JP2814291B2 - Method for stabilizing alkylene glycol monosorbate - Google Patents
Method for stabilizing alkylene glycol monosorbateInfo
- Publication number
- JP2814291B2 JP2814291B2 JP10826690A JP10826690A JP2814291B2 JP 2814291 B2 JP2814291 B2 JP 2814291B2 JP 10826690 A JP10826690 A JP 10826690A JP 10826690 A JP10826690 A JP 10826690A JP 2814291 B2 JP2814291 B2 JP 2814291B2
- Authority
- JP
- Japan
- Prior art keywords
- alkylene glycol
- stabilizing
- phosphite
- glycol monosorbate
- monosorbate
- 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 - Lifetime
Links
- -1 alkylene glycol Chemical compound 0.000 title claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims description 29
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 15
- 230000000087 stabilizing effect Effects 0.000 title claims description 13
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 12
- WJJPRLNGARPWEW-WJPDYIDTSA-N C\C=C\C=C\C(=O)OCCCO Chemical compound C\C=C\C=C\C(=O)OCCCO WJJPRLNGARPWEW-WJPDYIDTSA-N 0.000 claims description 9
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- BJLLGOQTEAOBJJ-MQQKCMAXSA-N 2-hydroxyethyl (2e,4e)-hexa-2,4-dienoate Chemical group C\C=C\C=C\C(=O)OCCO BJLLGOQTEAOBJJ-MQQKCMAXSA-N 0.000 claims description 2
- ZGRJLKBNVVUHIY-AOGGBPEJSA-N C\C=C\C=C\C(=O)OCCCCO Chemical compound C\C=C\C=C\C(=O)OCCCCO ZGRJLKBNVVUHIY-AOGGBPEJSA-N 0.000 claims description 2
- WYPOCAVDDXABIF-UHFFFAOYSA-N didecyl hydrogen phosphite Chemical compound CCCCCCCCCCOP(O)OCCCCCCCCCC WYPOCAVDDXABIF-UHFFFAOYSA-N 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000001879 gelation Methods 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229940075582 sorbic acid Drugs 0.000 description 2
- 235000010199 sorbic acid Nutrition 0.000 description 2
- 239000004334 sorbic acid Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- LERHZMJSGTXXMF-RJNTXXOISA-L (2e,4e)-hexa-2,4-dienoate;iron(2+) Chemical compound [Fe+2].C\C=C\C=C\C([O-])=O.C\C=C\C=C\C([O-])=O LERHZMJSGTXXMF-RJNTXXOISA-L 0.000 description 1
- GRTWTVFDPBKQNU-MQQKCMAXSA-N (2e,4e)-hexa-2,4-dienoyl chloride Chemical compound C\C=C\C=C\C(Cl)=O GRTWTVFDPBKQNU-MQQKCMAXSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YTIUSFKFCRAUDK-UHFFFAOYSA-N C(C=CC=CC)(=O)OCC(C)OC(C=CC=CC)=O Chemical compound C(C=CC=CC)(=O)OCC(C)OC(C=CC=CC)=O YTIUSFKFCRAUDK-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000012045 crude solution Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- NMAKPIATXQEXBT-UHFFFAOYSA-N didecyl phenyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OC1=CC=CC=C1 NMAKPIATXQEXBT-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、アルキレングリコールモノソルベートの安
定化方法に関する。更に詳しくはアルキレングリコール
モノソルベートに亜リン酸エステルを添加することによ
るアルキレングリコールモノソルベートの安定化方法に
関する。Description: TECHNICAL FIELD The present invention relates to a method for stabilizing an alkylene glycol monosorbate. More specifically, the present invention relates to a method for stabilizing an alkylene glycol monosorbate by adding a phosphite to the alkylene glycol monosorbate.
一般式〔Ｉ〕 （式中のCnHmは炭素数２〜４のアルキレン基を表わ
す。） で表わされるアルキレングリコールモノベートは、防カ
ビ剤、防菌剤として使用されている（ヨーロピアンジヤ
ーナルオブメデシナルケミストリーキミカテラペエテイ
ク（European Jourhal of Medicinal Chemistry Chimic
a Therapetique）18 p441〜445（1983））。General formula [I] (CnHm in the formula represents an alkylene group having 2 to 4 carbon atoms.) The alkylene glycol monobate represented by the following formula is used as a fungicide and a bactericide (European Journal of Medicinal Chemistry Kimikaterapeitake). (European Jourhal of Medicinal Chemistry Chimic
a Therapetique) 18 p441-445 (1983)).
また、磁気コーテイング剤（特開昭58−213065号）と
して使用されるなど種々の用途で使用されている。Also, it is used for various purposes such as being used as a magnetic coating agent (JP-A-58-213065).
（従来の技術） 上述の如き用途に有用なアルキレングリコールモノソ
ルベートの有効な安定化方法は低温下に保存する以外知
られていない。(Prior Art) An effective method for stabilizing an alkylene glycol monosorbate useful for the above-mentioned applications has not been known except for storage at a low temperature.
（発明が解決しようとする課題） 一般式〔Ｉ〕で表わされるアルキレングリコールモノ
ソルベートは、その高度に不飽和な構造に起因して、不
安定な物質であつて室温以上での長期の貯蔵において
は、重合、ゲル化を起こしやすく使用が困難となるとい
つた問題点を有している。(Problems to be Solved by the Invention) The alkylene glycol monosorbate represented by the general formula [I] is an unstable substance due to its highly unsaturated structure and is stored for a long time at room temperature or higher. Has a problem that polymerization and gelation are likely to occur and use becomes difficult.
貯蔵時における重合、ゲル化による変質は、製品の品
位を害して商品価値を低下させることとなる。この場合
貯蔵時において重合防止をするため安定化剤等の添加を
必要とするが、今までのところ有効な安定化剤は見い出
されておらず、有効な安定化方法が切望されているのが
現状である。Deterioration due to polymerization and gelation during storage impairs the quality of the product and lowers its commercial value. In this case, it is necessary to add a stabilizer or the like in order to prevent polymerization during storage, but no effective stabilizer has been found so far, and an effective stabilization method has been eagerly desired. It is the current situation.
本発明者らは、アルキレングリコールモノソルベート
の安定化方法について鋭意研究した。その結果、アルキ
レングリコールモノソルベートに亜リン酸エステルを添
加することにより該アルキレングリコールモノソルベー
トが長期に安定化されることを見い出し、この知見にも
とづき本発明を完成した。以上の記述から明らかなよう
に本発明の目的はアルキレングリコールモノソルベート
の安定化方法を提供することである。The present inventors have intensively studied a method for stabilizing an alkylene glycol monosorbate. As a result, they have found that the addition of a phosphite to an alkylene glycol monosorbate stabilizes the alkylene glycol monosorbate for a long period of time, and based on this finding, completed the present invention. As is apparent from the above description, an object of the present invention is to provide a method for stabilizing an alkylene glycol monosorbate.
（課題を解決するための手段） 本発明は、一般式〔Ｉ〕 （式中、CnHmは炭素数２〜４のアルキレン基を表わ
す。） で表わされるアルキレングリコールモノソルベートに亜
リン酸エステルを添加することを特徴とするアルキレン
グリコールモノソルベートの安定化方法である。本発明
でいう上記一般式〔Ｉ〕の構造を有するアルキレングリ
コールモノソルベートは、例えばヒドロキシエチルソル
ベート（ｎ＝２、ｍ＝４）、ヒドロキシプロピルソルベ
ート（ｎ＝３、ｍ＝７）、ヒドロキシブチルソルベート
（ｎ＝４、ｍ＝９）をあげることができる。(Means for Solving the Problems) The present invention relates to a compound represented by the general formula [I]: (Wherein, CnHm represents an alkylene group having 2 to 4 carbon atoms.) A method for stabilizing an alkylene glycol monosorbate comprising adding a phosphite to an alkylene glycol monosorbate represented by the formula: . The alkylene glycol monosorbate having the structure of the general formula [I] referred to in the present invention includes, for example, hydroxyethyl sorbate (n = 2, m = 4), hydroxypropyl sorbate (n = 3, m = 7), Hydroxybutyl sorbate (n = 4, m = 9) can be mentioned.
一般式〔Ｉ〕で表わされるアルキレングリコールモノ
ソルベートは、例えば有機塩基の存在下ソルビン酸クロ
ライドとアルキレングリコール（1.2−エタンジオー
ル、1,2−プロパンジオール、1,2−ブタンジオール）と
反応させる方法、ソルビン酸と酸化アルキレン（エチレ
ンオキサイド、プロピレンオキサイド、ブチレンオキサ
イド）を反応させる方法により製造され、次いで精製工
程を経て得られる。The alkylene glycol monosorbate represented by the general formula [I] is reacted, for example, with sorbic acid chloride and an alkylene glycol (1.2-ethanediol, 1,2-propanediol, 1,2-butanediol) in the presence of an organic base. It is produced by a method of reacting sorbic acid with an alkylene oxide (ethylene oxide, propylene oxide, butylene oxide), and then obtained through a purification step.
本発明において使用する亜リン酸エステルは、トリフ
エニルホスフアイト、ジデシルモノフエニルホスフアイ
ト、トリスノニルフエニルホスフアイトであり、一般式
〔Ｉ〕の化合物に亜リン酸エステルを添加することによ
り、効果的にアルキレンモノソルベートの重合、ゲル化
を防止でき、アルキレングリコールモノソルベートの安
定化が達成される。The phosphite used in the present invention is triphenyl phosphite, didecyl monophenyl phosphite, trisnonyl phenyl phosphite, by adding a phosphite to the compound of the general formula (I), Polymerization and gelation of the alkylene monosorbate can be effectively prevented, and stabilization of the alkylene glycol monosorbate is achieved.
該亜リン酸エステルは、アルキレングリコールモノソ
ルベートに添加する際、よく分散溶解させることが必要
で、機械的な攪拌もしくは不活性ガスを使用したバブリ
ングを行なうことが望ましい。The phosphite needs to be well dispersed and dissolved when added to the alkylene glycol monosorbate, and it is desirable to perform mechanical stirring or bubbling using an inert gas.
亜リン酸エステルの使用量は、特に限定されないがア
ルキレングリコールに対して0.001重量％〜５重量％が
好ましく、より好ましくは0.005重量％〜1.0重量％であ
る。0.001重量％より少ない場合は、安定化効果が小さ
く、また、５重量％以上では、経済的理由で有効でな
い。The amount of the phosphite is not particularly limited, but is preferably 0.001% by weight to 5% by weight, more preferably 0.005% by weight to 1.0% by weight, based on the alkylene glycol. If it is less than 0.001% by weight, the stabilizing effect is small, and if it is more than 5% by weight, it is not effective for economic reasons.
また本発明においては、他の酸化防止剤、例えば2,6
−ジ−tert−ブチル−ｐ−クレゾールやハイドロキノン
モノメチルエーテルを併用しても差支えなく、安定化効
果を妨げずに好結果が得られる。In the present invention, other antioxidants, for example, 2,6
-Di-tert-butyl-p-cresol or hydroquinone monomethyl ether can be used in combination, and good results can be obtained without hindering the stabilizing effect.
（実施例） 以下実施例にもとずき本発明を具体的に説明するが、
本発明は、これによつて限定されるものではない。(Examples) Hereinafter, the present invention will be specifically described based on Examples.
The present invention is not limited thereby.
実施例１〜７ トルエン中ソルビン酸と酸化プロピレンとをソルビン
酸鉄を触媒として反応させてヒドロキシプロピルソルベ
ートを合成した。この反応液を炭酸ナトリウム水溶液で
洗浄して、触媒を除去して粗ヒドロキシプロピルソルベ
ートを調製した。この粗精製液を真空下でトルエン留分
を前留分としてカツトしたのち、5mmHg真空下120〜135
℃のヒドロキシプロピルソルベート画分を得て蒸留精製
した。Examples 1 to 7 Hydroxypropyl sorbate was synthesized by reacting sorbic acid and propylene oxide in toluene with iron sorbate as a catalyst. This reaction solution was washed with an aqueous sodium carbonate solution to remove the catalyst, thereby preparing crude hydroxypropyl sorbate. This crude solution was cut under vacuum with a toluene fraction as a pre-fraction, and then 120-135 under 5 mmHg vacuum.
The hydroxypropyl sorbate fraction at ℃ was obtained and purified by distillation.
蒸留したヒドロキシプロピルソルベートのガスクロ純
度は99.5重量％で残り0.3重量％がジプロピレングリコ
ールモノソルベート、0.2重量％がプロピレングリコー
ルジソルベートであつた。また得られたヒドロキシプロ
ピルソルベートの酸価は0.03mgKOH/g、水酸価は331.0mg
KOH/gであつた。このようにして得たヒドロキシプロピ
ルソルベート各100gに安定化剤として後述の第１表に記
載の亜リン酸エステルを同表に記載の割合で添加してよ
く攪拌したのち、40℃±３℃に保れた保温器中に入れて
経時的に試料を取り出しその試料の粘度をＥ型粘度計を
用いて温度25℃で測定して安定性を評価した。The gas chromatographic purity of the distilled hydroxypropyl sorbate was 99.5% by weight, the remaining 0.3% by weight was dipropylene glycol monosorbate, and 0.2% by weight was propylene glycol disorbate. The obtained hydroxypropyl sorbate has an acid value of 0.03 mg KOH / g and a hydroxyl value of 331.0 mg.
It was KOH / g. To 100 g of each of the thus obtained hydroxypropyl sorbates, a phosphite described in Table 1 described below was added at a ratio shown in Table 1 as a stabilizer, and the mixture was stirred well. The sample was taken out with elapse of time in an incubator kept at, and the viscosity of the sample was measured at a temperature of 25 ° C. using an E-type viscometer to evaluate stability.
また比較例1,2として実施例１〜７に用いたのと同様
のヒドロキシプロピルソルベート各100gに比較例１は、
安定化剤を添加せず、比較例２は、2,6−ジ−ｔ−ブチ
ル−４−メチルフエノール0.04重量％を添加して実施例
１〜７に準じて保存し、粘度の経時的変化を測定して安
定性を評価した。Comparative Examples 1 and 2 each had the same hydroxypropyl sorbate as used in Examples 1 to 7 and Comparative Example 1 each containing 100 g.
Comparative Example 2 was prepared by adding 0.06% by weight of 2,6-di-t-butyl-4-methylphenol without addition of a stabilizer and stored according to Examples 1 to 7, and the viscosity was changed over time. Was measured to evaluate the stability.
実施各例、比較各例の結果を第１表にまとめて示し
た。Table 1 summarizes the results of the examples and comparative examples.
（発明の効果） 従来までアルキレングリコールモノソルベートは、低
温下で保存しなければならなかつたが、本発明の方法を
使用することにより、アルキレングリコールモノソルベ
ートを長期にわたつて室温で安定的に貯蔵、保存するこ
とが可能である。 (Effect of the Invention) Until now, alkylene glycol monosorbate had to be stored at a low temperature, but by using the method of the present invention, the alkylene glycol monosorbate can be stably stored at room temperature for a long period of time. Can be stored and stored.
Claims (4)
グリコールモノソルベートに亜リン酸エステルを添加す
ることを特徴とするアルキレングリコールモノソルベー
トの安定化方法。 （式中、CnHmは炭素数２〜４のアルキレン基を表わ
す。）1. A method for stabilizing an alkylene glycol monosorbate, comprising adding a phosphite to an alkylene glycol monosorbate represented by the following general formula [I]. (In the formula, CnHm represents an alkylene group having 2 to 4 carbon atoms.)
ソルベートに亜リン酸エステル0.005〜５重量％を添加
することを特徴とするアルキレングリコールモノソルベ
ートの安定化方法。2. A method for stabilizing an alkylene glycol monosorbate, comprising adding 0.005 to 5% by weight of a phosphite to the alkylene glycol monosorbate according to claim 1.
ドロキシエチルソルベート、ヒドロキシプロピルソルベ
ート、ヒドロキシブチルソルベートもしくはこれらの２
種以上の混合物である請求項１もしくは請求項２のいず
れか１項のアルキレングリコールモノソルベートの安定
化方法。3. The method of claim 1, wherein the alkylene glycol monosorbate is hydroxyethyl sorbate, hydroxypropyl sorbate, hydroxybutyl sorbate or a mixture thereof.
3. The method for stabilizing an alkylene glycol monosorbate according to claim 1, which is a mixture of at least one kind.
イト、ジデシルモノホスフアイト、トリスノニルフエニ
ルホスフアイトもしくはこれらの２種以上の混合物であ
る請求項１もしくは請求項２のいずれか１項記載のアル
キレングリコールモノソルベートの安定化方法。4. The phosphite according to claim 1, wherein the phosphite is triphenyl phosphite, didecyl monophosphite, trisnonyl phenyl phosphite or a mixture of two or more thereof. A method for stabilizing an alkylene glycol monosorbate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10826690A JP2814291B2 (en) | 1990-04-24 | 1990-04-24 | Method for stabilizing alkylene glycol monosorbate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10826690A JP2814291B2 (en) | 1990-04-24 | 1990-04-24 | Method for stabilizing alkylene glycol monosorbate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH045258A JPH045258A (en) | 1992-01-09 |
| JP2814291B2 true JP2814291B2 (en) | 1998-10-22 |
Family
ID=14480292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10826690A Expired - Lifetime JP2814291B2 (en) | 1990-04-24 | 1990-04-24 | Method for stabilizing alkylene glycol monosorbate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2814291B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0543413A (en) * | 1993-02-08 | 1993-02-23 | Asahi Denka Kogyo Kk | Underwater pest control agent |
-
1990
- 1990-04-24 JP JP10826690A patent/JP2814291B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH045258A (en) | 1992-01-09 |
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