CN102911379B - Method for preparing cellulose acetate microspheres and product prepared by method - Google Patents
Method for preparing cellulose acetate microspheres and product prepared by method Download PDFInfo
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- CN102911379B CN102911379B CN201110222485.5A CN201110222485A CN102911379B CN 102911379 B CN102911379 B CN 102911379B CN 201110222485 A CN201110222485 A CN 201110222485A CN 102911379 B CN102911379 B CN 102911379B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/14—Powdering or granulating by precipitation from solutions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/16—Powdering or granulating by coagulating dispersions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
- C08L1/12—Cellulose acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/10—Esters of organic acids
- C08J2301/12—Cellulose acetate
Abstract
The invention belongs to the technical field of chemical cellulose, and discloses a method for preparing cellulose acetate microspheres and a product prepared by the method. The method for preparing cellulose acetate microspheres comprises the following steps of dissolving a cellulose acetate tow with a plasticizer into a mixed solvent to obtain polymer slurry, then adding the obtained polymer slurry into dispersion liquid to be fully mixed to obtain suspension liquid, reducing the solubility of cellulose acetate, and separating out the cellulose acetate microspheres. The average grain diameter of the cellulose acetate microspheres is 5-1500 micrometers, the average pore size is 2-200 nm, and the specific surface area is 0.6m<2>*g<-1> to 10.0m<2>*g<-1>. The acetyl substitution degree of the cellulose acetate is 2.0-2.6, and the content of the residual plasticizer is 1.0-3.0 percent of the quality of the cellulose acetate microspheres. The microspheres have the advantages of easiness in regeneration, good biocompatibility, good hydrophily and the like.
Description
Technical field
The invention belongs to chemical cellulose technical field, relate to a kind of preparation method of cellulose acetate microballoon and the product of being prepared by the method.
Background technology
Cellulose acetate claims again cellulose acetate, i.e. cellulose acetate.Cellulose acetate be take the regenerated fiber that acetic acid and Mierocrystalline cellulose make through esterification as raw material.Lignocellulose obtains the Cellulose diacetate flake (being called for short " vinegar sheet ") of sheet through acetify, hydrolysis, the operation such as dry after processing, vinegar sheet obtains Celluloseacetate cigarette filter tow (being called for short " tow ") after spinning.
Cellulose acetate can obtain cellulosetri-acetate by the direct esterification under Glacial acetic acid, acetic anhydride, sulfuric acid condition of the Mierocrystalline celluloses such as cotton linter dissolving pulp, wood pulps, then triacetate fiber is carried out to partial hydrolysis and obtains the Cellulose diacetate product of degree of substitution with acetyl group between 2.0～2.6.
Cellulose diacetate, as a kind of important organic cellulose ester, has nontoxic, noninflammability, mainly for the manufacture of cigarette filter.In order to make filter stick that tow rolls into there is suitable stiffness, need to add softening agent.Softening agent is a kind of low-molecular-weight compound or polymkeric substance, is added in the polymkeric substance that needs plasticising, can increase the plasticity-of polymkeric substance.Softening agent is generally the liquid of high boiling more difficult volatilization or the solid of LMP, and great majority are ester class organic compound.Conventionally not with polymkeric substance react with, and the interaction of polymkeric substance is mainly the swelling action when rising temperature.Softening agent Performance Ratio comprehensively and production and easy to use, is applied very wide.Softening agent when Cellulose acetate element tow is manufactured cigarette filter is selected glycerine triacetate or glycol diacetate conventionally, and softening agent usage quantity accounts for 5%～12% of cellulose acetate tow quality.The discarded tow producing in tobacco processing process is mainly that the form that is mixed with softening agent exists.Except as otherwise noted, the discarded tow of the following stated is all mixed with softening agent.The annual acetate silk usage quantity of China reaches 260,000 tons, annual 2000～4000 tons, the discarded tow that produces.
Out of control in order to prevent tow outflow, Chinese tobacco monopoly bureau regulation all waste tow must fix a point to burn.Although burn, stop the approach that discarded tow enters false smoke manufacture link, inevitably brought the wasting of resources and unnecessary carbon emission.A little earlier, state-owned report directly will be discarded tow and add acetone, auxiliary agent to make polymkeric substance, after filtration, deaeration utilizes dry-spinning to make tow and reuses (useless vinegar fine (WCA) regeneration cigarette filter tip fiber research, regenerated fiber .1989,5:1-4.), but the softening agent being mixed with in discarded tow is to be difficult to remove with common filter type, and spinning process is very easily stuck with paste cap.Tow is washed by high temperature or the method for enzymic hydrolysis by discarding Patents, remove after softening agent again row reclaim again make that tow uses (US 5,328,934, US5,504,119, US5,504,120, Chinese Patent Application No. 200910064880.8), have patent to propose to adopt first high pressure/low temperature in encloses container, rear low pressure/high temperature water-washing method improves softening agent removal efficiency, and (US 5,402,893), but these methods all need to expend a large amount of water and energy and washes to be difficult to process.Also, after having discarded tow being pulverized, utilize biological enzyme that tow is degraded to monose (US4,298,013) and reuse again, but biodegradation rate is slow and discarded tow in softening agent be also difficult to process.Also have discarded tow is added after caustic soda hydrolysis, be mixed for paper industry (US5,662,773,2004/0214702 A1) with Mierocrystalline cellulose, but this class methods added value of industry is not high.Also have patent openly to adopt mixed solvent to carry out cellulose acetate recovery method (CN200910185996.7), but the toxic solvents adopting is unfavorable for follow-up relevant processing.
Cellulose acetate can have other application (such as cinefilm, film or fiber) according to the difference of its shape, and wherein cellulose acetate microballoon is a special dimension of cellulose acetate application.Cellulose acetate microballoon not only retains the original character of cellulose acetate, and there is wetting ability, porousness, compared with bigger serface and good swelling behavior etc., can be used as sorbent material and be widely used in chromatogram and isolation technique.Because the hydroxyl in cellulosic molecule is replaced by ethanoyl, slackened the reactive force of hydrogen bond, intermolecular distance is increased, greatly strengthen active group hydroxyl and carbonyl in molecule and, to noble metal avidity, therefore can be used as the sorbent material of noble metal.Due to its unique microscopic characteristics of cellulose acetate microballoon, industrial Applicability As etc. just progressively obtain concern, are expected to obtain widespread use in fields such as environmental protection, biochemistry, biotechnology, medical science, pharmacy.Japan Daicel company once disclosed gunite and had prepared cellulose acetate microballoon (US4,551,389, US4,663,447), the people such as Japan Nishikawa have also introduced " suspension method " preparation method (US4 of Cellulose diacetate microballoon, 390,691, US4,461,892), usining halohydrocarbon prepares microballoon as main solvent.The people such as Wagenknecht W disperse cellulose acetate also after evaporating solvent, to have made the deacetylated cellulose microsphere (EP 750007A1) of part cellulose acetate under alkaline condition in oxyethyl group alkyl phenol and ethyl acetate mixture.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of cellulose acetate microballoon.
Another object of the present invention is to provide a kind of cellulose acetate microballoon of being prepared by aforesaid method, and this microballoon has the advantages such as easy regeneration, good biocompatibility and good hydrophilic property.
Technical scheme of the present invention is as follows:
The preparation method who the invention provides a kind of cellulose acetate microballoon, the method comprises the following steps:
The cellulose acetate tow that contains softening agent is dissolved in mixed solvent, obtains polymer slurries, then the polymer slurries obtaining is joined in dispersion liquid, be fully mixed to get suspension, reduce cellulose acetate solubleness, separate out cellulose acetate microballoon.
Described softening agent is selected from a kind of in glycerine triacetate or glycol diacetate.
The degree of substitution with acetyl group of described cellulose acetate tow is 2.0～2.6.
Described mixed solvent is the mixture that alcohols and ester class form, and wherein: the volumn concentration of alcohols is 1～40%, the volumn concentration of ester class is 60～99%;
Wherein, described alcohols contains 1-3 carbon atom, is further selected from one or more the mixture in methyl alcohol, ethanol, n-propyl alcohol or Virahol; Described ester class is selected from C
2～C
5carboxylicesters, is further selected from one or more the mixture in ritalin, vinyl acetic monomer, n-propyl acetate or Iso Butyl Acetate.
Described dispersion liquid comprises Ester selected in water-soluble salt, emulsifying agent, protective colloid, water and mixed solvent, the mass concentration of water-soluble salt is 0.3～5% of dispersion liquid total mass, the mass concentration of emulsifying agent is 0.1～1.5% of dispersion liquid total mass, the mass concentration of protective colloid is 0～1.5% of dispersion liquid total mass, in mixed solvent, the mass concentration of selected Ester is the 5.0-15.0% of dispersion liquid total mass, and the mass concentration of water is the 77.0-94.6% of dispersion liquid total mass;
Wherein: water-soluble salt is acetic acid metal-salt, be further selected from one or both the mixture in sodium-acetate or Potassium ethanoate; Emulsifying agent is nonionogenic tenside, is further selected from one or both the mixture in polyoxyethylene sorbitan lauric acid monoester or sorbitan mono-laurate; Protective colloid is selected from one or more the mixture in methylcellulose gum, methylcellulose gum mixed ether, gelatin or polyvinyl alcohol.
Described reduction cellulose acetate solubleness is by underpressure distillation suspension or suspension is joined in deionized water and controlled; Wherein: vacuum distillation temperature is 40 ℃～60 ℃, vacuum tightness 260～180mbar; The volume ratio of suspension and deionized water is 1: 30～1: 140.
The quality percentage composition that contains softening agent in described cellulose acetate microballoon is 1.0～3.0%.
The invention provides a kind of cellulose acetate microballoon, the median size of this microballoon is 5～1500 μ m; Mean pore size is 20～1000nm; Specific surface area 0.6m
2g
-1～10.0m
2g
-1; The degree of substitution with acetyl group of cellulose acetate is 2.0～2.6, and remaining plasticizer loading is 1.0%～3.0% of cellulose acetate microspheres quality.
Described mixed solvent, is the solvent two or more, the product mixing according to a certain percentage.In the present invention, can select any mixed solvent, as long as this mixed solvent can dissolve cellulose acetate and softening agent in discarded tow, obtain the polymer slurries of a mixing that contains cellulose acetate and softening agent; Meanwhile, each solvent composition in mixed solvent can both be dispersed among dispersion liquid.
Described dispersion liquid, refers to a kind of aqueous solution that contains the components such as water-soluble salt, emulsifying agent, protective colloid, mixed solvent and softening agent in can dissolve polymer slurries; The cellulose acetate slightly soluble in polymer slurries or be insoluble in this dispersion liquid simultaneously, can be in this dispersion liquid the dispersed suspension that obtains;
Wherein, water-soluble salt is metallic salt soluble in water, and its effect is to improve conductive characteristic in dispersion liquid, regulates the δ current potential of dispersate in dispersion liquid, improves the stability of whole solution system;
Emulsifying agent is a class tensio-active agent, and its effect is, while being dispersed in dispersion medium surperficial, to form film or electrostatic double layer, can make disperse phase with electric charge, can stop the small droplets of disperse phase to condense mutually, makes the emulsion that forms more stable; By hydrophilic group or hydrophobic group kind, portion and the position in molecular structure on conversion emulsifying agent molecule, can reach the object of required hydrophilic-lipophilic balance simultaneously; Therefore after adding emulsifying agent, can effectively increase the mixed solvent component of the polymer slurries in dispersion liquid and solvability and the stability of plasticizer components;
Protective colloid is a class high molecular weight water soluble polymer, in dispersion liquid system, present reticulated structure and in protecting dispersion liquid cellulose acetate there is not mutual polymerization, can effectively improve the stability of whole dispersion liquid system.
Several different methods can reduce the solubleness of cellulose acetate in suspension, and sl. sol. most of cellulose acetate in original suspension is separated out.By selecting cellulose acetate separation method and condition can control the particle diameter of cellulose acetate microballoon, improve cellulose acetate microsphere surface performance.The present invention selects to reduce the solubleness of cellulose acetate in suspension by improving the ratio of water/mixed solvent in suspension.
Underpressure distillation suspension can distill mixed solvent effectively from suspension, improves the ratio of water/mixed solvent in suspension.Underpressure distillation is technology well known to those skilled in the art of the present technique, and the condition that the present invention selects comprises: 40 ℃～60 ℃ of distillation temperatures, vacuum tightness 260～180mbar.
The another kind of method that improves the ratio of water/mixed solvent in suspension is fully under whipped state, suspension to be joined in a certain amount of deionized water with given pace.It is 1: 30～1: 140 that the present invention selects the volume ratio of suspension and deionized water, and most of cellulose acetate is separated out.
In addition, adopt cellulose acetate microballoon prepared by above-mentioned preparation process after separation, repeatedly washing, centrifugation, the purification process such as dry, to make the finished product.Adopt deionized water washing can effectively remove alcohols, ester class, metallic salt, emulsifying agent and the protective colloid existing in cellulose acetate microballoon.
The cellulose acetate microballoon of further, separating out is purified through following purification step:
The thick product of cellulose acetate microballoon after underpressure distillation is naturally cooled to room temperature, add deionized water, after immigration vibrator, vibrate, proceed to recentrifuge separation in whizzer; Water-washing oscillation-step with centrifugal separation repeatedly after, product is put into loft drier, finally obtains after drying Cellulose diacetate microballoon.
Compared with the existing technology, tool has the following advantages and beneficial effect in the present invention:
1, the present invention prepares the method use waste acetate fibre element tow of cellulose acetate microballoon, and waste acetate fibre element tow can be utilized effectively.
2, the cellulose acetate microballoon that prepared by the present invention, the solvent using in making processes can recycling use, has fewer environmental impacts.
3, the cellulose acetate microballoon that prepared by the present invention has porosity characteristic and microspherulite diameter size can regulate.
4, the active group on the cellulose acetate microballoon that prepared by the present invention is many, and by modifying different aglucons, such as ion-exchange aglucon, affinity ligand etc., can meet multiple fractionation by adsorption requirement.
5, the cellulose acetate microballoon good biocompatibility that prepared by the present invention, good hydrophilic property, can be used as sorbent material, Harm reduction techniques and falls burnt additive, ion-exchanger, catalyzer, redox agent and process containing multiple uses such as the material of heavy metal ion, organism, pigment waste water and gas delivery, blood filtration, medicament slow release, chromatographic separation materials.
6, the present invention is intended to the discarded tow or the vinegar sheet that are mixed with softening agent to be made into cellulose acetate microballoon, properties-correcting agent and the sewage treatment project sorbent material of usining as additive (foundation cream, lipstick, eye shadow, emulsion, skin cream), medicine sustained release dosage, pigment and the paint of filter material of cigarette, makeup.
Accompanying drawing explanation
Fig. 1 is cellulose acetate microballoon stereoscan photograph (by embodiment 1 method, particle diameter 300 μ m～600 μ m).
Fig. 2 is cellulose acetate microballoon stereoscan photograph (by embodiment 2 methods, median size 100 μ m).
Fig. 3 is cellulose acetate microballoon stereoscan photograph (by embodiment 3 methods, median size 1500 μ m).
Fig. 4 is cellulose acetate microballoon stereoscan photograph (by embodiment 4 methods, particle diameter 5 μ m～50 μ m).
Embodiment
Below in conjunction with accompanying drawing illustrated embodiment, the present invention is further illustrated.
In the present invention, unless otherwise defined, all per-cent (%) is a certain composition in a certain system, for example, and the weight percent of solute in solution; All " in scopes " include end value, and for example, median size comprises 100 μ m and 150 μ m within the scope of 100 μ m～150 μ m; All rotating speed RPM all represent a rev/min (rmin
-1), for example, 60RPM represents that rotating speed is 60 revs/min.
In the present invention, all data units all adopt international unit and supplementary unit, and unit of length adopts mm, μ m, nm, wherein 1mm (millimeter)=10
-3m (rice), 1 μ m (micron)=10
-6m, 1nm (nanometer)=10
-9m; Time unit adopts min, 1min (dividing)=60s (second); Units of vacuum adopts mbar, 1mbar=10
-3bar, 1bar=100000Pa=0.98692327atm=750.06168mmHg.
Plasticizer loading detection method of the present invention is gas chromatographic detection, adopts Agilent6890N gas chromatograph, 30m * 0.53mm * 1.0 μ m DB-1701 capillary column, 170 ℃ of chromatographic column incubator temperature, flow 2.4mL/min, 250 ℃ of sample introduction temperature, 300 ℃ of fid detector temperature.
Specific surface area of the present invention detects the full-automatic specific surface area of ASAP2020M-V3 type and the test of micropore tester that adopts U.S. Mike Micromeritics, protection of liquid nitrogen, and analyzing and bathing temperature is-195.6 ℃, starting time 10s.
Underpressure distillation operation of the present invention adopts the Switzerland Buchi of BUCHI Labortechnik AG 250 model Rotary Evaporators, 40 ℃～60 ℃ of bath temperatures, instrument vacuum tightness 260～180mbar, matrass rotating speed 30～150RPM.
Centrifugation of the present invention adopts the Accuspin of Fisher company 400 type whizzers, sets rotating speed 3600RPM, centrifugation time 10min.
Vibrator of the present invention adopts the German IKA KS260 of company circle type shaker, sets rotating speed 300RPM, duration of oscillation 3min.
The cellulose acetate tow using in preparing the process of cellulose acetate microballoon, no matter be, use new cellulose acetate tow (is plasticizer-containing not) itself, still use discarded cellulose acetate tow (itself contains softening agent), can reach object of the present invention.The present invention's cellulose acetate tow used is discarded cellulose acetate tow, is manufacturing the waste products producing after adding softening agent in filter tip for cigarette, and a plasticiser component is contained in the inside.
Embodiment 1
By being dissolved under 13 grams of discarded cellulose acetate tow samples (wherein softening agent glycerine triacetate content accounts for 8.2% of sample total mass, and degree of substitution with acetyl group is 2.4) room temperature in the mixed solvent of 160 milliliters of vinyl acetic monomers and 28 milliliters of ethanol, obtain polymers soln.Under room temperature, obtained polymers soln is added and in dispersion liquid, obtain a suspension; (the mixed volume ratio of polymer slurries and dispersion liquid is 1: 2.34) dispersion liquid forms (mass concentration 7.7%) by mixture (two kinds of constituent mass ratios are 1: 1) (mass concentration 0.5%) and 38 milliliters of vinyl acetic monomers of the water-soluble methylcellulose gum (mass concentration 0.5%) of 400 ml waters (mass concentration 90.8%), 2.2 grams of energy, 2.4 grams of sodium-acetates (mass concentration is 0.5%), 2.0 grams of polyoxyethylene sorbitan lauric acid monoesters and sorbitan mono-laurate.Whole suspension is moved into rotatory evaporator, under 260～180mbar pressure, with 30～60RPM, at 40～60 ℃ of water-bath rotary evaporations, steam except majority of organic solvent and a small amount of water, separate out cellulose acetate microballoon.After about 150 minutes, close vaporizer, naturally cool to room temperature, proceed in whizzer centrifugal 10min under 3600RPM, separation is precipitated thing, add after 100mL deionized water, in vibrator, with after 300RPM vibration 3min, proceed to recentrifuge separation in whizzer.This washing methods (water-washing oscillation-centrifugation) repeats 3 times, and product is put into vacuum drying oven vacuum-drying 48 hours at 105 ℃, finally obtains Cellulose diacetate microballoon.
Cellulose diacetate ester microsphere is sieved to test, and 95% granular size scope is between 300 μ m～600 μ m, and Fig. 1 is the cellulose acetate microballoon stereoscan photograph of preparation, and microballoon presents the vesicular structure of height.Use BET specific surface tester to test microballoon, specific surface area is 1.0m
2g
-1～5.0m
2g
-1, mean pore size 20-50nm.Through gas chromatographic analysis, evaporating cold condensate is water, vinyl acetic monomer and alcohol mixture.In microballoon, softening agent glycerine triacetate content is 1.4%～2.5%.
Embodiment 2
By being dissolved under 13 grams of discarded cellulose acetate tow samples (wherein softening agent glycerine triacetate content accounts for 8.2% of sample total mass, and degree of substitution with acetyl group is 2.4) room temperature in the mixed solvent of 160 milliliters of vinyl acetic monomers and 28 milliliters of ethanol, obtain polymers soln.Under room temperature, obtained polymers soln is added and in dispersion liquid, obtain a suspension; (the mixed volume ratio of polymer slurries and dispersion liquid is 1: 2.34) dispersion liquid forms (mass concentration 7.7%) by mixture (two kinds of constituent mass ratios are 1: 1) (mass concentration 0.5%) and 38 milliliters of vinyl acetic monomers of the water-soluble methylcellulose gum (mass concentration 0.5%) of 400 ml waters (mass concentration 90.8%), 2.2 grams of energy, 2.4 grams of sodium-acetates (mass concentration is 0.5%), 2.0 grams of polyoxyethylene sorbitan lauric acid monoesters and sorbitan mono-laurate.At room temperature the suspension of gained speed with 5～20mL/min under the abundant stirring of 500RPM speed is slowly joined in 48L deionized water, cellulose acetate microballoon is separated out, and obtains solid vinegar acid cellulose microballoon after separation;
The solid vinegar acid cellulose microballoon of acquisition is added after 100mL deionized water, in vibrator, with after 300RPM vibration 3min, proceed in whizzer centrifugal 10min under 3600RPM.This washing methods (water-washing oscillation-centrifugation) repeats 3 times, and product is put into vacuum drying oven vacuum-drying 48 hours at 105 ℃, finally obtains Cellulose diacetate microballoon.
Cellulose diacetate ester microsphere is carried out to testing graininess, and 95% granular size scope is between 5 μ m～100 μ m, and Fig. 2 is the cellulose acetate microballoon stereoscan photograph of preparation, and microballoon presents the vesicular structure of height.Use BET specific surface tester to test microballoon, specific surface area is 4.0m
2g
-1～10.0m
2g
-1, mean pore size 70-150nm.Through gas chromatographic analysis, in microballoon, softening agent glycerine triacetate content is 1.0%～2.2%.
Embodiment 3
By being dissolved under 26 grams of discarded cellulose acetate tow samples (wherein softening agent glycerine triacetate content accounts for 8.2% of sample total mass, and degree of substitution with acetyl group is 2.3) room temperature in the mixed solvent of 160 milliliters of vinyl acetic monomers and 28 milliliters of ethanol, obtain polymers soln.Under room temperature, obtained polymers soln is added and in dispersion liquid, obtain a suspension; (the mixed volume ratio of polymer slurries and dispersion liquid is 1: 2.30) dispersion liquid forms (mass concentration 7.7%) by mixture (two kinds of constituent mass ratios are 1: 1) (mass concentration 0.5%) and 38 milliliters of vinyl acetic monomers of the water-soluble methylcellulose gum (mass concentration 0.5%) of 400 ml waters (mass concentration 90.8%), 2.2 grams of energy, 2.4 grams of sodium-acetates (mass concentration is 0.5%), 2.0 grams of polyoxyethylene sorbitan lauric acid monoesters and sorbitan mono-laurate.Whole suspension is moved into rotatory evaporator, under 260～180mbar pressure, with 30～60RPM speed, at 40～60 ℃ of water-bath rotary evaporations, steam except majority of organic solvent and a small amount of water, separate out cellulose acetate microballoon.After about 150 minutes, close vaporizer, naturally cool to room temperature, proceed in whizzer centrifugal 10min under 3600RPM, separation is precipitated thing and adds after 100mL deionized water, in vibrator, with after 300RPM vibration 3min, proceeds in whizzer recentrifuge separated.This washing methods (water-washing oscillation-centrifugation) repeats 3 times, and product is put into vacuum drying oven vacuum-drying 48 hours at 105 ℃, finally obtains Cellulose diacetate microballoon.
Cellulose diacetate ester microsphere is sieved to test, and 95% granular size scope is between 800 μ m～1600 μ m, and Fig. 3 is the cellulose acetate microballoon stereoscan photograph of preparing by embodiment 3 methods, and microballoon presents the vesicular structure of height.Use BET specific surface tester to test microballoon, specific surface area is 0.6m
2g
-1～2.0m
2g
-1, mean pore size 2-30nm.Through gas chromatographic analysis, evaporating cold condensate is water, vinyl acetic monomer and alcohol mixture.In microballoon, softening agent glycerine triacetate content is 1.6%～2.6%.
Embodiment 4
By being dissolved under 13 grams of discarded cellulose acetate tow samples (wherein softening agent glycerine triacetate content accounts for 8.2% of sample total mass, and degree of substitution with acetyl group is 2.3) room temperature in the mixed solvent of 160 milliliters of vinyl acetic monomers and 28 milliliters of ethanol, obtain polymers soln.Under room temperature, obtained polymers soln is added and in dispersion liquid, obtain a suspension; (the mixed volume ratio of polymer slurries and dispersion liquid is 1: 2.34) dispersion liquid forms (mass concentration 10.2%) by mixture (two kinds of constituent mass ratios are 1: 1) (mass concentration 0.5%) and 52 milliliters of vinyl acetic monomers of the water-soluble methylcellulose gum (mass concentration 0.5%) of 400 ml waters (mass concentration 88.3%), 2.2 grams of energy, 2.4 grams of sodium-acetates (mass concentration is 0.5%), 2.0 grams of polyoxyethylene sorbitan lauric acid monoesters and sorbitan mono-laurate.Whole suspension is moved into rotatory evaporator, under 260～180mbar pressure, with 60～150RPM speed, at 40～60 degrees Celsius of water-bath rotary evaporations, steam except majority of organic solvent and a small amount of water.After about 150 minutes, close vaporizer, naturally cool to room temperature, proceed in whizzer centrifugal 10min under 3600RPM, separation is precipitated thing and adds after 100mL deionized water, in vibrator, with after 300RPM vibration 3min, proceeds in whizzer recentrifuge separated.This washing methods (water-washing oscillation-centrifugation) repeats 3 times, and product is put into vacuum drying oven vacuum-drying 48 hours at 105 ℃, finally obtains Cellulose diacetate microballoon.
Cellulose diacetate ester microsphere is carried out to testing graininess, and 95% granular size scope is between 5 μ m～50 μ m, and Fig. 4 is the cellulose acetate microballoon stereoscan photograph of preparation, and microballoon presents the vesicular structure of height.Use BET specific surface tester to test microballoon, specific surface area is 4.0m
2g
-1～10.0m
2g
-1, mean pore size 100-200nm.Through gas chromatographic analysis, evaporating cold condensate is water, vinyl acetic monomer and alcohol mixture.In microballoon, softening agent glycerine triacetate content is 1.0%～2.2%.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (13)
1. a preparation method for cellulose acetate microballoon, is characterized in that: the method comprises the following steps:
The cellulose acetate tow that contains softening agent is dissolved in mixed solvent, obtains polymer slurries, then the polymer slurries obtaining is joined in dispersion liquid, be fully mixed to get suspension, reduce cellulose acetate solubleness, separate out cellulose acetate microballoon;
Described softening agent is selected from a kind of in glycerine triacetate or glycol diacetate;
The degree of substitution with acetyl group of described cellulose acetate tow is 2.0～2.6;
Described mixed solvent is the mixture that alcohols and ester class form, and wherein: the volumn concentration of alcohols is 1～40%, the volumn concentration of ester class is 60～99%;
The composition of described dispersion liquid comprises Ester selected in water-soluble salt, emulsifying agent, protective colloid, water and mixed solvent; the mass concentration of water-soluble salt is 0.3～5% of dispersion liquid total mass; the mass concentration of emulsifying agent is 0.1～1.5% of dispersion liquid total mass; the mass concentration of protective colloid is 0～1.5% of dispersion liquid total mass; in mixed solvent, the mass concentration of selected Ester is the 5.0-15.0% of dispersion liquid total mass, and the mass concentration of water is the 77.0-94.6% of dispersion liquid total mass.
2. the preparation method of cellulose acetate microballoon according to claim 1, is characterized in that: described alcohols is selected from one or more the mixture in methyl alcohol, ethanol, n-propyl alcohol or Virahol; Described ester class is selected from one or more the mixture in ritalin, vinyl acetic monomer, n-propyl acetate or Iso Butyl Acetate.
3. the preparation method of cellulose acetate microballoon according to claim 1, is characterized in that: described water-soluble salt is acetic acid metal-salt.
4. the preparation method of cellulose acetate microballoon according to claim 3, is characterized in that: described acetic acid metal-salt is selected from one or both the mixture in sodium-acetate or Potassium ethanoate.
5. the preparation method of cellulose acetate microballoon according to claim 1, is characterized in that: described emulsifying agent is nonionogenic tenside.
6. the preparation method of cellulose acetate microballoon according to claim 5, is characterized in that: described nonionogenic tenside is selected from one or both the mixture in polyoxyethylene sorbitan lauric acid monoester or sorbitan mono-laurate.
7. the preparation method of cellulose acetate microballoon according to claim 1, is characterized in that: described protective colloid is selected from one or more the mixture in methylcellulose gum, methylcellulose gum mixed ether, gelatin or polyvinyl alcohol.
8. the preparation method of cellulose acetate microballoon according to claim 1, is characterized in that: described reduction cellulose acetate solubleness is by underpressure distillation suspension or suspension is joined in deionized water and implemented.
9. the preparation method of cellulose acetate microballoon according to claim 8, is characterized in that: the temperature of described underpressure distillation is 40 ℃～60 ℃, vacuum tightness 260～180mbar.
10. the preparation method of cellulose acetate microballoon according to claim 8, is characterized in that: described suspension and the volume ratio of deionized water are 1:30～1:140.
The preparation method of 11. cellulose acetate microballoons according to claim 1, is characterized in that: the quality percentage composition that contains softening agent in described cellulose acetate microballoon is 1.0～3.0%.
The preparation method of 12. cellulose acetate microballoons according to claim 1, is characterized in that: the described cellulose acetate microballoon of separating out is purified through following purification step:
The thick product of cellulose acetate microballoon after underpressure distillation is naturally cooled to room temperature, add deionized water, after immigration vibrator, vibrate, proceed to recentrifuge separation in whizzer; Water-washing oscillation-step with centrifugal separation repeatedly after, product is put into loft drier, finally obtains after drying Cellulose diacetate microballoon.
Cellulose acetate microballoon prepared by the arbitrary described method of 13. claims 1 to 12, is characterized in that: the median size of this microballoon is 5～1500 μ m; Mean pore size is 20～1000nm; Specific surface area 0.6m
2g
-1～10.0m
2g
– 1; The degree of substitution with acetyl group of cellulose acetate is 2.0～2.6, and plasticizer loading is 1.0%～3.0% of cellulose acetate microspheres quality.
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| CN201110222485.5A CN102911379B (en) | 2011-08-04 | 2011-08-04 | Method for preparing cellulose acetate microspheres and product prepared by method |
| PCT/CN2012/077073 WO2013016982A1 (en) | 2011-08-04 | 2012-06-18 | Cellulose acetate microsphere preparation method and product prepared thereby |
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| CN201110222485.5A CN102911379B (en) | 2011-08-04 | 2011-08-04 | Method for preparing cellulose acetate microspheres and product prepared by method |
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| CN102911379B true CN102911379B (en) | 2014-04-23 |
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| CN103243481B (en) * | 2013-05-20 | 2016-06-08 | 东华大学 | A kind of electrospinning process prepared containing micro-nano ball fiber |
| WO2015029790A1 (en) | 2013-09-02 | 2015-03-05 | Jnc株式会社 | Method for producing porous cellulose particles, and porous cellulose particles |
| CN103724635B (en) * | 2013-12-06 | 2016-01-20 | 中国烟草总公司郑州烟草研究院 | Preparation method of a kind of cellulose acetate porous microsphere and products thereof |
| CN104831395B (en) * | 2014-12-16 | 2017-06-20 | 广东中烟工业有限责任公司 | Application of the PEO PPO PEO ternary block polymers in acetate silk is prepared |
| CN105214623B (en) * | 2015-10-31 | 2017-07-11 | 中山中测纺织产业技术研究中心 | A kind of preparation method of micro heavy Triafol T porous microsphere sorbent |
| CN105802468A (en) * | 2016-04-21 | 2016-07-27 | 安徽皖翎羽绒制品有限公司 | Water-borne polyurethane coating agent containing superfine down fiber-cellulose acetate composite microspheres |
| CN107118020A (en) * | 2017-05-12 | 2017-09-01 | 天长市翔净蔬菜种植发展有限公司 | A kind of high yield sustained release compoiste fertilizer of purslane |
| CN108126674A (en) * | 2017-11-21 | 2018-06-08 | 孝感市锐思新材科技有限公司 | A kind of preparation method of Menatetrenone purification material |
| US11628134B2 (en) | 2018-02-07 | 2023-04-18 | Daicel Corporation | Cellulose acetate particles, cosmetic composition, and method of producing cellulose acetate particles |
| KR102612143B1 (en) * | 2019-03-18 | 2023-12-08 | 주식회사 다이셀 | Particles containing cellulose acetate, cosmetic composition, and method for producing particles containing cellulose acetate |
| BR112022000453A2 (en) | 2019-07-10 | 2022-03-03 | Dainichiseika Color Chem | Method for manufacturing resin granules, resin granules and product employing resin granules |
| JP2021021044A (en) * | 2019-07-30 | 2021-02-18 | Jnc株式会社 | Method for Producing Cellulose Particles or Cellulose Acetate Particles |
| JP6872068B1 (en) | 2020-09-01 | 2021-05-19 | 大日精化工業株式会社 | Resin beads, manufacturing methods for resin beads, and products using resin beads |
| CN112191232B (en) * | 2020-09-16 | 2023-03-31 | 珠海健科医用材料有限公司 | Cellulose microsphere adsorbent, preparation method thereof and blood perfusion apparatus |
| CN112876140A (en) * | 2021-03-09 | 2021-06-01 | 南通绿能环保设备有限公司 | Preparation method of heat dissipation film for sweeper |
| CN115109300A (en) * | 2021-03-17 | 2022-09-27 | 四川大学 | Preparation method of macroporous cellulose diacetate microspheres |
| CN115109301A (en) * | 2021-03-18 | 2022-09-27 | 四川大学 | Preparation method of hollow open cellulose diacetate microspheres |
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| JPS5624429A (en) * | 1979-08-03 | 1981-03-09 | Yoshiaki Motozato | Preparation of porous spherical particle of cellulose |
| CA1235119A (en) * | 1984-01-24 | 1988-04-12 | Kazuhiro Yamazaki | Porous spherical cellulose acetate particles |
| JPH0629336B2 (en) * | 1986-05-15 | 1994-04-20 | ダイセル化学工業株式会社 | Process for producing cellulose ester ester beads |
| JPH0730203B2 (en) * | 1986-09-27 | 1995-04-05 | ダイセル化学工業株式会社 | Method for producing cellulose particles |
| US4888420A (en) * | 1987-12-08 | 1989-12-19 | Celanese Fibers, Inc. | Water soluble cellulose acetate microspheres |
| JPH06145202A (en) * | 1992-11-02 | 1994-05-24 | Tokuyama Soda Co Ltd | Production of cellulose particle |
| DE19522181C2 (en) * | 1995-06-19 | 1999-06-24 | Fraunhofer Ges Forschung | Process for the production of spherical microparticles based on cellulose acetate or cellulose |
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| WO2013016982A1 (en) | 2013-02-07 |
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