JPS59124933A - Method for dissolving cellulose - Google Patents
Method for dissolving celluloseInfo
- Publication number
- JPS59124933A JPS59124933A JP23011982A JP23011982A JPS59124933A JP S59124933 A JPS59124933 A JP S59124933A JP 23011982 A JP23011982 A JP 23011982A JP 23011982 A JP23011982 A JP 23011982A JP S59124933 A JPS59124933 A JP S59124933A
- Authority
- JP
- Japan
- Prior art keywords
- cellulose
- imidazolidinone
- dimethyl
- lithium chloride
- dissolving
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 14
- 229920000875 Dissolving pulp Polymers 0.000 title claims abstract description 7
- 229920002678 cellulose Polymers 0.000 claims abstract description 27
- 239000001913 cellulose Substances 0.000 claims abstract description 27
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 20
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims abstract description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- RBORURQQJIQWBS-QVRNUERCSA-N (4ar,6r,7r,7as)-6-(6-amino-8-bromopurin-9-yl)-2-hydroxy-2-sulfanylidene-4a,6,7,7a-tetrahydro-4h-furo[3,2-d][1,3,2]dioxaphosphinin-7-ol Chemical compound C([C@H]1O2)OP(O)(=S)O[C@H]1[C@@H](O)[C@@H]2N1C(N=CN=C2N)=C2N=C1Br RBORURQQJIQWBS-QVRNUERCSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は新規なセルロースの溶解方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for dissolving cellulose.
更に詳しくは、活性化されたセルロースと１゜３−ジメ
チル−２−イミダゾリジノン単独あるいはそれとＮ、Ｎ
−ジメチルアセトアミド又はＮ−メチル−２−ピロリド
ンとの２成分あるいは８成分混合物に塩化リチウムを加
えることによってセルロースを溶解させる方法に関する
ものである。More specifically, activated cellulose and 1゜3-dimethyl-2-imidazolidinone alone or together with N,N
- a method for dissolving cellulose by adding lithium chloride to a binary or eight-component mixture with dimethylacetamide or N-methyl-2-pyrrolidone.
セルロースの溶媒はこれ才で銅アンモニア法、ビスコー
ス法が主体であり、特に繊維や膜の製造ではセルロース
の重合度低下がさけ難く、より高性能にするには重合度
低下をおこさない方法が望捷れていた。ｔρ秀鴇法は水
、水酸化す） ＩＪウムを使用するため、セルロースの
反応、主としてエステル化等の反応には使用できなかっ
た。The main solvents for cellulose are the copper ammonia method and the viscose method, and it is difficult to avoid a decrease in the degree of polymerization of cellulose, especially in the production of fibers and membranes, so in order to achieve higher performance, a method that does not cause a decrease in the degree of polymerization is needed. I was hopeful. Since the Hideto method uses water and IJium (hydroxide), it cannot be used for cellulose reactions, mainly reactions such as esterification.
セルロースの非水系溶媒としては５Ｏ２−アミン系、Ｎ
２０４−ジメチルホルムアミド（ＤＭＦ）系、パラホル
ムアルデヒド−ジメチルスルホキシド（ＤＭＳＯ）系等
が提案されているが溶媒に使用する薬品の反応性のため
、満足できるものではなかった。 しかし、最近セルロ
ースがＮ、Ｎ−ジメチルアセトアミド又はＮ−メチル−
２−ピロリドンと塩化リチウムの混合系に溶解すること
が見出され、均−系での反応が検討されて来ている。Non-aqueous solvents for cellulose include 5O2-amine, N
204-dimethylformamide (DMF) system, paraformaldehyde-dimethylsulfoxide (DMSO) system, etc. have been proposed, but these have not been satisfactory due to the reactivity of the chemicals used as solvents. However, recently cellulose has been converted into N,N-dimethylacetamide or N-methyl-
It has been found that it dissolves in a mixed system of 2-pyrrolidone and lithium chloride, and a homogeneous reaction has been investigated.
この発明の発明者も、この溶媒系で硫ｒ蒙化反応を行な
えば、低置換度でも水に均一に溶解する硫酸セルロース
が得られること、ラクトン類との反応では新［７いセル
ロースニスプル誘導体が得られることを見出している。The inventor of this invention also discovered that if the sulfurization reaction is carried out in this solvent system, cellulose sulfate can be obtained which dissolves uniformly in water even at a low degree of substitution, and that in the reaction with lactones, cellulose sulfate can be obtained. It has been found that derivatives can be obtained.
この発明の発明者はセルロースの溶媒について鋭意検別
の結果、既に特願昭５７−１０７８２５号明細書に述べ
ているように、セルロースを活性化後、１．Ｓ−ジメチ
ル−２−イミダゾリジノン単独あるいはそれとＮ、Ｎ−
ジメチルアセトアミド又はＮ−メチル−２−ピロリドン
との２成分あるいは３成分混合系に塩化リチウムを加え
ることにより、セルロースを溶解することを見出した。The inventor of this invention has conducted extensive research on cellulose solvents and found that after activating cellulose, 1. S-dimethyl-2-imidazolidinone alone or together with N, N-
It has been found that cellulose can be dissolved by adding lithium chloride to a binary or ternary mixed system with dimethylacetamide or N-methyl-2-pyrrolidone.
この溶か法において、セルロースを活性化する方法とし
ては、セルロースを水に浸漬後、溶解させる溶媒で直換
する方法、あるいはセルロースを溶解させる溶媒に浸漬
後、加熱する方法があるが、これに限定されるものでは
ない。In this dissolution method, there are two methods for activating cellulose: immersing cellulose in water and then directly replacing it with a solvent to dissolve it, or immersing it in a solvent to dissolve cellulose and then heating it. It is not limited.
廿だ塩化リチウムは均一な溶液を得るためには、８重ｆ
ｆ１％以上存在することが望捷しい。 この溶液を使用
することにより、セルロースの再生によシフイルムある
いは繊維の製造が可能であると同時に米国特許第４２７
８７９０号に見られるような反応が可能である。In order to obtain a homogeneous solution, lithium chloride must be diluted with 8fold f.
It is desirable that f1% or more exists. By using this solution, it is possible to produce film or fiber by regenerating cellulose, and at the same time, US Pat.
Reactions such as those seen in No. 8790 are possible.
まだ、１．３ジメチル−２イミダゾリジノンは高分子化
合物を良く溶解するため、セルロースと混合して溶解す
ることにより、高分子化合物とセすが、この発明を限定
するものではない。However, since 1.3 dimethyl-2 imidazolidinone dissolves high molecular compounds well, it can be mixed with cellulose and dissolved to form a high molecular compound, but this is not intended to limit the present invention.
実施例１
サルファイド法木材バルブ（α−セルロース９４係、重
合度ｓｏｏ ）ａｙを１，３ジメチル−２−イミダゾリ
ジノン１５０りに浸漬し、１６５℃で３０分間攪拌しな
がら加熱した。Example 1 A sulfide-processed wood bulb (α-cellulose 94%, polymerization degree soo) ay was immersed in 150% 1,3 dimethyl-2-imidazolidinone and heated at 165° C. for 30 minutes with stirring.
放冷し、１００℃になったところで、無水塩化リチウム
８．８２を加え、攪拌しながら放冷したととる、セルロ
ースは均一に溶解した。The mixture was allowed to cool, and when the temperature reached 100°C, 8.82 g of anhydrous lithium chloride was added, and the mixture was allowed to cool while stirring, and the cellulose was uniformly dissolved.
実施例２
サルファイド法木材バルブ（α−セルロース９４係、重
合度８００ ）８ｒを１００？の水に３時間浸漬し、脱
液した後、１００ｖの１，３−ジメチル−２−イミダゾ
リジノンに浸漬し、脱液を５回くりかえすことにより、
脱水を行なった。 脱液して１．Ｂ−ジメチル−２−イ
ミダゾリジノンで湿ったセルロースにさらに１，８−ジ
メチル−２−イミダゾリジノン１５０りを加え、攪拌し
ながら無水塩化リチウム８．８２を加え、攪拌を続けた
ところセルロースは均一に溶解シた。Example 2 Sulfide method wood valve (α-cellulose 94%, degree of polymerization 800) 8r to 100%? By immersing it in water for 3 hours, removing the liquid, then immersing it in 100V of 1,3-dimethyl-2-imidazolidinone, and repeating the removal process 5 times.
I did dehydration. Remove fluid 1. To the cellulose moistened with B-dimethyl-2-imidazolidinone, 150 g of 1,8-dimethyl-2-imidazolidinone was added, and while stirring, 8.82 g of anhydrous lithium chloride was added and stirring was continued. Dissolved uniformly.
実ノイ１例１の１．８ジメチル−２−イミダゾリジノン
の代りに次の混合溶媒を使用した場合にもセルロースは
溶解した。 （数字は重量係を示す）実施例３実施例４
実施例５
１．３−ジメチル−２−イミダゾリジノン ５０％
５０％ ４０％Ｎ、Ｎ−ジメチルアセトアミド
５０％ −８０饅Ｎ−メチル−２−ピロリ
ドン − ５ｏチ ３ｏ％代理人弁
理士 野河信太部Cellulose was also dissolved when the following mixed solvent was used instead of 1.8 dimethyl-2-imidazolidinone in Example 1. (Numbers indicate weight) Example 3 Example 4
Example 5 1,3-dimethyl-2-imidazolidinone 50%
50% 40%N,N-dimethylacetamide
50% -80饅N-methyl-2-pyrrolidone - 5ochi 3o%Representative Patent Attorney Shintabe Nogawa
Claims (1)
イミダゾリジノン単独あるいはそれとＲ９１ｑ−ジメチ
ルアセトアミド又はＮ−メチル−２−ピロリドンとの２
成分あるいは８成分混合物に塩化リチウムを加えること
によるセルロースの溶解方法。1. Activated cellulose and 1,3-dimethyl-2-
Imidazolidinone alone or its combination with R91q-dimethylacetamide or N-methyl-2-pyrrolidone
A method of dissolving cellulose by adding lithium chloride to the components or eight-component mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23011982A JPS59124933A (en) | 1982-12-29 | 1982-12-29 | Method for dissolving cellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23011982A JPS59124933A (en) | 1982-12-29 | 1982-12-29 | Method for dissolving cellulose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59124933A true JPS59124933A (en) | 1984-07-19 |
| JPH0261974B2 JPH0261974B2 (en) | 1990-12-21 |
Family
ID=16902862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23011982A Granted JPS59124933A (en) | 1982-12-29 | 1982-12-29 | Method for dissolving cellulose |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59124933A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998017692A1 (en) * | 1996-10-19 | 1998-04-30 | University Of Wales, Bangor | Preparation of chemically reactive polysaccharides |
| JP2013010828A (en) * | 2011-06-28 | 2013-01-17 | Jsr Corp | Cellulose gel |
-
1982
- 1982-12-29 JP JP23011982A patent/JPS59124933A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998017692A1 (en) * | 1996-10-19 | 1998-04-30 | University Of Wales, Bangor | Preparation of chemically reactive polysaccharides |
| US6455691B1 (en) | 1996-10-19 | 2002-09-24 | University Of Wales, Bangor | Preparation of chemically reactive polysaccharides |
| JP2013010828A (en) * | 2011-06-28 | 2013-01-17 | Jsr Corp | Cellulose gel |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0261974B2 (en) | 1990-12-21 |
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