JPH0261974B2 - - Google Patents
Info
- Publication number
- JPH0261974B2 JPH0261974B2 JP23011982A JP23011982A JPH0261974B2 JP H0261974 B2 JPH0261974 B2 JP H0261974B2 JP 23011982 A JP23011982 A JP 23011982A JP 23011982 A JP23011982 A JP 23011982A JP H0261974 B2 JPH0261974 B2 JP H0261974B2
- Authority
- JP
- Japan
- Prior art keywords
- cellulose
- dimethyl
- imidazolidinone
- 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.)
- Expired
Links
- 229920002678 cellulose Polymers 0.000 claims description 23
- 239000001913 cellulose Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 229920000875 Dissolving pulp Polymers 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000002131 composite material 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
- 238000011978 dissolution method Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 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
- 238000005670 sulfation reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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３成
分混合物に塩化リチウムを加えることによつてセ
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-dimethylacetamide or N-
It relates to a method for dissolving cellulose by adding lithium chloride to a binary or ternary mixture with methyl-2-pyrrolidone.
セルロースの溶媒はこれまで銅アンモニア法、
ビスコース法が主体であり、特に繊維や膜の製造
のように大量の溶液を使用する場合、その廃液処
理が大きな間題となつている。また、これらの方
法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
望まれていた。またこれらの方法は水、水酸化ナ
トリ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つ
た。 Solvents for cellulose have so far been prepared using the copper ammonia method,
The viscose method is the main method, and especially when a large amount of solution is used, such as in the production of fibers or membranes, the disposal of the waste liquid is a major issue. Furthermore, in these methods, it is difficult to avoid a decrease in the degree of polymerization of cellulose, and in order to achieve higher performance, a method that does not cause a decrease in the degree of polymerization has been desired. Furthermore, since these methods use water and sodium hydroxide, they 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SO2−アミン
系、N2O2−ジメチルホルムアミド（DMF）系、
パラホルムアルデヒドー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
つた。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、均一系での反応が検討されて来ている。 Non-aqueous solvents for cellulose include SO 2 -amine type, N 2 O 2 -dimethylformamide (DMF) type,
Paraformaldehyde dimethyl sulfoxide (DMSO) systems have been proposed, but these have not been satisfactory due to the reactivity of the chemicals used as solvents. However, it has recently been discovered that cellulose can be dissolved in a mixed system of N,N-dimethylacetamide or N-methyl-2-pyrrolidone and lithium chloride, and a homogeneous reaction has been investigated.
この発明の発明者も、この溶媒系で硫酸化反応
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
応では新しいセルロースエステル誘導体が得られ
ることを見出している。 The inventor of this invention also found that if a sulfation reaction is carried out in this solvent system, cellulose sulfate can be obtained that dissolves uniformly in water even at a low degree of substitution, and that a new cellulose ester derivative can be obtained by reaction with lactones. I'm finding out.
この発明の発明者はセルロースの溶媒について
鋭意検討の結果、既に特願昭57−107825号明細書
（特開昭58−225101号公報参照）に述べているよ
うに、セルロースを活性化後、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。 As a result of intensive studies on solvents for cellulose, the inventor of this invention discovered that after activating cellulose, , 3-dimethyl-2-imidazolidinone alone or together with N,
N-dimethylacetamide or N-methyl-2-
It was discovered that cellulose can be dissolved by adding lithium chloride to a binary or ternary mixed system with pyrrolidone.
この溶解法において、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
せる溶媒で置換する方法、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, methods for activating cellulose include a method in which cellulose is immersed in water and then replaced with a solvent for dissolving it, or a method in which cellulose is immersed in a solvent in which cellulose is to be dissolved and then heated, but is not limited to these methods. It's not something you can do.
また塩化リチウムは均一な溶液を得るために
は、３重量％以上存在することが望ましい。この
溶液を使用することにより、セルロースの再生に
より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4278790号に見られるような反
応が可能である。 Further, in order to obtain a uniform solution, it is desirable that lithium chloride be present in an amount of 3% by weight or more. By using this solution, it is possible to produce films or fibers by regenerating cellulose, and at the same time it is possible to perform reactions such as those found in US Pat. No. 4,278,790.
また、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
ルロースの複合化が可能と考えられる。 In addition, since 1,3 dimethyl-2 imidazolidinone dissolves high molecular compounds well, it is thought that by mixing and dissolving the high molecular compound with cellulose, it is possible to form a composite between the high molecular compound and cellulose.
次にこの発明によるセルロースの溶解の実施例
を示すが、この発明を限定するものではない。 Next, examples of dissolving cellulose according to the present invention will be shown, but the present invention is not limited thereto.
実施例 １
サルフアイト法木材パルプ（α−セルロース94
％、重合度800）3gを１，３ジメチル−２−イミ
ダゾリジノン150gに浸漬し、165℃で30分間撹拌
しながら加熱した。Example 1 Sulfite process wood pulp (α-cellulose 94
%, degree of polymerization: 800) was immersed in 150 g of 1,3 dimethyl-2-imidazolidinone, and heated at 165°C for 30 minutes with stirring.
放冷し、100℃になつたところで、無水塩化リ
チウム8.8gを加え、撹拌しながら放冷したとこ
ろ、セルロースは均一に溶解した。 When the temperature reached 100°C, 8.8 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
サルフアイト法木材パルプ（α−セルロース94
％、重合度800）3gを100gの水に３時間浸漬し、
脱液した後、100g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、脱水を行なつた。脱液して１，３−
ジメチル−２−イミダゾリジノンで湿つたセルロ
ースにさらに１，３−ジメチル−２−イミダゾリ
ジノン150gを加え、撹拌しながら無水塩化リチ
ウム8.8gを加え、撹拌を続けたところセルロース
は均一に溶解した。Example 2 Sulfite process wood pulp (α-cellulose 94
%, degree of polymerization 800) was soaked in 100 g of water for 3 hours,
After removing the liquid, the sample was immersed in 100 g of 1,3-dimethyl-2-imidazolidinone, and dehydration was repeated five times. After dehydration, 1,3-
Another 150 g of 1,3-dimethyl-2-imidazolidinone was added to the cellulose moistened with dimethyl-2-imidazolidinone, and 8.8 g of anhydrous lithium chloride was added while stirring. When the stirring was continued, the cellulose was uniformly dissolved. .
実施例 ３，４，５
実施例１の１，３ジメチル−２−イミダゾリジ
ノンの代わ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％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％、 − 30％
Ｎ−メチル−２−ピロリドン − 50％ 30％Examples 3, 4, 5 Cellulose was also dissolved when the following mixed solvent was used instead of 1,3 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%, - 30% N-methyl-2-pyrrolidone - 50% 30%
Claims (1)
−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 3-dimethyl-2
-Imidazolidinone alone or together with N, N-
A method for dissolving cellulose by adding lithium chloride to a binary or ternary mixture with dimethylacetamide or N-methyl-2-pyrrolidone.
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 JPS59124933A (en) | 1984-07-19 |
| JPH0261974B2 true 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) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0946597B1 (en) | 1996-10-19 | 2003-08-13 | University Of Wales, Bangor | Preparation of chemically reactive starch |
| JP5708300B2 (en) * | 2011-06-28 | 2015-04-30 | Jsr株式会社 | Cellulose gel |
-
1982
- 1982-12-29 JP JP23011982A patent/JPS59124933A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59124933A (en) | 1984-07-19 |
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