JPH04368363A - Production of sulfosuccinic acid monoester salt - Google Patents
Production of sulfosuccinic acid monoester saltInfo
- Publication number
- JPH04368363A JPH04368363A JP3174416A JP17441691A JPH04368363A JP H04368363 A JPH04368363 A JP H04368363A JP 3174416 A JP3174416 A JP 3174416A JP 17441691 A JP17441691 A JP 17441691A JP H04368363 A JPH04368363 A JP H04368363A
- Authority
- JP
- Japan
- Prior art keywords
- acid monoester
- sulfosuccinic acid
- butyl
- tert
- mol
- 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
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 150000003839 salts Chemical class 0.000 title claims description 33
- 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 claims abstract description 19
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims abstract description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011976 maleic acid Substances 0.000 claims abstract description 14
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 14
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 8
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 claims abstract description 8
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 6
- -1 alkali metal sulfite Chemical class 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 11
- 230000009965 odorless effect Effects 0.000 abstract description 6
- 239000002453 shampoo Substances 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000002585 base Substances 0.000 abstract description 4
- 239000002537 cosmetic Substances 0.000 abstract description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 19
- 235000010265 sodium sulphite Nutrition 0.000 description 17
- 238000006277 sulfonation reaction Methods 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 11
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 7
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 5
- 150000003138 primary alcohols Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 3
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- BTFJIXJJCSYFAL-UHFFFAOYSA-N icosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 2
- 235000019252 potassium sulphite Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- IMOYOUMVYICGCA-UHFFFAOYSA-N 2-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C=C1C(C)(C)C IMOYOUMVYICGCA-UHFFFAOYSA-N 0.000 description 1
- QSHVAZMOLNGWSY-UHFFFAOYSA-N 3-butyl-4-methoxyphenol Chemical group CCCCC1=CC(O)=CC=C1OC QSHVAZMOLNGWSY-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 241000612703 Augusta Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 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
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical compound N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- BBLSYMNDKUHQAG-UHFFFAOYSA-L dilithium;sulfite Chemical compound [Li+].[Li+].[O-]S([O-])=O BBLSYMNDKUHQAG-UHFFFAOYSA-L 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SMYREFDDLSTNKQ-UHFFFAOYSA-N oxocan-2-ol Chemical compound OC1CCCCCCO1 SMYREFDDLSTNKQ-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Cosmetics (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、ほとんど無臭で長期間
の品質安定性に優れ、色相の良好な高純度スルホコハク
酸モノエステル塩の製造法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing highly purified sulfosuccinic acid monoester salts which are almost odorless, have excellent long-term quality stability, and have a good hue.
【０００２】0002
【従来の技術】スルホコハク酸モノエステルは、皮膚や
眼粘膜に対する刺激性が低いため、ボディ−シャンプ−
、ヘア−シャンプ−、バブルバス等の香粧品用基剤とし
て用いられている。[Prior Art] Sulfosuccinic acid monoester has low irritation to the skin and eye mucous membranes, so it is used as a body shampoo.
It is used as a base for cosmetic products such as hair shampoo, bubble bath, etc.
【０００３】従来、スルホコハク酸モノエステル塩は無
水マレイン酸とアルコ−ル類とによりマレイン酸モノエ
ステル塩を合成し、これに亜硫酸塩を水の存在下で反応
させて、スルホコハク酸モノエステル塩を製造する方法
は一般によく知られている。Conventionally, sulfosuccinic acid monoester salts are synthesized by synthesizing maleic acid monoester salts using maleic anhydride and alcohols, and reacting this with sulfite in the presence of water to produce sulfosuccinic acid monoester salts. Methods of manufacturing are generally well known.
【０００４】0004
【発明が解決しようとする課題】しかしながら、このよ
うな従来のスルホコハク酸モノエステル塩の製造法にお
いては、マレイン酸モノエステル化の段階で着色が生じ
、最終製品のスルホコハク酸モノエステルの色相が悪く
なるばかりでなく、特有の臭気があり、経時的にさらに
悪化するため、用途上において、商品価値を著しく低下
させることがあり、香粧品基剤としても、その使用は制
限を受けざるを得なかった。マレイン酸モノエステル塩
の合成方法については、特公昭５８−３４４６７号公報
には無水マレイン酸と第二級アルコ−ルエチレンオキシ
ド付加物を触媒として有機酸アルカリ金属塩の存在下に
反応させる方法が開示されているが、この方法では触媒
の有機酸臭が残る欠点がある。[Problems to be Solved by the Invention] However, in such conventional methods for producing sulfosuccinic acid monoester salts, coloration occurs during the maleic acid monoesterification step, and the color of the sulfosuccinic acid monoester in the final product is poor. Not only that, but it also has a unique odor that worsens over time, which can significantly reduce the product value, and its use as a cosmetic base must be restricted. Ta. Regarding the synthesis method of maleic acid monoester salt, Japanese Patent Publication No. 58-34467 discloses a method in which maleic anhydride and secondary alcohol ethylene oxide adduct are reacted in the presence of an organic acid alkali metal salt as a catalyst. However, this method has the disadvantage that the organic acid odor of the catalyst remains.
【０００５】また、スルホコハク酸モノエステル塩の処
理方法として、特公昭５８−２６３９７号公報には、水
素化ホウ素ナトリウム、クエン酸の水溶性塩及び２，６
−ジ第三ブチル−Ｐ−クレゾ−ルを添加する方法および
特公昭６１−２１２８０号公報には、水素化ホウ素ナト
リウムおよび２，６−ジ第三ブチル−Ｐ−クレゾ−ルを
添加する方法が開示されているが、臭気について充分な
効果がなく、とりわけ長期保存中に臭気が悪化し刺激臭
を発生するという問題点があった。[0005] Furthermore, as a method for treating sulfosuccinic acid monoester salt, Japanese Patent Publication No. 58-26397 discloses that sodium borohydride, a water-soluble salt of citric acid and 2,6
- Method of adding di-tert-butyl-P-cresol and Japanese Patent Publication No. 61-21280 describes a method of adding sodium borohydride and 2,6-di-tert-butyl-P-cresol. However, there is a problem in that it is not sufficiently effective against odor, and in particular, the odor deteriorates during long-term storage and generates an irritating odor.
【０００６】[0006]
【課題を解決するための手段】この発明は、このような
従来の問題点に着眼してなされたものであり、本発明者
らは無臭で長期間の安定性に優れ、色相の良好な高純度
スルホコハク酸モノエステル塩を得るべく鋭意研究を行
った結果、本発明に到達したものである。すなわち、本
発明は、炭素数８〜２２を有する脂肪族アルコ−ル又は
そのアルキレンオキシド付加物を、触媒として亜硫酸ア
ルカリ金属塩０．０５〜５重量％の存在下に無水マレイ
ン酸と反応せしめて、マレイン酸モノエステルを生成さ
せ、次いで、２，６−ジ第三ブチル−Ｐ−クレゾ−ル及
び／又は２（３）−第三ブチル−４−ヒドロキシアニソ
−ルの存在下、亜硫酸塩を使用して水中でスルホン化せ
しめることを特徴とするスルホコハク酸モノエステル塩
の製造法を提供するものである。なお、本発明で製造さ
れるスルホコハク酸モノエステル塩は、次の一般式（１
）で示される。[Means for Solving the Problems] The present invention has been made in view of these conventional problems. The present invention was achieved as a result of intensive research to obtain a pure sulfosuccinic acid monoester salt. That is, the present invention involves reacting an aliphatic alcohol having 8 to 22 carbon atoms or an alkylene oxide adduct thereof with maleic anhydride in the presence of 0.05 to 5% by weight of an alkali metal sulfite salt as a catalyst. , to form maleic acid monoester, and then to form the sulfite in the presence of 2,6-di-tert-butyl-P-cresol and/or 2(3)-tert-butyl-4-hydroxyanisole. The present invention provides a method for producing a sulfosuccinic acid monoester salt, which is characterized in that the sulfosuccinic acid monoester salt is sulfonated in water. The sulfosuccinic acid monoester salt produced in the present invention has the following general formula (1
).
【０００７】[0007]
【化１】
（式中、Ｒは炭素数８〜２２のアルキル基またはアルケ
ニル基、Ｍ１ はナトリウム、カリウム、アンモニウム
、Ｍ２ はナトリウム、カリウム、アンモニウム、マグ
ネシウム、アルカノ−ルアンモニウム、ＡＯは炭素数２
〜４のオキシアルキレン基、ｎは０〜２０の平均付加モ
ル数である）[Formula 1] (wherein, R is an alkyl group or alkenyl group having 8 to 22 carbon atoms, M1 is sodium, potassium, ammonium, M2 is sodium, potassium, ammonium, magnesium, alkanol ammonium, and AO is a carbon number 2
~4 oxyalkylene groups, n is the average number of added moles of 0 to 20)
【０００８】（手段を構成する要件）本発明で使用する
炭素数８〜２２の脂肪族アルコ−ルとしては、直鎖又は
分岐の飽和又は不飽和のアルコ−ル例えば、オクチルア
ルコ−ル、デシルアルコ−ル、ドデシルアルコ−ル、テ
トラデシルアルコ−ル、ヘキサデシルアルコ−ル、オク
タデシルアルコ−ル、エイコシルアルコ−ル、ドコシル
アルコ−ル、オレイルアルコ−ル等が挙げられる。また
、オレフィンからオキソ法で作られた分岐構造を有する
合成アルコ−ルを使用することもできる。(Requirements constituting the means) The aliphatic alcohol having 8 to 22 carbon atoms used in the present invention includes straight chain or branched saturated or unsaturated alcohols such as octyl alcohol and decyl alcohol. -ol, dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, eicosyl alcohol, docosyl alcohol, oleyl alcohol and the like. It is also possible to use synthetic alcohols having a branched structure produced from olefins by the oxo method.
【０００９】上記合成アルコ−ルとしては、『ドバノ−
ル』（シェル化学社製）、『オキソコ−ル』（日産化学
工業社製）、『ダイヤド−ル』（三菱化成工業社製）、
『リアル（ＬＩＡＬ）』（キミカアウグスタ社製）など
があげられる。これらの合成アルコ−ルは分岐を有する
アルコ−ルと直鎖状のアルコ−ルとの混合物であり、そ
の割合及び構造は反応条件、使用する触媒および出発原
料の種類により変動するが、いずれのものも使用できる
。[0009] As the above-mentioned synthetic alcohol, "Dovano-
"Oxocol" (manufactured by Nissan Chemical Industries, Ltd.), "Diador" (manufactured by Mitsubishi Chemical Industries, Ltd.),
Examples include "LIAL" (manufactured by Kimica Augusta). These synthetic alcohols are mixtures of branched alcohols and linear alcohols, and their proportions and structures vary depending on the reaction conditions, catalysts used, and types of starting materials; You can also use things.
【００１０】又、ｎ−パラフィンの酸化による第二級合
成アルコ−ルを使用することもできる。It is also possible to use secondary synthetic alcohols obtained by oxidizing n-paraffins.
【００１１】さらに、これら炭素数８〜２２の脂肪族ア
ルコ−ルのアルキレンオキシド付加物も使用できる。ア
ルキレンオキシドはエチレンオキシド、プロピレンオキ
シド、ブチレンオキシドが挙げられ、その平均付加モル
数はスルホコハク酸モノエステル塩の水に対する溶解性
から２０モル以下であり、特に１５モル以下が好ましい
。Furthermore, alkylene oxide adducts of these aliphatic alcohols having 8 to 22 carbon atoms can also be used. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide, and the average number of moles added thereto is 20 moles or less, particularly preferably 15 moles or less, in view of the solubility of the sulfosuccinic acid monoester salt in water.
【００１２】亜硫酸アルカリ金属塩はマレイン酸モノエ
ステル化物を生成するための触媒であり、亜硫酸ナトリ
ウム、亜硫酸水素ナトリウム、亜硫酸カリウム、亜硫酸
水素カリウム、亜硫酸リチウム等がある。この使用量は
、原料の無水マレイン酸と脂肪酸アルコ−ル又はそのア
ルキレンオキシド付加物の合計量に対して０．０５〜５
重量％、特に０．１〜１．０重量％存在させるのが好ま
しい。Alkali metal sulfites are catalysts for producing maleic acid monoesters, and include sodium sulfite, sodium hydrogen sulfite, potassium sulfite, potassium hydrogen sulfite, lithium sulfite, and the like. The amount used is 0.05 to 5% based on the total amount of maleic anhydride and fatty acid alcohol or their alkylene oxide adduct as raw materials.
Preferably it is present in an amount by weight, in particular from 0.1 to 1.0% by weight.
【００１３】２，６−ジ第三ブチル−Ｐ−クレゾ−ル（
ＢＨＴ）、２（３）−第三ブチル−４−ヒドロキシアニ
ソ−ル（ＢＨＡ）の添加量は脂肪族アルコ−ルまたはそ
のアルキレンオキシド付加物、無水マレイン酸及び亜硫
酸塩（亜硫酸水素アルカリ塩の場合は添加するアルカリ
量を含む）の合計量に対して０．０１〜０．２重量％、
好ましくは０．０２〜０．１重量％である。2,6-di-tert-butyl-P-cresol (
BHT), 2(3)-tert-butyl-4-hydroxyanisole (BHA) is added in the amount of aliphatic alcohol or its alkylene oxide adduct, maleic anhydride, and sulfite (in the case of alkali bisulfite salt). is 0.01 to 0.2% by weight based on the total amount of (including the amount of alkali added),
Preferably it is 0.02 to 0.1% by weight.
【００１４】スルホン化に使用する亜硫酸塩としては、
亜硫酸ナトリウム、亜硫酸カリウム、亜硫酸アンモニウ
ム、亜硫酸水素ナトリウム、亜硫酸水素カリウム、亜硫
酸水素アンモニウム等が挙げられる。[0014] As the sulfite used for sulfonation,
Examples include sodium sulfite, potassium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, and ammonium hydrogen sulfite.
【００１５】本発明製造方法は、次の方法により行われ
る。すなわち、脂肪族アルコ−ルまたはそのアルキレン
オキシド付加物と無水マレイン酸とのモル比は要すれば
１．００：１．００〜１．００：１．２０に触媒として
亜硫酸アルカリ金属塩を０．０５〜５重量％を加え、窒
素雰囲気下に、５０〜８５℃、好ましくは６０〜８０℃
でモノエステル化反応を行う。反応温度が５０℃未満で
は、反応速度が遅く、８５℃を越えるとマレイン酸ジエ
ステルの生成が増加するために好ましくない。The manufacturing method of the present invention is carried out by the following method. That is, the molar ratio of aliphatic alcohol or its alkylene oxide adduct and maleic anhydride is 1.00:1.00 to 1.00:1.20, if necessary, and an alkali metal sulfite salt is used as a catalyst. 05 to 5% by weight and heated to 50 to 85°C, preferably 60 to 80°C under nitrogen atmosphere.
Carry out the monoesterification reaction. If the reaction temperature is less than 50°C, the reaction rate is slow, and if it exceeds 85°C, the production of maleic acid diester increases, which is not preferable.
【００１６】次いで、用いた無水マレイン酸の１．００
〜１．０５倍の亜硫酸塩を水の存在下に混合し、２，６
−ジ第三ブチル−Ｐ−クレゾ−ル及び／又は２（３）−
第三ブチル−４−ヒドロキシアニソ−ルを添加したのち
、窒素雰囲気下、５０〜８０℃でスルホン化反応を行う
。５０℃未満では反応速度が遅く、又８０℃を越えると
エステルの加水分解が生じ好ましくない。Next, 1.00 of the maleic anhydride used
~1.05x sulfite is mixed in the presence of water, 2,6
-Ditert-butyl-P-cresol and/or 2(3)-
After adding tert-butyl-4-hydroxyanisole, a sulfonation reaction is carried out at 50 to 80°C under a nitrogen atmosphere. If it is less than 50°C, the reaction rate is slow, and if it exceeds 80°C, the ester will be hydrolyzed, which is undesirable.
【００１７】また、亜硫酸水素アルカリ塩を用いる場合
は、さらに亜硫酸水素アルカリ塩と等モルのナトリウム
、カリウム、マグネシウム等の水酸化物、アンモニア、
アルカノ−ルアミンを使用すればＭ１ とＭ２ の異な
るものができる。In addition, when using an alkali hydrogen sulfite salt, an equimolar amount of hydroxides such as sodium, potassium, magnesium, etc., ammonia,
If alkanolamines are used, products with different M1 and M2 can be obtained.
【００１８】スルホン化時の原料の仕込みは、いずれが
先でもよく、マレイン酸モノエステルの中に水、および
亜硫酸塩を投入してもよいし、水に亜硫酸塩を溶解させ
た中にマレイン酸モノエステルを投入してもよい。水の
使用量は、少ないとゲル状となり、取扱い難いが、生成
するスルホコハク酸モノエステル塩を溶解するに必要な
量を用いると透明な水溶液が得られ取扱い易い。[0018] The raw materials for sulfonation may be added in any order; water and sulfite may be added to maleic acid monoester, or maleic acid may be added to sulfite dissolved in water. A monoester may also be added. If the amount of water used is small, it will become gel-like and difficult to handle, but if the amount necessary to dissolve the sulfosuccinic acid monoester salt produced is used, a transparent aqueous solution will be obtained and easy to handle.
【００１９】２，６−ジ第三ブチル−Ｐ−クレゾ−ル及
び／又は２（３）−第三ブチル−４−ヒドロキシアニソ
−ルはスルホン化の所定の温度に調整するまでに、添加
しておく必要がある。すなわち、２，６−ジ第三ブチル
−Ｐ−クレゾ−ル、２（３）−第三ブチル−４−ヒドロ
キシアニソ−ルは抗酸化剤であり、スルホン化反応以降
において発生する有臭成分の生成を防止する効果があり
、本発明により製造したスルホコハク酸モノエステル塩
は、無臭のものが得られ、さらに長期間にわたり品質を
安定化できる。2,6-di-tert-butyl-P-cresol and/or 2(3)-tert-butyl-4-hydroxyanisole are added until the predetermined temperature for sulfonation is adjusted. It is necessary to keep it. In other words, 2,6-di-tert-butyl-P-cresol and 2(3)-tert-butyl-4-hydroxyanisole are antioxidants and are effective against odorous components generated after the sulfonation reaction. The sulfosuccinic acid monoester salt produced according to the present invention has the effect of preventing the formation, and the sulfosuccinic acid monoester salt produced according to the present invention is odorless, and the quality can be stabilized for a long period of time.
【００２０】[0020]
【実施例】以下に本発明を実施例により具体的に説明す
るが、本発明はこれら実施例により限定されるものでな
い。（％は重量基準を示す）[Examples] The present invention will be explained in detail below using Examples, but the present invention is not limited to these Examples. (% indicates weight basis)
【００２１】実施例１
ドデシルアルコ−ル１８６．０ｇ（１．００モル）と無
水マレイン酸１０２．９ｇ（１．０５モル）、亜硫酸ナ
トリウム０．８７ｇ（０．３０％）を反応容器にとり、
系内の空気を窒素ガスで充分置換した後、常圧、温度７
５℃で４時間モノエステル化反応を行った。Example 1 186.0 g (1.00 mol) of dodecyl alcohol, 102.9 g (1.05 mol) of maleic anhydride, and 0.87 g (0.30%) of sodium sulfite were placed in a reaction vessel.
After sufficiently replacing the air in the system with nitrogen gas, the temperature is reduced to normal pressure and temperature 7.
The monoesterification reaction was carried out at 5°C for 4 hours.
【００２２】これに２，６−ジ第三ブチル−Ｐ−クレゾ
−ル０．２１ｇ（アルコ−ル、無水マレイン酸、亜硫酸
ナトリウムの合計量に対して０．０５％）を加え、室温
まで冷却し、窒素雰囲気下、亜硫酸ナトリウム１３２．
３ｇ（１．０５モル）を水６００ｇに溶解して添加し、
７０℃にて３時間スルホン化を行ない、スルホコハク酸
モノエステル塩水溶液を得た。（表１に得られたマレイ
ン酸モノエステルの分析値と収率、及びスルホコハク酸
モノエステル塩の分析値と収率を示した。以下同じ）Add 0.21 g of 2,6-di-tert-butyl-P-cresol (0.05% based on the total amount of alcohol, maleic anhydride, and sodium sulfite) and cool to room temperature. Sodium sulfite 132.
3 g (1.05 mol) was dissolved in 600 g of water and added,
Sulfonation was carried out at 70°C for 3 hours to obtain an aqueous sulfosuccinic acid monoester salt solution. (Table 1 shows the analytical values and yield of the maleic acid monoester and the analytical value and yield of the sulfosuccinic acid monoester salt. The same applies hereinafter)
【
００２３】比較例１
実施例１において、モノエステル化反応の触媒である亜
硫酸ナトリウム及び２，６−ジ第三ブチル−Ｐ−クレゾ
−ルを用いない他は、同一の製造条件及び操作にて反応
を行なった。[
Comparative Example 1 The reaction was carried out under the same manufacturing conditions and operations as in Example 1, except that sodium sulfite and 2,6-di-tert-butyl-P-cresol, which are catalysts for the monoesterification reaction, were not used. I did this.
【００２４】実施例２
ドデシルアルコ−ルエチレンオキシド３モル付加物３１
８．０ｇ（１．００モル）と無水マレイン酸１００．０
ｇ（１．０２モル）及び亜硫酸水素カリウム２．０９ｇ
（０．５％）を用い、実施例１と同一の製造条件及び操
作にて、モノエステル化反応を行なった。これに２（３
）−第三ブチル−４−ヒドロキシアニソ−ル０．２７ｇ
（０．０５％）を加え、室温まで冷却し、水５５０ｇ、
亜硫酸ナトリウム１２８．５ｇ（１．０２モル）を添加
し、窒素雰囲気下で７５℃にて３時間スルホン化反応を
行ない、スルホコハク酸モノエステル塩水溶液を得た。Example 2 Dodecyl alcohol ethylene oxide 3 mole adduct 31
8.0g (1.00mol) and maleic anhydride 100.0
g (1.02 mol) and potassium bisulfite 2.09 g
(0.5%), a monoesterification reaction was carried out under the same manufacturing conditions and operations as in Example 1. 2 (3)
)-tert-butyl-4-hydroxyanisole 0.27g
(0.05%), cooled to room temperature, 550g of water,
128.5 g (1.02 mol) of sodium sulfite was added, and a sulfonation reaction was carried out at 75° C. for 3 hours under a nitrogen atmosphere to obtain a sulfosuccinic acid monoester salt aqueous solution.
【００２５】比較例２実施例２において、２（３）−第
三ブチル−４−ヒドロキシアニソ−ルを用いない他は、
同様の製造条件及び操作で反応を行なった。Comparative Example 2 In Example 2, except that 2(3)-tert-butyl-4-hydroxyanisole was not used,
The reaction was carried out under similar manufacturing conditions and operations.
【００２６】実施例３
炭素数１２〜１５の混合合成一級アルコ−ルエチレンオ
キシド７モル付加物５０６．０ｇ（１．００モル）と無
水マレイン酸１０２．９ｇ（１．０５モル）及び亜硫酸
ナトリウム１．８３ｇ（０．３％）を用い実施例１と同
一の製造条件及び操作でモノエステル化反応を行った。Example 3 Mixed synthetic primary alcohol having 12 to 15 carbon atoms - 506.0 g (1.00 mol) of 7 mol adduct of ethylene oxide, 102.9 g (1.05 mol) of maleic anhydride and 1.0 mol of sodium sulfite. A monoesterification reaction was carried out using 83 g (0.3%) under the same manufacturing conditions and operations as in Example 1.
【００２７】これを室温まで冷却し、２，６−ジ第三ブ
チル−Ｐ−クレゾ−ル０．３９ｇ（０．０５％）、水１
６７５ｇ、モノエタノ−ルアミン６４．２ｇ（１．０５
モル）、亜硫酸水素ナトリウム１０９．２（１．０５モ
ル）を添加、窒素雰囲気下、７０℃にて、３時間スルホ
ン化を行いスルホコハク酸モノエステル塩水溶液を得た
。[0027] This was cooled to room temperature, and 0.39 g (0.05%) of 2,6-di-tert-butyl-P-cresol and 1 part of water were added.
675g, monoethanolamine 64.2g (1.05g
109.2 (1.05 mol) of sodium bisulfite was added, and sulfonation was carried out at 70° C. for 3 hours in a nitrogen atmosphere to obtain a sulfosuccinic acid monoester salt aqueous solution.
【００２８】実施例４
炭素数１２〜１４の混合合成二級アルコ−ルエチレンオ
キシド５モル付加物４２２．０ｇ（１．００モル）と無
水マレイン酸１０５．８ｇ（１．０８モル）及び亜硫酸
ナトリウム１．５８ｇ（０．３％）を用い実施例１と同
一の製造条件及び操作でモノエステル化反応を行った。
これを室温まで冷却し、２，６−ジ第三ブチル−Ｐ−ク
レゾ−ル０．３３ｇ（０．０５％）、水１５５０ｇ、亜
硫酸ナトリウム１３６．１ｇ（１．０８モル）を添加、
窒素雰囲気下に、７０℃にて、３時間スルホン化を行い
スルホコハク酸モノエステル塩水溶液を得た。Example 4 Mixed synthetic secondary alcohol having 12 to 14 carbon atoms - 5 mol adduct of ethylene oxide 422.0 g (1.00 mol), maleic anhydride 105.8 g (1.08 mol) and sodium sulfite 1 A monoesterification reaction was carried out using .58 g (0.3%) under the same manufacturing conditions and operations as in Example 1. This was cooled to room temperature, and 0.33 g (0.05%) of 2,6-di-tert-butyl-P-cresol, 1550 g of water, and 136.1 g (1.08 mol) of sodium sulfite were added.
Sulfonation was performed at 70° C. for 3 hours in a nitrogen atmosphere to obtain a sulfosuccinic acid monoester salt aqueous solution.
【００２９】実施例５
炭素数１２〜１３の混合合成一級アルコ−ルエチレンオ
キシド３モル付加物３２６．０ｇ（１．００モル）と無
水マレイン酸１００．０ｇ（１．０２モル）及び亜硫酸
水素ナトリウム１．７０ｇ（０．４％）を用い、実施例
１と同一の製造条件及び操作でモノエステル化反応を行
った。これを室温まで冷却し、２，６−ジ第三ブチル−
Ｐ−クレゾ−ル０．２２ｇ（０．０４％）、水１０３０
ｇ、亜硫酸ナトリウム１２８．５ｇ（１．０２モル）を
添加、窒素雰囲気下、７０℃にて、４時間スルホン化を
行ないスルホコハク酸モノエステル塩水溶液を得た。Example 5 Mixed synthesis of primary alcohol having 12 to 13 carbon atoms - 3 mol adduct of ethylene oxide, 326.0 g (1.00 mol), 100.0 g (1.02 mol) of maleic anhydride, and 1 mol of sodium bisulfite Using .70 g (0.4%), a monoesterification reaction was carried out under the same manufacturing conditions and operations as in Example 1. This was cooled to room temperature and 2,6-di-tert-butyl-
P-cresol 0.22g (0.04%), water 1030
g, and 128.5 g (1.02 mol) of sodium sulfite were added thereto, and sulfonation was carried out at 70° C. for 4 hours in a nitrogen atmosphere to obtain a sulfosuccinic acid monoester salt aqueous solution.
【００３０】比較例３
炭素数１２〜１３の混合合成一級アルコ−ルエチレンオ
キシド３モル付加物３２６．０ｇ（１．００モル）と無
水マレイン酸１００．０ｇ（１．０２モル）及び酢酸ナ
トリウム１．７０ｇ（０．４％）を用い、実施例１と同
一の製造条件及び操作でモノエステル化反応を行った。
これを室温まで冷却し、水１０３０ｇ、亜硫酸ナトリウ
ム１２８．５ｇ（１．０２モル）を添加し、窒素雰囲気
下、７０℃にて、４時間スルホン化を行ないスルホコハ
ク酸モノエステル塩水溶液を得た。このものに、スルホ
コハク酸モノエステル塩に対して０．０２％の水素化ホ
ウ素ナトリウム及び０．０５％の２，６−ジ第三ブチル
−Ｐ−クレゾ−ルを添加して完全に溶解した。Comparative Example 3 A mixture of 326.0 g (1.00 mol) of a 3-mol adduct of a primary alcohol having 12 to 13 carbon atoms and ethylene oxide, 100.0 g (1.02 mol) of maleic anhydride, and 1.0 g (1.02 mol) of sodium acetate. Using 70 g (0.4%), a monoesterification reaction was carried out under the same manufacturing conditions and operations as in Example 1. This was cooled to room temperature, 1030 g of water and 128.5 g (1.02 mol) of sodium sulfite were added, and sulfonation was carried out at 70° C. for 4 hours in a nitrogen atmosphere to obtain an aqueous solution of sulfosuccinic acid monoester salt. To this, 0.02% sodium borohydride and 0.05% 2,6-di-tert-butyl-P-cresol were added and completely dissolved based on the sulfosuccinic acid monoester salt.
【００３１】比較例４
実施例５と同一の製造条件及び操作でモノエステル化反
応を行なった。これを室温まで冷却し、水１０３０ｇ、
亜硫酸ナトリウム１２８．５ｇ（１．０２モル）を添加
し、窒素雰囲気下、７０℃にて、４時間スルホン化を行
ないスルホコハク酸塩水溶液を得た。このものに、２，
６−ジ第三ブチル−Ｐ−クレゾ−ル０．２２ｇ（０．０
４％）を添加し、完全に溶解した。Comparative Example 4 A monoesterification reaction was carried out under the same manufacturing conditions and operations as in Example 5. Cool this to room temperature, add 1030g of water,
128.5 g (1.02 mol) of sodium sulfite was added, and sulfonation was carried out at 70° C. for 4 hours in a nitrogen atmosphere to obtain an aqueous sulfosuccinate solution. To this thing, 2,
6-di-tert-butyl-P-cresol 0.22g (0.0
4%) was added and completely dissolved.
【００３２】実施例６
ドデシルアルコ−ルプロピレンオキシド１モル・エチレ
ンオキシド４モル付加物３７６．０ｇ（１モル）と無水
マレイン酸１０２．９ｇ（１．０５モル）及び亜硫酸ナ
トリウム０．９６ｇ（０．２％）を用い、実施例１と同
一の製造条件及び操作でモノエステル化反応を行なった
。Example 6 376.0 g (1 mol) of an adduct of 1 mol of dodecyl alcohol propylene oxide and 4 mol of ethylene oxide, 102.9 g (1.05 mol) of maleic anhydride, and 0.96 g (0.2 mol) of sodium sulfite. %), and the monoesterification reaction was carried out under the same manufacturing conditions and operations as in Example 1.
【００３３】これを室温まで冷却し、２，６−ジ第三ブ
チル−Ｐ−クレゾ−ル０．３１ｇ（０．０５％）、水１
４２０ｇ、亜硫酸ナトリウム１３２．３ｇ（１．０５モ
ル）を添加し、窒素雰囲気下、７０℃にて、４時間スル
ホン化を行ないスルホコハク酸モノエステル塩水溶液を
得た。[0033] This was cooled to room temperature, and 0.31 g (0.05%) of 2,6-di-tert-butyl-P-cresol and 1 part of water were added.
420 g of sodium sulfite and 132.3 g (1.05 mol) of sodium sulfite were added thereto, and sulfonation was carried out at 70° C. for 4 hours in a nitrogen atmosphere to obtain a sulfosuccinic acid monoester salt aqueous solution.
【００３４】実施例７
ドデシルアルコ−ル（合成一級アルコ−ル）エチレンオ
キシド８モル付加物５５２．０ｇ（１．００モル）と無
水マレイン酸１０４．９ｇ（１．０７モル）及び亜硫酸
水素ナトリウム３．２８ｇ（０．５％）を用い、実施例
１と同一の製造条件及び操作でモノエステル化反応を行
なった。これを室温まで冷却し、２，６−ジ第三ブチル
−Ｐ−クレゾ−ル０．１６ｇ（０．０２％）、２（３）
−第三ブチル−４−ヒドロキシアニソ−ル０．１６ｇ（
０．０２％）、水２３７５ｇ、亜硫酸ナトリウム１３４
．８ｇ（１．０７モル）を添加し、窒素雰囲気下、７０
℃にて、４時間スルホン化を行ないスルホコハク酸モノ
エステル塩水溶液を得た。Example 7 Dodecyl alcohol (synthetic primary alcohol) ethylene oxide 8 mol adduct 552.0 g (1.00 mol), maleic anhydride 104.9 g (1.07 mol) and sodium bisulfite 3. A monoesterification reaction was carried out using 28 g (0.5%) under the same manufacturing conditions and operations as in Example 1. This was cooled to room temperature, 0.16 g (0.02%) of 2,6-di-tert-butyl-P-cresol, 2 (3)
-Tertiary butyl-4-hydroxyanisole 0.16g (
0.02%), water 2375g, sodium sulfite 134g
．． 8 g (1.07 mol) was added, and 70 g (1.07 mol) was added under a nitrogen atmosphere.
Sulfonation was carried out at ℃ for 4 hours to obtain a sulfosuccinic acid monoester salt aqueous solution.
【００３５】[0035]
【表１】
［注１］電位差滴定法によりマレイン酸モノエステル及
びマレイン酸の酸価より求めた。（以下同じ）［注２］
エプトン法によりアニオン活性分を求め、理論収量に対
する収率を計算した。（以下同じ）［注３］２５℃での
官能試験により以下の通り、判定した。（以下同じ）○
：ほとんど無臭
△：わずかに臭気あり
×：わずかに刺激臭あり
××：刺激臭あり[Table 1] [Note 1] Determined from the acid value of maleic acid monoester and maleic acid by potentiometric titration method. (The same applies hereafter) [Note 2]
The anionic activity was determined by Epton's method, and the yield was calculated relative to the theoretical yield. (The same applies hereinafter) [Note 3] Judgment was made as follows by a sensory test at 25°C. (same below)○
: Almost odorless △ : Slight odor × : Slightly irritating odor × × : Irritating odor
【００３６】［経日安定性試験］実施例及び比較例で得
られたスルホコハク酸モノエステル塩水溶液を、温度４
０℃の恒温器に放置し、１０日後、２０日後、４０日後
、８０日後、１２０日後の臭気及び８０日後、１２０日
後のアニオン活性分の加水分解率を評価した。その結果
を表２に示した。[Daily stability test] The sulfosuccinic acid monoester salt aqueous solutions obtained in the Examples and Comparative Examples were heated at a temperature of 4.
The sample was left in a thermostatic chamber at 0° C., and the odor after 10 days, 20 days, 40 days, 80 days, and 120 days, and the hydrolysis rate of anionic active components after 80 days and 120 days were evaluated. The results are shown in Table 2.
【００３７】[0037]
【表２】
表１より明らかな通り、、モノエステル化反応時に、触
媒として亜硫酸塩を用いた場合は、マレイン酸モノエス
テルの収率が高いことが確認できる。さらに、２，６−
ジ第三ブチル−Ｐ−クレゾ−ル及び／又は２（３）−第
三ブチル−４−ヒドロキシアニソ−ルを添加して、スル
ホン化反応して得られたスルホコハク酸モノエステル塩
水溶液は収率が高く、ほとんど無臭で色相が良好である
ことが確認できる。また、表２から明らかな通り、本発
明の製造法で得られたスルホコハク酸モノエステル塩水
溶液は長期間放置しても、臭気の発生がなく、加水分解
率も少なく、安定性に優れていることが確認できる。[Table 2] As is clear from Table 1, it can be confirmed that the yield of maleic acid monoester is high when a sulfite is used as a catalyst during the monoesterification reaction. Furthermore, 2,6-
The aqueous solution of sulfosuccinic acid monoester salt obtained by adding di-tert-butyl-P-cresol and/or 2(3)-tert-butyl-4-hydroxyanisole and performing the sulfonation reaction has a yield of It can be confirmed that the color is high, almost odorless, and has a good hue. Furthermore, as is clear from Table 2, the sulfosuccinic acid monoester salt aqueous solution obtained by the production method of the present invention does not generate any odor even when left for a long period of time, has a low hydrolysis rate, and has excellent stability. This can be confirmed.
【００３８】[0038]
【発明の効果】本発明製造法により、ほとんど無臭で色
相の良好な高純度スルホコハク酸モノエステル塩が得ら
れる。本発明製造法で得られたスルホコハク酸モノエス
テル塩は、長期安定性に優れた品質を有し、ボディ−シ
ャンプ−、ヘア−シャンプ−、バブルバス等の香粧品用
基剤として好適である。[Effects of the Invention] By the production method of the present invention, a highly purified sulfosuccinic acid monoester salt which is almost odorless and has a good hue can be obtained. The sulfosuccinic acid monoester salt obtained by the production method of the present invention has excellent long-term stability and is suitable as a base for cosmetic products such as body shampoo, hair shampoo, and bubble bath.
Claims (1)
−ル又はそのアルキレンオキシド付加物を、触媒として
亜硫酸アルカリ金属塩０．０５〜５重量％の存在下に無
水マレイン酸と反応せしめて、マレイン酸モノエステル
を生成させ、次いで、２，６−ジ第三ブチル−Ｐ−クレ
ゾ−ル及び／又は２（３）−第三ブチル−４−ヒドロキ
シアニソ−ルの存在下、亜硫酸塩を使用して水中でスル
ホン化せしめることを特徴とするスルホコハク酸モノエ
ステル塩の製造法。Claim: 1. An aliphatic alcohol having 8 to 22 carbon atoms or an alkylene oxide adduct thereof is reacted with maleic anhydride in the presence of 0.05 to 5% by weight of an alkali metal sulfite as a catalyst, Formation of maleic acid monoester followed by use of sulfite in the presence of 2,6-di-tert-butyl-P-cresol and/or 2(3)-tert-butyl-4-hydroxyanisole A method for producing a sulfosuccinic acid monoester salt, which comprises sulfonating the sulfosuccinic acid monoester salt in water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3174416A JPH072707B2 (en) | 1991-06-18 | 1991-06-18 | Process for producing sulfosuccinic acid monoester salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3174416A JPH072707B2 (en) | 1991-06-18 | 1991-06-18 | Process for producing sulfosuccinic acid monoester salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04368363A true JPH04368363A (en) | 1992-12-21 |
| JPH072707B2 JPH072707B2 (en) | 1995-01-18 |
Family
ID=15978173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3174416A Expired - Fee Related JPH072707B2 (en) | 1991-06-18 | 1991-06-18 | Process for producing sulfosuccinic acid monoester salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH072707B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009013017A (en) * | 2007-07-05 | 2009-01-22 | Dai Ichi Kogyo Seiyaku Co Ltd | Foaming agent for concretes |
| CN102260199A (en) * | 2011-05-18 | 2011-11-30 | 清新县汉科化工科技有限公司 | Composite sulfonating agent and application thereof |
| JP2018162446A (en) * | 2017-03-24 | 2018-10-18 | 三洋化成工業株式会社 | Method for producing surfactant composition |
-
1991
- 1991-06-18 JP JP3174416A patent/JPH072707B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009013017A (en) * | 2007-07-05 | 2009-01-22 | Dai Ichi Kogyo Seiyaku Co Ltd | Foaming agent for concretes |
| CN102260199A (en) * | 2011-05-18 | 2011-11-30 | 清新县汉科化工科技有限公司 | Composite sulfonating agent and application thereof |
| JP2018162446A (en) * | 2017-03-24 | 2018-10-18 | 三洋化成工業株式会社 | Method for producing surfactant composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH072707B2 (en) | 1995-01-18 |
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