JPH09255701A - Production of cellulose ester - Google Patents
Production of cellulose esterInfo
- Publication number
- JPH09255701A JPH09255701A JP8066099A JP6609996A JPH09255701A JP H09255701 A JPH09255701 A JP H09255701A JP 8066099 A JP8066099 A JP 8066099A JP 6609996 A JP6609996 A JP 6609996A JP H09255701 A JPH09255701 A JP H09255701A
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- JP
- Japan
- Prior art keywords
- cellulose
- polymerization
- weight
- degree
- solution
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はセルロースの重合度
を低下させないセルロース・エステルの製造方法に関す
る。TECHNICAL FIELD The present invention relates to a method for producing a cellulose ester which does not reduce the degree of polymerization of cellulose.
【０００２】[0002]
【従来の技術】セルロース・エステルの製造方法として
は、酢酸、ジクロロメタン、トルエン等を希釈剤、酸無
水物、酸塩化物等をエステル化剤、硫酸、過塩素酸等を
触媒として製造する方法が広く行われている。このよう
な公知のセルロース・エステルの製造方法においては、
エステル化と並行してセルロースの著しい重合度低下が
生じる。例えば、高度に精製した木材パルプは重量平均
重合度が 2,000程度のセルロースからなるが、このよう
な木材パルプを原料として公知の方法で得られるセルロ
ース・アセテート、セルロース・アセテート・プロピオ
ネート、セルロース・アセテート・ブチレート等のセル
ロースエステルの重量平均重合度は通常は1,000以下で
ある。セルロース・エステルから得られるフィルム、繊
維などの成形品において、セルロース・エステルの重合
度と成形品の強度は正の相関を持つことから、高強度の
成形品を目的とした場合、公知のエステル化方法におけ
るセルロースの著しい重合度低下は大きな問題である。2. Description of the Related Art As a method for producing cellulose ester, there is a method of producing acetic acid, dichloromethane, toluene or the like as a diluent, acid anhydride, acid chloride or the like as an esterifying agent, and sulfuric acid or perchloric acid or the like as a catalyst. It is widely practiced. In such a known method for producing a cellulose ester,
Along with the esterification, a significant decrease in the degree of polymerization of cellulose occurs. For example, highly refined wood pulp is composed of cellulose having a weight average degree of polymerization of about 2,000. Cellulose acetate, cellulose acetate propionate, cellulose acetate. The weight average degree of polymerization of cellulose ester such as butyrate is usually 1,000 or less. In the case of molded products such as films and fibers obtained from cellulose ester, the degree of polymerization of cellulose ester and the strength of the molded product have a positive correlation. The significant decrease in the degree of polymerization of cellulose in the method is a big problem.
【０００３】公知のエステル化方法において重合度が低
下する理由としては、セルロース固体の不均一系エステ
ル化反応を含んでおり、不均一系エステル化反応を進行
させるために苛酷な酸性の反応条件を採用しているため
である。著しい重合度低下を避けるためには、溶解して
いるセルロースに対して均一系エステル化を行う方法が
考えられるが、セルロースの重合度を低下させずにセル
ロースを溶解させることは一般に困難である。例えば、
USP 4,302,252 には極度な重合度低下を伴わないセルロ
ース溶液の調製方法が開示されており、該特許の実施例
によれば低重合度のセルロースは重合度低下を伴わずに
溶解可能であるが、通常セルロース・エステルの原料と
して用いられるような高重合度のセルロースの場合は溶
解の際に重合度低下を伴うことがわかる。The reason why the degree of polymerization is lowered in the known esterification method is that it involves a heterogeneous esterification reaction of cellulose solids, and a harsh acidic reaction condition is used in order to proceed the heterogeneous esterification reaction. This is because it is adopted. In order to avoid a significant decrease in the degree of polymerization, a method in which the dissolved cellulose is subjected to homogeneous esterification can be considered, but it is generally difficult to dissolve the cellulose without lowering the degree of polymerization of the cellulose. For example,
USP 4,302,252 discloses a method for preparing a cellulose solution without extreme decrease in polymerization degree, and according to the examples of the patent, cellulose having a low polymerization degree can be dissolved without decreasing the polymerization degree, It can be seen that in the case of cellulose having a high degree of polymerization, which is usually used as a raw material for cellulose ester, the degree of polymerization is lowered upon dissolution.
【０００４】[0004]
【発明が解決しようとする課題】従って、本発明の目的
は重合度を低下させずにセルロースを溶解し、該溶液か
ら高重合度のセルロース・エステルを製造することにあ
る。SUMMARY OF THE INVENTION It is therefore an object of the present invention to dissolve cellulose without lowering the degree of polymerization and to produce a cellulose ester having a high degree of polymerization from the solution.
【０００５】[0005]
【課題を解決するための手段】本発明者らは鋭意検討の
結果、セルロースを12重量％以上の塩化リチウムを含む
アミド類で 100℃以下で処理して溶解し、酸無水物、酸
塩化物などで80℃以下でエステル化反応を行うことによ
り、セルロースの重合度を殆ど低下させずにセルロース
・エステルを製造できることを見出し、本発明を完成し
た。Means for Solving the Problems As a result of intensive investigations by the present inventors, cellulose was treated with an amide containing 12% by weight or more of lithium chloride at 100 ° C. or lower to dissolve the acid anhydride and acid chloride. The present invention was completed by finding that a cellulose ester can be produced with almost no decrease in the degree of polymerization of cellulose by carrying out an esterification reaction at 80 ° C. or lower with the above method.
【０００６】即ち、本発明は、セルロースを12重量％以
上の塩化リチウムを含むアミド類溶媒で 100℃以下で処
理することを特徴とするセルロース溶液の製造方法、及
び該方法で溶解したセルロースを酸無水物又は酸塩化物
を用いて80℃以下でエステル化することを特徴とするセ
ルロース・エステルの製造方法に関する。That is, the present invention provides a method for producing a cellulose solution, which comprises treating cellulose with an amide solvent containing 12% by weight or more of lithium chloride at 100 ° C. or less, and the cellulose dissolved by the method is treated with an acid. The present invention relates to a method for producing a cellulose ester, which comprises esterification with an anhydride or an acid chloride at a temperature of 80 ° C. or lower.
【０００７】[0007]
【発明の実施の形態】塩化リチウムを含むアミド類への
セルロースの溶解に関する先行技術はUSP 4,302,252 に
詳しく開示されている。該先行文献においては、適当な
前処理を施したセルロース試料を約 165℃のジメチルア
セトアミドで活性化した後、対溶液３〜12重量％の塩化
リチウムを加えてセルロースを溶解させているが、該先
行文献の実施例においては低重合度のセルロースを用い
た場合について詳しく言及されており、一方、高重合度
のセルロース試料を用いた場合は明らかに重合度低下を
伴っている。また、該先行文献の発明者らは塩化リチウ
ム濃度12重量％以上の条件は塩化リチウムの析出が起こ
ることから好ましくないとしている。The prior art relating to the dissolution of cellulose in amides containing lithium chloride is disclosed in detail in USP 4,302,252. In the prior art document, a cellulose sample which has been subjected to an appropriate pretreatment is activated with dimethylacetamide at about 165 ° C., and then 3 to 12% by weight of lithium chloride is added to dissolve the cellulose. In the examples of the prior art documents, reference is made in detail to the case of using a low degree of polymerization of cellulose, while the use of a high degree of polymerization of cellulose sample is accompanied by a clear decrease in the degree of polymerization. In addition, the inventors of the prior art document say that the condition of the lithium chloride concentration of 12% by weight or more is not preferable because the precipitation of lithium chloride occurs.
【０００８】本発明者らは、該先行文献において高重合
度のセルロースを溶解する際に重合度低下を生じる原因
が、 100℃を超える高温度でのセルロースの活性化処理
にあることを見出すと同時に、12重量％以上さらに好ま
しくは14重量％以上の塩化リチウムを含むアミド類溶媒
を用いることで重合度低下の原因である 100℃以上の活
性化処理を行うことなしにセルロースを溶解できること
を見出した。即ち、本発明の一部であるセルロースの溶
解方法は、12重量％以上、さらに好ましくは14重量％以
上の塩化リチウムを含むジメチルアセトアミド、Ｎ−メ
チルピロリドン（１−メチル−２−ピロリジノン）等の
アミド類溶媒で 100℃以下でセルロースを処理すること
を特徴とする。12重量％以上の塩化リチウムを使用する
と、室温付近で塩化リチウムが析出するが、より高い温
度では塩化リチウムは完全に溶解する。後のエステル化
反応に際しては、必要に応じてアミド類溶媒によって得
られたセルロース溶液を希釈し、塩化リチウムの析出を
阻止することができる。セルロースを溶解する際の処理
温度は 100℃以下が好ましく、これは前述のようにより
高温での処理はセルロースの著しい重合度低下を伴うた
めである。The inventors of the present invention found that the cause of the decrease in the degree of polymerization when the cellulose having a high degree of polymerization is dissolved is the activation treatment of cellulose at a high temperature of more than 100 ° C. At the same time, it was found that by using an amide solvent containing 12% by weight or more, and more preferably 14% by weight or more of lithium chloride, cellulose can be dissolved without performing activation treatment at 100 ° C or more, which is a cause of the decrease in the degree of polymerization. It was That is, the method for dissolving cellulose which is a part of the present invention is 12% by weight or more, more preferably 14% by weight or more lithium chloride containing dimethylacetamide, N-methylpyrrolidone (1-methyl-2-pyrrolidinone) and the like. It is characterized in that cellulose is treated with an amide solvent at 100 ° C or lower. When 12% by weight or more of lithium chloride is used, lithium chloride is deposited near room temperature, but at higher temperatures, lithium chloride is completely dissolved. In the subsequent esterification reaction, the cellulose solution obtained can be diluted with an amide solvent, if necessary, to prevent the precipitation of lithium chloride. The treatment temperature at the time of dissolving the cellulose is preferably 100 ° C. or lower, because the treatment at a higher temperature causes a remarkable decrease in the degree of polymerization of cellulose as described above.
【０００９】溶解したセルロースのエステル化に際して
は、酸塩化物、酸無水物等のエステル化剤を用い、反応
を80℃以下、さらに好ましくは60℃以下で行う。これ
は、80℃を超える反応温度はセルロースの重合度を著し
く低下させるためである。また、好ましくはこの反応に
おいてエステル化剤と等モル以上の三級アミンを共存さ
せる。これは反応の触媒として働くと同時に、エステル
化剤から副生し、解重合を惹き起こす酸性物質を中和す
るためである。Upon esterification of the dissolved cellulose, an esterification agent such as an acid chloride or an acid anhydride is used and the reaction is carried out at 80 ° C. or lower, more preferably 60 ° C. or lower. This is because the reaction temperature exceeding 80 ° C. significantly reduces the degree of polymerization of cellulose. Also, preferably, an equimolar amount or more of a tertiary amine is allowed to coexist in this reaction. This is because it acts as a catalyst for the reaction and at the same time neutralizes the acidic substance that is by-produced from the esterifying agent and causes depolymerization.
【００１０】本発明において、酸無水物としては、例え
ば、無水酢酸、無水プロピオン酸、無水酪酸等が挙げら
れ、酸塩化物としては、例えば、塩化プロピオニル、塩
化ブチリル、塩化ステアロイル、塩化ベンゾイル等が挙
げられ、その他イソシアナートとしてフェニルイソシア
ナートなどが挙げられる。In the present invention, examples of acid anhydrides include acetic anhydride, propionic anhydride, butyric anhydride, and examples of acid chlorides include propionyl chloride, butyryl chloride, stearoyl chloride, benzoyl chloride and the like. Other examples of the isocyanate include phenyl isocyanate and the like.
【００１１】[0011]
【実施例】以下、実施例により本発明をより詳細に説明
するが、本発明はこれらの実施例に限定されるものでは
ない。EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
【００１２】（セルロース・アセテートの重量平均重合
度の測定）0.1ｇの試料を10mlのジクロロメタンに溶解
し、以下の条件でＧＰＣ分析を行い、重量平均分子量を
求めた。試料の重量平均分子量と平均酢化度から、以下
の式により重量平均重合度を決定した。 ＧＰＣ条件 溶離液 ：ジクロロメタン 流速 ：１ml／min カラム ：ＧＭＨ ＸＬ（東ソー） 打ち込み量：300 μl 検出方法 ：示差屈折率及び低角レーザー光散乱 重量平均重合度 重量平均重合度＝（重量平均分子量）／(162＋42×Ｄ
Ｓ） ただし、ＤＳ＝162 ×（平均酢化度）／（6000−42×
（平均酢化度））。(Measurement of Weight-Average Polymerization Degree of Cellulose Acetate) A sample of 0.1 g was dissolved in 10 ml of dichloromethane and subjected to GPC analysis under the following conditions to determine the weight-average molecular weight. From the weight average molecular weight of the sample and the average acetylation degree, the weight average polymerization degree was determined by the following formula. GPC conditions Eluent: Dichloromethane Flow rate: 1 ml / min Column: GMH XL (Tosoh) Injection amount: 300 μl Detection method: Differential refractive index and low-angle laser light scattering Weight average degree of polymerization Weight average degree of polymerization = (weight average molecular weight) / (162 + 42 x D
S) However, DS = 162 × (average degree of acetylation) / (6000−42 ×
(Average degree of acetylation)).
【００１３】実施例１ １重量部のαセルロース97％の木材パルプ（銅エチレン
ジアミン溶液粘度から評価した重量平均重合度1820) を
50重量部の純水に30分間浸漬したのち、グラスフィルタ
ーを用いて脱液し、10重量部のジメチルアセトアミドで
３回洗浄、脱液した。上記の前処理を施した木材パルプ
を塩化リチウム濃度15重量％のジメチルアセトアミドに
加え、 100℃で１時間加熱、マイナス80℃で１時間冷却
する操作を３回繰り返した。室温で85重量部のジメチル
アセトアミドを加え、均一なセルロース溶液を得た。EXAMPLE 1 1 part by weight of α-cellulose 97% wood pulp (weight average degree of polymerization 1820 evaluated from the viscosity of copper ethylenediamine solution)
After immersing in 50 parts by weight of pure water for 30 minutes, it was drained using a glass filter, washed with 10 parts by weight of dimethylacetamide three times, and then drained. The above-mentioned pretreated wood pulp was added to dimethylacetamide having a lithium chloride concentration of 15% by weight, and heating at 100 ° C for 1 hour and cooling at -80 ° C for 1 hour were repeated three times. At room temperature, 85 parts by weight of dimethylacetamide was added to obtain a uniform cellulose solution.
【００１４】実施例２ １重量部の再生セルロース（重量平均重合度1750) に実
施例１と同様の方法で前処理を施したのち、塩化リチウ
ム濃度13重量％のジメチルアセトアミド溶液に加え、 1
00℃で５時間加熱した。さらに室温で85重量部のジメチ
ルアセトアミドを加え、均一なセルロース溶液を得た。Example 2 1 part by weight of regenerated cellulose (weight average degree of polymerization: 1750) was pretreated in the same manner as in Example 1 and then added to a dimethylacetamide solution having a lithium chloride concentration of 13% by weight.
Heated at 00 ° C. for 5 hours. Further, 85 parts by weight of dimethylacetamide was added at room temperature to obtain a uniform cellulose solution.
【００１５】比較例１ １重量部のαセルロース97％の木材パルプ（銅エチレン
ジアミン溶液粘度から評価した重量平均重合度1820) に
実施例１と同様の方法で前処理を施したのち、塩化リチ
ウム濃度10重量％のジメチルアセトアミド溶液に加え、
100℃で１時間加熱、マイナス80℃で１時間冷却する操
作を５回繰り返したが、均一な溶液を得ることはできな
かった。COMPARATIVE EXAMPLE 1 1 part by weight of α-cellulose 97% wood pulp (weight average degree of polymerization 1820 evaluated from the viscosity of copper ethylenediamine solution) was pretreated in the same manner as in Example 1 and then the concentration of lithium chloride was changed. Add to 10 wt% dimethylacetamide solution,
The operation of heating at 100 ° C for 1 hour and cooling at -80 ° C for 1 hour was repeated 5 times, but a uniform solution could not be obtained.
【００１６】比較例２ １重量部のαセルロース97％の木材パルプ（銅エチレン
ジアミン溶液粘度から評価した重量平均重合度1820) に
実施例１と同様の方法で前処理を施したのち、塩化リチ
ウム濃度10重量％のジメチルアセトアミド溶液に加え、
150℃で１時間加熱、マイナス80℃で１時間冷却する操
作を５回繰り返し、均一なセルロース溶液を得た。Comparative Example 2 1 part by weight of α-cellulose 97% wood pulp (weight average degree of polymerization 1820 evaluated from the viscosity of copper ethylenediamine solution) was pretreated in the same manner as in Example 1 and then the concentration of lithium chloride was increased. Add to 10 wt% dimethylacetamide solution,
The operation of heating at 150 ° C for 1 hour and cooling at -80 ° C for 1 hour was repeated 5 times to obtain a uniform cellulose solution.
【００１７】実施例３ 実施例１で得られたセルロース溶液に60重量部のピリジ
ン及び 120重量部の無水酢酸を加え、60℃で５時間反応
を行った。反応浴を2000重量部の純水に投入し、生成物
のセルロース・アセテートを回収した。得られたセルロ
ース・アセテートの平均酢化度、重量平均重合度を元の
セルロース試料の重量平均重合度とともに表１に示す。Example 3 60 parts by weight of pyridine and 120 parts by weight of acetic anhydride were added to the cellulose solution obtained in Example 1 and the reaction was carried out at 60 ° C. for 5 hours. The reaction bath was poured into 2000 parts by weight of pure water to recover the product cellulose acetate. The average degree of acetylation and the weight average degree of polymerization of the obtained cellulose acetate are shown in Table 1 together with the weight average degree of polymerization of the original cellulose sample.
【００１８】実施例４ 実施例２で得られたセルロース溶液に60重量部のピリジ
ン及び 120重量部の無水酢酸を加え、60℃で５時間反応
を行った。反応浴を2000重量部の純水に投入し、生成物
のセルロース・アセテートを回収した。得られたセルロ
ース・アセテートの平均酢化度、重量平均重合度を元の
セルロース試料の重量平均重合度とともに表１に示す。Example 4 To the cellulose solution obtained in Example 2, 60 parts by weight of pyridine and 120 parts by weight of acetic anhydride were added and reacted at 60 ° C. for 5 hours. The reaction bath was poured into 2000 parts by weight of pure water to recover the product cellulose acetate. The average degree of acetylation and the weight average degree of polymerization of the obtained cellulose acetate are shown in Table 1 together with the weight average degree of polymerization of the original cellulose sample.
【００１９】比較例３ 比較例１で得られた不均一セルロース溶液に60重量部の
ピリジン及び 120重量部の無水酢酸を加え、60℃で５時
間反応を行った。反応浴を2000重量部の純水に投入し、
生成物のセルロース・アセテートを回収した。得られた
セルロース・アセテートの平均酢化度（表１）は例えば
実施例３、４に比べて明らかに低く、セルロース・アセ
テートの一般的な溶媒であるジクロロメタン／メタノー
ル（９／１、重量比）混合溶媒にも完溶しなかった。Comparative Example 3 To the heterogeneous cellulose solution obtained in Comparative Example 1, 60 parts by weight of pyridine and 120 parts by weight of acetic anhydride were added and reacted at 60 ° C. for 5 hours. Pour the reaction bath into 2000 parts by weight of pure water,
The product, cellulose acetate, was recovered. The average degree of acetylation of the obtained cellulose acetate (Table 1) is obviously lower than that in Examples 3 and 4, and dichloromethane / methanol (9/1, weight ratio), which is a general solvent for cellulose acetate, is used. It was not completely dissolved in the mixed solvent.
【００２０】比較例４ 比較例２で得られたセルロース溶液に60重量部のピリジ
ン及び 120重量部の無水酢酸を加え、60℃で５時間反応
を行った。反応浴を2000重量部の純水に投入し、生成物
のセルロース・アセテートを回収した。得られたセルロ
ース・アセテートの平均酢化度、重量平均重合度を元の
セルロース試料の重量平均重合度とともに表１に示す。Comparative Example 4 To the cellulose solution obtained in Comparative Example 2, 60 parts by weight of pyridine and 120 parts by weight of acetic anhydride were added and reacted at 60 ° C. for 5 hours. The reaction bath was poured into 2000 parts by weight of pure water to recover the product cellulose acetate. The average degree of acetylation and the weight average degree of polymerization of the obtained cellulose acetate are shown in Table 1 together with the weight average degree of polymerization of the original cellulose sample.
【００２１】比較例５ 重量平均重合度642 の再生セルロースから実施例１の方
法でセルロース溶液を調製し、60重量部のピリジン及び
120重量部の無水酢酸を加え、 100℃で２時間反応を行
った。反応浴を2000重量部の純水に投入し、生成物のセ
ルロース・アセテートを回収した。得られたセルロース
・アセテートの平均酢化度、重量平均重合度を元のセル
ロース試料の重量平均重合度とともに表１に示す。Comparative Example 5 A cellulose solution was prepared by the method of Example 1 from regenerated cellulose having a weight average degree of polymerization of 642, and 60 parts by weight of pyridine and
120 parts by weight of acetic anhydride was added, and the reaction was carried out at 100 ° C for 2 hours. The reaction bath was poured into 2000 parts by weight of pure water to recover the product cellulose acetate. The average degree of acetylation and the weight average degree of polymerization of the obtained cellulose acetate are shown in Table 1 together with the weight average degree of polymerization of the original cellulose sample.
【００２２】[0022]
【表１】 [Table 1]
Claims (3)
ムを含むアミド類溶媒で 100℃以下で処理することを特
徴とするセルロース溶液の製造方法。1. A method for producing a cellulose solution, which comprises treating cellulose with an amide solvent containing 12% by weight or more of lithium chloride at 100 ° C. or lower.
ムを含むアミド類溶媒で 100℃以下で処理することを特
徴とするセルロース溶液の製造方法。2. A method for producing a cellulose solution, which comprises treating cellulose with an amide solvent containing 14% by weight or more of lithium chloride at 100 ° C. or lower.
ルロースを酸無水物又は酸塩化物を用いて80℃以下でエ
ステル化することを特徴とするセルロース・エステルの
製造方法。3. A method for producing a cellulose ester, which comprises esterifying the cellulose dissolved by the method according to claim 1 or 2 with an acid anhydride or an acid chloride at 80 ° C. or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8066099A JPH09255701A (en) | 1996-03-22 | 1996-03-22 | Production of cellulose ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8066099A JPH09255701A (en) | 1996-03-22 | 1996-03-22 | Production of cellulose ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09255701A true JPH09255701A (en) | 1997-09-30 |
Family
ID=13306103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8066099A Pending JPH09255701A (en) | 1996-03-22 | 1996-03-22 | Production of cellulose ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09255701A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006089574A (en) * | 2004-09-22 | 2006-04-06 | Daicel Chem Ind Ltd | Cellulose ester and its preparation method |
| JP2006223152A (en) * | 2005-02-16 | 2006-08-31 | Hitachi Zosen Corp | Method for treating biomass through combination of dissolution by cellulose solvent and hydrolysis |
| WO2012077798A1 (en) * | 2010-12-10 | 2012-06-14 | 株式会社ブリヂストン | Method for dissolving cellulose and method for measuring molecular weight distribution of cellulose |
| JP2013049867A (en) * | 2012-11-28 | 2013-03-14 | Daicel Corp | Method for producing cellulose ester |
-
1996
- 1996-03-22 JP JP8066099A patent/JPH09255701A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006089574A (en) * | 2004-09-22 | 2006-04-06 | Daicel Chem Ind Ltd | Cellulose ester and its preparation method |
| JP2006223152A (en) * | 2005-02-16 | 2006-08-31 | Hitachi Zosen Corp | Method for treating biomass through combination of dissolution by cellulose solvent and hydrolysis |
| WO2012077798A1 (en) * | 2010-12-10 | 2012-06-14 | 株式会社ブリヂストン | Method for dissolving cellulose and method for measuring molecular weight distribution of cellulose |
| JP2013049867A (en) * | 2012-11-28 | 2013-03-14 | Daicel Corp | Method for producing cellulose ester |
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