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WO2013016982A1 - Procédé de préparation de microsphères d'acétate de cellulose et produit ainsi obtenu - Google Patents

Procédé de préparation de microsphères d'acétate de cellulose et produit ainsi obtenu Download PDF

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Publication number
WO2013016982A1
WO2013016982A1 PCT/CN2012/077073 CN2012077073W WO2013016982A1 WO 2013016982 A1 WO2013016982 A1 WO 2013016982A1 CN 2012077073 W CN2012077073 W CN 2012077073W WO 2013016982 A1 WO2013016982 A1 WO 2013016982A1
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WIPO (PCT)
Prior art keywords
cellulose acetate
microspheres
dispersion
water
microspheres according
Prior art date
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Ceased
Application number
PCT/CN2012/077073
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English (en)
Chinese (zh)
Inventor
曹建国
窦峰
彭为骏
张�杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nantong Cellulose Fibers Co Ltd
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Nantong Cellulose Fibers Co Ltd
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Publication of WO2013016982A1 publication Critical patent/WO2013016982A1/fr
Anticipated expiration legal-status Critical
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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
    • 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
    • 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
    • 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

Definitions

  • the invention belongs to the technical field of chemical cellulose, and relates to a preparation method of cellulose acetate microspheres and a product prepared by the method. Background technique
  • Acetate fiber is also known as cellulose acetate, that is, cellulose acetate.
  • a rayon fiber obtained by esterification of cellulose acetate with acetic acid and cellulose as raw materials.
  • the lignocellulose is treated by acetification, hydrolysis, drying, etc. to obtain a sheet of cellulose diacetate sheet (referred to as "vinegar sheet”), and the vinegar sheet is spun to obtain a cellulose diacetate tow (referred to as "tow” for short). ).
  • Cellulose acetate can be directly esterified by cellulose such as cotton linter pulp or wood pulp under glacial acetic acid, acetic anhydride and sulfuric acid to obtain cellulose triacetate, and then partially hydrolyzed triacetate to obtain acetyl substitution degree.
  • cellulose diacetate product between 2.0 and 2.6.
  • cellulose diacetate is non-toxic and non-flammable, and is mainly used in the manufacture of cigarette filters.
  • a plasticizer is a low molecular weight compound or polymer that is added to a polymer that requires plasticization to increase the plasticity of the polymer.
  • Plasticizers are generally high boiling point, less volatile liquids or low melting point solids, and are mostly ester organic compounds. It usually does not chemically react with the polymer, and the interaction with the polymer is mainly the swelling at elevated temperatures. Plasticizers are more comprehensive and easy to produce and use, and are widely used.
  • the plasticizer used in the manufacture of cigarette filters for cellulose acetate tow is usually triacetin or ethylene glycol diacetate, and the amount of plasticizer used is 5% to 12% of the mass of cellulose acetate tow. .
  • the waste tow produced during the processing of tobacco processing is mainly in the form of a mixture of plasticizers. Unless otherwise stated, the discarded tows described below are mixed with a plasticizer. China's annual consumption of acetate tow is 260,000 tons, and waste tow is produced every year from 2000 to 4000 tons.
  • the waste tow is subjected to high-temperature water washing or enzymatic hydrolysis, and the plasticizer is removed, and then recycled to be used for reconstitution (US 5,328,934, US 5,504,119, US 5,504,120, Chinese Patent Application No. 200910064880.8).
  • the patent proposes to increase the plasticizer removal efficiency by using high pressure/low temperature and low pressure/high temperature water washing in a closed container (US 5,402,893), but these methods require a large amount of water and energy and the washing wastewater is difficult to handle.
  • Cellulose acetate can be used in other applications (such as film, film or fiber) depending on its shape, and cellulose acetate microspheres are a special field of cellulose acetate application.
  • Cellulose acetate microspheres not only retain the original properties of cellulose acetate, but also have hydrophilicity, porosity, large specific surface area and good swelling properties. They can be widely used as adsorbents in chromatography and separation techniques.
  • Another object of the present invention is to provide a cellulose acetate microsphere prepared by the above method, which has the advantages of easy regeneration, good biocompatibility and good hydrophilicity.
  • the invention provides a preparation method of cellulose acetate microspheres, the method comprising the following steps:
  • the plasticizer is selected from one of triacetin or ethylene glycol diacetate.
  • the cellulose acetate tow has an acetyl substitution degree of 2.0 to 2.6.
  • the mixed solvent is a mixture of an alcohol and an ester, wherein: the volume percentage of the alcohol is 1 to 40%, and the volume percentage of the ester is 60 to 99% ;
  • the alcohol contains 1-3 carbon atoms, further selected from the group consisting of methanol, ethanol, n-propanol or isopropanol; and the ester is selected from the group consisting of C 2 ⁇ C
  • the 5 carboxylate is further selected from the group consisting of one or more of methyl acetate, ethyl acetate, n-propyl acetate or isopropyl acetate.
  • the dispersion includes a water-soluble salt, an emulsifier, a protective colloid, water, and an ester selected from the mixed solvent.
  • the mass concentration of the water-soluble salt is 0.3 to 5% of the total mass of the dispersion
  • the mass concentration of the emulsifier is 0.1 to 1.5% of the total mass of the dispersion
  • the mass concentration of the protective colloid is 0 to 1.5% of the total mass of the dispersion
  • the mass concentration of the ester substance selected in the solvent is 5.0-15.0% of the total mass of the dispersion
  • the mass concentration of water is 77.0-94.6% of the total mass of the dispersion;
  • the water-soluble salt is a metal acetate salt, further selected from the group consisting of one or a mixture of sodium acetate or potassium acetate;
  • the emulsifier is a nonionic surfactant, further selected from the group consisting of polyoxyethylene sorbitan lauric acid a mixture of one or both of ester or sorbitan monolaurate;
  • a protective colloid selected from the group consisting of methyl cellulose, methyl cellulose mixed ether, gelatin or polyvinyl alcohol.
  • the reducing the solubility of cellulose acetate is controlled by distilling the suspension under reduced pressure or adding the suspension to deionized water; wherein: the distillation temperature under reduced pressure is 40 ° C to 60 ° C, the degree of vacuum is 260 to 180 mbar ; The volume ratio of liquid to deionized water is 1: 30 to 1: 140.
  • the cellulose acetate microspheres contain a plasticizer in an amount of 1.0 to 3.0% by mass.
  • the present invention provides a cellulose acetate microspheres, the average particle size of the microspheres is 5 ⁇ 1500 ⁇ ; average pore diameter of 20 ⁇ lOOOnm; specific surface area of 0.6 m 2 'g - 1 ⁇ 10.0m 2' g- 1; acetic acid
  • the cellulose has an acetyl substitution degree of 2.0 to 2.6, and the residual plasticizer content is 1.0% to 3.0% by mass of the cellulose acetate microspheres.
  • the mixed solvent is a product in which two or more solvents are mixed together in a certain ratio. Any mixed solvent may be selected in the present invention as long as the mixed solvent is capable of dissolving cellulose acetate and a plasticizer in the waste tow to obtain a mixed polymer slurry containing cellulose acetate and a plasticizer; Each solvent component in the mixed solvent can be dispersed in the dispersion.
  • the dispersion liquid refers to an aqueous solution containing a component such as a water-soluble salt, an emulsifier, a protective colloid, etc., capable of dissolving a mixed solvent and a plasticizer in the polymer slurry; and at the same time, the cellulose acetate microparticle in the polymer slurry Soluble or insoluble in the dispersion, capable of being dispersed in the dispersion to obtain a suspension;
  • a component such as a water-soluble salt, an emulsifier, a protective colloid, etc.
  • the water-soluble salt is a metal salt which is easily soluble in water, and its function is to improve the conductive property in the dispersion, adjust the ⁇ potential of the dispersion in the dispersion, and improve the stability of the entire solution system;
  • An emulsifier is a type of surfactant which acts to form a film or an electric double layer when dispersed on the surface of a dispersion medium, so that the dispersed phase can be charged, and the droplets of the dispersed phase can be prevented from coagulating with each other, so that the formed milk
  • the turbid liquid is more stable; at the same time, by changing the hydrophilic group or the hydrophobic group on the emulsifier molecule, the proportion and the position in the molecular structure, the desired hydrophilic-lipophilic balance can be achieved; It can effectively increase the solubility and stability of the mixed solvent component and the plasticizer component of the polymer slurry in the dispersion;
  • the protective colloid is a kind of water-soluble polymer which exhibits a network structure in the dispersion system and protects the cellulose acetate in the dispersion from mutual polymerization, thereby effectively improving the stability of the entire dispersion system.
  • a variety of methods can reduce the solubility of cellulose acetate in the suspension, and precipitate most of the cellulose acetate which is slightly soluble in the original suspension.
  • the particle size of the cellulose acetate microspheres can be controlled, and the surface properties of the cellulose acetate microspheres can be improved.
  • the present invention selects to reduce the solubility of cellulose acetate in the suspension by increasing the ratio of water/mixed solvent in the suspension.
  • the vacuum distillation suspension can effectively distill the mixed solvent from the suspension to increase the ratio of water/mixed solvent in the suspension. Vacuum distillation is a technique well known to those skilled in the art, and the conditions selected by the present invention include: distillation temperature 40 ° C ⁇
  • Another way to increase the ratio of water/mixed solvent in the suspension is to add the suspension to a quantity of deionized water at a rate that is sufficiently agitated.
  • the volume ratio of the suspension to the deionized water is 1:30 to 1:140, and most of the cellulose acetate is precipitated.
  • the cellulose acetate microspheres prepared by the above preparation steps can be subjected to a purification process such as separation, multiple water washing, centrifugation, and drying to obtain a final product. Washing with deionized water can effectively remove alcohols, esters, metal salts, emulsifiers and protective colloids present in cellulose acetate microspheres.
  • precipitated cellulose acetate microspheres are purified by the following purification steps:
  • the crude acetic acid microspheres after vacuum distillation are naturally cooled to room temperature, added with deionized water, transferred to a shaker, shaken, and transferred to a centrifuge for centrifugation again; the water washing oscillation-centrifugation step is repeated several times, the product is repeated. It is placed in a dry box and dried to finally obtain cellulose diacetate microspheres.
  • the present invention has the following advantages and beneficial effects:
  • the method of preparing cellulose acetate microspheres of the present invention uses spent cellulose acetate tow to enable efficient utilization of spent cellulose acetate tow.
  • the cellulose acetate microspheres prepared by the invention can be recycled and recycled in the production process, and have little impact on the environment.
  • the cellulose acetate microspheres prepared by the present invention have porous characteristics and the particle size of the microspheres can be adjusted.
  • the cellulose acetate microspheres prepared by the invention have many reactive groups, and can modify various ligands, such as ion exchange ligands and affinity ligands, to meet various adsorption separation requirements.
  • the cellulose acetate microsphere prepared by the invention has good biocompatibility and good hydrophilicity, and can be used as an adsorbent, a cigarette harm reduction coke additive, an ion exchanger, a catalyst, a redox agent and a treatment of heavy metal ions and organic substances. , pigment waste water and gas separation, blood filtration, drug release, chromatographic separation of substances and other uses.
  • the invention aims to prepare a waste tow or vinegar sheet mixed with a plasticizer into cellulose acetate microspheres, as an additive for cigarette filter materials and cosmetics (foundation, lipstick, eye shadow, lotion, body lotion), Drug slow release agents, modifiers for pigments and paints, and sewage treatment engineering adsorbents.
  • Fig. 1 is a scanning electron micrograph of cellulose acetate microspheres (particle diameter 300 ⁇ to 600 ⁇ according to the method of Example 1).
  • Figure 2 is a scanning electron micrograph of cellulose acetate microspheres (average particle size 100 ⁇ according to the method of Example 2).
  • Figure 3 is a scanning electron micrograph of cellulose acetate microspheres (average particle size 1500 ⁇ according to the method of Example 3).
  • Figure 4 is a scanning electron micrograph of cellulose acetate microspheres (particle size 5 ⁇ 50 ⁇ according to the method of Example 4). detailed description
  • all percentages (%) are a component in a system, for example, the weight percentage of the solute in the solution; all "inside" include the terminal value, for example, average
  • the particle size ranges from 100 ⁇ m to 150 ⁇ m and includes ⁇ and 150 ⁇ m ; all RPMs represent revolutions per minute (rmin ⁇ , for example, 60 RPM means 60 rpm).
  • the plasticizer content detection method of the invention is gas chromatography detection, using Agilent 6890N gas chromatograph, 30mx0.53mmx l. ( ⁇ m DB-1701 capillary column, column temperature oven temperature 170 ° C, flow rate 2.4mL / min, The injection temperature is 250 °C and the FID detector temperature is 300 °C.
  • the specific surface area detection of the present invention is tested by the ASAP2020M-V3 type automatic surface area and micropore tester of the American Micromeritics, liquid nitrogen protection, and the analysis bath temperature is -195.6 ° C, and the equilibrium time is 10 s.
  • the vacuum distillation operation of the present invention adopts a Buchi 250 type rotary evaporator of Swiss Buchi, the temperature of the water bath is 40 ° C to 60 ° C, the vacuum degree of the instrument is 260 to 180 mbar, and the rotation speed of the distillation flask is 30 to 150 RPM.
  • the centrifugation of the present invention was carried out using a Fisher company Accuspin 400 centrifuge with a set speed of 3600 RPM and a centrifugal separation time of 10 min.
  • the oscillator of the invention adopts the German KS260 circumferential oscillation instrument of IKA Company, and sets the rotation speed of 300 RPM and the oscillation time is 3 min.
  • the cellulose acetate tow used in the preparation of cellulose acetate microspheres can achieve the object of the present invention.
  • the cellulose acetate tow used in the present invention is a waste cellulose acetate tow, which is a waste product which is produced by adding a plasticizer to a filter for producing tobacco, and contains a plasticizer component.
  • a sample of 13 g of waste cellulose acetate tow (in which the plasticizer triacetin content was 8.2% of the total mass of the sample, and the degree of acetyl substitution was 2.4) was dissolved in 160 ml of ethyl acetate and 28 ml of ethanol at room temperature.
  • the polymer solution was taken up in a solvent.
  • the obtained polymer solution is added to the dispersion at room temperature to obtain a suspension; (the mixed volume ratio of the polymer slurry to the dispersion is 1: 2.34)
  • the dispersion is composed of 400 ml of water (mass concentration: 90.8%), 2.2 g.
  • the evaporator was turned off, naturally cooled to room temperature, centrifuged at 3600 RPM for 10 min in a centrifuge, and the precipitate was separated. After adding 100 mL of deionized water, it was shaken at 300 RPM for 3 min in a shaker, and then transferred to a centrifuge. Centrifuge again. This washing method (water washing shaking-centrifugation) was repeated 3 times, and the product was vacuum-dried at 105 ° C for 48 hours in a vacuum drying oven to finally obtain cellulose diacetate microspheres.
  • FIG. 1 is a scanning electron micrograph of the prepared cellulose acetate microspheres, and the microspheres exhibited a highly porous structure.
  • the microspheres were tested using a BET specific surface tester with a specific surface area of 1.0 m 2 , g - 1 to 5.01 ⁇ , and an average pore diameter of 20 to 50 nm. After gas chromatography analysis, the condensate was evaporated to a mixture of water, ethyl acetate and ethanol. The content of the plasticizer triacetin in the microspheres is from 1.4% to 2.5%.
  • Example 2 Example 2
  • a sample of 13 g of waste cellulose acetate tow (in which the plasticizer triacetin content was 8.2% of the total mass of the sample, and the degree of acetyl substitution was 2.4) was dissolved in 160 ml of ethyl acetate and 28 ml of ethanol at room temperature.
  • the polymer solution was taken up in a solvent.
  • the obtained polymer solution is added to the dispersion at room temperature to obtain a suspension; (the mixed volume ratio of the polymer slurry to the dispersion is 1: 2.34)
  • the dispersion is composed of 400 ml of water (mass concentration: 90.8%), 2.2 g.
  • the obtained solid cellulose acetate microspheres were added to 100 mL of deionized water, shaken at 300 RPM for 3 min in a shaker, and transferred to a centrifuge at 3600 RPM for 10 min. This washing method (washing shaking-centrifugation) was repeated 3 times, and the product was vacuum-dried at 105 ° C for 48 hours in a vacuum drying oven to finally obtain cellulose diacetate microspheres.
  • FIG. 1 is a scanning electron micrograph of the prepared cellulose acetate microspheres, and the microspheres exhibited a highly porous structure.
  • the microspheres were tested using a BET specific surface tester with a specific surface area of The average pore diameter is 70-150 nm.
  • the content of the plasticizer triacetin in the microspheres was 1.0% to 2.2% by gas chromatography.
  • a sample of 26 g of waste cellulose acetate tow (in which the plasticizer triacetin content was 8.2% of the total mass of the sample, and the degree of acetyl substitution was 2.3) was dissolved in 160 ml of ethyl acetate and 28 ml of ethanol at room temperature.
  • the polymer solution was taken up in a solvent.
  • the obtained polymer solution is added to the dispersion at room temperature to obtain a suspension; (the mixing ratio of the polymer slurry to the dispersion is 1: 2.30).
  • the dispersion is composed of 400 ml of water (mass concentration: 90.8%), 2.2 g.
  • the evaporator was turned off, naturally cooled to room temperature, centrifuged at 3600 RPM for 10 min in a centrifuge, and the precipitate was separated and added to 100 mL of deionized water. After shaking at 300 RPM for 3 min in a shaker, it was transferred to a centrifuge again. Centrifugal separation. This washing method (water washing shaking-centrifugation) was repeated 3 times, and the product was vacuum-dried at 105 ° C for 48 hours in a vacuum drying oven to finally obtain cellulose diacetate microspheres.
  • FIG. 3 is a scanning electron micrograph of the cellulose acetate microsphere prepared by the method of Example 3.
  • the microspheres were highly elevated. porous structure.
  • the microspheres were tested using a BET specific surface tester with a specific surface area of ⁇ . ⁇ ⁇ . ⁇ 2 ⁇ with an average pore diameter of 2-30 nm. After gas chromatography analysis, the condensate was evaporated to a mixture of water, ethyl acetate and ethanol.
  • the content of the plasticizer triacetin in the microspheres is 1.6% to 2.6%.
  • a sample of 13 g of waste cellulose acetate tow (in which the plasticizer triacetin content was 8.2% of the total mass of the sample, and the degree of acetyl substitution was 2.3) was dissolved in 160 ml of ethyl acetate and 28 ml of ethanol at room temperature.
  • the polymer solution was taken up in a solvent.
  • the obtained polymer solution is added to the dispersion at room temperature to obtain a suspension; (the mixing ratio of the polymer slurry to the dispersion is 1: 2.34)
  • the dispersion is composed of 400 ml of water (mass concentration: 88.3%), 2.2 g.
  • the evaporator was turned off, naturally cooled to room temperature, centrifuged at 3600 RPM for 10 min in a centrifuge, and the precipitate was separated and added to 100 mL of deionized water. After shaking at 300 RPM for 3 min in a shaker, it was transferred to a centrifuge again. Centrifugal separation. This washing method (washing shaking-centrifugation) was repeated 3 times, and the product was vacuum-dried at 105 ° C for 48 hours to finally obtain cellulose diacetate microspheres.
  • FIG. 4 is a scanning electron micrograph of the prepared cellulose acetate microspheres, and the microspheres exhibited a highly porous structure.
  • the microspheres were tested using a BET specific surface tester with a specific surface area of The average pore diameter is 100-200 nm. After gas chromatography analysis, the condensate was evaporated to a mixture of water, ethyl acetate and ethanol. The content of the plasticizer triacetin in the microspheres is 1.0% to 2.2%.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne le domaine technique des celluloses chimiques. L'invention concerne un procédé de préparation de microsphères d'acétate de cellulose et le produit ainsi obtenu. Le procédé de préparation de microsphères d'acétate de cellulose de la présente invention comprend les étapes suivantes : dissoudre dans un solvant mixte une mèche d'acétate de cellulose contenant un plastifiant et obtenir une suspension polymère; ajouter ensuite la suspension polymère obtenue à un liquide de dispersion, mélanger totalement et obtenir un liquide de suspension; réduire la solubilité de l'acétate de cellulose et séparer la microsphère d'acétate de cellulose. La microsphère d'acétate de cellulose de la présente invention a un diamètre moyen des particules de 5 à 1500 μm, un diamètre moyen des pores de 2 à 200 nm, une surface spécifique de 0,6 m²•g-1-10,0 m²•g-1, le degré de substitution de l'acétyle d'acétate de cellulose étant 2,0-2,6, et le niveau du plastifiant résiduel étant 1,0 %-3,0 % en poids de microsphère d'acétate de cellulose. La microsphère de la présente invention présente les avantages d'une régénération facile, d'une bonne biocompatibilité et d'une bonne hydrophilicité.
PCT/CN2012/077073 2011-08-04 2012-06-18 Procédé de préparation de microsphères d'acétate de cellulose et produit ainsi obtenu Ceased WO2013016982A1 (fr)

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CN201110222485.5 2011-08-04
CN201110222485.5A CN102911379B (zh) 2011-08-04 2011-08-04 一种醋酸纤维素微球的制备方法及由该方法制备的产品

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CN112876140A (zh) * 2021-03-09 2021-06-01 南通绿能环保设备有限公司 一种扫地车用散热薄膜的制备方法
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