CN104558640A - Preparation method of cellulose diacetate particles - Google Patents
Preparation method of cellulose diacetate particles Download PDFInfo
- Publication number
- CN104558640A CN104558640A CN201310517113.4A CN201310517113A CN104558640A CN 104558640 A CN104558640 A CN 104558640A CN 201310517113 A CN201310517113 A CN 201310517113A CN 104558640 A CN104558640 A CN 104558640A
- Authority
- CN
- China
- Prior art keywords
- cellulose diacetate
- solvent
- preparation
- precipitating
- particulate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention belongs to the technical field of materials, and relates to a preparation method of cellulose diacetate particles. The preparation method comprises the following steps: (1) preparing a cellulose diacetate solution, uniformly stirring, and heating the cellulose diacetate solution to a precipitation temperature; (2) adding a preheated precipitating agent obtained by mixing a solvent and a non-solvent into the cellulose diacetate solution prepared in the step (1), so that the mass ratio of the solvent and the non-solvent achieves a proportion near a precipitation-point proportion, and after the adding is completed, further stirring for 10-30 minutes at the same rotating speed; and (3) maintaining the precipitation temperature, and adding the precipitating agent at a uniform speed, so that the mass ratio of the solvent and the non-solvent in a final solution achieves the precipitation-point proportion, and after the adding is completed, further stirring for 10-30 minutes, so that cellulose diacetate particles are precipitated out, and high-specific-surface-area cellulose diacetate particles are obtained. Microspheres prepared according to the invention have a porosity characteristic and the sizes of the microspheres can be adjusted, the surface and the inside of each particle are respectively of a porous structure, and the surface area is 30-60m<2>/g.
Description
Technical field
The invention belongs to field of material technology, relate to a kind of preparation method of Cellulose diacetate particulate.
Background technology
Cellulose acetate, English name Cellulose Acetate (abbreviation CA), be also called cellulose acetate, molecular formula is [C
6h
7o
2(OCOCH
3)
x(OH)
3-x]
n, n=200-400.Its industrial application product mainly cellulosetri-acetate and Cellulose diacetate.When x close to 3 time be cellulosetri-acetate; Be Cellulose diacetate when x=2.28-2.49 (being equivalent to combined acid content 53-56%).Combined acid is the binding capacity of acetic acid in cellulose acetate product, is expressed as the mass percent of the acetic acid that every cellulose acetate unit mass combines.Combined acid can be measured for measuring cellulose acetate combined acid method according in ASTM D871-2004 (testing method of cellulose acetate etc.).Measuring method is as follows: first by 1.9 grams of dried cellulose acetate dissolves in the mixed solvent of 150ml acetone/dimethyl sulfoxide (DMSO) (4:1, v/v), add the aqueous sodium hydroxide solution of 30ml1N, and saponification 2 hours under 25 DEG C of conditions; Then 2 ~ 3 phenolphthalein indicators are dripped, and the sodium hydroxide of sulfuric acid overtitration with 1N.Blank test is carried out by above-mentioned same method, and by equation calculations incorporated acid below:
Combined acid (%)=(6.005 × (B-A) × F)/W
In formula, A represents the consumption (ml) adding 1N sulfuric acid in sample to, and B represents the consumption (ml) adding 1N sulfuric acid in check sample to, and F represents the concentration factor of 1N sulfuric acid, and W is the weight (g) of sample.
Its production process of Cellulose diacetate is (Encyclopedia of Chemical Technology, Kirk-Othmer, volume5, p5000-5002): wood pulps raw material is carried out after pulverizing mills, use acetic acid pre-treatment and activation, then take sulfuric acid as catalyzer, acetic acid carries out esterification with aceticanhydride under making the condition of solvent, obtain cellulosetri-acetate slurries, obtain Cellulose diacetate slurries (being called for short ager slurries) through partial hydrolysis and then made by precipitating, washing and drying and other steps.The precipitating of current ager slurries has two kinds of modes, and one adds aqueous acetic acid under agitation, obtains the Powdered Cellulose diacetate that tap density is little; Also having one to be extruded by little aperture apparatus by ager slurries to enter in dilute acetic acid aqueous solution, obtaining fine and close high-bulk-density Cellulose diacetate particle through cutting off.By analyzing, the Cellulose diacetate surface-area of these two kinds of precipitating explained hereafter is respectively 4.2m
2/ g and 0.6m
2/ g.
Cellulose diacetate has good soffening, and can dissolve in common solvent (as acetone, acetic acid, vinyl acetic monomer), and therefore its product generally presents the face shapings such as sheet, powder, fiber, film.Because Cellulose diacetate itself has reasonable adsorptivity, weather resisteant, shock-resistant, the characteristic such as oil resistant, not static electrification, if it is processed to have unique microscopic characteristics porous do ball or particulate, then can be used as the carrier of chromatographic column filler, enzyme, the additive (foundation cream, lipstick, eye shadow, emulsion, skin cream) of makeup, the properties-correcting agent of medicine sustained release dosage, pigment and paint, sewage treatment project sorbent material, fragrance delivery vehicles, deodovization agent and filter material of cigarette.
The people (DE2,507,551) such as B.V.Chandler in 1975 adopt the method for cooling to obtain cellulose acetate from the DMSO/ acetone soln of Cellulose diacetate and make ball.Li Fuchun (Biotechnical Bioeng, 18,1507-1516 (1979)) adopts the method for disperseing in water to obtain the result identical with Chandler.From 1981, people (USP4,390,691 such as the people such as Y.Motozato (Nippon KagakaKuishi, 1892-1898,12 (1981)), Japanese Nishikawa; ) describe and use halohydrocarbon methylene dichloride to be ball preparation method as " suspension method " of primary solvent.Daicel company of Japan (USP4,663,447), Celanese company of the U.S. (USP5,047,180, US5064949) once to disclose with Cellulose diacetate acetic acid slurries be raw material, acetic acid is prepared cellulose acetate do ball patent as solvent, gunite.The people such as WagenknechtW (EP0750007) adopt methyl alcohol and ethyl acetate to be solvent, and the cellulose acetate that " suspension method " method of utilization prepares median size 1-20 micron makees ball.Lolanda (The Journal ofSupercritical Fluids [J] .2011,55:1095-1103) adopt acetone to be solvent, utilize super-critical anti-solvent precipitating technology to prepare the above-mentioned cellulose acetate of preparing of cellulose acetate nanoparticle and do ball or particulate method.There is following shortcoming in above method: uses noxious solvent, or use energy consumption equipment.
Summary of the invention
On the one hand, the present invention is a kind of Cellulose diacetate particulate preparation method of high-specific surface area, comprises the steps:
(1) prepare certain density Solution of CA-Acetone, stir, be heated to precipitating temperature.The combined acid content of described Cellulose diacetate is 50%-57%.Described Solution of CA-Acetone can obtain with the mixture diluted Cellulose diacetate ager slurries of solvent, non-solvent or solvent and non-solvent, also can obtain with the mixture dissolved solids Cellulose diacetate of solvent or solvent and non-solvent.Described finite concentration is Cellulose diacetate mass percent in the solution, can practical range be 6-15%, preferred 7-14%;
(2) under the condition of first stirring velocity and precipitating temperature, in first time period, add the precipitating agent be mixed to get by solvent and non-solvent of preheating with uniform speed in the Solution of CA-Acetone of preparation in step (1), the mass ratio of solvent and non-solvent is made to reach nearly precipitating point ratio, after reinforced, continue under same rotating speed to stir 10-30 minute;
(3) stirring velocity is adjusted to second stirring velocity, keep precipitating temperature, precipitating agent is added with uniform speed within the second time period, the mass ratio of solvent and non-solvent in final solution is made to reach precipitating ratio, after adding precipitating agent, continue again to stir 10-30 minute, make Cellulose diacetate particulate precipitating out, obtain high-specific surface area Cellulose diacetate particulate.
The Cellulose diacetate particulate obtained obtains dry solia particle by filtration, washing and drying; The specific surface area of particulate is 30-60m
2/ g, diameter of particle is 250-850 micron.
Preparation method of the present invention is by selective solvent and non-solvent, and the stirring velocity of control different steps, solvent and non-solvent ratio in the solution, precipitating temperature, precipitating agent add the conditions such as speed to control particle diameter and the specific surface area of prepared Cellulose diacetate particulate.Described solvent is acetic acid, acetone or both mixtures, and described non-solvent is water, ethanol or both mixtures, and preferred solvent is acetic acid, and non-solvent is water.
The main purpose of preparation method's second step of the present invention makes the mass ratio of the solvent in Solution of CA-Acetone and non-solvent reach nearly precipitating point ratio and don't local precipitating occurs.In order to reach this purpose, first stirring velocity selects 500-4000rpm, preferred 1000-2000rpm.First time period selects 5-60 minute, preferred 10-30 minute, and the concrete precipitating dosage selecting to need with this time period to add is relevant.Precipitating agent adds speed=precipitating dosage/first time period.Uniform speed refers to and precipitating agent to be added by substantially same speed in whole first time period.
For a certain amount of Solution of CA-Acetone, first time period precipitating agent consumption is relevant to nearly precipitating point ratio.Nearly precipitating point ratio is defined as the viscosity can observing Solution of CA-Acetone when the mass ratio of solvent and non-solvent reaches this ratio and obviously declines, and starts to occur Solution of CA-Acetone expulsion events.So, after selected solvent, non-solvent and precipitating temperature range, need to found through experiments nearly precipitating point proportional range.Selective solvent be acetic acid, non-solvent be water time, nearly precipitating point ratio (mass ratio) of acetic acid and water is within the scope of 45/55-50/50.
Precipitating agent preheating temperature is also very important to avoiding that local precipitating occurs.If precipitating agent temperature is significantly lower than precipitating temperature, such as: (precipitating temperature-precipitating agent temperature) > 20 DEG C, just likely there is local precipitating.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-precipitating agent preheating temperature)≤5 DEG C.
In the 3rd step of preparation method of the present invention, add by controlling precipitating temperature, stirring velocity and precipitating agent particle diameter and the specific surface area that speed (the second time period) controls prepared Cellulose diacetate particulate.Precipitating temperature is relevant with non-solvent with selected solvent; Select the minimum boiling point lower than solvent or non-solvent, higher than 40 DEG C.Precipitating ratio, is chosen as the solubleness of solid Cellulose diacetate in the solvent of 100 grams of precipitating ratios and the mixture of non-solvent and is less than 2 grams, be preferably less than 1 gram, obtain by experiment.Second time period selected 15-60 minute, preferred 20-55 minute, and the concrete precipitating dosage selecting to need with this time period to add is relevant.Second time period needed the precipitating agent consumption added that Solution of CA-Acetone concentration and consumption, first time period precipitating agent consumption and precipitating ratio can be used to calculate.The size distribution of second stirring velocity to the Cellulose diacetate particulate generated has a direct impact; In the scope of 1000-4000rpm, low stirring velocity is conducive to generating Large stone particulate (250-850 micron), and high stirring velocity is conducive to generating small particle size particulate and is less than 250 microns).
An embodiment of the present invention is that selection acetic acid is solvent, water is non-solvent.In this embodies, described certain density Cellulose diacetate slurry package is containing the component of following mass percent: 6-15% Cellulose diacetate, 75-82% acetic acid, 10-15% water; Precipitating thermal creep stress 60-95 DEG C, preferred 65-90 DEG C; First stirring velocity is 500-4000rpm, preferred 1000-2000rpm; Precipitating agent preheating temperature is 55-90 DEG C, preferred 50-85 DEG C; Very first time scope is 5-60 minute; Experiment finds that the nearly precipitating point ratio of acetic acid and water is within the scope of 45/55-50/50; Second time range is 15-60 minute; Second stirring velocity is 1000-3000rpm, preferred 1100-2500rpm; The acetic acid of measuring and the precipitating ratio (mass ratio) of water are within the scope of 25/75-35/65.
The solvent/non-solvent mixed waste liquor that preparation process of the present invention produces can Separation and Recovery, concentrate recycling.Such as, solvent be acetic acid, non-solvent is in the system of water, acetic acid water lean solution, the acetic acid recovery technology of existing maturation (the commentary chemical industry environmental protection of the bright Separation and Recovery acetic acid method from the aqueous solution of Yang Chun China Ceng Guang can be utilized, 1995,15 (2), 78-81) acetic acid recovery concentrate recycling, is carried out.
On the other hand, the present invention is the Cellulose diacetate particulate that a kind of aforesaid method obtains, and the specific surface area of this particulate is 30-60m
2/ g; Diameter of particle is 250-850 micron.Obtained Cellulose diacetate particulate can be used for chromatographic column filler, the carrier of enzyme, the additive (foundation cream, lipstick, eye shadow, emulsion, skin cream) of makeup; Also can be used for the properties-correcting agent of medicine sustained release dosage, pigment and paint, sewage treatment project sorbent material, fragrance delivery vehicles, deodovization agent and filter material of cigarette.Simultaneously can make ball to Cellulose diacetate to be hydrolyzed and to obtain Mierocrystalline cellulose and make ball, and by crosslinked, grafting with prepare matrix material and improve its Application Areas of its behavior extension further.
Accompanying drawing explanation
Fig. 1 is that particulate SEM prepared by the embodiment of the present invention schemes.
Fig. 2 is that particulate SEM prepared by another embodiment of the present invention schemes.
Interparticle structure SEM prepared by Fig. 3 embodiment of the present invention schemes.
Embodiment
Following examples and accompanying drawing are to further illustrate the present invention.
Following percentage ratio (%), except as otherwise noted, is mass percent.
Embodiment 1
(1) get 154g Cellulose diacetate ager slurries, the combined acid wherein containing 18% in these slurries is the Cellulose diacetate of 55.5%, 70% acetic acid, 12% water.Add the aqueous acetic acid that 91g contains 70% to dilute, make the mass concentration of Cellulose diacetate in dilution rear slurry be 11%.And use cross paddle, under 1500rpm stirring velocity, above-mentioned slurries are mixed, after stopping stirring, slurries obtained above are placed in 85 DEG C of airtight heating of water-bath.
(2) reach after balance until temperature, under 2000rpm stirring velocity, in 10 minutes, add 10% (massfraction) aqueous acetic acid that 65g has been preheating to 80 DEG C, after reinforced, the viscosity can observing Solution of CA-Acetone obviously declines, and starts to occur Solution of CA-Acetone expulsion events, now slurries are close to precipitating point, continue stirring 15 minutes under same rotating speed.
(3) 85 DEG C, 2500rpm stir under, in 20 minutes, add 10% (massfraction) aqueous acetic acid that 375g has been preheating to 80 DEG C, after reinforced, Cellulose diacetate particulate precipitating from acetic acid slurries is allowed out, to continue under same rotating speed to stir 15min;
(4) stop stirring, vacuum filtration while hot, and carry out washing 4-5 time with the hot water of 60-65 DEG C; Then be placed in 105 DEG C of baking ovens to dry for 3 hours.
Sieve after drying, make that particle diameter is 425-825 μm, specific surface area is 45.9m
2g
-1porous cellulose acetate particulate.As shown in Figure 1, SEM test shows, its surface presentation vesicular structure.Section sem analysis is carried out to the particulate of preparation simultaneously, the results are shown in Figure 3.By SEM sectional view, can obviously find out, interparticle presents abundant cellular vesicular structure.Thus there is higher specific surface area.
Embodiment 2
(1) 636g Cellulose diacetate ager slurries are got, be the Cellulose diacetate quality 19% of 55.5% containing combined acid in these slurries, 69% acetic acid, 12% water, and be placed in the glass reaction still that 5L heats with chuck, add the aqueous acetic acid that 364g contains 70% to dilute, make the mass concentration of Cellulose diacetate in dilution rear slurry be 12%.And use cross paddle, under 2000rpm stirring velocity, above-mentioned slurries are mixed, after stopping stirring, slurries obtained above are heated to 85 DEG C with hot water jacket.
(2) reach after balance until temperature, under 2000rpm stirring velocity, in 10 minutes, add 10% (massfraction) aqueous acetic acid 270 grams being preheating to 80 DEG C, after reinforced, the viscosity can observing Solution of CA-Acetone obviously declines, and starts to occur Solution of CA-Acetone expulsion events, now slurries are close to precipitating point, continue stirring 15 minutes under same rotating speed.
(3) 85 DEG C, 1200rpm stir under, in 30 minutes, then add remaining aqueous acetic acid, altogether add aqueous acetic acid 2000g.After reinforced, Cellulose diacetate particulate precipitating from acetic acid slurries is allowed out, to continue under 1200rpm rotating speed to stir 15min;
(4) stop stirring, vacuum filtration while hot, and carry out washing 4-5 time with the hot water of 60-65 DEG C; Then be placed in 105 DEG C of baking ovens to dry for 3 hours.
Sieve after drying, make that particle diameter is 425-825 μm, specific surface area is 58.5m
2g
-1porous cellulose acetate particulate.As shown in Figure 2, SEM test shows, its surface presentation vesicular structure.
Embodiment 3
(1) get 157g Cellulose diacetate ager slurries, the combined acid wherein containing 18% in these slurries is the Cellulose diacetate of 55.5%, 70% acetic acid, 12% water.Add the aqueous acetic acid that 79g contains 70% to dilute, make the mass concentration of Cellulose diacetate in dilution rear slurry be 12%.And use cross paddle, under 1500rpm stirring velocity, above-mentioned slurries are mixed, after stopping stirring, slurries obtained above are placed in 85 DEG C of airtight heating of water-bath.
(2) reach after balance until temperature, under 2000rpm stirring velocity, in 10 minutes, add 10% (massfraction) aqueous acetic acid that 70g has been preheating to 80 DEG C, after reinforced, the viscosity can observing Solution of CA-Acetone obviously declines, and starts to occur Solution of CA-Acetone expulsion events, now slurries are close to precipitating point, continue stirring 15 minutes under same rotating speed.
(3) again 85 DEG C, 1100rpm stir under, in 20 minutes, add 10% (massfraction) aqueous acetic acid that 410g has been preheating to 80 DEG C, after reinforced, Cellulose diacetate particulate precipitating from acetic acid slurries is allowed out, to continue under same rotating speed to stir 15min;
(4) stop stirring, vacuum filtration while hot, and carry out washing 4-5 time with the hot water of 60-65 DEG C; Then be placed in 105 DEG C of baking ovens to dry for 3 hours.
Sieve after drying, the particle mass per-cent of different-grain diameter scope is in table 1.When diameter of particle is 250-425 micron, specific surface area is 42.2m
2g
-1.
Embodiment 4
(1) get 156g Cellulose diacetate ager slurries, the combined acid wherein containing 18% in these slurries is the Cellulose diacetate of 55.5%, 70% acetic acid, 12% water.Add the aqueous acetic acid that 78g contains 70% to dilute, make the mass concentration of Cellulose diacetate in dilution rear slurry be 12%.And use cross paddle, under 1500rpm stirring velocity, above-mentioned slurries are mixed, after stopping stirring, slurries obtained above are placed in 85 DEG C of airtight heating of water-bath.
(2) reach after balance until temperature, under 2000rpm stirring velocity, in 10 minutes, add 10% (massfraction) aqueous acetic acid that 70g has been preheating to 80 DEG C, after reinforced, the viscosity can observing Solution of CA-Acetone obviously declines, and starts to occur Solution of CA-Acetone expulsion events, now slurries are close to precipitating point, continue stirring 15 minutes under same rotating speed.
(3) 85 DEG C, 2000rpm stir under, in 20 minutes, add 10% (massfraction) aqueous acetic acid that 410g has been preheating to 80 DEG C, after reinforced, Cellulose diacetate particulate precipitating from acetic acid slurries is allowed out, to continue under same rotating speed to stir 15min;
(4) stop stirring, vacuum filtration while hot, and carry out washing 4-5 time with the hot water of 60-65 DEG C; Then be placed in 105 DEG C of baking ovens to dry for 3 hours.
Sieve after drying, the particle mass per-cent of different-grain diameter scope is in table 1.When diameter of particle is 250-425 micron, specific surface area is 38.5m
2g
-1.
Embodiment 5:
(1) get 149g Cellulose diacetate ager slurries, the combined acid wherein containing 18% in these slurries is the Cellulose diacetate of 55.5%, 70% acetic acid, 12% water.Add the aqueous acetic acid that 75g contains 70% to dilute, make the mass concentration of Cellulose diacetate in dilution rear slurry be 12%.And use cross paddle, under 1500rpm stirring velocity, above-mentioned slurries are mixed, after stopping stirring, slurries obtained above are placed in 85 DEG C of airtight heating of water-bath.
(2) reach after balance until temperature, under 2000rpm stirring velocity, in 10 minutes, add 10% (massfraction) aqueous acetic acid that 70g has been preheating to 80 DEG C, after reinforced, the viscosity can observing Solution of CA-Acetone obviously declines, and starts to occur Solution of CA-Acetone expulsion events, now slurries are close to precipitating point, continue stirring 15 minutes under same rotating speed.
(3) 85 DEG C, 4000rpm stir under, in 20 minutes, add 10% (massfraction) aqueous acetic acid that 410g has been preheating to 80 DEG C, after reinforced, Cellulose diacetate particulate precipitating from acetic acid slurries is allowed out, to continue under same rotating speed to stir 15min;
(4) stop stirring, vacuum filtration while hot, and carry out washing 4-5 time with the hot water of 60-65 DEG C; Then be placed in 105 DEG C of baking ovens to dry for 3 hours.
Sieve after drying, the particle mass per-cent of different-grain diameter scope is in table 1.When diameter of particle is 250-425 micron, specific surface area is 40.1m
2g
-1.
Table 1: particle size distribution under embodiment 3,4,5 step (3) different stirring velocity
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment portion should within protection scope of the present invention.
Claims (18)
1. a preparation method for Cellulose diacetate particulate, is characterized in that: comprise the steps:
(1) prepare certain density Solution of CA-Acetone, stir, be heated to precipitating temperature;
(2) under the condition of first stirring velocity and precipitating temperature, in first time period, add the precipitating agent be mixed to get by solvent and non-solvent of preheating with uniform speed in the Solution of CA-Acetone of preparation in step (1), the mass ratio of solvent and non-solvent is made to reach nearly precipitating point ratio, after reinforced, continue under same rotating speed to stir 10-30 minute;
(3) stirring velocity is adjusted to second stirring velocity, keep precipitating temperature, precipitating agent is added with uniform speed within the second time period, the mass ratio of solvent and non-solvent in final solution is made to reach precipitating ratio, after adding precipitating agent, continue again to stir 10-30 minute, make Cellulose diacetate particulate precipitating out, obtain high-specific surface area Cellulose diacetate particulate.
2. the preparation method of Cellulose diacetate particulate according to claim 1, is characterized in that: the combined acid content of described Cellulose diacetate is 50%-57%.
3. the preparation method of Cellulose diacetate particulate according to claim 1, is characterized in that: the Cellulose diacetate particulate obtained obtains dry solia particle by filtration, washing and drying, and the specific surface area of this particulate is 30-60m
2/ g, diameter of particle is 250-850 micron.
4. the preparation method of Cellulose diacetate particulate according to claim 3, is characterized in that: the solvent in the mixed waste liquor that Separation and Recovery produces in preparation process and non-solvent.
5. the preparation method of Cellulose diacetate particulate according to claim 1, is characterized in that: the certain density Solution of CA-Acetone described in step (1) obtains with solvent and non-solvent dilution Cellulose diacetate ager slurries or obtain with solvent and non-solvent dissolved solids Cellulose diacetate.
6. the preparation method of Cellulose diacetate particulate according to claim 1, is characterized in that, first stirring velocity is 500-4000rpm.
7. the preparation method of Cellulose diacetate particulate according to claim 1, is characterized in that, very first time scope is 5-30 minute.
8. the preparation method of Cellulose diacetate particulate according to claim 1, is characterized in that, the second time range is 15-60 minute.
9. the preparation method of Cellulose diacetate particulate according to claim 1, is characterized in that: second stirring velocity is 1000-3000rpm.
10. the preparation method of Cellulose diacetate particulate according to claim 1, is characterized in that: precipitating agent preheating temperature is no more than 15 DEG C lower than precipitating temperature.
The preparation method of 11. Cellulose diacetate particulates according to claim 1, is characterized in that: described solvent is acetic acid, acetone or both mixtures, and described non-solvent is water, ethanol or both mixtures.
The preparation method of 12. Cellulose diacetate particulates according to claim 1, is characterized in that: described solvent is acetic acid, and described non-solvent is water.
The preparation method of 13. Cellulose diacetate particulates according to claim 12, it is characterized in that: described certain density Cellulose diacetate slurry package is containing the component of following mass percent: 6-15% Cellulose diacetate, 75-82% acetic acid, 10-15% water.
The preparation method of 14. Cellulose diacetate particulates according to claim 12, is characterized in that: precipitating temperature is 60-95 DEG C.
The preparation method of 15. Cellulose diacetate particulates according to claim 12, is characterized in that, precipitating agent preheating temperature is 55-90 DEG C.
The preparation method of 16. Cellulose diacetate particulates according to claim 12, is characterized in that, the nearly precipitating point ratio of acetic acid/water is within the scope of 45/55-50/50.
The preparation method of 17. Cellulose diacetate particulates according to claim 12, is characterized in that, the precipitating ratio of acetic acid/water is within the scope of 25/75-35/65.
The Cellulose diacetate particulate that in 18. 1 kinds of claim 1-17, arbitrary described method is obtained, is characterized in that: the specific surface area of this particulate is 30-60m
2/ g; Diameter of particle is 250-850 micron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310517113.4A CN104558640B (en) | 2013-10-28 | 2013-10-28 | A kind of preparation method of cellulose diacetate microgranule |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310517113.4A CN104558640B (en) | 2013-10-28 | 2013-10-28 | A kind of preparation method of cellulose diacetate microgranule |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104558640A true CN104558640A (en) | 2015-04-29 |
| CN104558640B CN104558640B (en) | 2017-03-15 |
Family
ID=53075771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310517113.4A Active CN104558640B (en) | 2013-10-28 | 2013-10-28 | A kind of preparation method of cellulose diacetate microgranule |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104558640B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108070140A (en) * | 2016-11-09 | 2018-05-25 | 神华集团有限责任公司 | Fibre modifier and modified fibre and its preparation method and application and PP composite material and preparation method thereof |
| CN109016340A (en) * | 2018-08-23 | 2018-12-18 | 温州金余塑胶板有限公司 | A kind of composite material and its moulding process using acetate fiber production spectacle frame |
| CN109541002A (en) * | 2018-11-01 | 2019-03-29 | 中峰化学有限公司 | The measuring method of acid is combined in a kind of cellulose acetate hydrolytic process |
| CN110079884A (en) * | 2019-05-08 | 2019-08-02 | 东华大学 | A kind of preparation method of high-specific surface area polyimides fibrid |
| CN110437475A (en) * | 2018-05-03 | 2019-11-12 | 青岛农业大学 | A method of preparing hollow structure guar gum nano particle |
| CN111253616A (en) * | 2020-03-02 | 2020-06-09 | 万华化学集团股份有限公司 | Method and device for precipitating cellulose acetate butyrate |
| CN111826165A (en) * | 2020-06-23 | 2020-10-27 | 成都新柯力化工科技有限公司 | Acidified soil cellulose-based modifier and preparation method thereof |
| 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 |
| CN115109278A (en) * | 2021-03-18 | 2022-09-27 | 四川大学 | Preparation method of cellulose diacetate particles |
| CN115109300A (en) * | 2021-03-17 | 2022-09-27 | 四川大学 | Preparation method of macroporous cellulose diacetate microspheres |
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 |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108070140A (en) * | 2016-11-09 | 2018-05-25 | 神华集团有限责任公司 | Fibre modifier and modified fibre and its preparation method and application and PP composite material and preparation method thereof |
| CN110437475A (en) * | 2018-05-03 | 2019-11-12 | 青岛农业大学 | A method of preparing hollow structure guar gum nano particle |
| CN109016340A (en) * | 2018-08-23 | 2018-12-18 | 温州金余塑胶板有限公司 | A kind of composite material and its moulding process using acetate fiber production spectacle frame |
| CN109541002A (en) * | 2018-11-01 | 2019-03-29 | 中峰化学有限公司 | The measuring method of acid is combined in a kind of cellulose acetate hydrolytic process |
| CN109541002B (en) * | 2018-11-01 | 2021-03-12 | 中峰化学有限公司 | Method for determining bound acid in cellulose acetate hydrolysis process |
| CN110079884A (en) * | 2019-05-08 | 2019-08-02 | 东华大学 | A kind of preparation method of high-specific surface area polyimides fibrid |
| CN111253616A (en) * | 2020-03-02 | 2020-06-09 | 万华化学集团股份有限公司 | Method and device for precipitating cellulose acetate butyrate |
| CN111253616B (en) * | 2020-03-02 | 2022-07-12 | 万华化学集团股份有限公司 | Method and device for precipitating cellulose acetate butyrate |
| CN111826165A (en) * | 2020-06-23 | 2020-10-27 | 成都新柯力化工科技有限公司 | Acidified soil cellulose-based modifier and preparation method thereof |
| 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104558640B (en) | 2017-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104558640A (en) | Preparation method of cellulose diacetate particles | |
| Luo et al. | Creation of regenerated cellulose microspheres with diameter ranging from micron to millimeter for chromatography applications | |
| CN102553545B (en) | Cellulose composite microsphere and preparation method thereof | |
| CN104845301B (en) | A kind of ultraviolet light screener and preparation method thereof and polylactic acid film comprising the ultraviolet light screener and preparation method thereof | |
| CN103132169B (en) | A kind of cellulose nano-fibrous preparation method of energy stable dispersion | |
| CN104892936B (en) | A kind of cellulose/polyaniline nano porous complex microsphere and preparation method thereof and purposes | |
| CN114245757B (en) | Ion exchange type nanofiber skeleton three-dimensional separation material with controllable structure and preparation method thereof | |
| CN101595168A (en) | Cellulose fine particle and dispersion liquid thereof and dispersion | |
| WO2013016982A1 (en) | Cellulose acetate microsphere preparation method and product prepared thereby | |
| CN103724635B (en) | Preparation method of a kind of cellulose acetate porous microsphere and products thereof | |
| CN103521149B (en) | Containing the preparation method of energy polymer microsphere | |
| CN102580691B (en) | Cellulose base - silicon hybridization microsphere and preparation method thereof | |
| CN106750436B (en) | A kind of sulfonating surface polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone composite membrane and preparation method thereof | |
| CN102964539A (en) | Preparation method of porous magnetic polystyrene microspheres | |
| CN101519543A (en) | Method for preparing coupling agent modified nanometer zinc oxide with reaction groups | |
| CN114149295B (en) | Coated molecular perovskite energetic material and preparation method thereof | |
| CN102093147A (en) | Modified expanded ammonium nitrate explosive and preparation method thereof | |
| CN106147259A (en) | The preparation method of a kind of surface hydrophobicity sheet-like fiber element and this sheet-like fiber element | |
| US20180044439A1 (en) | Cellulose suspension, method for the production and use thereof | |
| Elhi et al. | Ionic liquids as solvents for making composite materials from cellulose | |
| CN107285301B (en) | A kind of high concentration graphene dispersion liquid and preparation method thereof | |
| Yao et al. | Application of cellulose to chromatographic media: Cellulose dissolution, and media fabrication and derivatization | |
| JP2018070411A (en) | Nanodiamond organic solvent dispersion and process for preparing diamond organic solvent dispersion | |
| Dai et al. | Preparation and protein adsorption of porous dextran microspheres | |
| CN108251097B (en) | A kind of microcapsule degelling agent and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |