CN104558640B - A kind of preparation method of cellulose diacetate microgranule - Google Patents
A kind of preparation method of cellulose diacetate microgranule Download PDFInfo
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Abstract
The invention belongs to field of material technology, is related to a kind of preparation method of cellulose diacetate microgranule, comprises the steps：(1) Solution of CA-Acetone is prepared, stirs, be heated to precipitating temperature；(2) the precipitating agent being mixed to get by solvent and non-solvent of preheating is added in the Solution of CA-Acetone for preparing in step (1), solvent and the mass ratio of non-solvent is made to reach nearly precipitating point ratio, after charging is finished, under same rotating speed, continue stirring 10 30 minutes；(3) precipitating temperature is kept, precipitating agent is added with uniform speed, so that the mass ratio of solvent and non-solvent reaches precipitating ratio in final solution, after adding precipitating agent, it is further continued for stirring 10 30 minutes, make cellulose diacetate microgranule precipitating out, obtain high-specific surface area cellulose diacetate microgranule.What the present invention made does ball has porosity characteristic and does that ball size is adjustable, and the surface and inside of microgranule have loose structure, and surface area is in 30 60m2Between/g.
Description
Technical field
The invention belongs to field of material technology, is related to a kind of preparation method of cellulose diacetate microgranule.
Background technology
Cellulose acetate, English name Cellulose Acetate (abbreviation CA), is also called cellulose acetate, molecular formula
For [C6H7O2(OCOCH3)x(OH)3-x]n, n=200-400.Its commercial Application product is mainly Triafol T and two acetic acid are fine
Dimension element.It is Triafol T when x is close to 3；It is two vinegar when x=2.28-2.49 (equivalent to acid content 53-56% is combined)
Acid cellulose.Combined acid is the binding capacity of acetic acid in cellulose acetate product, is expressed as every cellulose acetate unit mass and combines
Acetic acid mass percent.Combined acid can according in ASTM D871-2004 (method of testing of cellulose acetate etc.) be used for survey
Measure cellulose acetate combined acid method to measure.Measuring method is as follows：First 1.9 grams of dried cellulose acetate are dissolved in
150ml acetone/dimethyl sulfoxide (4：1, v/v) in mixed solvent, add the sodium hydrate aqueous solution of 30ml1N, and at 25 DEG C
Under the conditions of saponification 2 hours；Then the drop of Deca 2～3 phenolphthalein indicator, and the sodium hydroxide of the sulphuric acid overtitration with 1N.Use
State same method and enter line blank test, and by the acid of equation below calculations incorporated：
Combined acid (%)=(6.005 × (B-A) × F)/W
In formula, A represents that the consumption (ml) for being added to 1N sulphuric acid in sample, B are represented and be added to 1N sulphuric acid in blank sample
Consumption (ml), F represent the concentration factor of 1N sulphuric acid, weight (g) of the W for sample.
Cellulose diacetate its production process is (Encyclopedia of Chemical Technology, Kirk-
Othmer, volume5, p5000-5002)：Carry out after crushing mills, using acetic acid pre-treatment and activation, Ran Hou by wood pulps raw material
With sulphuric acid as catalyst, acetic acid carry out esterification with acetic anhydride under conditions of making solvent, obtain Triafol T serosity, through portion
Hydrolysis is divided to obtain cellulose diacetate serosity (abbreviation ager serosity) and then pass through precipitating, washing and drying and other steps system again
Into.At present the precipitating of ager serosity has a two ways, and one kind is addition aqueous acetic acid under agitation, obtains piling up close
The little powder cellulose diacetate of degree；Also one kind is that ager serosity is extruded into spirit of vinegar by little aperture apparatus is water-soluble
In liquid, through the high-bulk-density cellulose diacetate particle that cut-out obtains densification.By analysis, both precipitating technique productions
Cellulose diacetate surface area be respectively 4.2m2/ g and 0.6m2/g.
Cellulose diacetate has good soffening, and energy in common solvent (such as acetone, acetic acid, ethyl acetate)
Enough dissolvings, therefore its product typically assumes the face shapings such as lamellar, powder, fiber, film.As cellulose diacetate has ratio in itself
Preferable adsorptivity, weather resisteant, impact resistance, not oil resistant, the characteristic such as static electrification, if it is processed to unique microcosmic spy
Property porous does ball or microgranule, then can serve as chromatographic column filler, the carrier of enzyme, cosmetics additive (foundation cream, lipstick, eye shadow,
Emulsion, skin cream), medicine slow releasing agent, the modifying agent of pigment and paint, sewage treatment project adsorbent, fragrance delivery vehicles, remove
Taste agent and filter material of cigarette.
B.V.Chandler in 1975 et al. (DE2,507,551) using cooling method from cellulose diacetate
DMSO/ acetone solns are obtained cellulose acetate and make ball.Li Fuchun (Biotechnical Bioeng, 18,1507-1516
(1979)) obtained and Chandler identical results using scattered method in water.From the beginning of 1981, Y.Motozato et al.
(Nippon Kagaka Kuishi, 1892-1898,12 (1981)), Japan Nishikawa et al. (USP4,390,691；) be situated between
Continued use halogenated hydrocarbons dichloromethane ball preparation method to be done as " suspension method " of primary solvent.Japanese Daicel companies (USP4,
663,447), Celanese companies of the U.S. (USP5,047,180, US5064949) once disclosed with cellulose diacetate acetic acid starch
Liquid is raw material, and acetic acid prepares cellulose acetate as solvent, spurt method and does ball patent.WagenknechtW et al.
(EP0750007) methanol and ethyl acetate are adopted for solvent, utilizes " suspension method " method to prepare the vinegar of mean diameter 1-20 micron
Sour fiber makees ball.Lolanda (The Journal of Supercritical Fluids [J] .2011,55：1095-1103)
Acetone is adopted for solvent, prepares using super-critical anti-solvent precipitating technology that acetate fiber nanoparticle is above-mentioned to prepare cellulose acetate
Do ball or microgranule method.Above method is suffered from the drawback that：Using toxic solvent, or use energy consumption equipment.
Content of the invention
On the one hand, the present invention is a kind of cellulose diacetate microgranule preparation method of high-specific surface area, comprises the steps：
(1) certain density Solution of CA-Acetone is prepared, stirs, be heated to precipitating temperature.Two described vinegar
The combination acid content of acid cellulose is 50%-57%.Described Solution of CA-Acetone can use solvent, non-solvent or molten
The mixture dilution cellulose diacetate ager serosity of agent and non-solvent is obtained, it is also possible to solvent or solvent and non-solvent
Mixture dissolved solid cellulose diacetate is obtained.Described finite concentration is cellulose diacetate quality percentage in the solution
Than, can practical range be 6-15%, preferably 7-14%；
(2) under conditions of first mixing speed and precipitating temperature, the cellulose diacetate for preparing in step (1) is molten
Add the precipitating agent being mixed to get by solvent and non-solvent of preheating in liquid in first time period with uniform speed, make solvent
Nearly precipitating point ratio is reached with the mass ratio of non-solvent, after charging is finished, continue stirring 10-30 minutes under same rotating speed；
(3) mixing speed is adjusted to second mixing speed, keeps precipitating temperature, with uniform in second time period
Speed adds precipitating agent so that in final solution, the mass ratio of solvent and non-solvent reaches precipitating ratio, after adding precipitating agent,
It is further continued for stirring 10-30 minutes, makes cellulose diacetate microgranule precipitating out, obtain high-specific surface area cellulose diacetate micro-
Grain.
Obtained cellulose diacetate microgranule is filtered, washed and dried and obtains dry solid microgranule；The ratio table of microgranule
Area is 30-60m2/ g, diameter of particle are 250-850 microns.
Preparation method of the present invention by selecting solvent and non-solvent, and the mixing speed of control different phase, solvent and
Non-solvent ratio in the solution, precipitating temperature, precipitating agent add the conditions such as speed to control prepared cellulose diacetate
The particle diameter of microgranule and specific surface area.Described solvent be acetic acid, acetone, or both mixture, described non-solvent is water, second
Alcohol, or both mixture, preferred solvent is acetic acid, and non-solvent is water.
The main purpose of preparation method second step of the present invention is to make the solvent and non-solvent in Solution of CA-Acetone
Mass ratio reaches nearly precipitating point ratio and local precipitating does not occur.In order to reach this purpose, first mixing speed choosing
Select 500-4000rpm, preferably 1000-2000rpm.First time period selects 5-60 minutes, preferably 10-30 minutes, specifically chosen
Need the precipitating dosage for adding relevant with this time period.Precipitating agent adds speed=precipitating dosage/first time period.Uniform speed
Degree is referred to and is added precipitating agent with substantially same speed in whole first time period.
For a certain amount of Solution of CA-Acetone, first time period precipitating agent consumption and nearly precipitating point ratio correlation.
Nearly precipitating point ratio is defined as being observed that cellulose diacetate when the mass ratio of solvent and non-solvent reaches the ratio
The viscosity of solution is decreased obviously, and starts Solution of CA-Acetone expulsion events occur.So, selected solvent, non-solvent and
After precipitating temperature range, need nearly precipitating point proportion is found through experiments.Select solvent be acetic acid, non-solvent be water
When, nearly precipitating point ratio (mass ratio) of acetic acid and water is in the range of 45/55-50/50.
Precipitating agent preheating temperature is to avoiding generation local precipitating also critically important.If precipitating agent temperature is significantly less than precipitating
Temperature, for example：(precipitating temperature-precipitating agent temperature) 20 DEG C of ＞, it is possible to which local precipitating occurs.So select (precipitating temperature-
Precipitating agent preheating temperature)≤15 DEG C, preferably (precipitating temperature-precipitating agent preheating temperature)≤10 DEG C, more preferably (precipitating temperature-heavy
Analysis agent preheating temperature)≤5 DEG C.
In the 3rd step of preparation method of the present invention, speed is added by controlling precipitating temperature, mixing speed and precipitating agent
(second time period) is controlling particle diameter and the specific surface area of prepared cellulose diacetate microgranule.Precipitating temperature with selected
Solvent is relevant with non-solvent；The minimum boiling point less than solvent or non-solvent is selected, higher than 40 DEG C.Precipitating ratio, is chosen as solid
Dissolubility of the cellulose diacetate in the mixture of the solvent and non-solvent of 100 grams of precipitating ratios is less than 2 grams, and preferably smaller than 1
Gram, obtained by experiment.Second time period selects 15-60 minutes, preferably 20-55 minutes, specifically chosen and this time period to need
The precipitating dosage of addition is relevant.Second time period needs the precipitating agent consumption for adding use Solution of CA-Acetone concentration
Calculate with consumption, first time period precipitating agent consumption and precipitating ratio.Diacetate fiber of second mixing speed to generation
The particle diameter distribution of plain microgranule has a direct impact；In the range of 1000-4000rpm, low mixing speed is conducive to generating big particle diameter
Microgranule (250-850 microns), high mixing speed are conducive to generating small particle microgranule less than 250 microns).
The present invention one embody be select acetic acid be solvent, water be non-solvent.In this embodiment, described is certain dense
Component of the cellulose diacetate serosity of degree comprising following mass percent：6-15% cellulose diacetates, 75-82% acetic acid,
10-15% water；Precipitating temperature selects 60-95 DEG C, preferably 65-90 DEG C；First mixing speed is 500-4000rpm, preferably
1000-2000rpm；Precipitating agent preheating temperature is 55-90 DEG C, preferably 50-85 DEG C；Very first time scope is 5-60 minutes；Experiment
It was found that the nearly precipitating point ratio of acetic acid and water is in the range of 45/55-50/50；Second time range is 15-60 minutes；Second
Mixing speed is 1000-3000rpm, preferably 1100-2500rpm；Precipitating ratio (the mass ratio of the acetic acid and water of measuring
Example) in the range of 25/75-35/65.
The solvent/non-solvent mixed waste liquor that preparation process of the present invention is produced can be separated and recovered, concentration is recycled.For example,
It is acetic acid water lean solution in the system of acetic acid, non-solvent for water in solvent, it is possible to use existing ripe acetic acid recovery technology
(the bright commentary chemical industry environmental protection for separating and recovering acetic acid method from aqueous solution of Yang Chun China Ceng Guang, 1995,15 (2), 78-81), is carried out
Acetic acid recovery concentration is recycled.
On the other hand, the present invention is cellulose diacetate microgranule obtained in a kind of said method, the specific surface area of the microgranule
For 30-60m2/g；Diameter of particle is 250-850 microns.Obtained cellulose diacetate microgranule can be used for chromatographic column filler, enzyme
Carrier, the additive (foundation cream, lipstick, eye shadow, emulsion, skin cream) of cosmetics；Can be additionally used in medicine slow releasing agent, pigment and paint
Modifying agent, sewage treatment project adsorbent, fragrance delivery vehicles, eliminating smell agent and filter material of cigarette.Simultaneously can be to two
Cellulose acetate makees ball and is hydrolyzed and obtains cellulose and make ball, and is further changed by being crosslinked, being grafted and prepare composite
It is apt to its behavior extension its application.
Description of the drawings
Fig. 1 is microgranule SEM figures prepared by the embodiment of the present invention.
Fig. 2 is microgranule SEM figures prepared by another embodiment of the present invention.
Interparticle structure SEM figure prepared by Fig. 3 embodiment of the present invention.
Specific embodiment
Following examples and accompanying drawing are to further illustrate the present invention.
Following percent (%), unless otherwise stated, is mass percent.
Embodiment 1
(1) 154g cellulose diacetate ager serosity is taken, and wherein in the serosity, the combined acid containing 18% is 55.5%
Cellulose diacetate, 70% acetic acid, 12% water.The aqueous acetic acid for adding 91g to contain 70% is diluted, and starches after making dilution
In liquid, the mass concentration of cellulose diacetate is 11%.And cross paddle is used, above-mentioned serosity under 1500rpm mixing speeds
Serosity obtained above, after stopping stirring, is placed in airtight heating in 85 DEG C of water-baths by mix homogeneously.
(2), after temperature reaches balance, under 2000rpm mixing speeds, in 10 minutes, 65g is added to have been preheated with 80
DEG C 10% (mass fraction) aqueous acetic acid, charging finish after, it can be observed that the viscosity of Solution of CA-Acetone is obvious
Decline, start Solution of CA-Acetone expulsion events occur, now serosity is close to precipitating point, under same rotating speed, continue stirring 15
Minute.
(3), under 85 DEG C, 2500rpm stirrings, in 20 minutes, addition 375g has been preheated with 80 DEG C of 10% (quality point
Number) aqueous acetic acid, charging finish after, allow cellulose diacetate microgranule from precipitating in acetic acid serosity out, under same rotating speed after
Continuous stirring 15min；
(4) stop stirring, while hot vacuum filter, and washing 4-5 time is carried out with 60-65 DEG C of hot water；It is subsequently placed in 105 DEG C
Dry within 3 hours in baking oven.
Sieved after drying, it is 45.9m to make particle diameter for 425-825 μm, specific surface area2·g-1Porous acetate fiber
Plain microgranule.As shown in figure 1, SEM tests show that its surface assumes loose structure.Microgranule to preparing carries out section SEM point simultaneously
Analysis, is as a result shown in Fig. 3.By SEM profiles, it can be clearly seen that, interparticle assumes abundant cellular loose structure.So as to
There is higher specific surface area.
Embodiment 2
(1) 636g cellulose diacetate ager serosity is taken, containing the diacetate fiber that combined acid is 55.5% in the serosity
Quality amount 19%, 69% acetic acid, 12% water are placed in glass reaction kettles of the 5L with chuck heating, add 364g to contain
70% aqueous acetic acid is diluted, and the mass concentration for making cellulose diacetate in dilution rear slurry is 12%.And use cross
Paddle, above-mentioned serosity mix homogeneously under 2000rpm mixing speeds, after stopping stirring, by serosity obtained above warm
Water leg is heated to 85 DEG C.
(2), after temperature reaches balance, under 2000rpm mixing speeds, in 10 minutes, add and have been preheated with 80 DEG C
270 grams of 10% (mass fraction) aqueous acetic acid, after charging is finished, it can be observed that the viscosity of Solution of CA-Acetone is obvious
Decline, start Solution of CA-Acetone expulsion events occur, now serosity is close to precipitating point, under same rotating speed, continue stirring 15
Minute.
(3) under 85 DEG C, 1200rpm stirrings, in 30 minutes, remaining aqueous acetic acid is added, adds altogether acetic acid
Aqueous solution 2000g.Charging finish after, allow cellulose diacetate microgranule from precipitating in acetic acid serosity out, under 1200rpm rotating speeds after
Continuous stirring 15min；
(4) stop stirring, while hot vacuum filter, and washing 4-5 time is carried out with 60-65 DEG C of hot water；It is subsequently placed in 105 DEG C
Dry within 3 hours in baking oven.
Sieved after drying, it is 58.5m to make particle diameter for 425-825 μm, specific surface area2·g-1Porous acetate fiber
Plain microgranule.As shown in Fig. 2 SEM tests show that its surface assumes loose structure.
Embodiment 3
(1) 157g cellulose diacetate ager serosity is taken, and wherein in the serosity, the combined acid containing 18% is 55.5%
Cellulose diacetate, 70% acetic acid, 12% water.The aqueous acetic acid for adding 79g to contain 70% is diluted, and starches after making dilution
In liquid, the mass concentration of cellulose diacetate is 12%.And cross paddle is used, above-mentioned serosity under 1500rpm mixing speeds
Serosity obtained above, after stopping stirring, is placed in airtight heating in 85 DEG C of water-baths by mix homogeneously.
(2), after temperature reaches balance, under 2000rpm mixing speeds, in 10 minutes, 70g is added to have been preheated with 80
DEG C 10% (mass fraction) aqueous acetic acid, charging finish after, it can be observed that the viscosity of Solution of CA-Acetone is obvious
Decline, start Solution of CA-Acetone expulsion events occur, now serosity is close to precipitating point, under same rotating speed, continue stirring 15
Minute.
(3), again under 85 DEG C, 1100rpm stirrings, in 20 minutes, addition 410g has been preheated with 80 DEG C of 10% (quality
Fraction) aqueous acetic acid, charging finish after, allow cellulose diacetate microgranule from precipitating in acetic acid serosity out, under same rotating speed
Continue stirring 15min；
(4) stop stirring, while hot vacuum filter, and washing 4-5 time is carried out with 60-65 DEG C of hot water；It is subsequently placed in 105 DEG C
Dry within 3 hours in baking oven.
Sieved after drying, the particle mass percentage ratio of different-grain diameter scope is shown in Table 1.Diameter of particle is that 250-425 is micro-
Meter Shi, specific surface area are 42.2m2·g-1.
Embodiment 4
(1) 156g cellulose diacetate ager serosity is taken, and wherein in the serosity, the combined acid containing 18% is 55.5%
Cellulose diacetate, 70% acetic acid, 12% water.The aqueous acetic acid for adding 78g to contain 70% is diluted, and starches after making dilution
In liquid, the mass concentration of cellulose diacetate is 12%.And cross paddle is used, above-mentioned serosity under 1500rpm mixing speeds
Serosity obtained above, after stopping stirring, is placed in airtight heating in 85 DEG C of water-baths by mix homogeneously.
(2), after temperature reaches balance, under 2000rpm mixing speeds, in 10 minutes, 70g is added to have been preheated with 80
DEG C 10% (mass fraction) aqueous acetic acid, charging finish after, it can be observed that the viscosity of Solution of CA-Acetone is obvious
Decline, start Solution of CA-Acetone expulsion events occur, now serosity is close to precipitating point, under same rotating speed, continue stirring 15
Minute.
(3), under 85 DEG C, 2000rpm stirrings, in 20 minutes, addition 410g has been preheated with 80 DEG C of 10% (quality point
Number) aqueous acetic acid, charging finish after, allow cellulose diacetate microgranule from precipitating in acetic acid serosity out, under same rotating speed after
Continuous stirring 15min；
(4) stop stirring, while hot vacuum filter, and washing 4-5 time is carried out with 60-65 DEG C of hot water；It is subsequently placed in 105 DEG C
Dry within 3 hours in baking oven.
Sieved after drying, the particle mass percentage ratio of different-grain diameter scope is shown in Table 1.Diameter of particle is that 250-425 is micro-
Meter Shi, specific surface area are 38.5m2·g-1.
Embodiment 5：
(1) 149g cellulose diacetate ager serosity is taken, and wherein in the serosity, the combined acid containing 18% is 55.5%
Cellulose diacetate, 70% acetic acid, 12% water.The aqueous acetic acid for adding 75g to contain 70% is diluted, and starches after making dilution
In liquid, the mass concentration of cellulose diacetate is 12%.And cross paddle is used, above-mentioned serosity under 1500rpm mixing speeds
Serosity obtained above, after stopping stirring, is placed in airtight heating in 85 DEG C of water-baths by mix homogeneously.
(2), after temperature reaches balance, under 2000rpm mixing speeds, in 10 minutes, 70g is added to have been preheated with 80
DEG C 10% (mass fraction) aqueous acetic acid, charging finish after, it can be observed that the viscosity of Solution of CA-Acetone is obvious
Decline, start Solution of CA-Acetone expulsion events occur, now serosity is close to precipitating point, under same rotating speed, continue stirring 15
Minute.
(3), under 85 DEG C, 4000rpm stirrings, in 20 minutes, addition 410g has been preheated with 80 DEG C of 10% (quality point
Number) aqueous acetic acid, charging finish after, allow cellulose diacetate microgranule from precipitating in acetic acid serosity out, under same rotating speed after
Continuous stirring 15min；
(4) stop stirring, while hot vacuum filter, and washing 4-5 time is carried out with 60-65 DEG C of hot water；It is subsequently placed in 105 DEG C
Dry within 3 hours in baking oven.
Sieved after drying, the particle mass percentage ratio of different-grain diameter scope is shown in Table 1.Diameter of particle is that 250-425 is micro-
Meter Shi, specific surface area are 40.1m2·g-1.
Table 1：Particle size distribution under 3,4,5 step (3) of embodiment difference mixing speed
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and apply this
Bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiment without through performing creative labour.Therefore, the invention is not restricted to enforcement here
Example, announcement of the those skilled in the art according to the present invention, the improvement that is made without departing from scope and modification portion should be
Within protection scope of the present invention.
Claims (18)
1. a kind of preparation method of cellulose diacetate microgranule, it is characterised in that：Comprise the steps：
(1) certain density Solution of CA-Acetone is prepared, stirs, be heated to precipitating temperature；
(2) under conditions of first mixing speed and precipitating temperature, in the Solution of CA-Acetone for preparing in step (1)
Add the precipitating agent being mixed to get by solvent and non-solvent of preheating in the first time period with uniform speed, make solvent with non-
The mass ratio of solvent reaches nearly precipitating point ratio, after charging is finished, continues stirring 10-30 minutes under same mixing speed；
(3) mixing speed is adjusted to second mixing speed, keeps precipitating temperature, with uniform speed in second time period
Add precipitating agent so that the mass ratio of solvent and non-solvent reaches precipitating ratio in final solution, after adding precipitating agent, followed by
Continuous stirring 10-30 minutes, make cellulose diacetate microgranule precipitating out, obtain high-specific surface area cellulose diacetate microgranule；
The specific surface area of the high-specific surface area cellulose diacetate microgranule is 38.5-60m2/g；Diameter of particle is that 250-850 is micro-
Rice.
2. the preparation method of cellulose diacetate microgranule according to claim 1, it is characterised in that：Two described acetic acid are fine
The combination acid content of dimension element is 50%-57%.
3. the preparation method of cellulose diacetate microgranule according to claim 1, it is characterised in that：Two obtained acetic acid
Cellulose fine particle is filtered, washed and dried and obtains dry solid microgranule.
4. the preparation method of cellulose diacetate microgranule according to claim 3, it is characterised in that：Prepared by separation and recovery
During produce mixed waste liquor in solvent and non-solvent.
5. the preparation method of cellulose diacetate microgranule according to claim 1, it is characterised in that：Described in step (1)
Certain density Solution of CA-Acetone be with solvent and non-solvent dilution cellulose diacetate ager serosity obtain or
Person is obtained with solvent and non-solvent dissolved solid cellulose diacetate.
6. the preparation method of cellulose diacetate microgranule according to claim 1, it is characterised in that first mixing speed
For 500-4000rpm.
7. the preparation method of cellulose diacetate microgranule according to claim 1, it is characterised in that first time period is 5-
30 minutes.
8. the preparation method of cellulose diacetate microgranule according to claim 1, it is characterised in that second time period is
15-60 minutes.
9. the preparation method of cellulose diacetate microgranule according to claim 1, it is characterised in that：Second mixing speed
For 1000-3000rpm.
10. the preparation method of cellulose diacetate microgranule according to claim 1, it is characterised in that：Precipitating agent preheating temperature
Degree is less than 15 DEG C less than precipitating temperature.
The preparation method of 11. cellulose diacetate microgranules according to claim 1, it is characterised in that：Described solvent is
Acetic acid, acetone, or both mixture, described non-solvent be water, ethanol, or both mixture.
The preparation method of 12. cellulose diacetate microgranules according to claim 1, it is characterised in that：Described solvent is
Acetic acid, described non-solvent are water.
The preparation method of 13. cellulose diacetate microgranules according to claim 12, it is characterised in that：Described is certain dense
Component of the Solution of CA-Acetone of degree comprising following mass percent：6-15% cellulose diacetates, 75-82% acetic acid,
10-15% water.
The preparation method of 14. cellulose diacetate microgranules according to claim 12, it is characterised in that：Precipitating temperature is
60-95℃.
The preparation method of 15. cellulose diacetate microgranules according to claim 12, it is characterised in that precipitating agent preheating temperature
Spend for 55-90 DEG C.
The preparation method of 16. cellulose diacetate microgranules according to claim 12, it is characterised in that acetic acid/water near
Precipitating point ratio is in the range of 45/55-50/50.
The preparation method of 17. cellulose diacetate microgranules according to claim 12, it is characterised in that acetic acid/water heavy
Analysis ratio is in the range of 25/75-35/65.
Cellulose diacetate microgranule obtained in a kind of arbitrary described method of 18. claim 1-17, it is characterised in that：The microgranule
Specific surface area be 38.5-60m2/g；Diameter of particle is 250-850 microns.
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| CN115109300A (en) * | 2021-03-17 | 2022-09-27 | 四川大学 | Preparation method of macroporous cellulose diacetate microspheres |
| CN115109278A (en) * | 2021-03-18 | 2022-09-27 | 四川大学 | Preparation method of cellulose diacetate particles |
| CN113951558A (en) * | 2021-11-15 | 2022-01-21 | 红云红河烟草(集团)有限责任公司 | Filter tip capable of adsorbing tar in cigarette smoke |
| CN114009833A (en) * | 2021-11-15 | 2022-02-08 | 红云红河烟草(集团)有限责任公司 | Preparation method of cellulose diacetate and filter tip |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3420245A (en) * | 1965-02-05 | 1969-01-07 | Eastman Kodak Co | Particulate cellulose acetate tobacco smoke filter |
| US4663447A (en) * | 1984-01-24 | 1987-05-05 | Daicel Chemical Industries, Ltd. | Porous spherical cellulose acetate particles |
| DE10031655C2 (en) * | 2000-06-29 | 2002-07-04 | Cellcat Gmbh Hallein | Method and device for producing cellulose particles |
-
2013
- 2013-10-28 CN CN201310517113.4A patent/CN104558640B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3420245A (en) * | 1965-02-05 | 1969-01-07 | Eastman Kodak Co | Particulate cellulose acetate tobacco smoke filter |
| US4663447A (en) * | 1984-01-24 | 1987-05-05 | Daicel Chemical Industries, Ltd. | Porous spherical cellulose acetate particles |
| DE10031655C2 (en) * | 2000-06-29 | 2002-07-04 | Cellcat Gmbh Hallein | Method and device for producing cellulose particles |
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