JPS62236801A - Production of soluble cellulose - Google Patents
Production of soluble celluloseInfo
- Publication number
- JPS62236801A JPS62236801A JP7917286A JP7917286A JPS62236801A JP S62236801 A JPS62236801 A JP S62236801A JP 7917286 A JP7917286 A JP 7917286A JP 7917286 A JP7917286 A JP 7917286A JP S62236801 A JPS62236801 A JP S62236801A
- Authority
- JP
- Japan
- Prior art keywords
- cellulose
- degree
- polymerization
- solubility
- steam
- 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
- 239000001913 cellulose Substances 0.000 title claims abstract description 66
- 229920002678 cellulose Polymers 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims abstract description 13
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 13
- 238000010025 steaming Methods 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 abstract description 36
- 230000007423 decrease Effects 0.000 abstract description 10
- 239000002360 explosive Substances 0.000 abstract 4
- 238000010411 cooking Methods 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 235000010980 cellulose Nutrition 0.000 description 57
- 238000005422 blasting Methods 0.000 description 17
- 238000011282 treatment Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000004880 explosion Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000019814 powdered cellulose Nutrition 0.000 description 2
- 229920003124 powdered cellulose Polymers 0.000 description 2
- 241000218657 Picea Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はセルロースの改質方法に関する。より詳しくは
セルロースの重合度を過度に低下させることなく水酸化
アルカリ水溶液への溶解性が飛躍的に向上した可溶性セ
ル四−スを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for modifying cellulose. More specifically, the present invention relates to a method for producing soluble cellulose whose solubility in an aqueous alkali hydroxide solution is dramatically improved without excessively lowering the degree of polymerization of cellulose.
セルロースの用途を広げるために従来よりセルロースに
種々の処理が行なわれてきた。ボールミル、振動ミルに
よる乾式での機械的衝撃による構造破壊、湿式による摩
砕・粉砕、あるいは酸による加水分解がその代表的なも
のであるが、近年多く用いられるようになったものとし
て爆砕処理がある。しかしいずれも微細フィブリル化あ
るいは微粒子化したセルロースを得ることを狙いとした
もので、その大きい比表面積１表面活性、コロイド分散
性を利用しようとしたものである。In order to expand the uses of cellulose, various treatments have been carried out on cellulose. Typical examples include structural destruction due to dry mechanical impact using a ball mill or vibration mill, wet grinding and pulverization, and hydrolysis using acids, but blasting has become increasingly popular in recent years. be. However, all of them aim to obtain fine fibrillated or microparticulate cellulose, and attempt to utilize its large specific surface area, surface activity, and colloidal dispersibility.
上記各種処理方法によって得られる処理セルロースも結
果的にある程度の水酸化アルカリ水溶液可溶性を有して
はいる。しかしこの場合は重合度もまた相当に低下して
おり、水酸化アルカリ水溶液可溶性の向上はこの重合度
低下に由来するものである。したがってこれらの処理で
は重合度の相当な低下を伴なわずして可溶性を向上させ
ることは不可能であり、このように低重合度の可溶性セ
ルロースを用いて糸あるいはフィルムを成形することは
困難である。又成形できたとしてもその物性は極めて貧
弱で実用に耐えない。そして従来の技術では重合度４０
０以上で溶解度Ｓａを９０％以上に高めることは不可能
であった。The treated cellulose obtained by the various treatment methods described above also has a certain degree of solubility in aqueous alkali hydroxide solutions. However, in this case, the degree of polymerization is also considerably reduced, and the improvement in solubility in aqueous alkali hydroxide solutions is due to this decrease in the degree of polymerization. Therefore, with these treatments, it is impossible to improve the solubility without significantly reducing the degree of polymerization, and it is difficult to form threads or films using soluble cellulose with such a low degree of polymerization. be. Even if it can be molded, its physical properties are so poor that it cannot be put to practical use. In conventional technology, the degree of polymerization is 40.
It was impossible to increase the solubility Sa to 90% or more when the solubility was 0 or more.
本発明はセルロースの重合度を過度に低下させることな
く水酸化アルカリ水溶液への溶解度が飛躍的に向上した
可溶性セルロースの製造方法を提供することを目的とす
る０
〔問題点を解決するための手段〕
本発明の目的は結晶化度３５係以下に非晶化処理したセ
ルロースを加圧水蒸気中で蒸煮したのち瞬間的に大気圧
中に噴出膨張させることを特徴とする水酸化アルカリ水
溶液可溶性セルロースの製造方法によって達成される。An object of the present invention is to provide a method for producing soluble cellulose in which the solubility in an aqueous alkali hydroxide solution is dramatically improved without excessively lowering the degree of polymerization of cellulose. The purpose of the present invention is to produce cellulose soluble in an aqueous alkali hydroxide solution by steaming cellulose that has been amorphized to a degree of crystallinity of 35 or less in pressurized steam and then instantaneously ejecting and expanding it into atmospheric pressure. achieved by the method.
なお以下の説明において瞬間的に大気圧中に噴出膨張さ
せる処理を爆砕処理と称す０
爆砕によりセルロースを処理する技術は既に本発明以前
にも知られてはいる。例えば特開昭６０−１７３００１
号公報にはその代表的な例が開示されている。この例で
はセルロースを５〜３０ｋｇ／ｄゲージの飽和水蒸気を
用いて蒸煮・爆砕処理してセルロース微粒子体を得てい
るｏしかしながらこの例の如く単純に爆砕処理を施こす
だけでは、結晶部Ｉ７？：まで処理の効果が及ぶことな
く、むしろ蒸煮中に非晶部の結晶化が促進されて、アル
カリ可溶性を十分に付与することはできない。通常の爆
砕処理方法に於ても蒸煮温度の上昇あるいは蒸煮時間の
延長と共にアルカリ可溶性は少しずつ向上するが、その
時点では重合度もまた大幅に低下している口即ちこの場
合の水酸化アルカリ水溶液可溶性は重合度の低下によっ
てもたらされたものであり、このようなセルロースは繊
維ヤフィルムに成形しても強度が低く利用価値は低い。In the following description, the process of instantaneously ejecting and expanding cellulose into atmospheric pressure will be referred to as blasting process. The technology of treating cellulose by blasting has already been known before the present invention. For example, JP-A-60-173001
A typical example is disclosed in the publication. In this example, cellulose is steamed and exploded using 5 to 30 kg/d gauge saturated steam to obtain cellulose fine particles. : The effect of the treatment is not exerted until the point where the amorphous portion crystallizes during the steaming, and alkali solubility cannot be sufficiently imparted. Even in the normal blasting treatment method, the alkali solubility gradually increases as the steaming temperature increases or the steaming time increases, but at that point the degree of polymerization also decreases significantly. Solubility is brought about by a decrease in the degree of polymerization, and even when such cellulose is formed into a fiber film, its strength is low and its utility value is low.
これに対して本発明は、重合度の不都合な低下を伴なう
ことなくすぐれた水酸化アルカリ水溶液可溶性を付与し
たものである。In contrast, the present invention provides excellent solubility in an aqueous alkali hydroxide solution without undesirably lowering the degree of polymerization.
本発明者等の予備的検討によれば、セルロースを爆砕処
理するに邑たっては、蒸煮圧力（温度）、蒸煮時間およ
び／又は原料セルロースと共に存在する水分率をかえる
ことにより、爆砕処理されたセルロースの構造及び性質
を幅広く変化させることができる。一般的には蒸煮圧力
（温度）を上げるにつれ、蒸煮時間を長くするにつれ、
あるいは原料セルロースと共に存在する水分率を少なく
するにつれて、セルロースの溶解性は向上し、重合度は
低下する。本発明はこのようなセルロースの爆砕処理方
法に於て、先行して結晶化度を３５嗟以下に非晶化処理
したセルロースを加圧水蒸気中で蒸煮したのち瞬間的に
大気圧中に噴出膨張させることを特徴とするものであり
、これによシセルロースの重合度を過度に低下させるこ
となく溶解性を飛躍的に改良することができる。According to a preliminary study by the present inventors, when blasting cellulose, it is possible to change the steaming pressure (temperature), steaming time, and/or moisture content of cellulose as a raw material. The structure and properties of can vary widely. Generally speaking, as the steaming pressure (temperature) is increased and the steaming time is lengthened,
Alternatively, as the moisture content present together with the raw material cellulose is reduced, the solubility of cellulose improves and the degree of polymerization decreases. In the method of blasting cellulose, the present invention involves first steaming cellulose which has been amorphized to a degree of crystallinity of 35 degrees or less in pressurized steam, and then instantaneously ejecting and expanding it into atmospheric pressure. This feature allows the solubility of cellulose to be dramatically improved without excessively lowering the degree of polymerization of cellulose.
本発明の方法の特徴は、セルロースの分解解重合あるい
は結晶化をほとんど惹き起さないような比較的穏やかな
条件で爆砕を行なうことである◎本来°ならば重合度低
下にも溶解性向上にも大きな効果を生じないような穏や
かな条件にもかかわらず結晶化度３５チ以下に非晶化処
理したセルロースを原料として爆砕することにより溶解
性だけを著しく改良することができる。The feature of the method of the present invention is that the explosion is carried out under relatively mild conditions that hardly cause decomposition, depolymerization or crystallization of cellulose. Although cellulose is amorphized to have a crystallinity of 35 degrees or less under such mild conditions that no significant effect is produced, it is possible to significantly improve only the solubility by blasting cellulose as a raw material.
加圧水蒸気による蒸煮過程に於て、水蒸気はセルロース
の結晶領域以外に浸透するため、結晶化度が低い和水蒸
気のセルロース内部への浸透廿は多くなるｎそのため爆
砕時の圧力差が小さくとも爆砕によりセルロースの構造
はより強く掻乱された状態になるものと思われる。これ
は特に分子内の水素結合量の減少として現われている。During the steaming process using pressurized steam, the steam penetrates into areas other than the crystalline regions of cellulose, so the amount of water vapor that has a low crystallinity penetrating into the cellulose increases. Therefore, even if the pressure difference during explosion is small, the explosion It is thought that the structure of cellulose becomes more strongly disturbed. This is particularly manifested as a decrease in the amount of intramolecular hydrogen bonds.
その結果水酸化アルカリ水溶液への著しい可溶性の向上
がもたらされるものと思われる。As a result, it is thought that the solubility in an aqueous alkali hydroxide solution is significantly improved.
有効な爆砕処理の条件は非晶化処理の程度によって異な
り、結晶化度が小さい程穏やかな条件で満足な結果が得
られるようになる。Effective blasting treatment conditions vary depending on the degree of amorphization treatment, and the lower the degree of crystallinity, the more satisfactory results can be obtained under milder conditions.
具体的な爆砕条件は、セルロースの種類、重合度、爆砕
器の構造、処理時のセルロースの含水量その他によって
も異なり、−律に規定できるものではないが、適正条件
として次のような一例を挙げることができる。すなわち
容量２１の爆砕器、容量２０Ｊの受器および内径２２ｍ
φで長さ６００鵬の前記爆砕器と受器をつなぐパイプを
用い、原料にアラスカパルプ（含水率５０〜２ｏｏ１）
から溶解度Ｓａが９９部以」二で重合度低下率１０チ以
下のセルロースを得るための爆砕の好ましい蒸点圧力を
第１表に示す。なお蒸煮時間は全ての場合で１５〜２０
秒とする。Specific blasting conditions vary depending on the type of cellulose, degree of polymerization, structure of the blasting device, water content of cellulose at the time of treatment, etc. - Although they cannot be prescribed by law, the following is an example of appropriate conditions: can be mentioned. That is, a crusher with a capacity of 21, a receiver with a capacity of 20 J, and an inner diameter of 22 m.
A pipe with a diameter of 600 mm and a length of 600 mm was used to connect the crusher and the receiver, and the raw material was Alaskan pulp (moisture content 50 to 2 oo1).
Table 1 shows the preferred steam point pressures for explosion to obtain cellulose from which the solubility Sa is 99 parts or more and the degree of polymerization decrease is 10 parts or less. In addition, the steaming time is 15 to 20 minutes in all cases.
Seconds.
第１表
蒸煮圧力がさらに低い領域では溶解度Ｓａは十分高くな
らず、他方さらに高い場合には重合度の低下が大きく且
つＳａもかえって低くなる。Table 1 In the region where the steaming pressure is lower, the solubility Sa does not become sufficiently high.On the other hand, when the steaming pressure is higher, the degree of polymerization decreases significantly and Sa also becomes lower.
爆砕処理にかける原料セルロースの結晶化度が３５係よ
り大きい場合には上記のような穏やかな爆砕処理条件で
はＳａを十分向上させることはできず、Ｓａを十分大き
くするためにはより激しい爆砕条件が必要となりその結
果重合度低下が著しくなる。If the crystallinity of the raw cellulose to be subjected to blasting treatment is higher than 35, the mild blasting treatment conditions described above will not be able to sufficiently improve Sa, and in order to increase Sa sufficiently, more severe blasting conditions will be required. is required, resulting in a significant decrease in the degree of polymerization.
爆砕処理は次のような装置および方法にて行なうことが
できる。装置は原料を高温高圧の蒸気で蒸煮する圧力容
器である爆砕器、爆砕器に高温高圧蒸気を送り込むボイ
ラー、爆砕器から瞬間的に大気圧中へ噴出された処理物
を受ける受器、噴出された蒸気と処理物とを分離するサ
イクロンおよびこれらをつなぐパイプとから成り、必要
に応じて蒸気弁、ドレイントラリプその他を有するもの
である。The blasting process can be carried out using the following equipment and method. The equipment consists of a detonator, which is a pressure vessel that steams raw materials with high-temperature, high-pressure steam, a boiler that sends high-temperature, high-pressure steam to the detonator, a receiver that receives the treated material that is instantaneously ejected into the atmospheric pressure from the detonator, and a receiver that receives the processed material that is instantaneously ejected into the atmospheric pressure from the detonator. It consists of a cyclone that separates steam from the processed material and a pipe that connects them, and is equipped with a steam valve, drain trap, etc. as necessary.
所定温度に外部加熱している爆砕器に原料を所定量入れ
、所定温度に加熱した蒸気をボイラーから爆砕器に導入
する。爆砕器内の蒸気圧がボイラー内と同じ圧に達した
時点から一定時間の蒸煮を行なう。所定時間の蒸煮の後
、爆砕器のボイラー側の蒸気パルプを閉じ、直ちに爆砕
器の受器側ボールパルプを瞬間的に開けて蒸煮処理の終
ったセルロースを受器の方へ噴出させればよい。A predetermined amount of raw material is put into a detonator that is externally heated to a predetermined temperature, and steam heated to a predetermined temperature is introduced from the boiler into the decomposer. Steaming is carried out for a certain period of time from the point at which the steam pressure in the detonator reaches the same pressure as in the boiler. After steaming for a predetermined period of time, the steam pulp on the boiler side of the detonator is closed, and the ball pulp on the receiver side of the detonator is immediately opened to eject the cellulose that has been steamed toward the receiver. .
以下実施例を説明するに先立ち、本明細書中に用いられ
る用語の定義およびその測定方法を下記に示す。Before describing the Examples below, definitions of terms used in this specification and methods for measuring the same are shown below.
結晶化度はＸ線回折図の回折強度値からＳｅｇａｌ法に
より算出したもので次式によって定義される。The degree of crystallinity is calculated by the Segal method from the diffraction intensity value of the X-ray diffraction diagram, and is defined by the following formula.
Ｉ２Ｏ３：回折角２θ＝２２６°での回折強度Ｉａｍ：
２θ＝１９°附近のベースライン強度（極小値強度）
溶解度Ｓａは次のように定義される。セルロース１０．
９を０℃の１０重量％水酸化ナトリウム水溶液１９０Ｉ
！に攪拌溶解させ、０℃で１５〜２０時間静置したのち
、０℃１０重量係の水酸化ナトリウム水溶液で５倍に稀
釈しだのち不溶分を遠心分離器で分離回収し、その乾燥
重量ｗｇを計量する０
’Ｗ［＋ −’Ｗ
Ｓ ａ ＝ −Ｘ ］ ＯＯチ
Ｏ
ｗｏ＝遠心分離器にかけた５倍稀釈溶液中に含まれるセ
ルロース（７） 全ｔ （ｇ）。I2O3: Diffraction intensity Iam at diffraction angle 2θ=226°:
Baseline intensity (minimum intensity) around 2θ=19° Solubility Sa is defined as follows. Cellulose 10.
9 in 10% by weight aqueous sodium hydroxide solution 190I at 0°C
! After stirring and dissolving the mixture, it was left to stand at 0°C for 15 to 20 hours, and then diluted 5 times with a 10% weight sodium hydroxide aqueous solution at 0°C.The insoluble matter was separated and collected using a centrifuge, and its dry weight wg Weigh out 0'W[+-'WSa=-X]OO=Total t (g) of cellulose (7) contained in the 5-fold diluted solution that was centrifuged.
重合度は、カドキセン溶液での極限粘度〔η〕の測定値
からＷ Ｂｒｏｗｎ の式より計算した粘度平均重合度
で表わした。The degree of polymerization was expressed as the viscosity average degree of polymerization calculated from the measured value of the intrinsic viscosity [η] of the cadoxene solution using the formula W Brown.
ＢｒｏｗｎＯ式 （η） ＝ ａ、８５ ｘ １０−２
Ｍ”６含水率は１１０℃で３時間乾燥後の乾燥重量Ｗ。BrownO formula (η) = a, 85 x 10-2
M"6 moisture content is dry weight W after drying at 110°C for 3 hours.
に対する含有水分の重量で表わした。It is expressed as the weight of water content.
なお、本発明の水酸化アルカリは、水酸化ナトリウム、
水酸化リチウム及び水酸化カリウムである０
〔実 施例〕
以下本発明を実施例により説明するが、本発明は何らこ
れに限定されるものではない。Note that the alkali hydroxide of the present invention includes sodium hydroxide,
0 which are lithium hydroxide and potassium hydroxide [Examples] The present invention will be explained below with reference to Examples, but the present invention is not limited thereto in any way.
実施例・１
針葉樹アラスカパルプ（主原木はとうひ：結晶化ＷＸｃ
＝６３ ％ 、重合度１．０５０）のシート状物を１
０〜２０ｍａ＋角くらいに裁断し、振動ボー゛ルミル用
内径２００ｍｍ長さ３００ｍｍのステンレスのポットに
、やはりステンレス製の直径２５■及び１０順のポール
と共に入れて１２時間振動ボールミルにかけて機械的打
砕力を加えて粉状化した○得られた粉状セルロースは線
結晶化度Ｘｃ＝７％、重合度６１０であり十分非晶化さ
れていた。Example 1 Coniferous Alaskan pulp (main log is spruce: crystallized WXc
= 63%, degree of polymerization 1.050)
Cut into pieces of about 0 to 20 mm + square, put them in a stainless steel pot with an inner diameter of 200 mm and a length of 300 mm for a vibrating ball mill, along with a stainless steel pole of diameter 25 mm and 10 mm, and apply mechanical crushing force to the vibrating ball mill for 12 hours. The powdered cellulose thus obtained had a linear crystallinity Xc of 7%, a degree of polymerization of 610, and was sufficiently amorphous.
次にこの非晶化セルロース１００ｇを水を含ませて２０
０ｇとし、１１容の爆砕器に入れ、ボイラ′−から２０
ｋｇ／ｃｄの加圧水蒸気を導入し、爆砕器内が２０ｋｇ
／−になってから２０秒間蒸煮を続けた。２０秒間の蒸
煮が終れば直ち九ボイラー側のパルプを閉じ、爆砕器の
受器側の弁を急激に開放して、爆砕器内のセルロースお
よび水蒸気を内径２２鵬のパイプを通して受器の中へ膨
張噴出させたう
受器中のセルロースを回収し、脱水乾燥して８９．９の
セルロースを得た。Next, add 100 g of this amorphized cellulose to 20 g of water.
0g, put it in an 11-volume detonator, and 20 g from the boiler.
Introducing pressurized steam of kg/cd, the inside of the blasting machine is 20 kg.
After reaching /-, steaming was continued for 20 seconds. Immediately after 20 seconds of steaming, the pulp on the nine-boiler side is closed, and the valve on the receiver side of the blaster is suddenly opened, allowing the cellulose and steam in the blaster to pass through a pipe with an inner diameter of 22 mm into the receiver. The expanded and ejected cellulose in the container was collected and dehydrated and dried to obtain 89.9 cellulose.
このセルロースの溶解度シよび重合度を測定したところ
、３０％水酸化す） ＋１ウム水溶液への溶解度Ｓａは
９９．８％以上、重合度は４５０であって、すばらしい
水酸化アルカリ水溶液可溶性を示した。When the solubility and degree of polymerization of this cellulose were measured, it was found that the solubility (Sa) in an aqueous solution of 30% hydroxide was 99.8% or more, and the degree of polymerization was 450, indicating excellent solubility in an aqueous alkali hydroxide solution. .
なお振動ボールミルで処理した段階のセルロースはＳａ
が７９チであった。また未処理パルプのＳａは２７％で
あった。Note that the cellulose treated with the vibrating ball mill is Sa
was 79chi. Moreover, the Sa of the untreated pulp was 27%.
実施例・２
実施例・１の振動ボールミル処理セルロースを爆砕器に
入れ、１５ｋｇ／ｃＪの水蒸気で１５秒間蒸煮し爆砕処
理した。このものは５ａ＝９８’ｌ、重合度で５２５で
あった。Example 2 The vibratory ball mill-treated cellulose of Example 1 was placed in an explosion machine and steamed for 15 seconds with 15 kg/cJ of steam to undergo explosion treatment. This product had 5a=98'l and a degree of polymerization of 525.
実施例・３
実施例・１と同様にしてアラスカパルプを６時間振動ボ
ールミル処理した。このセルロースは結晶化度Ｘｃ＝３
０チ、重合度８３０であった。これを２０ｋｇ／ｄの加
熱水蒸気で２０秒間蒸煮して爆砕処理することにより５
ａ＝９２チ、重合度６４０の水酸化アルカリ可溶性のセ
ルロースが得られた。Example 3 Alaska pulp was subjected to vibratory ball mill treatment for 6 hours in the same manner as in Example 1. This cellulose has crystallinity Xc=3
The polymerization degree was 830. By steaming this with heated steam at 20 kg/d for 20 seconds and blasting it,
Alkali hydroxide soluble cellulose with a=92 and a degree of polymerization of 640 was obtained.
実施例・４
シート状アラスカパルプを８０１ＴＩＩ１１径、長さ７
００ｉｎｎのスクリューを持つ２軸押比機にかけバレル
温度７０℃、スクリュー回転数１４ Ｏｒｐｍで、３５
皿径の内形ノズルから押しだした０バルブは粉状になっ
て吐出され結晶化度Ｘｃ及び重合度を測定したところ、
Ｘｃ＝２２％、重合度７３５であった。このセルロース
を２０ｋｇ／ｃｄの加熱水蒸気で１５秒間蒸煮して爆砕
処理することにより５ａ＝９６係、重合度５８０の水酸
化アルカリ可溶性のセルロースが得られた。Example 4 Sheet Alaska pulp 801TII 11 diameter, length 7
The barrel temperature was 70°C, the screw rotation speed was 14 Orpm, and the
The 0 bulb extruded from the internal nozzle with a dish diameter was discharged in the form of powder, and the degree of crystallinity Xc and degree of polymerization were measured.
Xc=22% and degree of polymerization was 735. This cellulose was steamed with heated steam at 20 kg/cd for 15 seconds and exploded to obtain an alkali hydroxide-soluble cellulose having a ratio of 5a=96 and a degree of polymerization of 580.
比較例・１
実施例・１と同じアラスカバルブを５規定の硫酸に６０
℃で３時間浸漬して加水分解したところ、Ｘｃ＝５９４
、重合度６５０のセルロースが得られた。このセルロー
スを第２表（ａ）及び（ｂ）の蒸煮処理条件で爆砕処理
した。、ｌ爆砕処理後のセルロースは第１表に示すよう
に、重合度を４００以上に保とうすればＳａは十分に向
上せず、Ｓａを９５チ以上に十分に向上させようとすれ
ば重合度は極端に低下する。Comparative Example 1 The same Alaska valve as Example 1 was soaked in 5N sulfuric acid for 60 minutes.
When hydrolyzed by immersion at ℃ for 3 hours, Xc = 594
, cellulose with a degree of polymerization of 650 was obtained. This cellulose was subjected to explosion treatment under the steaming treatment conditions shown in Table 2 (a) and (b). As shown in Table 1, cellulose after blasting is not sufficiently improved in Sa if the degree of polymerization is maintained at 400 or higher, and if the Sa is attempted to be sufficiently increased to 95 or higher, the degree of polymerization is decreases dramatically.
第２表
比較例・２
実施例・１と同じアラスカバルブを、実施例・１と同じ
ようにポットに入れ、１０Ｉｎｉ′［ｌ直径のステンレ
スポールだけを加えて３時間振動ボールミルにかけた。Table 2 Comparative Example 2 The same Alaska bulb as in Example 1 was placed in a pot in the same manner as in Example 1, and subjected to a vibrating ball mill for 3 hours with only a stainless steel pole having a diameter of 10 Ini' [l added thereto.
得られた粉状セルロースは結晶化度Ｘｃ＝３９係、重合
度８４０であった。The obtained powdered cellulose had a crystallinity Xc of 39 and a polymerization degree of 840.
このセルロースを第２表（ａ）及び（ト））の蒸気処理
条件で爆砕処理したｎ停砕処理後のセルロースは第３表
に示すよりなＳａ及び重合度となったＯ第３表
〔発明の効果〕
本発明による可溶性セルロースの製造方法は前述のよう
に構成されているので２この方法を用いることによりセ
ルロースの重合度を過度に低下させることなく水酸化ア
ルカリ水溶液への溶解性が飛躍的に向上した可溶性セル
ロースを得ることができる。This cellulose was subjected to explosion treatment under the steam treatment conditions shown in Table 2 (a) and (g)).The cellulose after the crushing treatment had Sa and polymerization degree as shown in Table 3.OTable 3 [Invention [Effect] Since the method for producing soluble cellulose according to the present invention is configured as described above, 2 By using this method, the solubility in an aqueous alkali hydroxide solution can be dramatically increased without excessively lowering the degree of polymerization of cellulose. It is possible to obtain soluble cellulose with improved properties.
Claims (1)
加圧水蒸気中で蒸煮したのち瞬間的に大気圧中に噴出膨
張させることを特徴とする水酸化アルカリ水溶液可溶性
セルロースの製造方法。1. A method for producing cellulose soluble in an aqueous alkali hydroxide solution, which comprises steaming cellulose amorphized to have a crystallinity of 35% or less in pressurized steam and then instantaneously ejecting and expanding it into atmospheric pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7917286A JPS62236801A (en) | 1986-04-08 | 1986-04-08 | Production of soluble cellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7917286A JPS62236801A (en) | 1986-04-08 | 1986-04-08 | Production of soluble cellulose |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62236801A true JPS62236801A (en) | 1987-10-16 |
Family
ID=13682555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7917286A Pending JPS62236801A (en) | 1986-04-08 | 1986-04-08 | Production of soluble cellulose |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62236801A (en) |
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