WO2001070820A1 - Procede de preparation d'esters cellulosiques - Google Patents

Procede de preparation d'esters cellulosiques Download PDF

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Publication number
WO2001070820A1
WO2001070820A1 PCT/JP2001/002340 JP0102340W WO0170820A1 WO 2001070820 A1 WO2001070820 A1 WO 2001070820A1 JP 0102340 W JP0102340 W JP 0102340W WO 0170820 A1 WO0170820 A1 WO 0170820A1
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WO
WIPO (PCT)
Prior art keywords
cellulose
acid
khz
producing
catalyst
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Application number
PCT/JP2001/002340
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English (en)
Japanese (ja)
Inventor
Mitsuo Takai
Nobuhiro Nagai
Original Assignee
Hokkaido Technology Licensing Office Co.,Ltd.
Daicel Chemical Industries,Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hokkaido Technology Licensing Office Co.,Ltd., Daicel Chemical Industries,Ltd. filed Critical Hokkaido Technology Licensing Office Co.,Ltd.
Priority to AU2001244558A priority Critical patent/AU2001244558A1/en
Priority to JP2001569020A priority patent/JP4845317B2/ja
Publication of WO2001070820A1 publication Critical patent/WO2001070820A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids

Definitions

  • the present invention relates to a method for producing a cellulose ester by esterifying cellulose.
  • Cellulose esters are used in fibers, films, plastics, and tobacco fills.
  • Cellulose is the main component of the cell membrane of plants and accounts for 1/3 to 1/2 of plants, and is the most abundant in all organic matter. Natural cellulose is insoluble in water and common solvents and is not thermoplastic. Three hydroxyl groups per glucose residue have been converted into derivatives by chemical reactions such as esterification and etherification, and their solubility and compatibility with plasticizers have been changed, and they have been used for various purposes.
  • Cellulose acetate is a representative of cellulose esters. Among them, cellulose diacetate has the largest production volume and is widely used.
  • Cellulose diacetate is usually produced by a two-stage process of acetylation and aging.
  • cellulose is reacted with acetic anhydride to form acetyl.
  • This acetylation process occurs according to the following equation.
  • This primary cellulose acetate is then hydrolyzed to give acetone-soluble cellulose.
  • Sudiacetate secondary cellulose acetate, degree of substitution of acetyl group about 2.5
  • the deacetylation reaction by hydrolysis is called a ripening reaction and occurs according to the following formula.
  • Esterification of cellulose is a reaction in which three hydroxyl groups (2-, 3-, and 6-positions) in a glucose residue in the cellulose chain nucleophilically attack the carbonyl carbon of the carboxylic acid.
  • the three hydroxyl groups have different reactivities, and are considered to be higher in the order of 6th, 2nd, and 3rd positions. This difference in reactivity is due to the nucleophilicity and steric hindrance of each hydroxyl group, and is considered to be independent of the type of carboxylic acid. Due to such a difference in reactivity between hydroxyl groups, if the reaction is stopped in the course of the acetylation step, a diester having a random substitution distribution is generated.
  • the polyester is produced by a two-step method, and the diester produced in this manner has a uniform substitution distribution and is soluble in aqueous acetone.
  • Japanese Patent Publication No. 62-54321 discloses a method for activating a system in which lithium chloride is coexisted with an amide selected from the group consisting of dimethylacetamide, 1-methyl-2-pyrrolidone and a mixture thereof.
  • Cellulose is added and dissolved, and in a homogeneous solution obtained, acetylation of cellulose is performed using sulfuric acid as a catalyst and acetic anhydride as an acetylating agent.
  • a method for producing the cellulose acetate of the present invention is disclosed.
  • International Publication Nos. WO 96/20960 and WO 96/20961 JP-A-10-511728, JP-A-10-511729 disclose a direct method for producing a cellulose ester.
  • Methods for producing cellulose diacetate in one step are also known, but all use expensive reagents or special catalysts.
  • an object of the present invention is to provide a method for producing a cellulose ester, particularly a cellulose diester, in a simple process and in one step without using an expensive reagent or a special catalyst.
  • Another object of the present invention is to provide a method for producing a cellulose ester, particularly a cellulose diester, having a uniform substituent distribution in one step and soluble in a solvent such as aqueous acetone.
  • Another object of the present invention is to provide a method for producing a cellulose ester, particularly a cellulose diester, having a high production efficiency.
  • the present inventors have found that the above problems can be solved by performing ultrasonic irradiation in the esterification step, and have reached the present invention.
  • the present invention relates to a method for producing a cellulose ester or a cellulose diester in which esterification of cellulose is performed under irradiation with ultrasonic waves.
  • the present invention relates to a method for producing a cellulose ester or a cellulose ester, which comprises reacting cellulose with an esterifying agent in the presence of a solvent and a catalyst and under ultrasonic irradiation.
  • FIG. 1 shows an NMR spectrum of cellulose diacetate obtained by the method of the present invention.
  • FIG. 2 is a graph showing the relationship between the degree of substitution and the reaction time when subjected to ultrasonic treatment using an ultrasonic cleaner.
  • FIG. 3 is a graph showing the relationship between the degree of substitution and the reaction time when sonication was performed using a cell disrupter.
  • FIG. 4 shows a cellulose diacetate spectrum obtained by a conventional one-step method.
  • cellulose used in the method of the present invention there is no particular limitation on the cellulose used in the method of the present invention, and those of various origins and qualities can be used.
  • Regenerated cellulose such as rayon can be used in addition to vegetable cellulose such as cotton phosphorus, ramie, and dissolved pulp, and bacterial cellulose produced by microorganisms belonging to the genus Acetobak.
  • vegetable cellulose such as cotton phosphorus, ramie, and dissolved pulp
  • bacterial cellulose produced by microorganisms belonging to the genus Acetobak.
  • not only high-grade cellulose with high cellulose content, but also hemicellulose lignin And low-grade cellulose containing impurities such as.
  • the esterifying agent is selected from the group consisting of one or more combinations of acid halides, acid anhydrides, diketene or ketene, and acid esters.
  • An organic acid or an inorganic acid can be used as the acid which is a halide, an anhydride, or an ester.As the organic acid, a carboxylic acid, an organic sulfonic acid, an organic sulfinic acid, phenol, enol, imide, oxime And aromatic sulfone amides.
  • examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid.
  • carboxylic acids Of the carboxylic acids, acetic acid, propionic acid, butyric acid, valeric acid, cabronic acid, enanthic acid, caprylic acid, capric acid, lauric acid, myristic acid, and palmitic acid are preferred.
  • halide examples include fluoride, chloride, bromide, and iodide, with chloride being preferred.
  • esterifying agents when producing an ester having a short carbon chain (for example, having 4 or less carbon atoms), an acid anhydride is preferably used, and acetic anhydride is more preferably used. When producing an ester having a long carbon chain, it is preferable to use an acid chloride.
  • Esterification agents can be used alone or in combination of a plurality of esterification agents.
  • any mixed esters such as cellulose acetate butyrate and cellulose nitrate acetate
  • the amount of the esterifying agent to be used may be in excess of the theoretical value capable of esterifying cellulose, and there is no particular upper limit. Since cellulose has three hydroxyl groups per anhydroglucose, use at least 3 equivalents of esterifying agent per anhydroglucose. It is possible to use 3 to 10 equivalents, more preferably 4 to 6 equivalents.
  • Solvents usually used for the esterification of cellulose for example, carboxylic acids, especially acetic acid, dimethylsulfoxide, dimethylformamide, benzene and the like can be used.
  • carboxylic acids especially acetic acid, dimethylsulfoxide, dimethylformamide, benzene and the like
  • an acid ester is used as the esterifying agent, it can also serve as a solvent.
  • the solvent be present in excess of the esterifying agent.
  • an acid catalyst for example, sulfuric acid, sulfoacetic acid, perchloric acid, dilute sulfuric acid, hydrochloric acid, hydrogen peroxide, hypochlorous acid, or the like, or a base catalyst, for example, pyridine or the like, is usually used for esterification of cellulose.
  • the used catalyst is used.
  • sulfuric acid is preferred from the viewpoint of reaction time and reaction efficiency.
  • the catalyst is added at about 1.0 to about 20% by weight of the cellulose.
  • the esterification step is performed by adding cellulose to a mixture of a solvent, a catalyst and an esterifying agent, and irradiating the mixture with ultrasonic waves.
  • the reaction temperature is preferably from 0 to about 200 ° C, more preferably from about 15 to about 100 ° C, and even more preferably from about 20 to about 60 ° C. If the reaction temperature exceeds the upper limit, depolymerization of cellulose occurs, and the molecular weight is significantly reduced. The lower the reaction temperature, the longer the reaction time.
  • the frequency of the irradiated ultrasonic wave is preferably 20 to 100 kHz.
  • the output depends on the amount of the esterification reaction mixture to be treated, the treatment time and the degree of substitution, and is preferably from 0.1 W • hr / g to 1 OOW'hr / g per gram of the reaction mixture.
  • pretreatment and activation of cellulose are usually performed.
  • a pretreatment in the production of cellulose acetate a method of immersing cellulose in an acetic acid solution, a method of spraying a mixture of sulfuric acid and glacial acetic acid on a cellulose raw material, and the like are known, and are also used in the method of the present invention. be able to.
  • the esterification reaction is stopped by adding an alcohol such as methanol, ethanol, or water or a mixture thereof to the reaction mixture to insolubilize the reaction product.
  • the resulting precipitate is isolated and purified by filtration and washing to obtain the desired cellulose ester.
  • the obtained cellulose ester is analyzed using FT-IR and NMR.
  • the FT-IR is performed by a transmission method at room temperature using JascoFT-IR manufactured by JASCO.
  • the measurement conditions are: Resolution: 4,000 cm, Aparture: 5.00 mm, Scan Speed: 2.00 mm / sec Gain: 4s Zero filling: off, Apodization: Cosine.
  • NMR NMR is performed using Bruker's MSL400. Approximately 25 mg of a sample is dissolved in 1 ml of heavy DMS0 and injected into the 5 thigh tubes to prepare a sample for measurement. The measurement conditions were room temperature, a delay time of 10 seconds, an integration count of 2000, and decoupling measurement with a reverse gate.
  • the substituent distribution is measured by the Deconvolution method of the three-line carboxycarbonyl peak appearing at around 170 ppm.
  • the quantification of the substituent distribution was performed by 13 C NMR, ⁇ NMR or methylation. This is the most reliable method in the present invention.
  • the 13 C NMR method is adopted.
  • the substitution degree is measured by an NMR method and an alkali saponification method.
  • NMR method the intensity of the carbonyl carbon peak appearing at around 170 ppm when the intensity of the ring force peak appearing between 55 and llOppm is set to 1 is obtained by multiplying by six.
  • alkaline saponification method the cellulose ester is saponified with an alcohol and the amount of alcohol required for saponification is determined by titration.
  • a cellulose diester having a uniform substituent distribution can be produced.
  • Cavitation is a phenomenon in which small bubbles that appear during ultrasonic irradiation collapse, and in that case, an extreme state of thousands of degrees and thousands of atmospheres occurs.
  • the high temperature and high pressure act as driving forces for the chemical reaction, increasing the reactivity at the 2nd and 3rd positions, or simultaneously causing deesterification during the esterification reaction, resulting in a uniform distribution as a result of repeated substitution and elimination. May have been given.
  • the method of the present invention can be applied to all esterifying agents.
  • Cellulose dicarboxylates such as sudicaprylate, cellulose dilaurate, cellulose dimyristate, cellulose dipalmitate, cellulose acetate propionate, cellulose acetate butylate, and cellulose acetate valerate; inorganic acid esters of cellulose; Cellulose organic Mixed esters of acids and inorganic acids are included.
  • the method of the present invention makes it possible to produce a cellulose diester having a substitution degree of preferably 0.1 to 3.0, more preferably 1.0 to 3.0, and still more preferably 2.0 to 2.9.
  • the degree of substitution is defined as the number of ester groups per anhydroglucose ring.
  • test tube was charged with 250 mg of cellulose powder (Whatmann CF11) and 1 ml of acetic acid (special grade), and immersed at room temperature for 12 hours. 2 ml of acetic anhydride and 2 ml of acetic acid (special grade) were added thereto, and the mixture was stirred at room temperature for 5 minutes. After 25 mg of concentrated sulfuric acid was added, the test tube was placed in an ultrasonic cleaner and the reaction was started under ultrasonic irradiation. The frequency of the ultrasonic cleaner was 35 kHz and the output was 45 W. During the reaction, cooling was performed so that the reaction temperature did not rise to 35 ° C or more.
  • Example 1 was repeated except that the reaction time was set to 1 minute, 2 minutes, 5 minutes, 10 minutes, 20 minutes, 60 minutes, and 120 minutes.
  • FIG. 2 shows the relationship between the reaction time and the degree of substitution of the cellulose diacetate thus obtained. All of these cellulose diacetates contain water Dissolved uniformly and completely in seton.
  • Example 1 Example 1 was repeated except that the ultrasonic treatment was performed using a cell disrupter (frequency: 20 kHz, output: 150 W, 180 W) instead of the ultrasonic washer, and the reaction time was changed to 5, 40, 70, and 120 minutes. Was repeated.
  • FIG. 3 shows the relationship between the reaction time and the degree of substitution of the cellulose diacetate thus obtained. All of these cellulose diacetates were uniformly and completely dissolved in hydrated acetone.
  • a test tube was charged with 250 mg of cellulose powder (Whatmaiin CF11) and 1 ml of acetic acid (special grade) and immersed at room temperature for 12 hours. 2 ml of acetic anhydride and 2 ml of acetic acid (special grade) were added thereto, and the mixture was stirred at room temperature for 5 minutes. Further, 25 mg of concentrated sulfuric acid was added to start the reaction. The reaction was cooled so that the reaction temperature did not rise to 35 ° C or higher during the reaction. X minutes after the start of the reaction, the reaction solution was poured into a large amount of deionized water with stirring to precipitate the product. The resulting precipitate was isolated by filtration. Washing and filtration were repeated several times for purification.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

L'invention porte sur un procédé de préparation d'esters cellulosiques en une étape, (en particulier de diesters cellulosiques) présentant une répartition uniforme des substituants et solubles dans l'acétone hydratée et d'autres solvants. Ledit procédé consiste à estérifier la cellulose en la soumettant à des ultrasons.
PCT/JP2001/002340 2000-03-23 2001-03-23 Procede de preparation d'esters cellulosiques WO2001070820A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2001244558A AU2001244558A1 (en) 2000-03-23 2001-03-23 Process for preparing cellulose esters
JP2001569020A JP4845317B2 (ja) 2000-03-23 2001-03-23 セルロースエステルの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000082464 2000-03-23
JP2000-82464 2000-03-23

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006025371A1 (fr) * 2004-08-30 2006-03-09 Kaneka Corporation Adsorbant de granulocytes
CN101845100A (zh) * 2010-06-17 2010-09-29 杨占平 以竹原纤维为原料制造二醋酸纤维素的方法
WO2011019064A1 (fr) 2009-08-12 2011-02-17 富士フイルム株式会社 Dérivé cellulosique, composition de résine, article moulé et son procédé de production et boîtier pour dispositif électrique et électronique
WO2011019063A1 (fr) 2009-08-12 2011-02-17 富士フイルム株式会社 Dérivé cellulosique, matériau thermoformé, corps moulé et son procédé de production, et boîtier pour équipement électrique et électronique
JP2012233205A (ja) * 2003-11-28 2012-11-29 Eastman Chemical Co セルロースインターポリマー及び酸化方法
CN107474146A (zh) * 2016-06-08 2017-12-15 四川普什醋酸纤维素有限责任公司 一种二醋酸纤维素及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0892302A (ja) * 1994-09-24 1996-04-09 Kameda Seika Kk 末端反応性多糖及びその製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58152002A (ja) * 1982-03-05 1983-09-09 Daicel Chem Ind Ltd アセトン可溶性セルロ−ス・アセテ−トの新規な製造方法
JP3392470B2 (ja) * 1992-09-24 2003-03-31 ダイセル化学工業株式会社 二酢酸セルロース及びその製造方法
JPH1171463A (ja) * 1997-08-28 1999-03-16 Konica Corp セルローストリアセテート溶液の調製方法、セルローストリアセテートフィルムの製造方法及びセルローストリアセテートフィルム

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0892302A (ja) * 1994-09-24 1996-04-09 Kameda Seika Kk 末端反応性多糖及びその製造方法

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012233205A (ja) * 2003-11-28 2012-11-29 Eastman Chemical Co セルロースインターポリマー及び酸化方法
WO2006025371A1 (fr) * 2004-08-30 2006-03-09 Kaneka Corporation Adsorbant de granulocytes
JPWO2006025371A1 (ja) * 2004-08-30 2008-05-08 株式会社カネカ 顆粒球吸着材
US7850858B2 (en) 2004-08-30 2010-12-14 Kaneka Corporation Granulocyte adsorbent
WO2011019064A1 (fr) 2009-08-12 2011-02-17 富士フイルム株式会社 Dérivé cellulosique, composition de résine, article moulé et son procédé de production et boîtier pour dispositif électrique et électronique
WO2011019063A1 (fr) 2009-08-12 2011-02-17 富士フイルム株式会社 Dérivé cellulosique, matériau thermoformé, corps moulé et son procédé de production, et boîtier pour équipement électrique et électronique
CN101845100A (zh) * 2010-06-17 2010-09-29 杨占平 以竹原纤维为原料制造二醋酸纤维素的方法
JP2012021152A (ja) * 2010-06-17 2012-02-02 ▲楊▼占平 竹繊維を原料とする二酢酸セルロースの製造方法
CN101845100B (zh) * 2010-06-17 2012-06-27 杨占平 以竹原纤维为原料制造二醋酸纤维素的方法
CN107474146A (zh) * 2016-06-08 2017-12-15 四川普什醋酸纤维素有限责任公司 一种二醋酸纤维素及其制备方法
CN107474146B (zh) * 2016-06-08 2019-12-13 四川普什醋酸纤维素有限责任公司 一种二醋酸纤维素及其制备方法

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AU2001244558A1 (en) 2001-10-03

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