problem, can be recycled.
Description
Technical field
The invention belongs to cellulose fields, and in particular to a method of synthesis acetyl cellulose, more particularly to it is a kind of
Chloroacetic chloride is catalyzed using perfluorinated sulfonic acid carried superstrong solid acid and cellulose is the method for Material synthesis acetyl cellulose.
Background technique
Cellulose acetate is a kind of cellulose esters obtained by native cellulose through acetylation, is and its important fiber
Plain organic acid esters.The degree replaced according to hydroxyl hydrogen in cellulose by acetyl group is different, and cellulose acetate can be divided into two acetic acid
Cellulose (DAC) and Triafol T (TAC).Wherein, DAC degree of substitution is 2.2 ~ 2.50, and acetic acid binding capacity is 52 ~ 56%；
TAC degree of substitution is 2.71 ~ 3.0, acetic acid binding capacity 59 ~ 62.5%.It is mostly used in existing Triafol T mass production techniques
Using glacial acetic acid as solvent, carry out esterification using various native celluloses and acetic anhydride, then by saponification adjustment degree of substitution after,
The process route of cellulose acetate is prepared through processes such as filtering, molding, cleaning, dehydration, drying, in the synthesis process, catalysis
The selection and application of agent play a crucial role.In existing public technology, mostly using sulfuric acid is catalyst, and dosage is high
Up to 15%.Chinese patent CN107286258B, CN102153660B etc. individually disclose it is a kind of using glacial acetic acid be solvent, fiber
Element and the excess acetic anhydride method that reaction prepares Triafol T under sulfuric acid catalysis.In Publication No. CN100484960C
State's patent uses 60 ~ 90 DEG C of hot conditions, with 98% sulfuric acid and high concentration perchloric acid Compound-acid catalytic cellulose substance and acetic anhydride
Esterification sufficiently occurs, obtains the cellulose acetate of high viscosity higher.But the use of the liquid strong protonic acid such as sulfuric acid, a side
Face can cause to corrode to production equipment, shorten service life；On the other hand cellulose sulfuric acid ester can be formed in conjunction with product, influence
The apparent masses such as the transparency of product.Patent CN105085690A discloses one kind and substitutes the concentrated sulfuric acid with acetic acid dissolubility molysite, is used for
The acetylization reaction of cellulose and acetic anhydride will not occur drying process product caused by remaining because of sulfuric acid and change colour and with tart flavour
The phenomenon that, later period use is influenced, iron salt catalyst is relatively smaller to cellulose corrosivity, and will not corrode equipment, but big
Amount document shows that metal ion is easily reacted with acidic-group in cellulose acetate, generates the gelling material for making solution filtration difficulty.
Catalytic cellulose and acetic anhydride are total to using nucleophilic acylation catalyst and Bronsted acid in Chinese patent CN108383915A
Reaction prepares acetyl cellulose, catalyst amount and preparation cost is effectively reduced, but the pyridines acetylation of nucleophilic is catalyzed
Agent needs to remove by processing modes such as vacuum distillation, extractions, and is not directed to recycling for such catalyst, is unfavorable for pacifying
Loopful is protected.Patent CN103509123B describes one kind in the system existing for ionic liquid, utilizes sulfonation solid acid
Amberlyst15 catalytic cellulose reacts the preparation method for preparing cellulose diacetate, this method esterification with acylating reagent
Temperature is high, the reaction time is long, and energy consumption is high and post-processing is cumbersome.
Summary of the invention
Cellulose acetate is synthesized for existing catalyst, the present invention provides a kind of utilization perfluor type sulphur
The method that acetylization reaction synthesis cellulose acetate occurs for sour supported solid superacid acid catalysis chloroacetic chloride and cellulose.Perfluor type sulphur
Sour supported solid superacid acid catalyst is a kind of support type perfluorinated sulfonic resin, has super acids by porous functional material load
The perfluorinated sulfonic acid of catalytic performance improves its catalytic activity and stability, avoids catalytic erosion problem, can be recycled.
A method of cellulose acetate is prepared using carried superstrong solid acid catalysis, the specific steps are as follows:
(1) it activates: smashed cellulose and glacial acetic acid being added in reaction unit according to certain mass ratio, at 25 ~ 30 DEG C
It is activated；
(2) acetylation: after activation, catalyst being added into reaction unit, and 50 DEG C are warming up under stirring condition and starts to add
Enter acylating reagent and carry out acetylization reaction, acylating reagent is added dropwise, and continues insulation reaction for a period of time；
(3) catalyst recycles: above-mentioned reaction system is cooled to room temperature, and is separated by filtration recycling solid catalyst；
(4) it hydrolyzes and post-processes: injecting deionized water to filtrate obtained by step (3), the white precipitate of precipitation is filtered, washed,
The Triafol T that dry acetic acid conjugation is 59 ~ 61%.
Wherein, the mass ratio of cellulose described in above-mentioned steps (1) and glacial acetic acid is 1:2 ~ 10.
Preferably, the mass ratio of the cellulose and glacial acetic acid is 1:4 ~ 6.
Wherein, activation time described in above-mentioned steps (1) is 1 ~ 3 hour.
Preferably, the activation time is 1.5 ~ 2 hours.
Wherein, catalyst described in above-mentioned steps (2) is perfluor type sulfonic acid supported solid superacid acid, and dosage is accounted for into kettle fibre
The mass percent for tieing up element can be 5 ~ 15%.
Preferably, it is 8 ~ 12% that the catalyst amount, which accounts for cellulose mass percent,.
Wherein, acylating reagent described in above-mentioned steps (2) can be any one of acetic anhydride or chloroacetic chloride.
Wherein, the mass ratio of acylating reagent described in above-mentioned steps (2) and cellulose is (2 ~ 6): 1.
Preferably, the mass ratio of the acylating reagent and cellulose is (3.5 ~ 5): 1.
Wherein, when acylating reagent described in above-mentioned steps (2) is chloroacetic chloride, the chlorination of generation during acetylization reaction
Hydrogen is handled through device for absorbing tail gas.
Wherein, reaction kettle is added in acylating reagent described in above-mentioned steps (2) in a manner of being added dropwise.
Wherein, insulation reaction temperature described in above-mentioned steps (2) is 50 ~ 60 DEG C.
Wherein, the insulation reaction time described in above-mentioned steps (2) is 2 ~ 6 hours.
Preferably, the insulation reaction time is 3 ~ 4 hours.
Wherein, the acylation that catalyst described in above-mentioned steps (3) can be directly recycled for step (2) after being recovered by filtration is urged
Change reaction.
Wherein, above-mentioned steps (4) deionized water and the mass ratio of filtrate of being added is 0.3 ~ 1:1.
Preferably, the deionized water and the mass ratio of gained filtrate of being added is 0.5 ~ 1:1.
Wherein, filter type described in above-mentioned steps (4) is normal pressure centrifugal filtration or suction filtration.
Wherein, washing described in above-mentioned steps (4) is deionized water with liquid.
Wherein, drying described in above-mentioned steps (4) is 30 ~ 40 DEG C of vacuum drying or forced air drying mode.
Beneficial effect of the invention:
(1) synthesis acetic acid conjugation is reacted with acylating reagent using perfluor type sulfonic acid supported solid superacid acid catalysis cellulose is 59
~ 61% Triafol T, catalyst amount is few, catalytic performance is good；
(2) a large amount of corrosivenesses using to equipment of traditional catalyst are efficiently avoided, recycling is conducive to and is Ke Xunhuanliyong；
(3) acylating reagent enters kettle by the way of being added dropwise, and the utilization efficiency of raw material can be improved, and reduces raw material usage amount, reduces
Energy consumption when acetic acid rectification and purification post-processes.
Specific embodiment
For further description meaning of the present invention, content according to the present invention is carried out below with reference to embodiment
It illustrates, but its content is not defined.
Embodiment 1
Smashed cellulose 100g and 500g glacial acetic acid are added at one time in reaction unit, 2 hours are activated at 25 ~ 30 DEG C extremely
Mixture is in uniform pulpous state system；10g catalyst perfluor type sulfonic acid supported solid superacid acid is added, is warming up to 50 under stirring condition
DEG C, 350g acylating reagent chloroacetic chloride is added dropwise to kettle at 55 DEG C or so by control system reaction temperature, and acylating reagent is added dropwise, and 55
± 1 DEG C continuation insulation reaction 4 hours, the hydrogen chloride gas for reacting generation enters device for absorbing tail gas；Reaction system is down to room temperature
Afterwards, it is separated by filtration recycling catalyst；Deionized water 500g is injected to gained filtrate, white precipitate is precipitated and filtered, gone with 300g
Ionized water washs in three times, 30 ~ 40 DEG C of vacuum drying treatments obtain Triafol T.
Product is detected through chemical analysis, and acetic acid conjugation is 60.31%, degree of substitution 2.95.
Embodiment 2
Smashed cellulose 100g and 600g glacial acetic acid are added at one time in reaction unit, activated 1.5 hours at 25 ~ 30 DEG C
It is in uniform pulpous state system to mixture；12g perfluor type sulfonic acid supported solid superacid acid is added as catalyst, is risen under stirring condition
Temperature is to 50 DEG C, and 400g acylating reagent acetic anhydride is added dropwise to kettle by 60 DEG C of control system reaction temperature or so, and acylating reagent drips
Finish, 60 ± 1 DEG C continuation insulation reaction 3 hours；Reaction system is cooled to room temperature, and is separated by filtration recycling catalyst；To gained filtrate
Middle injection deionized water 500g, precipitation white precipitate is filtered, is washed in three times with 300g deionized water, 30 ~ 40 DEG C of vacuum are dry
It is dry to handle to obtain Triafol T.
Product is detected through chemical analysis, and acetic acid conjugation is 60.75%, degree of substitution 2.98.
Comparative example (compares) with the traditional catalyst concentrated sulfuric acid
Smashed cellulose 100g and 600g glacial acetic acid are added at one time in reaction unit, activated 1.5 hours at 25 ~ 30 DEG C
It is in uniform pulpous state system to mixture；Into the system after activation be added 12g mass percent be 85% sulfuric acid catalyst and
600g acylating reagent acetic anhydride is warming up to 60 DEG C or so insulation reactions 8 hours under stirring condition；Reaction system is down to 25 ~ 30 DEG C,
Deionized water 500g is injected into gained filtrate to hydrolyze 0.5 hour, and after hydrolysis, quality percentage is slowly added under stirring condition
In the sodium acetate aqueous solution 70g that specific concentration is 15% and unreacted catalyst, other techniques and operating condition with embodiment 2,
Faint yellow Triafol T is obtained, product is detected through chemical analysis, and acetic acid conjugation is 59.83%, degree of substitution 2.87.
Claims (9)
1. a kind of method for preparing cellulose acetate using carried superstrong solid acid catalysis, which is characterized in that specifically include as
Lower step:
Activation: smashed cellulose and glacial acetic acid are added in reaction unit, activated at 25 ~ 30 DEG C；
Acetylation: after activation, catalyst is added into reaction unit, 50 DEG C are warming up under stirring condition and is initially added into acyl
Change reagent and carry out acetylization reaction, acylating reagent is added dropwise, and continues insulation reaction for a period of time；
Catalyst recycling: above-mentioned reaction system is cooled to room temperature, and is separated by filtration recycling solid catalyst；
Hydrolysis and post-processing: deionized water is injected to filtrate obtained by step (3), the white precipitate of precipitation is filtered, washed, is dried
Obtain Triafol T.
2. the method according to claim 1, wherein in the step (1) cellulose and glacial acetic acid mass ratio
For 1:2 ~ 10.
3. the method according to claim 1, wherein catalyst is the load of perfluor type sulfonic acid in the step (2)
Solid super-strong acid.
4. according to claim 1 or 3 any methods, which is characterized in that the catalyst amount accounts for cellulose quality hundred
Dividing than being 5 ~ 15%, % is quality %.
5. the method according to claim 1, wherein in the step (2) acylating reagent can for acetic anhydride or
Any one of chloroacetic chloride;The mass ratio of the acylating reagent and cellulose is 2 ~ 6:1.
6. according to claim 1 and described in 5, which is characterized in that when the acylating reagent is chloroacetic chloride, during acetylization reaction is crossed into
The hydrogen chloride of generation is handled through device for absorbing tail gas.
7. the method according to claim 1, wherein acylating reagent is added in a manner of being added dropwise in the step (2)
Enter reaction kettle.
8. the method according to claim 1, wherein insulation reaction temperature is 50 ~ 60 DEG C in the step (2);
The insulation reaction time is 2 ~ 6 hours.
9. the method according to claim 1, wherein the matter of deionized water and filtrate is added in the step (4)
Amount is than being (0.3 ~ 1): 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111171337A (en) * | 2020-02-20 | 2020-05-19 | 广州楹鼎生物科技有限公司 | Preparation method of acetylated lignocellulose |
| CN114075299A (en) * | 2022-01-04 | 2022-02-22 | 江苏瑞佳新材料有限公司 | Cellulose triacetate and preparation method thereof |
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| CN103874713A (en) * | 2011-10-14 | 2014-06-18 | 塞拉尼斯醋酸纤维有限公司 | Methods for synthesizing acylated cellulose through instillation of an acidic catalyst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111171337A (en) * | 2020-02-20 | 2020-05-19 | 广州楹鼎生物科技有限公司 | Preparation method of acetylated lignocellulose |
| CN114075299A (en) * | 2022-01-04 | 2022-02-22 | 江苏瑞佳新材料有限公司 | Cellulose triacetate and preparation method thereof |
| CN114075299B (en) * | 2022-01-04 | 2022-08-09 | 江苏瑞佳新材料有限公司 | Cellulose triacetate and preparation method thereof |
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Application publication date: 20191105 |