JPH02129201A - Preparation of cellulose acetate ether having long chain alkyl group - Google Patents
Preparation of cellulose acetate ether having long chain alkyl groupInfo
- Publication number
- JPH02129201A JPH02129201A JP28170988A JP28170988A JPH02129201A JP H02129201 A JPH02129201 A JP H02129201A JP 28170988 A JP28170988 A JP 28170988A JP 28170988 A JP28170988 A JP 28170988A JP H02129201 A JPH02129201 A JP H02129201A
- Authority
- JP
- Japan
- Prior art keywords
- long
- chain alkyl
- cellulose acetate
- alkyl group
- ether
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229920002301 cellulose acetate Polymers 0.000 title claims abstract description 41
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 39
- 230000021736 acetylation Effects 0.000 claims abstract description 18
- 238000006640 acetylation reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 9
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012312 sodium hydride Substances 0.000 claims abstract description 5
- 229910000104 sodium hydride Inorganic materials 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 6
- 230000009257 reactivity Effects 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- -1 alkyl glycidyl ether Chemical compound 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229960005235 piperonyl butoxide Drugs 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 10
- 229920013820 alkyl cellulose Polymers 0.000 abstract description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 102000004169 proteins and genes Human genes 0.000 abstract description 2
- 108090000623 proteins and genes Proteins 0.000 abstract description 2
- 239000005871 repellent Substances 0.000 abstract description 2
- 230000002745 absorbent Effects 0.000 abstract 1
- 239000002250 absorbent Substances 0.000 abstract 1
- 150000001350 alkyl halides Chemical class 0.000 abstract 1
- 238000007796 conventional method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- 238000006266 etherification reaction Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 235000002597 Solanum melongena Nutrition 0.000 description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ZCZCZLVSKGCRTD-UHFFFAOYSA-N 2-(tridecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCCOCC1CO1 ZCZCZLVSKGCRTD-UHFFFAOYSA-N 0.000 description 1
- GFLVAXOSSLICAX-UHFFFAOYSA-N BrCCCCCCCCCCCCCCCC.C(CCCCCCCCCCCCCCC)Br Chemical compound BrCCCCCCCCCCCCCCCC.C(CCCCCCCCCCCCCCC)Br GFLVAXOSSLICAX-UHFFFAOYSA-N 0.000 description 1
- 102100030386 Granzyme A Human genes 0.000 description 1
- 101001009599 Homo sapiens Granzyme A Proteins 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- QHKNLARMWXIVSM-UHFFFAOYSA-N dodecyl 4-methylbenzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=C(C)C=C1 QHKNLARMWXIVSM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は種々の有機溶媒に可溶で成形性が良好であり、
撥水性の紙や疎水性タンパク質の吸着体の原料として利
用可能な長鎖アルキル基を有スる酢酸セルロースエーテ
ルの製法に関する。[Detailed description of the invention] [Industrial application field] The present invention is soluble in various organic solvents and has good moldability,
This invention relates to a method for producing cellulose acetate ether having a long-chain alkyl group that can be used as a raw material for water-repellent paper and hydrophobic protein adsorbents.
［従来の技術・発明が解決しようとする課題］長鎖アル
キル基を有する酢酸セルロースエーテルは、長鎖アルキ
ルセルロースの有機溶媒への溶解性を上げるために考え
られたものである。[Prior Art/Problems to be Solved by the Invention] Cellulose acetate ether having a long-chain alkyl group was designed to increase the solubility of long-chain alkyl cellulose in organic solvents.
この種の化合物は主に長鎖アルキルセルロースエーテル
のアシル化という方法により合成が行なわれており、こ
のような方法で前述の目的化合物を合成するためには、
まず長鎖アルキルセルロースエーテルを合成したのちア
セチル化するという２段階の方法をとらねばならず、煩
雑で、しかも時間のかかるものである。This type of compound is mainly synthesized by the method of acylation of long-chain alkyl cellulose ether, and in order to synthesize the above-mentioned target compound by this method,
This requires a two-step process of first synthesizing a long-chain alkyl cellulose ether and then acetylating it, which is complicated and time-consuming.
［課題を解決するための手段］
本発明者らは、容易に入手可能な酢酸セルロースに存在
するエステルとの反応性の低い強塩基を用い、エステル
のケン化を抑えながらアルキル基をエーテル結合させて
１段階で長鎖アルキル基を有する酢酸セルロースエーテ
ルを製造しうろことを見出し、本発明を完成するに至っ
た。[Means for Solving the Problems] The present inventors used a strong base with low reactivity with the ester present in cellulose acetate, which is easily available, to form an ether bond between alkyl groups while suppressing saponification of the ester. They discovered that cellulose acetate ether having a long-chain alkyl group could be produced in one step, and completed the present invention.
すなわち本発明は、酢酸セルロースにエステルとの反応
性の低い強塩基を作用させたのち長鎖アルキル基を有す
るエーテル化剤を反応させることを特徴とする長鎖アル
キル基を有する酢酸セルロースエーテルの製法に関する
。That is, the present invention provides a method for producing cellulose acetate ether having a long-chain alkyl group, which is characterized in that cellulose acetate is reacted with a strong base having low reactivity with esters and then reacted with an etherifying agent having a long-chain alkyl group. Regarding.
［実施例］
本発明に用いる酢酸セルロースにはとくに限定はなく、
セルロースに存在する水酸基の一部がアセチル化されて
おり、一部が水酸基のままのこっているものであれば使
用しうる。前記酢酸セルロースのうち酢化度が１５〜６
０％のものが各種溶媒の溶解度、長鎖アルキル基の導入
量などの点から好ましく、４０〜５５％のものがさらに
好ましい。[Example] Cellulose acetate used in the present invention is not particularly limited,
Cellulose can be used as long as some of the hydroxyl groups present in the cellulose are acetylated and some remain as hydroxyl groups. The degree of acetylation of the cellulose acetate is 15 to 6.
0% is preferable from the viewpoint of solubility in various solvents, the amount of long-chain alkyl groups introduced, etc., and 40 to 55% is more preferable.
本発明に用いるエステルとの反応性の低い強塩基とは、
エステル結合が存在してもこれを攻撃してケン化させに
くい強塩基のことで、たとえば求核性が低くて強塩基性
であるカリウム１−ブトキシド、水素化ナトリウム、リ
チウムジイソプロピルアミドなどが具体例としてあげら
れる。このような強塩基を用いるため、酢酸エステルの
ケン化をほとんどおこすことなく、酢酸セルロースをエ
ーテル化しうる。酢酸セルロースと前記強塩基とから生
成するアルコキシドは、分子内または分子間でアセチル
基と反応してもエステル基とアルコキシド基の位置が変
換するだけで酢化度およびアルコキシドの数はほとんど
変化しない。The strong base with low reactivity with the ester used in the present invention is
A strong base that is difficult to attack and saponify an ester bond even if it exists. Specific examples include potassium 1-butoxide, sodium hydride, and lithium diisopropylamide, which have low nucleophilicity and are strongly basic. It can be given as Since such a strong base is used, cellulose acetate can be etherified with almost no saponification of acetate ester. Even if the alkoxide produced from cellulose acetate and the strong base reacts with an acetyl group intramolecularly or intermolecularly, only the positions of the ester group and the alkoxide group are changed, and the degree of acetylation and the number of alkoxides hardly change.
本発明に用いる長鎖アルキル基を有するエーテル化剤と
は、エステルとの反応性の低い強塩基を作用させた酢酸
セルロースと反応させて酢酸セルロースをエーテル化す
る薬剤のことであり、長鎖アルキル基を有するエーテル
化剤であるかぎりとくに限定はない。The etherifying agent having a long-chain alkyl group used in the present invention is an agent that etherifies cellulose acetate by reacting with cellulose acetate treated with a strong base that has low reactivity with esters. There are no particular limitations as long as the etherifying agent has a group.
前記長鎖アルキル基を有するエーテル化剤における長鎖
アルキル基とは、アルキル基の主鎖部分の炭素数が６以
上のものが好ましい。該長鎖アルキル基は、酢酸セルロ
ースがエーテル化されたばあいに長鎖アルキルオキシ基
として導入されてもよく、長鎖アルキル基と水酸基との
間にアルキレンオキシ基、置換アルキレン基などの他の
基が存在するように導入されていてもよい。The long-chain alkyl group in the etherification agent having a long-chain alkyl group is preferably one in which the main chain portion of the alkyl group has 6 or more carbon atoms. The long-chain alkyl group may be introduced as a long-chain alkyloxy group when cellulose acetate is etherified. It may be introduced so that a group exists.
前記のごとき長鎖アルキル基を有するエーテル化剤の具
体例としては、たとえば１−ハロゲン化長鎖アルキル（
ＲＸ ： Ｒは０６以上の長鎖アルキル基、ＸはＣＩ、
Ｂｒまたは１）などのハロゲン化長鎖アルキル、ｐ−ト
ルエンスルホン酸長鎖アルキル（ＲＯ３Ｏ２Ｃｊ Ｈ４
ＣＨｓ ： Ｒは前記と同じ）、長鎖１−７ハ
長鎖アルキルグリシジルエーテル（ＲＯＣＨ２ＣｌＣＨ
２：Ｒは前記と同じ）などがあげられる。Specific examples of the etherifying agent having a long-chain alkyl group as described above include, for example, 1-halogenated long-chain alkyl (
RX: R is a long chain alkyl group of 06 or more, X is CI,
Br or halogenated long chain alkyl such as 1), p-toluenesulfonic acid long chain alkyl (RO3O2Cj H4
CHs: R is the same as above), long chain 1-7 long chain alkyl glycidyl ether (ROCH2ClCH
2: R is the same as above).
本発明では、溶媒としてジメチルスルホキシド（ＤＭＳ
Ｏ）、Ｎ−メチルピロリドン（ＮＭＰ）のような酢酸セ
ルロース溶解性の非プロトン性極性溶媒のほか、酢酸セ
ルロースを溶解することのない三級ブチルアルコール、
テトラヒドロフラン（Ｔ）ＩＰ）などの溶媒も使用可能
であるが、実際には使用する塩基によって使い分けるこ
とが望ましい。たとえばカリウムｔ−ブトキシドを用い
るばあい、どの溶媒でも使用しうるが、水素化ナトリウ
ムを用いるばあいにはＴＨＰやＤＭＳＯのような溶媒を
用いるのが好ましく、リチウムジイソプロピルアミドを
用いるばあいにはＴＩ（Ｆを使用するのが好ましい。In the present invention, dimethyl sulfoxide (DMS) is used as a solvent.
O), aprotic polar solvents that dissolve cellulose acetate, such as N-methylpyrrolidone (NMP), as well as tertiary butyl alcohol that does not dissolve cellulose acetate;
Solvents such as tetrahydrofuran (T) IP) can also be used, but in reality it is desirable to use them properly depending on the base used. For example, when using potassium t-butoxide, any solvent can be used, but when using sodium hydride, it is preferable to use a solvent such as THP or DMSO, and when using lithium diisopropylamide, it is preferable to use a solvent such as THP or DMSO. (It is preferable to use F.
また溶液状態で反応を行なうときには、粘度が高くなる
と反応が均一に進行しにくくなるため、このようなばあ
いには、反応時の溶液粘度が３０〜１０００ｃＰである
ことが望ましい。Further, when the reaction is carried out in a solution state, if the viscosity becomes high, it becomes difficult for the reaction to proceed uniformly, so in such a case, it is desirable that the solution viscosity during the reaction is 30 to 1000 cP.
本発明における反応は、通常θ〜５０℃の範囲で行なえ
ばよいが、溶液状態で反応を行なうばあいには、前述の
ように粘度が高いと長鎖アルキル基を有する基の導入量
が減少するため、高い温度で反応を行なう方が良好な結
果を与える。The reaction in the present invention can normally be carried out in the range of θ to 50°C, but when the reaction is carried out in a solution state, as mentioned above, if the viscosity is high, the amount of the group having a long chain alkyl group introduced will be reduced. Therefore, performing the reaction at a higher temperature gives better results.
しかし、５０℃以上の高温で反応を行なうと副反応が無
視できないほど起こりやすいため、反応は５０℃以下で
行なうのが望ましい。However, if the reaction is carried out at a high temperature of 50°C or higher, side reactions are likely to occur which cannot be ignored, so it is desirable to carry out the reaction at a temperature of 50°C or lower.
また反応時間としては、酢酸セルロースと強塩基とから
のアルコキシドの生成にＩＯ分〜１時間程度、エーテル
化に１〜４時間程度みておけば充分である。As for the reaction time, it is sufficient to allow about 10 minutes to 1 hour for the production of alkoxide from cellulose acetate and a strong base, and about 1 to 4 hours for etherification.
本発明の製法でえられる長鎖アルキル基を有する酢酸セ
ルロースエーテルのエーテル化度は、用いる酢酸セルロ
ースにもよるが、グルコース単位１個あたり０．０１〜
１．２個であり、酢化度は１３〜５５％である。なお、
これらの値は次の方法により求めることができる。The degree of etherification of cellulose acetate ether having a long-chain alkyl group obtained by the production method of the present invention varies from 0.01 to 1 glucose unit, although it depends on the cellulose acetate used.
The number of particles is 1.2, and the degree of acetylation is 13 to 55%. In addition,
These values can be determined by the following method.
（酢化度）
試料的ｉ、ｏｇを１００〜１０５℃で２時間乾燥したの
ち精秤し、三角フラスコに移す。そののち、８０％アセ
トン４０ｍ１を加えて１時間撹拌し、浸漬または溶解さ
せる。ついで、０．２Ｎ水酸化ナトリウム水溶液１００
ｍ１を加えて１時間撹拌したのち２時間放置し、ケン化
を行ない、フェノールフタレインを指示薬として０．２
Ｎ塩酸で滴定し、５ｍｌ過剰に加える。そののち、０．
２Ｎ水酸化ナトリウム水溶液で逆滴定し、淡紅色を呈す
る点を終点とし、次式により酢化度ａを算出する。(Acetylation degree) Samples i and og were dried at 100 to 105°C for 2 hours, weighed accurately, and transferred to an Erlenmeyer flask. Thereafter, 40 ml of 80% acetone is added and stirred for 1 hour to immerse or dissolve. Then, 0.2N sodium hydroxide aqueous solution 100
After adding m1 and stirring for 1 hour, it was left to stand for 2 hours for saponification, and phenolphthalein was used as an indicator.
Titrate with N-hydrochloric acid and add 5 ml excess. After that, 0.
Back titrate with a 2N aqueous sodium hydroxide solution, the end point is the point at which it turns pale pink, and the degree of acetylation a is calculated using the following formula.
なお、ブランクテストとして試料を加えずに同様の操作
を行なう。In addition, as a blank test, the same operation is performed without adding a sample.
０．２×げＮａｏＨ（Ａ−Ａ’）
（式中、ｒＮａＯＨは０．２Ｎ ＮａＯＨ水溶液のファ
クタＡはサンプルに用いた０、２Ｎ ＮａＯＨ水溶液の
全量（逆滴定用も含む）、Ａ゛はブランクに要した０、
２Ｎ ＮａＯＨ水溶液の量、’ＩＩｃＩは０．２Ｎ Ｈ
ＣＩ水溶液のファクター、Ｂはサンプルに用いた０、２
Ｎ ＨＣＩ水溶液の全量、Ｂ゛はブランクに要した０、
２Ｎ ｌｌＣｌ水溶液の量である。）（エーテル化度（
グルコース単位１個あたりに存在するエーテル結合の数
））
ＮＭＲの積分値から長鎖アルキル基を有する基およびア
セチル基の数の比Ｘ−（長鎖アルキル基を有する基の数
）／（アセチル基の数）を求める。一方、長鎖アルキル
基を存する基が導入されたことによりグルコース単位当
り増加する分子量をｖ１グルコース単位当りに存在する
アセチル基の数をｄとすると、
ａ−１６２ａ
６００５−ａ（４２＋ｖｘ）
であり、エーテル化度５（−ｄｘ）は次式で与えられる
。0.2×NaoH(A-A') (where rNaOH is 0.2N NaOH aqueous solution factor A is the total amount of 0 and 2N NaOH aqueous solution used in the sample (including for back titration), A' is blank 0 required for
The amount of 2N NaOH aqueous solution, 'IIcI is 0.2N H
Factor of CI aqueous solution, B is 0, 2 used for sample
Total amount of N HCI aqueous solution, B゛ is 0 required for blank,
This is the amount of 2N llCl aqueous solution. ) (degree of etherification (
From the NMR integral value, the ratio of the number of groups having a long-chain alkyl group and the number of acetyl groups (X-(number of groups having a long-chain alkyl group)/(acetyl group) ). On the other hand, when the molecular weight increased per glucose unit due to the introduction of a group containing a long-chain alkyl group, v1 is the number of acetyl groups present per glucose unit, then a-162a 6005-a (42+vx), The degree of etherification 5 (-dx) is given by the following formula.
５＝ ｄｘ−１６２ａｘ
６００５−ａ（４２＋ｖｘ）
上記のような方法により、酢化度の減少をほとんど起こ
さずに長鎖アルキル基を有する酢酸セルロースエーテル
の合成を行なうことができる。5=dx-162ax 6005-a(42+vx) By the method described above, cellulose acetate ether having a long-chain alkyl group can be synthesized with almost no reduction in the degree of acetylation.
つぎに本発明の製法を実施例に基づき説明する。Next, the manufacturing method of the present invention will be explained based on Examples.
実施例Ｉ
ＬＯＯｍｌのナスフラスコに酢酸セルロース（酢化度５
５％、平均重合度１７０）１．３２ｇとＤＮＳｏ ４０
ｍｌとを入れ、撹拌して均一な溶液を調製した。この
溶液にカリウムｔ−ブトキシドｏ、ｅｇを含むＤＭＳＯ
溶液１０ｍ１を室温で加えて１時間撹拌し、そののち臭
化セチル（１−ブロモヘキサデカン） １．［ｉ ｍｌ
を加えて４時間撹拌した。そののち、反応混合物をエタ
ノールに注ぎ込み沈澱させたのち濾過を行ない、さらに
エタノールおよび水で洗浄したのち７０℃で１０時間真
空乾燥を行ない、酢化度４５．７％、長鎖アルキル基に
よるエーテル化度０．１２の酢酸セルロースエーテル１
．１８ｇをえた。Example I Cellulose acetate (degree of acetylation 5) was placed in a LOOml eggplant flask.
5%, average degree of polymerization 170) 1.32g and DNSo 40
ml and stirred to prepare a homogeneous solution. DMSO containing potassium t-butoxide o, eg in this solution
Add 10 ml of the solution at room temperature and stir for 1 hour, then add cetyl bromide (1-bromohexadecane) 1. [i ml
was added and stirred for 4 hours. After that, the reaction mixture was poured into ethanol to precipitate, filtered, further washed with ethanol and water, and vacuum dried at 70°C for 10 hours, resulting in an acetylation degree of 45.7% and etherification using long-chain alkyl groups. Cellulose acetate ether of 0.12 degree 1
．． I got 18g.
実施例２
ｐ−トルエンスルホン酸ドデシル１．８ｇをＡ化セチル
の代わりに用いたほかは実施例１と同様にして酢化度４
４．６％、長鎖アルキル基によるエーテル化度０．２４
の酢酸セルロースエーテル１．１２ｇをえた。Example 2 The degree of acetylation was 4 in the same manner as in Example 1 except that 1.8 g of dodecyl p-toluenesulfonate was used instead of cetyl A.
4.6%, degree of etherification due to long chain alkyl group 0.24
1.12 g of cellulose acetate ether was obtained.
実施例３
１．２−エポキシヘキサデカン１．５ｍｌを臭化セチル
の代わりに用いたほかは実施例１と同様にして酢化度４
３．５％、エーテル化度０．３２の酢酸セルロースエー
テル１．０５ｇをえた。Example 3 The acetylation degree was 4 in the same manner as in Example 1 except that 1.5 ml of 1.2-epoxyhexadecane was used instead of cetyl bromide.
1.05 g of cellulose acetate ether having a concentration of 3.5% and a degree of etherification of 0.32 was obtained.
実施例４
トリデシルグリシジルエーテル１．５ｍｌを臭化セチル
の代わりに用いたほかは実施例１と同様にして酢化度４
６．５％、エーテル化度０．２８の酢酸セルロースエー
テル１．０２ｇをえた。Example 4 Acetylation degree was 4 in the same manner as in Example 1 except that 1.5 ml of tridecyl glycidyl ether was used instead of cetyl bromide.
1.02 g of cellulose acetate ether having a concentration of 6.5% and a degree of etherification of 0.28 was obtained.
実施例５〜７
溶媒をそれぞれＮＭＰ １三級ブチルアルコールおよび
ＴＩＦにかえたほかは実施例１と同様にして酢酸セルロ
ースエーテルをえた。ただし、三級ブチルアルコールと
ＴＨＰを用いたばあいには、酢酸セルロースは溶解しな
いため不均一な状態で反応を行なった。結果を第１表に
示す。Examples 5 to 7 Cellulose acetate ether was obtained in the same manner as in Example 1 except that the solvents were changed to NMP 1-tertiary butyl alcohol and TIF, respectively. However, when tertiary butyl alcohol and THP were used, cellulose acetate was not dissolved, so the reaction was conducted in a non-uniform manner. The results are shown in Table 1.
第 １
表
実施例８
１００ｍ１のナスフラスコに酢酸セルロース（酢化度５
５％、重合度１７ＯＮ、３２ｇとＴＨＰ ３０ｍ１とを
加え、室温で撹拌して懸濁液を調製した。この懸濁液に
水素化ナトリウム２００ｍｇ（８０重量％ミネラルオイ
ル分散物）を室温で加え、５０℃で１時間撹拌したのち
室温に戻し、臭化セチル１．６ｍｌを加えてさらに４時
間撹拌した。反応混合物を水に注ぎ込んだのち、濾過、
エタノール洗浄、水洗浄を行ない、７０℃で１０時間真
空乾燥し、酢化度４６．０％、長鎖アルキル基によるエ
ーテル化度０．３８の酢酸セルロースエーテル１．１５
ｇをえた。Table 1 Example 8 Cellulose acetate (degree of acetylation 5) was placed in a 100 ml eggplant flask.
5%, polymerization degree 17ON, 32 g and THP 30 ml were added and stirred at room temperature to prepare a suspension. 200 mg of sodium hydride (80% by weight mineral oil dispersion) was added to this suspension at room temperature, and the mixture was stirred at 50°C for 1 hour, then returned to room temperature, 1.6 ml of cetyl bromide was added, and the mixture was further stirred for 4 hours. After pouring the reaction mixture into water, filtration,
Washed with ethanol and water, dried under vacuum at 70°C for 10 hours, and obtained cellulose acetate ether 1.15 with a degree of acetylation of 46.0% and a degree of etherification due to long-chain alkyl groups of 0.38.
I got g.
実施例９
１００ｍ１のナスフラスコに酢酸セルロース（酢化度２
９．４％、重合度１５ＯＮ、１１ｇとＤＮＳｏ ３０
ｍｌとを加え、室温で撹拌したのちカリウムｔ−ブトキ
シド１４ｇのＤＭＳＯ溶液１５ｍ１を加え、さらに１時
間撹拌した。ついで臭化セチル３．２ｍｌを加えて４時
間撹拌した。反応混合物をエタノールに注ぎ込み沈澱さ
せたのち濾過を行ない、さらにエタノールおよび水で洗
浄したのち７０℃で１０時間真空乾燥を行ない、酢化度
２７．４％、長鎖アルキル基によるエーテル化度０．８
５の酢酸セルロースエーテル０．９８ｇをえた。Example 9 Cellulose acetate (degree of acetylation 2) was placed in a 100 ml eggplant flask.
9.4%, degree of polymerization 15ON, 11g and DNSo 30
After stirring at room temperature, 15 ml of a DMSO solution containing 14 g of potassium t-butoxide was added, and the mixture was further stirred for 1 hour. Then, 3.2 ml of cetyl bromide was added and stirred for 4 hours. The reaction mixture was poured into ethanol to precipitate, filtered, further washed with ethanol and water, and vacuum dried at 70°C for 10 hours, resulting in a degree of acetylation of 27.4% and a degree of etherification due to long-chain alkyl groups of 0. 8
0.98 g of cellulose acetate ether of No. 5 was obtained.
［発明の効果］
本発明により酢酸セルロースから一段階で長鎖アルキル
基を有する酢酸セルロースエーテルを簡便に製造するこ
とができる。[Effects of the Invention] According to the present invention, cellulose acetate ether having a long-chain alkyl group can be easily produced from cellulose acetate in one step.
Claims (1)
を作用させたのち長鎖アルキル基を有するエーテル化剤
を反応させることを特徴とする長鎖アルキル基を有する
酢酸セルロースエーテルの製法。 ２ 原料とする酢酸セルロースの酢化度が１５〜６０％
の範囲である請求項１記載の製法。 ３ エステルとの反応性の低い強塩基が、カリウムｔ−
ブトキシド、水素化ナトリウムまたはリチウムジイソプ
ロピルアミドである請求項１記載の製法。 ４ 長鎖アルキル基を有するエーテル化剤が、ハロゲン
化長鎖アルキル、ｐ−トルエンスルホン酸長鎖アルキル
、長鎖１−アルケンオキシドまたは長鎖アルキルグリシ
ジルエーテルである請求項１記載の製法。 ５ 長鎖アルキル基の主鎖部分の炭素数が６以上である
請求項１記載の製法。 ６ 反応温度が０〜５０℃である請求項１記載の製法。[Scope of Claims] 1. Cellulose acetate ether having a long-chain alkyl group, which is characterized in that cellulose acetate is reacted with a strong base having low reactivity with esters and then reacted with an etherifying agent having a long-chain alkyl group. manufacturing method. 2 The degree of acetylation of cellulose acetate used as raw material is 15 to 60%.
The manufacturing method according to claim 1, which is within the range of . 3 A strong base with low reactivity with esters is potassium t-
The method according to claim 1, which is butoxide, sodium hydride or lithium diisopropylamide. 4. The method according to claim 1, wherein the etherifying agent having a long-chain alkyl group is a halogenated long-chain alkyl, a long-chain p-toluenesulfonic acid long-chain alkyl, a long-chain 1-alkene oxide, or a long-chain alkyl glycidyl ether. 5. The method according to claim 1, wherein the main chain portion of the long-chain alkyl group has 6 or more carbon atoms. 6. The method according to claim 1, wherein the reaction temperature is 0 to 50°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28170988A JPH02129201A (en) | 1988-11-08 | 1988-11-08 | Preparation of cellulose acetate ether having long chain alkyl group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28170988A JPH02129201A (en) | 1988-11-08 | 1988-11-08 | Preparation of cellulose acetate ether having long chain alkyl group |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02129201A true JPH02129201A (en) | 1990-05-17 |
Family
ID=17642890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28170988A Pending JPH02129201A (en) | 1988-11-08 | 1988-11-08 | Preparation of cellulose acetate ether having long chain alkyl group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02129201A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006335842A (en) * | 2005-06-01 | 2006-12-14 | Konica Minolta Opto Inc | Cellulose ester compound, cellulose ester film, method for producing the cellulose ester film, polarizing plate, and liquid crystal display device |
| WO2013094883A1 (en) * | 2011-12-20 | 2013-06-27 | 삼성정밀화학(주) | Acetylated cellulose ether, method for preparing same, and article comprising the acetylated cellulose ether |
| WO2013100357A1 (en) * | 2011-12-30 | 2013-07-04 | 삼성정밀화학(주) | Preparation method of acetylated cellulose ether, and acetylated cellulose ether prepared thereby |
-
1988
- 1988-11-08 JP JP28170988A patent/JPH02129201A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006335842A (en) * | 2005-06-01 | 2006-12-14 | Konica Minolta Opto Inc | Cellulose ester compound, cellulose ester film, method for producing the cellulose ester film, polarizing plate, and liquid crystal display device |
| WO2013094883A1 (en) * | 2011-12-20 | 2013-06-27 | 삼성정밀화학(주) | Acetylated cellulose ether, method for preparing same, and article comprising the acetylated cellulose ether |
| WO2013100357A1 (en) * | 2011-12-30 | 2013-07-04 | 삼성정밀화학(주) | Preparation method of acetylated cellulose ether, and acetylated cellulose ether prepared thereby |
| US9469694B2 (en) | 2011-12-30 | 2016-10-18 | Lotte Fine Chemical Co., Ltd. | Preparation method of acetylated cellulose ether, and acetylated cellulose ether prepared thereby |
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