KR20200095741A - Process for the preparation of acyloxybenzenesulfonates - Google Patents

Process for the preparation of acyloxybenzenesulfonates Download PDF

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KR20200095741A
KR20200095741A KR1020190013476A KR20190013476A KR20200095741A KR 20200095741 A KR20200095741 A KR 20200095741A KR 1020190013476 A KR1020190013476 A KR 1020190013476A KR 20190013476 A KR20190013476 A KR 20190013476A KR 20200095741 A KR20200095741 A KR 20200095741A
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chloride
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distilled water
bromide
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김선기
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주식회사 비제이바이오켐
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0239—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/57—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing carboxyl groups bound to the carbon skeleton
    • C07C309/58—Carboxylic acid groups or esters thereof

Abstract

The present invention relates to a method for synthesizing acyloxy benzene sulfonate, which is a bleaching activator, from an aqueous solution at a low temperature. A production unit cost can be reduced as acyloxy benzene sulfonate is prepared from an aqueous solution at a low temperature, and acyloxy benzene sulfonate, which is a bleaching activator, can be prepared in an environment-friendly manner.

Description

아실옥시벤젠술포네이트 화합물의 제조방법{Process for the preparation of acyloxybenzenesulfonates}Process for the preparation of acyloxybenzenesulfonates {Process for the preparation of acyloxybenzenesulfonates}

본 발명은 표백 활성제인 아실옥시벤젠술포네이트 화합물을 제조하는 방법에 관한 것이다. The present invention relates to a method for preparing an acyloxybenzenesulfonate compound as a bleaching activator.

아실옥시벤젠술포네이트의 제조방법은 종래 수많은 방법이 알려져 있다.Numerous methods have been known for the production of acyloxybenzenesulfonate.

미국 등록특허 6,822,113호 에서는 소듐 파라 페놀 술포네이트(Sodium para-phenol sulfonate, SPS)을 220℃에서 무수물과 카르복실산 유도체(carboxylic acid derivative)를 이용하여 아이소파 G(isopar G) 용매상에서 120 내지 130℃로 반응시켜 아실옥시벤젠술포네이트(acyloxybenzeneSulfonates)를 제조하는 방법을 개시하고 있다.In U.S. Patent No. 6,822,113, sodium para-phenol sulfonate (SPS) is used in an isopar G (120-130) solvent using an anhydride and a carboxylic acid derivative at 220°C. Disclosed is a method for preparing acyloxybenzenesulfonates by reacting at °C.

대한민국 공개특허 제10-2013-0086553호에서 탈수 처리한 4-히드록시벤젠술폰산나트륨과 라우린산클로라이드를 N, N-디메틸포름아미드(DMF) 용액상에서 50℃로 적하 시키고 3시간 반응시키고 용매를 제거하고 아세톤 세정 후 물/아세톤(1/1mol) 용매 중에서 재결정한 후, 정제하여 표백 활성제 4-도데카노일옥시벤젠술폰산나트륨을 합성하는 방법을 개시하고 있다. 그러나 N, N-디메틸포름아미드라는 독성을 가진 용매를 사용한다는 단점이 있다.Sodium 4-hydroxybenzenesulfonic acid and lauric acid chloride dehydrated in Republic of Korea Patent Publication No. 10-2013-0086553 are added dropwise to N,N-dimethylformamide (DMF) solution at 50°C, reacted for 3 hours, and the solvent. Disclosed is a method of synthesizing bleach activator 4-dodecanoyloxybenzenesulfonic acid sodium salt after removal, recrystallization in water/acetone (1/1 mol) solvent after acetone washing. However, there is a disadvantage in that a toxic solvent such as N, N-dimethylformamide is used.

미국 공개특허 1,437,724호에서 하이드록시벤젠 술포네이트 염(hydroxybenzene sulfonate salt)과 아릴 에스터(aryl ester)를 유기용매와 200 내지 350℃로 반응시켜 아실옥시벤젠술포네이트(acyloxybenzenesulfonates)를 제조하는 방법을 개시하고 있다.U.S. Patent Publication No. 1,437,724 discloses a method for preparing acyloxybenzenesulfonates by reacting a hydroxybenzene sulfonate salt and an aryl ester with an organic solvent at 200 to 350°C have.

그러나 이들 발명은 고온에서 유기용매를 이용하여 제조하여 생산비용이 높으며, 인체에 유해한 유기용매 등을 다량 사용하며, 환경에 유해하다. 따라서 생산이 용이하여 경제적이고, 친환경적인 제조공정의 개발이 요구되고 있다.However, these inventions are manufactured using organic solvents at high temperatures, resulting in high production costs, and use a large amount of organic solvents that are harmful to the human body, and are harmful to the environment. Therefore, it is required to develop an economical and eco-friendly manufacturing process due to easy production.

이에 본 발명자들은 생산이 용이하고 친환경적인 공정을 개발하고자, 저온으로 수용액상에서 반응시켜도 고수득율로 목적 화합물을 얻을 수 있음을 확인하고, 본 발명을 완성하였다.Accordingly, the present inventors confirmed that the target compound can be obtained with a high yield even when reacted in an aqueous solution at a low temperature in order to develop an easy and eco-friendly process.

대한민국 공개특허 제10-2013-0086553호Republic of Korea Patent Publication No. 10-2013-0086553

본 발명의 하나의 목적은 반응식Ⅰ과 같이 아실클로라이드와 소듐하이드록시벤젠술포네이트를 반응용매(solvent) 하에서 반응시키는 단계를 포함하는, 화학식1로 표시되는 소듐 아실옥시벤젠술포네이트를 제조하는 방법을 제공하는 것이다.One object of the present invention is a method for preparing sodium acyloxybenzenesulfonate represented by Chemical Formula 1, comprising reacting acyl chloride and sodium hydroxybenzenesulfonate under a reaction solvent as in Reaction Scheme I. Is to provide.

반응식Ⅰ 및 화학식1의 상기 R은 C6 내지 C22의 직쇄상 또는 분쇄상의 포화 알킬기이고, 상기 반응용매(solvent)는 물과 아세톤이 10:0 내지 6.5:3.5의 중량비로 혼합된 것이다.R in Reaction Scheme I and Formula 1 is a C6 to C22 linear or pulverized saturated alkyl group, and the reaction solvent is water and acetone mixed in a weight ratio of 10:0 to 6.5:3.5.

상기 목적을 달성하기 위하여 본 발명은 하나의 양태로 하기 반응식Ⅰ과 같이 아실클로라이드와 소듐하이드록시벤젠술포네이트를 반응용매(solvent) 하에서 반응시키는 단계를 포함하는, 화학식1로 표시되는 소듐 아실옥시벤젠술포네이트를 제조하는 방법을 제공하는 것이다.In order to achieve the above object, the present invention includes, in one embodiment, a reaction of acyl chloride and sodium hydroxybenzenesulfonate under reaction solvent as shown in Reaction Scheme I, sodium acyloxybenzene represented by Chemical Formula 1 It is to provide a method for preparing a sulfonate.

[화학식1][Formula 1]

Figure pat00001
Figure pat00001

[반응식Ⅰ][Reaction Scheme I]

Figure pat00002
Figure pat00002

상기 반응식Ⅰ 및 화학식1의 상기 R은 C6 내지 C22의 직쇄상 또는 분쇄상의 포화 알킬기이고, 상기 반응용매(solvent)는 물과 아세톤이 10:0 내지 6.5:3.5의 중량비로 혼합된 것이다. The R of Formula 1 and Formula 1 is a C6 to C22 linear or pulverized saturated alkyl group, and the reaction solvent is water and acetone mixed in a weight ratio of 10:0 to 6.5:3.5.

본 발명의 소듐 아실옥시벤젠술포네이트는 상기 화학식1로 표시된다.The sodium acyloxybenzenesulfonate of the present invention is represented by Formula 1 above.

상기 소듐 아실옥시벤젠술포네이트는 표백활성물질로 활용이 가능하다. The sodium acyloxybenzenesulfonate can be used as a bleaching active material.

상기 화학식1의 R은 C6 내지 C22의 직쇄상 또는 분쇄상의 포화 알킬기이다.R in Formula 1 is a C6 to C22 linear or branched saturated alkyl group.

상기 화학식1로 표시되는 소듐 아실옥시벤젠술포네이트는 구체적으로 라우릴옥시벤젠술포네이트 또는 노나노일옥시벤젠술포네이트를 포함한다.The sodium acyloxybenzenesulfonate represented by Formula 1 specifically includes lauryloxybenzenesulfonate or nonanoyloxybenzenesulfonate.

상기 화학식1로 표시되는 소듐 아실옥시벤젠술포네이트는 상기 반응식Ⅰ과 같이 아실클로라이드와 소듐하이드록시벤젠술포네이트를 반응용매 하에서 반응시켜 제조될 수 있다.Sodium acyloxybenzenesulfonate represented by Chemical Formula 1 may be prepared by reacting acyl chloride and sodium hydroxybenzenesulfonate under a reaction solvent as in Reaction Scheme I.

상기 반응식Ⅰ의 R은 상기 화학식1에서 정의한 바와 같다. R of Reaction Scheme I is as defined in Chemical Formula 1.

본 발명에 실시예에서 라우릴클로라이드 또는 노나노일클로라이드를 소듐하이드록시벤젠술포네이트와 반응용매에서 반응시켜서 소듐 라우릴옥시벤젠술포네이트 또는 소듐 노나노일옥시벤젠술포네이트를 제조하였다. In the present invention, lauryl chloride or nonanoyl chloride was reacted with sodium hydroxybenzenesulfonate in a reaction solvent to prepare sodium lauryloxybenzenesulfonate or sodium nonanoyloxybenzenesulfonate.

따라서 상기 아실클로라이드는 라우릴클로라이드 또는 노나노일클로라이드를 포함한다.Therefore, the acyl chloride includes lauryl chloride or nonanoyl chloride.

본 발명의 실시예에서 라우릴클로라이드, 소듐하이드록시벤젠술포네이트 및 반응용매로 증류수을 이용하여 28℃에서 반응을 진행하였을 때 소듐 라우릴옥시벤젠술포네이트의 수득율이 73%이었으며, 동일한 조건에서 반응용매를 아세톤, 에틸아세테이트, 톨루엔, 아이소파-G 및 테트라하이트로퓨란(tetrahydrofuran, THF)을 이용하였을 때 반응이 진행되지 않음을 확인하였다.In the embodiment of the present invention, when the reaction proceeded at 28°C using distilled water as lauryl chloride, sodium hydroxybenzenesulfonate and reaction solvent, the yield of sodium lauryloxybenzenesulfonate was 73%, and the reaction solvent under the same conditions. It was confirmed that the reaction did not proceed when using acetone, ethyl acetate, toluene, isopa-G, and tetrahydrofuran (THF).

본 발명의 다른 실시예에서 노나노일클로라이드, 소듐하이드록시벤젠술포네이트 및 반응용매로 증류수 및 아세톤, 에틸아세테이트, 톨루엔, 아이소파-G 및 테트라하이트로퓨란(tetrahydrofuran, THF)을 이용하여 28℃에서 반응을 진행하였을 때, 증류수에서 소듐 노나노일옥시벤젠술포네이트의 수득율이 65%이었으며, 반응용매로 아세톤, 에틸아세테이트, 톨루엔, 아이소파-G 및 테트라하이트로퓨란(tetrahydrofuran, THF)을 이용하였을 때 반응이 진행되지 않음을 확인하였다.In another embodiment of the present invention, nonanoyl chloride, sodium hydroxybenzenesulfonate and distilled water and acetone, ethyl acetate, toluene, isopa-G and tetrahydrofuran (THF) were used as reaction solvents at 28° C. When the reaction was carried out at, the yield of sodium nonanoyloxybenzenesulfonate in distilled water was 65%, and acetone, ethyl acetate, toluene, isopa-G and tetrahydrofuran (THF) were used as reaction solvents. When it was confirmed that the reaction did not proceed.

본 발명의 다른 실시예에서 반응용매로 물과 유기용매(아세톤, 에틸아세테이트, 톨루엔, 아이소파-G 또는 테트라하이트로퓨란(tetrahydrofuran, THF))의 혼합용매를 이용하여 소듐 라우릴옥시벤젠술포네이트 또는 소듐 노나노일옥시벤젠술포네이트의 제조하고, 유기용매의 종류 및 혼합비율에 따른 수득율을 분석하였다.In another embodiment of the present invention, sodium lauryloxybenzenesulfonate using a mixed solvent of water and an organic solvent (acetone, ethyl acetate, toluene, isopa-G or tetrahydrofuran (THF)) as a reaction solvent Alternatively, sodium nonanoyloxybenzenesulfonate was prepared, and the yield according to the type and mixing ratio of the organic solvent was analyzed.

분석결과, 에틸아세테이트, 톨루엔, 아이소파-G 또는 테트라하이트로퓨란(tetrahydrofuran, THF)을 혼합한 용매에서는 소듐 라우릴옥시벤젠술포네이트 또는 소듐 노나노일옥시벤젠술포네이트의 수득율이 증류수만 이용할 때보다 감소함을 확인하였다. As a result of the analysis, in a solvent mixed with ethyl acetate, toluene, isopa-G or tetrahydrofuran (THF), the yield of sodium lauryloxybenzenesulfonate or sodium nonanoyloxybenzenesulfonate was more than when only distilled water was used. It was confirmed that all decreased.

반면, 반응용매로 물과 아세톤의 9:1 내지 7:3의 중량비로 혼합된 용매를 사용하는 경우에 증류수만 이용하였을 때보다, 소듐 라우릴옥시벤젠술포네이트 또는 소듐 노나노일옥시벤젠술포네이트의 수득율이 증가하는 것을 확인하였다.On the other hand, sodium lauryloxybenzenesulfonate or sodium nonanoyloxybenzenesulfonate than when only distilled water was used when using a solvent mixed in a weight ratio of 9:1 to 7:3 of water and acetone as the reaction solvent. It was confirmed that the yield was increased.

구체적으로, 물와 아세톤의 혼합비율이 9:1 내지 7:3인 혼합용매를 반응용매로 소듐 라우릴옥시벤젠술포네이트의 제조반응을 수행하는 경우, 증류수만 이용할 때 보다 수득율이 증가하는 것을 확인하였으며, 혼합비율이 8:2일 때 78%로 수득율이 가장 높음을 확인하였다. 반면, 증류수와 유기용매의 비율이 6:4일 때 수득율이 61%로 나타나, 증류수만 이용할 때보다 수득율이 감소함을 확인하였다. Specifically, when performing the reaction of the production of sodium lauryloxybenzenesulfonate as a reaction solvent using a mixed solvent having a mixing ratio of 9:1 to 7:3 with water and acetone, it was confirmed that the yield increased when using only distilled water. , When the mixing ratio was 8:2, it was confirmed that the yield was the highest with 78%. On the other hand, when the ratio of distilled water and organic solvent is 6:4, the yield is 61%, and it is confirmed that the yield is reduced than when only distilled water is used.

소듐 노나노일옥시벤젠술포네이트의 제조반응에서 반응용매의 증류수와 유기용매의 혼합비율에 따른 수득율을 확인한 결과, 증류수와 유기용매의 혼합비율이 9:1 내지 7:3일 때 증류수만 이용할 때 보다 수득율이 증가하는 것을 확인하였으며, 혼합비율이 8:2일 때 77%로 수득율이 가장 높음을 확인하였다. 반면, 증류수와 유기용매의 비율이 6:4일 때 수득율이 52%로 나타나 증류수만 이용할 때보다 수득율이 감소하여 확인하였다. When checking the yield according to the mixing ratio of distilled water and organic solvent of the reaction solvent in the production reaction of sodium nonanoyloxybenzenesulfonate, when using only distilled water when the mixing ratio of distilled water and organic solvent is 9:1 to 7:3 It was confirmed that the yield was more increased, and when the mixing ratio was 8:2, it was confirmed that the yield was highest at 77%. On the other hand, when the ratio of distilled water and organic solvent is 6:4, the yield is 52%, which is confirmed by a decrease in yield than when only distilled water is used.

즉, 반응용매로 물 또는 유기용매(아세톤, 에틸아세테이트, 톨루엔, 아이소파-G 및 테트라하이트로퓨란(tetrahydrofuran, THF))를 단독으로 이용하여 반응을 수행한 결과, 아세톤, 에틸아세테이트, 톨루엔, 아이소파-G 또는 테트라하이트로퓨란(tetrahydrofuran, THF)을 단독으로 사용하여 반응을 진행할 때는 반응이 진행되지 않았으나, 물을 반응용매로 이용할 경우, 소듐 아실옥시벤젠술포네이트를 제조할 수 있음을 확인하였다.That is, as a reaction solvent, water or an organic solvent (acetone, ethyl acetate, toluene, isopa-G, and tetrahydrofuran (tetrahydrofuran, THF)) was used as a result of the reaction, acetone, ethyl acetate, toluene, The reaction did not proceed when the reaction was carried out using isopha-G or tetrahydrofuran (THF) alone, but it was confirmed that sodium acyloxybenzenesulfonate can be prepared when water is used as the reaction solvent. Did.

다음으로 물과 유기용매의 혼합용액을 반응용매로 이용하여 소듐 아실옥시벤젠술포네이트을 제조하고, 수득율을 비교한 결과, 에틸아세테이트, 톨루엔, 아이소파-G 또는 테트라하이트로퓨란(tetrahydrofuran, THF)을 혼합한 경우, 수득율이 증류수만 이용하였을 때 보다 감소하였다. 반면, 물과 아세톤을 9:1 내지 7:3로 혼합한 용매를 반응용매로 이용하였을 때 증류수만 이용하였을 때보다 수득율이 증가하는 것을 확인하였다.Next, sodium acyloxybenzenesulfonate was prepared by using a mixed solution of water and an organic solvent as a reaction solvent, and as a result of comparing the yield, ethyl acetate, toluene, isopa-G or tetrahydrofuran (THF) was used. When mixed, the yield decreased compared to when only distilled water was used. On the other hand, when the solvent mixed with water and acetone 9:1 to 7:3 was used as a reaction solvent, it was confirmed that the yield increased than when only distilled water was used.

따라서, 본 발명에서 반응용매는 물과 아세톤의 혼합용매로, 물과 아세톤이 10:0 내지 6.5:3.5의 중량비로 혼합되며, 구체적으로 물과 아세톤이 9.5:0.5 내지 6.5:3.5의 중량비로 혼합된 것일 수 있고, 더욱 구체적으로 물과 아세톤이 9:1 내지 7:3의 중량비로 혼합된 것 일 수 있다. Therefore, in the present invention, the reaction solvent is a mixed solvent of water and acetone, water and acetone are mixed in a weight ratio of 10:0 to 6.5:3.5, and specifically water and acetone are mixed in a weight ratio of 9.5:0.5 to 6.5:3.5. It may be, and more specifically, may be a mixture of water and acetone in a weight ratio of 9:1 to 7:3.

반응용매에서 물과 아세톤의 혼합비율이 6.5:3.5와 비교하여, 아세톤의 중량비가 증가하면, 소듐 아실옥시벤젠술포네이트의 수득율이 떨어지는 문제가 발생한다.When the mixing ratio of water and acetone in the reaction solvent is compared to 6.5:3.5, when the weight ratio of acetone is increased, a problem that the yield of sodium acyloxybenzenesulfonate falls is caused.

본 발명의 일실시예에서 반응용매 1000g에 소듐하이드록시벤젠술포네이트 1몰, 50% 소듐하이드록사이드 수용액 40g에 촉매를 첨가하여 교반한 후, 라우릴클로라이드 0.95몰을 서서히 적하하면서 교반하였다. 적하가 끝난 뒤 반응기의 온도를 28℃로, pH는 7 내지 9로 유지하면서 1시간동안 반응을 진행하였다. 상기 촉매는 4급 암모늄염인 테트라 n-부틸암모늄 브로마이드(Tetra-n-butylammonium bromide, TBAB)를 사용하였으며, 반응용매, 소듐하이드록시벤젠술포네이트, 소듐하이드록사이드 수용액 및 라우릴클로라이드의 전체중량 기준으로 0.4 중량%를 첨가하여 소듐 라우릴옥시벤젠술포네이트를 제조하였다. 또한, 라우릴클로라이드를 노나노일클로라이드로 달리한 것을 제외하고 동일한 방법으로 반응을 수행하여 소듐 노나노일옥시벤젠술포네이트를 제조하였다.In one embodiment of the present invention, a catalyst was added to 1 g of sodium hydroxybenzene sulfonate and 40 g of a 50% sodium hydroxide aqueous solution in 1000 g of the reaction solvent, followed by stirring, while 0.95 mol of lauryl chloride was slowly added dropwise thereto. After the dropping was completed, the reaction was performed for 1 hour while maintaining the temperature of the reactor at 28°C and the pH at 7 to 9. The catalyst was used as a quaternary ammonium salt, tetra-n-butylammonium bromide (TBAB), based on the total weight of the reaction solvent, sodium hydroxybenzenesulfonate, sodium hydroxide aqueous solution and lauryl chloride Sodium lauryloxybenzenesulfonate was prepared by adding 0.4% by weight. In addition, sodium lauronyloxybenzenesulfonate was prepared by performing the reaction in the same manner, except that lauryl chloride was changed to nonanoyl chloride.

따라서 본 발명의 반응시키는 단계는 반응기에 상기 반응용매를 첨가하는 단계, 소듐하이드록시벤젠술포네이트를 첨가하는 단계, 소듐하이드록사이드 수용액을 첨가하는 단계, 촉매를 첨가하고 교반하는 단계 및 상기 아실클로라이드를 첨가하여 반응을 진행하는 단계를 포함할 수 있다.Therefore, the step of reacting the present invention includes adding the reaction solvent to the reactor, adding sodium hydroxybenzenesulfonate, adding a sodium hydroxide aqueous solution, adding a catalyst and stirring, and the acyl chloride It may include the step of adding to proceed the reaction.

상기 아실클로라이드는 반응기에 서서히 적하하여 첨가할 수 있으며, 적하가 끝난 뒤 0.5 내지 4시간 동안 반응을 수행할 수 있다.The acyl chloride may be slowly added dropwise to the reactor, and the reaction may be performed for 0.5 to 4 hours after the dropping is completed.

상기 반응시키는 단계에서 반응용매 800 내지 1200g 기준으로, 상기 소듐하이드록시벤젠술포네이트 0.5 내지 1.5몰(mol), 20 내지 80% 소듐하이드록사이드 수용액 50 내지 100g 및 상기 아실클로라이드 0.5 내지 1.5몰(mol)으로 첨가할 수 있다.In the reaction step, based on the reaction solvent 800 to 1200 g, the sodium hydroxybenzene sulfonate 0.5 to 1.5 mol (mol), 20 to 80% sodium hydroxide aqueous solution 50 to 100 g and the acyl chloride 0.5 to 1.5 mol (mol) ).

상기 촉매는 상기 반응시키는 단계에서 첨가된 상기 반응용매, 상기 소듐하이드록시벤젠술포네이트, 상기 소듐하이드록사이드 수용액 및 상기 아실클로라이드의 전체중량 기준으로 0.1 내지 1.5 중량%로 첨가할 수 있다. The catalyst may be added in an amount of 0.1 to 1.5% by weight based on the total weight of the reaction solvent, the sodium hydroxybenzene sulfonate, the aqueous sodium hydroxide solution and the acyl chloride added in the step of reacting.

촉매가 0.1 중량% 미만으로 첨가될 경우, 반응시 수득율이 떨어지고, 생성되는 부반응물이 많으며, 촉매가 1.5 중량% 초과로 첨가될 경우, 수득율이 크게 증가하지 않으며 효율이 떨어지는 단점이 있다.When the catalyst is added in an amount of less than 0.1% by weight, the yield decreases when reacting, and many side reaction products are produced. When the catalyst is added in an amount of more than 1.5% by weight, the yield does not significantly increase and efficiency is deteriorated.

본 발명의 일실시예에서 반응온도에 따른 소듐 라우릴옥시벤젠술포네이트 또는 소듐 노나노일옥시벤젠술포네이트의 수득율을 비교하고자, 증류수를 반응용매로 이용하여 60 내지 150℃에서 반응을 진행하고, 수득율을 분석하였다. 분석결과, 반응온도가 증가할수록 소듐 라우릴옥시벤젠술포네이트 또는 소듐 노나노일옥시벤젠술포네이트의 수득율이 감소하는 것을 확인하였으며, 150℃에서는 반응이 진행되지 않음을 확인하였다.In an embodiment of the present invention, in order to compare the yield of sodium lauryloxybenzenesulfonate or sodium nonanoyloxybenzenesulfonate according to the reaction temperature, the reaction was conducted at 60 to 150°C using distilled water as a reaction solvent, The yield was analyzed. As a result of the analysis, it was confirmed that the yield of sodium lauryloxybenzenesulfonate or sodium nonanoyloxybenzenesulfonate decreased as the reaction temperature increased, and the reaction did not proceed at 150°C.

따라서, 상기 반응시키는 단계는 상기 반응기의 온도를 10 내지 40℃로 유지하는 단계를 더 포함할 수 있다.Accordingly, the reacting may further include maintaining the temperature of the reactor at 10 to 40°C.

상기 반응기의 온도가 10℃ 미만인 경우, 반응이 속도가 느려지며, 생성되는 부반응물이 많아져 수득율이 떨어질 수 있으며, 40℃ 초과인 경우, 반응속도는 빠르나 아실클로라이드가 쉽게 분해되어 soap가 많이 생성되어 수득율이 떨어지거나 또는 반응이 진행되지 않는 문제가 발생한다.When the temperature of the reactor is less than 10°C, the reaction is slow, and the number of side reaction products generated increases, so the yield may drop. If it is more than 40°C, the reaction rate is fast, but acyl chloride is easily decomposed and soap is generated more There is a problem that the yield is lowered or the reaction does not proceed.

상기 반응시키는 단계는 pH를 7 내지 9로 유지하는 단계를 더 포함할 수 있다. The reacting may further include maintaining the pH at 7 to 9.

상기 반응시키는 단계에서 pH가 7 미만이 되는 경우 소량의 소듐하이드록사이드를 첨가하여 pH를 7 내지 9로 유지시킨다.When the pH is less than 7 in the reaction step, a small amount of sodium hydroxide is added to maintain the pH at 7-9.

pH가 7 미만인 경우 아실클로라이드가 쉽게 분해되어 수득율이 낮아질 수 있으며, pH가 9 초과인 경우 아실클로아드와 소듐하이드록시벤젠술포네이트와 반응이 느려지면서 생성되는 부반응물이 증가하는 문제가 있다.When the pH is less than 7, acyl chloride is easily decomposed and the yield may be lowered. When the pH is more than 9, there is a problem in that side reaction products generated increase as the reaction with the acyl chloride and sodium hydroxybenzene sulfonate becomes slow.

상기 반응시키는 단계에서 상기 아실클로라이드와 상기 소듐하이드록시벤젠술포네이트가 0.8 내지 1.0: 1.0 내지 1.2의 몰비로 첨가하여 반응시키는 것일 수 있다. In the reacting step, the acyl chloride and the sodium hydroxybenzenesulfonate may be added in a molar ratio of 0.8 to 1.0: 1.0 to 1.2 to react.

본 발명에서 상기 촉매는 산 화합물, 염기 화합물, 금속 화합물 및 암모늄 염 화합물으로 이루어진 군에서 선택되는 1종 이상일 수 있다.In the present invention, the catalyst may be at least one selected from the group consisting of acid compounds, base compounds, metal compounds, and ammonium salt compounds.

상기 산 화합물은 파라톨루엔술포닉산, 인산, 차아인산, 차아인산소다 및 황산 중에서 선택된 1종 이상이고, 상기 염기 화합물은 알칼리금속수산화물이며, 상기 금속 화합물은 Fe, Cu, Co, Ti, Sn 및 Mn 중에서 선택된 1종 이상의 금속을 함유하는 화합물이며, 상기 암모늄염은 4급 암모늄염일 수 있다.The acid compound is at least one selected from paratoluene sulfonic acid, phosphoric acid, hypophosphorous acid, sodium hypophosphite and sulfuric acid, the base compound is an alkali metal hydroxide, and the metal compound is Fe, Cu, Co, Ti, Sn and Mn It is a compound containing at least one metal selected from the above, and the ammonium salt may be a quaternary ammonium salt.

상기 알카리 금속은 리튬, 소듐, 칼륨, 루비듐, 세슘, 프랑슘, 우누넨늄 중에 선택되는 1종 이상일 수 있다.The alkali metal may be at least one selected from lithium, sodium, potassium, rubidium, cesium, francium, and ununennium.

상기 암모늄염은 구체적으로 세틸트리메닐암모늄 클로라이드(Cetyltrimethylammonium chloride), (3-클로로-2-하이드록시프로필)트리메틸암모늄 클로라이드((3-Chloro-2-hydroxypropyl)trimethylammonium chloride), 디아릴디메틸암모늄 클로라이드(Diallyldimethylammonium chloride), 디도데실디메틸암모늄 브로마이드(Didodecyldimethylammonium bromide), 디메틸옥타데실[2-(트리메톡실란)프로필]암모늄 클로라이드(Dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride), (하이드라지노카르보닐메틸)트리메틸암모늄 클로라이드((Hydrazinocarbonylmethyl)trimethylammonium chloride), 글리시틸트리메틸암모늄 클로라이드(Glycidyltrimethylammonium chloride), 헥사데실(2-하이드록시에틸)디메틸암모늄 디하이드로젠 포스페이트(Hexadecyl(2-hydroxyethyl)dimethylammonium dihydrogen phosphate), 헥사데실트리메틸암모늄 브로마이드(Hexadecyltrimethylammonium bromide), 미리스틸트리메틸암모늄 브로마이드(Myristyltrimethylammonium bromide), 테트라뷰틸암모늄 바이설페이트(Tetrabutylammonium bisulfate), 테트라뷰틸암모늄 브로마이드(Tetrabutylammonium bromide), 테트라뷰틸암모늄 클로라이드(Tetrabutylammonium chloride), 테트라뷰틸암모늄 헥사플로오로포스페이트(Tetrabutylammonium hexafluorophosphate), 테트라뷰틸암모늄 하이드로젠설페이트(Tetrabutylammonium hydrogensulfate), 테트라뷰틸암모늄 퍼클로레이트(Tetrabutylammonium perchlorate), 테트라뷰틸암모늄 셀페이트(Tetrabutylammonium sulfate), 메틸트리옥틸암모늄 클로라이드(Methyltrioctylammonium chloride), 테트라뷰틸암모늄 트리브로마이드(Tetrabutylammonium tribromide), 테트라뷰틸암모늄 아세테이트(Tetraethylammonium acetate), 테트라에틸암모늄 브로마이드(Tetraethylammonium bromide), 테트라에틸암모늄 클로라이드(Tetraethylammonium chloride), 테트라에틸암모늄 아이오다이드(Tetraethylammonium iodide), 테트라메틸암모늄 브로마이드(Tetramethylammonium bromide), 테트라메틸암모늄 클로라이드(Tetramethylammonium chloride), 테트라메틸암모늄 포르메이트(Tetramethylammonium formate), 테트라메틸암모늄 아이오다이드(Tetramethylammonium iodide), 테트라메틸암모늄 실리케이트(Tetramethylammonium silicate), 테트라프로필암모늄 브로마이드(Tetrapropylammonium bromide), 트리뷰틸메틸암모늄 클로라이드(Tributylmethylammonium chloride), 트리뷰틸메틸암모늄 브로마이드(Tributylmethylammonium bromide), 트리에틸메틸암모늄 클로라이드(Triethylmethylammonium chloride), 트리메틸페닐암모늄 브로마이드(Trimethylphenylammonium bromide), 트리메틸페닐암모늄 클로라이드(Trimethylphenylammonium chloride) 및 (비닐벤질)트리메틸암모늄 클로라이드((Vinylbenzyl)trimethylammonium chloride)로 이루어진 군에서 선택되는 1종 이상일 수 있다.The ammonium salt is specifically, cetyltrimethylammonium chloride, (3-chloro-2-hydroxypropyl) trimethylammonium chloride ((3-Chloro-2-hydroxypropyl)trimethylammonium chloride), diaryldimethylammonium chloride ( Diallyldimethylammonium chloride), Didodecyldimethylammonium bromide, Dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, (Hydrazinocarbonylmethyl) ) Trimethylammonium Chloride ((Hydrazinocarbonylmethyl)trimethylammonium chloride), Glycidyltrimethylammonium chloride, Hexadecyl(2-hydroxyethyl)dimethylammonium dihydrogen phosphate (Hexadecyl(2-hydroxyethyl)dimethylammonium dihydrogen phosphate), Hexadecyltrimethylammonium bromide, Myristyltrimethylammonium bromide, Tetrabutylammonium bisulfate, Tetrabutylammonium bromide, Tetrabutylammonium bromide, Tetrabutylammonium chloride, Tetrabutylammonium chloride Tetrabutylammonium hexafluorophosphate, Tetrabutylammonium hydrogensulfate, Tetrabutylammonium perchlorate, Tetrabutylammonium sulfate, Methyltrioctylammonium chloride, Tetrabutylammonium tribromide, Tetraethylammonium acetate, Tetraethylammonium bromide, Tetraethyl Tetraethylammonium chloride, Tetraethylammonium iodide, Tetramethylammonium bromide, Tetramethylammonium chloride, Tetramethylammonium formate, Tetramethylammonium formate, Tetramethylammonium formate Tetramethylammonium iodide, Tetramethylammonium silicate, Tetrapropylammonium bromide, Tributylmethylammonium chloride, Tributylmethylammonium bromide, Triethylmethyl It may be one or more selected from the group consisting of triethylmethylammonium chloride, trimethylphenylammonium bromide, trimethylphenylammonium chloride and (vinylbenzyl)trimethylammonium chloride. .

본 발명의 일실시예에서 얇은층 크로마토그래피(Thin Layer Chromatography, TLC)를 이용하여 반응의 유무를 확인하고, 잔류하는 소듐하이드록시벤젠술포네이트가 없는 경우 미반응물 및 부반응물로 생성되는 soap을 제거하기 위해서 반응기에 증류수를 투입하고 약 30분 교반 후 필터로 여과하고, 여과된 합성물을 건조하여 소듐 라우릴옥시벤젠술포네이트 또는 소듐 노나노일옥시벤젠술포네이트을 수득하였다.In one embodiment of the present invention, the presence or absence of the reaction is confirmed by using thin layer chromatography (TLC), and when there is no residual sodium hydroxybenzenesulfonate, soap generated as an unreacted material and a side reactant is removed. In order to do so, distilled water was added to the reactor, stirred for about 30 minutes, filtered through a filter, and the filtered composite was dried to obtain sodium lauryloxybenzenesulfonate or sodium nonanoyloxybenzenesulfonate.

따라서 본 발명에 따른 제조하는 방법은, 여과하여 수득하는 단계를 더 포함할 수 있다.Therefore, the production method according to the present invention may further include the step of obtaining by filtration.

여과하여 수득하는 단계는 반응시키는 단계가 끝난 용액을 필터를 통해 용매와 고체인 소듐 아실옥시벤젠술포네이트를 분리하여 소듐 아실옥시벤젠술포네이트를 수득하는 것을 의미한다. 수득한 소듐 아실옥시벤젠술포네이트는 80 내지 140℃에서 건조시킬 수 있다. The step obtained by filtration means that the solution after the step of reacting is separated from the solvent and solid sodium acyloxybenzenesulfonate through a filter to obtain sodium acyloxybenzenesulfonate. The obtained sodium acyloxybenzenesulfonate can be dried at 80 to 140°C.

본 발명은 표백 활성제인 아실옥시벤젠술포네이트를 저온으로 수용액상에서 합성하는 방법에 관한 것이다. 저온으로 수용액상에서 제조하기 때문에 생산단가를 낮출 수 있으며, 환경친화적으로 표백활성 물질인 아실옥시벤젠술포네이트를 제조할 수 있다.The present invention relates to a method for synthesizing a bleach activator acyloxybenzenesulfonate in an aqueous solution at low temperature. Since it is manufactured in an aqueous solution at a low temperature, the production cost can be lowered, and acyloxybenzenesulfonate, an environmentally friendly bleaching substance, can be prepared.

이하, 실시예를 들어 본 발명을 상세히 기술할 것이나 본 발명의 범위를 이들 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail by way of examples, but the scope of the present invention is not limited by these examples.

<실험예1> 라우로일록시벤젠술포네이트(4-Lauroyloxybenzenesulfonate sodium, LOBS)의 제조<Experimental Example 1> Preparation of lauroyloxybenzenesulfonate sodium (LOBS)

기계식 교반기, 온도계, 콘덴서(condenser)가 설치된 5구 플라스크 반응기에 (A) 반응용매 1000g을 넣고 (B) 소듐하이드록시벤젠술포네이트 232.2g(1몰, 분자량 232.2)과 (C) 50% 소듐하이드록사이드 수용액 80g(1몰, 분자량 40, 물 50 중량% 포함), 촉매 6.08g(A+B+C+D의 중량의 0.4wt%)를 넣고 상온에서 1시간 정도 교반하였다. 서서히 교반하면서 (D) 라우로릴클로라이드 207.86g(0.95몰, 분자량 218.8)를 서서히 적하하였다. 이때 반응기의 온도는 28℃를 유지하였다. 라우로릴클로라이드 적하가 끝나면 반응기의 내부온도를 28℃로 유지하면서 1시간 동안 반응을 진행하였다. 반응기 내부의 pH를 확인하여 7 미만이 되지 않도록 유지하고, pH가 7 미만이 될 경우, 소량의 50% 소듐하이드록사이드를 투입하여 pH를 7 내지 9로 조절하였다.In a 5-neck flask reactor equipped with a mechanical stirrer, thermometer, and condenser, (A) 1000 g of the reaction solvent was added (B) 232.2 g of sodium hydroxybenzenesulfonate (1 mole, molecular weight 232.2) and (C) 50% sodium hydroxide Aqueous solution 80g (1 mole, molecular weight 40, 50% by weight of water), catalyst 6.08g (0.4% by weight of the weight of A+B+C+D) was added and stirred at room temperature for 1 hour. 207.86 g (0.95 mol, molecular weight 218.8) of lauryl chloride (D) was slowly added dropwise while stirring slowly. At this time, the temperature of the reactor was maintained at 28°C. When the dropping of lauryl chloride was completed, the reaction was performed for 1 hour while maintaining the internal temperature of the reactor at 28°C. The pH inside the reactor was checked to keep it below 7, and when the pH was below 7, a small amount of 50% sodium hydroxide was added to adjust the pH to 7-9.

얇은층 크로마토그래피(Thin Layer Chromatography, TLC)로 반응 유무를 확인한 후, 잔류하는 소듐하이드록시벤젠술포네이트가 없을 경우, 반응기에 증류수 300㎖를 투입하여 30분 정도 교반하고, 필터로 여과하였다. 필터로 여과된 합성물을 110℃에서 건조하여 4-Lauroyloxybenzenesulfonate sodium를 수득하였다. After confirming the presence or absence of the reaction by thin layer chromatography (ThLC), if there is no residual sodium hydroxybenzene sulfonate, 300 ml of distilled water is added to the reactor and stirred for 30 minutes, and filtered through a filter. The filtered product was dried at 110°C to obtain 4-Lauroyloxybenzenesulfonate sodium.

<실험예1-1> 반응용매의 종류에 따른 라우로일록시벤젠술포네이트의 수득율 비교<Experimental Example 1-1> Comparison of the yield of lauroyloxybenzenesulfonate according to the type of reaction solvent

구체적으로, 반응용매를 표 1과 같이 달리하여 라우로일록시벤젠술포네이트를 제조하였다. 표 1에 따르면 반응용매로 증류수를 이용하여 테트라 n-부틸암모늄브롬화물(Tetra-n-butylammonium bromide, TBAB)/ NaOH 촉매 조건하에 28℃로 2시간 동안 반응시키면 73%의 수득율로 4-Lauroyloxybenzenesulfonate sodium이 제조됨을 확인하였다(실시예1-1). Specifically, lauroyloxybenzenesulfonate was prepared by varying the reaction solvent as shown in Table 1. According to Table 1, tetra-n-butylammonium bromide (TBAB)/ NaOH catalyst was reacted at 28° C. for 2 hours under distilled water as a reaction solvent to yield 4-Lauroyloxybenzenesulfonate sodium with a yield of 73%. It was confirmed that this was prepared (Example 1-1).

반면 반응용매를 아세톤, 에틸아세테이트, 톨루엔, 아이소파-G 또는 테트라하이트로퓨란(tetrahydrofuran, THF)으로 달리한 것을 제외하고 동일한 조건으로 반응시켜 제조하였을 때는 반응이 진행되지 않음을 확인하였다(비교예1-1 내지 비교예1-5). On the other hand, when the reaction solvent was prepared by reacting under the same conditions, except that acetone, ethyl acetate, toluene, isopa-G or tetrahydrofuran (THF) was different, it was confirmed that the reaction did not proceed (Comparative Example 1-1 to Comparative Example 1-5).

또한 반응용매로 에틸아세테이트, 톨루엔, 아이소파-G 또는 테트라하이트로퓨란(tetrahydrofuran, THF)을 사용하고, 촉매로 TBAB를 사용한 것을 제외하고 동일한 조건으로 반응시켰을 때 반응이 진행되지 않음을 확인하였다(비교예1-6 내지 비교예1-9). In addition, it was confirmed that the reaction did not proceed when reacting under the same conditions except that ethyl acetate, toluene, isopar-G or tetrahydrofuran (THF) was used as a reaction solvent, and TBAB was used as a catalyst ( Comparative Examples 1-6 to Comparative Examples 1-9).

구분division 반응용매(solvent)Solvent 온도(℃)Temperature (℃) 촉매catalyst 시간time 수득율(%)Yield (%) 실시예1-1Example 1-1 증류수Distilled water 2828 TBAB / NaOHTBAB / NaOH 22 7373 비교예1-1Comparative Example 1-1 아세톤Acetone 2828 TBAB / NaOHTBAB / NaOH 22 -- 비교예1-2Comparative Example 1-2 에틸아세테이트Ethyl acetate 2828 TBAB / NaOHTBAB / NaOH 22 -- 비교예1-3Comparative Example 1-3 톨루엔toluene 2828 TBAB / NaOHTBAB / NaOH 22 -- 비교예1-4Comparative Example 1-4 아이소파-GIsopha-G 2828 TBAB / NaOHTBAB / NaOH 22 -- 비교예1-5Comparative Example 1-5 THFTHF 2828 TBAB / NaOHTBAB / NaOH 22 -- 비교예1-6Comparative Example 1-6 에틸아세테이트Ethyl acetate 2828 TBABTBAB 22 -- 비교예1-7Comparative Example 1-7 톨루엔toluene 2828 TBABTBAB 22 -- 비교예1-8Comparative Example 1-8 아이소파-GIsopha-G 2828 TBABTBAB 22 -- 비교예1-9Comparative Example 1-9 THFTHF 2828 TBABTBAB 22 --

<실험예1-2> 반응온도에 따른 라우로일록시벤젠술포네이트의 수득율 비교<Experimental Example 1-2> Comparison of the yield of lauroyloxybenzenesulfonate according to the reaction temperature

실험예1-1에서 반응이 진행되지 않은 용매를 이용하여, 온도 조건과 촉매조건을 표 2와 같이 달리하여 반응을 진행하고, 수득율을 확인하였다. 또한 증류수에서 온도조건을 달리하여 반응을 진행하고 수득율을 확인하였다.In Experimental Example 1-1, using a solvent in which the reaction did not proceed, the temperature conditions and the catalyst conditions were varied as shown in Table 2 to proceed the reaction, and the yield was confirmed. In addition, the reaction was performed by varying the temperature conditions in distilled water and the yield was confirmed.

표 2는 반응온도에 따른 라우로일록시벤젠술포네이트의 수득율이다. 비교예1-10 내지 비교예1-14에서 유기용매(아세톤, 에틸아세테이트, 톨루엔, 아이소파-G, THF)에서 반응온도를 올려 60 내지 150℃에서 수행하였으나, 반응이 진행되지 않음을 확인하였다. 또한 증류수인 비교예1-15 내지 비교예1-17을 보면 60℃에서 반응시, 수득율은 45%었고, 100℃로 반응 온도가 증가함에 따라 20%로 수득율이 감소하는 것을 확인하였으며, 150℃에서는 반응이 진행되지 않음을 확인하였다Table 2 shows the yield of lauroyloxybenzenesulfonate according to the reaction temperature. In Comparative Examples 1-10 to Comparative Examples 1-14, the organic solvents (acetone, ethyl acetate, toluene, isopar-G, THF) were heated at a reaction temperature of 60 to 150° C., but the reaction did not proceed. . In addition, when looking at Comparative Examples 1-15 to Comparative Examples 1-17, which is distilled water, when reacting at 60°C, the yield was 45%, and it was confirmed that the yield decreased to 20% as the reaction temperature increased to 100°C, and 150°C. Estimated that the reaction did not proceed

구분division 반응용매(solvent)Solvent 온도(℃)Temperature (℃) 촉매catalyst 시간time 수득율(%)Yield (%) 비교예1-10Comparative Example 1-10 아세톤Acetone 6060 p-TSAp-TSA 22 -- 비교예1-11Comparative Example 1-11 에틸아세테이트Ethyl acetate 6060 H2SO4 H 2 SO 4 22 -- 비교예1-12Comparative Example 1-12 톨루엔toluene 100100 p-TSAp-TSA 22 -- 비교예1-13Comparative Example 1-13 아이소파-GIsopha-G 150150 p-TSAp-TSA 22 -- 비교예1-14Comparative Example 1-14 THFTHF 6060 H2SO4H2SO4 22 -- 비교예1-15Comparative Example 1-15 증류수Distilled water 6060 TBAB / NaOHTBAB / NaOH 22 4545 비교예1-16Comparative Example 1-16 증류수Distilled water 100100 TBAB / NaOHTBAB / NaOH 22 2020 비교예1-17Comparative Example 1-17 증류수Distilled water 150150 TBAB / NaOHTBAB / NaOH 22 --

<실험예1-3> 유기용매의 종류 및 혼합비율에 따른 라우로일록시벤젠술포네이트의 수득율 비교<Experimental Example 1-3> Comparison of the yield of lauroyloxybenzenesulfonate according to the type and mixing ratio of the organic solvent

다음으로 증류수와 유기용매의 혼합비율에 따른 라우로일록시벤젠술포네이트의 수득율을 분석하였다. 유기용매는 아세톤, 에틸아세테이트, 톨루엔, 아이소파-G, 테트라하이트로퓨란(tetrahydrofuran, THF)을 사용하였다. Next, the yield of lauroyloxybenzenesulfonate was analyzed according to the mixing ratio of distilled water and organic solvent. As the organic solvent, acetone, ethyl acetate, toluene, isopa-G, and tetrahydrofuran (THF) were used.

아세톤Acetone

표 3은 증류수와 아세톤의 혼합비율에 따른 라우로일록시벤젠술포네이트의 수득율을 나타낸 것이다. 실시예1-1에서 증류수만 이용하였을 때 73%의 수득율을 보였으나, 증류수 90%, 아세톤 10%의 혼합용액(실시예1-4)에서는 수득율이 74%로 증가하였으며, 증류수 80%, 아세톤 20%의 혼합용액(실시예1-2) 사용시 78%로 아세톤을 20%가 포함된 용액을 반응용매로 사용시 수득율이 가장 높음을 확인하였다. 반면 증류수 60%, 아세톤 40%의 용액에서는 수득율이 61%로 증류수만 이용하였을 때 보다 수득율이 감소되는 것을 확인하였다(비교예1-18-1).Table 3 shows the yield of lauroyloxybenzenesulfonate according to the mixing ratio of distilled water and acetone. When only distilled water was used in Example 1-1, the yield was 73%, but in a mixed solution of 90% distilled water and 10% acetone (Example 1-4), the yield increased to 74%, 80% distilled water, acetone When using a 20% mixed solution (Example 1-2), it was confirmed that the yield was highest when using a solution containing 20% acetone as 78% as a reaction solvent. On the other hand, in the solution of 60% distilled water and 40% acetone, it was confirmed that the yield was 61%, which was lower than when only distilled water was used (Comparative Examples 1-18-1).

또한, 수득율이 가장 좋은 실시예1-2와 동일한 조건에서 촉매를 사용하지 않고 반응을 수행하였을 때, 반응이 진행되지 않음을 확인하였다. In addition, it was confirmed that the reaction did not proceed when the reaction was performed without using a catalyst under the same conditions as in Example 1-2 where the yield was the best.

구분division 반응용매 혼합비율
(중량비)Reaction solvent mixing ratio
(Weight ratio) 온도(℃)Temperature (℃) 촉매21Catalyst 21 시간time 수득율(%)Yield (%) 실시예1-2Example 1-2 증류수(8) / 아세톤(2)Distilled water (8) / Acetone (2) 2828 TBAB / NaOHTBAB / NaOH 22 7878 실시예1-3Example 1-3 증류수(7) / 아세톤(3)Distilled water (7) / Acetone (3) 2828 TBAB / NaOHTBAB / NaOH 22 7575 비교예1-18-1Comparative Example 1-18-1 증류수(6) / 아세톤(4)Distilled water (6) / Acetone (4) 2828 TBAB / NaOHTBAB / NaOH 22 6161 실시예1-4Example 1-4 증류수(9) / 아세톤(1)Distilled Water (9) / Acetone (1) 2828 TBAB / NaOHTBAB / NaOH 22 7474 비교예1-18-2Comparative Example 1-18-2 증류수(8) / 아세톤(2)Distilled water (8) / Acetone (2) 2828 -- 22 --

에틸아세테이트Ethyl acetate

표 4는 증류수와 에틸아세테이트의 혼합비율에 따른 라우로일록시벤젠술포네이트의 수득율을 나타낸 것이다. 실시예1-1에서 증류수만 이용하였을 때 73%의 수득율을 보였고, 에틸아세테이트를 10 내지 40%로 혼합한 용매에서는 수득율이 54 내지 63%로 증류수만 사용하였을 때 보다 감소하였다. Table 4 shows the yield of lauroyloxybenzenesulfonate according to the mixing ratio of distilled water and ethyl acetate. In Example 1-1, when only distilled water was used, the yield was 73%, and in the solvent mixed with ethyl acetate at 10 to 40%, the yield was 54 to 63%, which was lower than when only distilled water was used.

또한, 증류수 80%, 에틸아세테이트 20%의 혼합용액 비교예1-19와 동일한 조건에서 촉매를 사용하지 않고 반응을 수행하였을 때, 반응이 진행되지 않음을 확인하였다.In addition, it was confirmed that the reaction did not proceed when the reaction was performed without using a catalyst under the same conditions as Comparative Example 1-19 of a mixed solution of 80% distilled water and 20% ethyl acetate.

구분division 반응용매 혼합비율
(중량비)Reaction solvent mixing ratio
(Weight ratio) 온도(℃)Temperature (℃) 촉매catalyst 시간time 수득율(%)Yield (%) 비교예1-19Comparative Example 1-19 증류수(8) / 에틸아세테이트(2)Distilled water (8) / Ethyl acetate (2) 2828 TBAB / NaOHTBAB / NaOH 22 6363 비교예1-20Comparative Example 1-20 증류수(7) / 에틸아세테이트(3)Distilled water (7) / ethyl acetate (3) 2828 TBAB / NaOHTBAB / NaOH 22 6060 비교예1-21Comparative Example 1-21 증류수(6) / 에틸아세테이트(4)Distilled water (6) / ethyl acetate (4) 2828 TBAB / NaOHTBAB / NaOH 22 5454 비교예1-22Comparative Example 1-22 증류수(9) / 에틸아세테이트(1)Distilled Water (9) / Ethyl Acetate (1) 2828 TBAB / NaOHTBAB / NaOH 22 5656 비교예1-23Comparative Example 1-23 증류수(8) / 에틸아세테이트(2)Distilled water (8) / Ethyl acetate (2) 2828 -- 22 --

톨루엔toluene

표 5는 증류수와 톨루엔의 혼합비율에 따른 라우로일록시벤젠술포네이트의 수득율을 나타낸 것이다. 실시예1-1에서 증류수만 이용하였을 때 73%의 수득율을 보였고, 톨루엔을 10 내지 40%로 혼합한 용매에서는 수득율이 50 내지 65%로 증류수만 사용하였을 때 보다 감소하였다. Table 5 shows the yield of lauroyloxybenzenesulfonate according to the mixing ratio of distilled water and toluene. In Example 1-1, when only distilled water was used, the yield was 73%, and in the solvent mixed with 10 to 40% of toluene, the yield was 50 to 65%, which was lower than when only distilled water was used.

또한, 증류수 80%, 톨루엔 20%의 혼합용액 비교에 1-24와 동일한 조건에서 촉매를 사용하지 않고 반응을 수행하였을 때, 반응이 진행되지 않음을 확인하였다.In addition, it was confirmed that the reaction did not proceed when the reaction was performed without using a catalyst under the same conditions as 1-24 in comparing the mixed solution of 80% distilled water and 20% toluene.

구분division 반응용매 혼합비율
(중량비)Reaction solvent mixing ratio
(Weight ratio) 온도(℃)Temperature (℃) 촉매catalyst 시간time 수득율(%)Yield (%) 비교예1-24Comparative Example 1-24 증류수(8) / 톨루엔(2)Distilled water (8) / Toluene (2) 2828 TBAB / NaOHTBAB / NaOH 22 6161 비교예1-25Comparative Example 1-25 증류수(7) / 톨루엔(3)Distilled water (7) / Toluene (3) 2828 TBAB / NaOHTBAB / NaOH 22 6565 비교예1-26Comparative Example 1-26 증류수(6) / 톨루엔(4)Distilled water (6) / Toluene (4) 2828 TBAB / NaOHTBAB / NaOH 22 5050 비교예1-27Comparative Example 1-27 증류수(9) / 톨루엔 (1)Distilled Water (9) / Toluene (1) 2828 TBAB / NaOHTBAB / NaOH 22 5858 비교예1-28Comparative Example 1-28 증류수(8) / 톨루엔(2)Distilled water (8) / Toluene (2) 2828 -- 22 --

아이소파GIsopa G

표 6은 증류수와 아이소파G의 혼합비율에 따른 라우로일록시벤젠술포네이트의 수득율을 나타낸 것이다. 실시예 1-1에서 증류수만 이용하였을 때 73%의 수득율을 보였고, 아이소파G를 10 내지 40%로 혼합한 용매에서는 수득율이 55 내지 65%로 증류수 단독보다 감소하였다. 또한, 증류수 80%, 아이소파G 20%의 혼합용액 비교예1-29와 동일한 조건에서 촉매를 사용하지 않고 반응을 수행하였을 때, 반응이 진행되지 않음을 확인하였다. Table 6 shows the yield of lauroyloxybenzenesulfonate according to the mixing ratio of distilled water and isopar G. When only distilled water was used in Example 1-1, a yield of 73% was observed, and in a solvent mixed with isopar G at 10 to 40%, the yield was 55 to 65%, which was lower than that of distilled water alone. In addition, it was confirmed that the reaction did not proceed when the reaction was performed without using a catalyst under the same conditions as Comparative Example 1-29 of a mixed solution of 80% distilled water and 20% of isopar G.

구분division 반응용매 비율
(중량비)Reactive solvent ratio
(Weight ratio) 온도(℃)Temperature (℃) 촉매catalyst 시간time 수득율(%)Yield (%) 비교예1-29Comparative Example 1-29 증류수(8) / 아이소파G(2)Distilled water (8) / Isopha G (2) 2828 TBAB / NaOHTBAB / NaOH 22 6363 비교예1-30Comparative Example 1-30 증류수(7) / 아이소파G(3)Distilled water (7) / Isopha G (3) 2828 TBAB / NaOHTBAB / NaOH 22 6565 비교예1-31Comparative Example 1-31 증류수(6) /아이소파G (4)Distilled water (6) / Isopha G (4) 2828 TBAB / NaOHTBAB / NaOH 22 5555 비교예1-32Comparative Example 1-32 증류수(9) / 아이소파G(1)Distilled water(9) / Isopar G(1) 2828 TBAB / NaOHTBAB / NaOH 22 6060 비교예1-33Comparative Example 1-33 증류수(8) / 아이소파G(2)Distilled water (8) / Isopha G (2) 2828 -- 22 --

테트라하이트로퓨란(tetrahydrofuran, THF)Tetrahydrofuran (THF)

표 7은 증류수와 THF의 혼합비율에 따른 라우로일록시벤젠술포네이트의 수득율을 나타낸 것이다. 실시예 1-1에서 증류수만 이용하였을 때 73%의 수득율을 보였고, THF를 10 내지 40% 혼합한 용매에서는 수득율이 53 내지 62%로 증류수만 사용하였을 때 보다 감소하였다. 또한, 증류수 80%, THF 20%의 혼합용액 비교예1-34와 동일한 조건에서 촉매를 사용하지 않고 반응을 수행하였을 때, 반응이 진행되지 않음을 확인하였다. Table 7 shows the yield of lauroyloxybenzenesulfonate according to the mixing ratio of distilled water and THF. In Example 1-1, when only distilled water was used, a yield of 73% was shown, and in a solvent in which 10 to 40% of THF was mixed, the yield was 53 to 62%, which was lower than when only distilled water was used. In addition, it was confirmed that the reaction did not proceed when the reaction was performed without using a catalyst under the same conditions as Comparative Example 1-34 in a mixed solution of distilled water 80% and THF 20%.

구분division 반응용매 혼합비율
(중량비)Reaction solvent mixing ratio
(Weight ratio) 온도(℃)Temperature (℃) 촉매catalyst 시간time 수득율(%)Yield (%) 비교예1-34Comparative Example 1-34 증류수(8) / THF(2)Distilled Water(8) / THF(2) 2828 TBAB / NaOHTBAB / NaOH 22 5959 비교예1-35Comparative Example 1-35 증류수(7) / TFH(3)Distilled water (7) / TFH (3) 2828 TBAB / NaOHTBAB / NaOH 22 6262 비교예1-36Comparative Example 1-36 증류수(6) / THF (4)Distilled Water (6) / THF (4) 2828 TBAB / NaOHTBAB / NaOH 22 5353 비교예1-37Comparative Example 1-37 증류수(9) / THF (1)Distilled Water (9) / THF (1) 2828 TBAB / NaOHTBAB / NaOH 22 5555 비교예1-38Comparative Example 1-38 증류수(8) / THF (2)Distilled Water (8) / THF (2) 2828 -- 22 --

<실험예2> 노나노일록시벤젠술포네이트(Nonanoyloxybenzenesulfonate sodium, NOBS)의 제조<Experimental Example 2> Preparation of Nonanoyloxybenzenesulfonate sodium (NOBS)

기계식 교반기, 온도계, 콘덴서(condenser)가 설치된 5구 플라스크 반응기에 (E) 반응용매 1000g을 넣고 (F) 소듐하이드록시벤젠술포네이트 232.2g(1 몰, 분자량 232.2)과 (G) 50% 소듐하이드록사이드 수용액 80g(1몰, 분자량 40, 물 50 중량%), 촉매 5.92g(E+F+G+H 중량의 0.4wt%)를 넣고 상온에서 1시간 정도 교반하였다. 서서히 교반하면서 (H) 노나노일클로라이드 167.8g(0.95몰, 분자량 176.6)를 서서히 적하하였다. 반응기의 온도는 28℃를 유지하였다. 노나노일클로라이드의 적하가 끝나면 반응기의 내부온도를 28℃ 이하로 유지하면서 1시간 동안 반응을 진행하였다. 반응기 내부의 pH를 확인하여 7 미만이 되지 않도록 유지하고, pH가 7 미만이 될 경우, 소량의 50% 소듐하이드록사이드를 투입하여 pH를 7 내지 9로 조절하였다. TLC (Thin Layer Chromatography)로 반응 유무를 확인한 후, 잔류하는 소듐하이드록시벤젠술포네이트가 없을 경우, 반응기에 증류수 300mL를 투입하여 30분 정도 교반을 진행한 후, 필터로 여과하였다. 필터로 여과된 합성물을 110℃에서 건조하여 노나노일록시벤젠술포네이트(Nonanoyloxybenzenesulfonate sodium, NOBS)를 수득하였다. In a 5-neck flask reactor equipped with a mechanical stirrer, thermometer, and condenser, (E) 1000 g of the reaction solvent was added (F) 232.2 g of sodium hydroxybenzenesulfonate (1 mole, molecular weight 232.2) and (G) 50% sodium hydroxide Aqueous solution of 80g (1 mol, molecular weight 40, water 50% by weight), catalyst 5.92g (E + F + G + H weight 0.4wt%) was added and stirred at room temperature for about 1 hour. While stirring slowly, (H) nonanoyl chloride 167.8 g (0.95 mol, molecular weight 176.6) was slowly added dropwise. The temperature of the reactor was maintained at 28°C. When the dropwise addition of nonanoyl chloride was completed, the reaction was carried out for 1 hour while maintaining the internal temperature of the reactor below 28°C. The pH inside the reactor was checked to keep it below 7, and when the pH was below 7, a small amount of 50% sodium hydroxide was added to adjust the pH to 7-9. After confirming the presence or absence of the reaction by TLC (Thin Layer Chromatography), if there is no residual sodium hydroxybenzene sulfonate, 300 mL of distilled water is added to the reactor, followed by stirring for about 30 minutes, followed by filtration with a filter. The synthetic product filtered through the filter was dried at 110° C. to obtain Nonanoyloxybenzenesulfonate sodium (NOBS).

<실험예2-1> 반응용매의 종류에 따른 노나노일록시벤젠술포네이트의 수득율 비교<Experimental Example 2-1> Comparison of the yield of nonanoyl oxybenzene sulfonate according to the type of reaction solvent

구체적으로, 반응용매를 표 8과 같이 달리하여 노나노일록시벤젠술포네이트를 제조하였다. 표 8에 따르면 반응용매로 증류수를 이용하여 테트라 n-부틸암모늄브롬화물(Tetra-n-butylammonium bromide, TBAB)/ NaOH 촉매 조건하에 28℃로 2시간 동안 반응시키면 65%의 수득율로 4-노나노일록시벤젠술포네이트 소듐이 제조됨을 확인하였다(실시예2-1). Specifically, nonanoyloxybenzenesulfonate was prepared by changing the reaction solvent as shown in Table 8. According to Table 8, tetra-n-butylammonium bromide (TBAB)/distilled water is used as a reaction solvent and reacted at 28° C. under NaOH catalyst conditions for 2 hours to obtain 4-nonano with a yield of 65%. It was confirmed that sodium oxybenzenesulfonate was prepared (Example 2-1).

반면 반응용매를 아세톤, 에틸아세테이트, 톨루엔, 아이소파-G 또는 테트라하이트로퓨란(tetrahydrofuran, THF)으로 달리한 것을 제외하고 실시예2-1과 동일한 조건으로 반응시켜 제조하였을 때는 반응이 진행되지 않음을 확인하였다(비교예2-1 내지 비교예2-5). On the other hand, when the reaction solvent was prepared by reacting under the same conditions as in Example 2-1 except that it was changed to acetone, ethyl acetate, toluene, isopa-G or tetrahydrofuran (THF), the reaction did not proceed. It was confirmed (Comparative Example 2-1 to Comparative Example 2-5).

또한 반응용매로 에틸아세테이트, 톨루엔, 아이소파-G 또는 테트라하이트로퓨란(tetrahydrofuran, THF)을 사용하고, 촉매로 TBAB를 사용한 것을 제외하고 동일한 조건으로 반응시켰을 때 반응이 진행되지 않음을 확인하였다(비교예2-6 내지 비교예2-9). In addition, it was confirmed that the reaction did not proceed when reacting under the same conditions except that ethyl acetate, toluene, isopa-G, or tetrahydrofuran (THF) was used as a reaction solvent, and TBAB was used as a catalyst ( Comparative Examples 2-6 to Comparative Examples 2-9).

구분division 반응용매 혼합비율
(중량비)Reaction solvent mixing ratio
(Weight ratio) 온도(℃)Temperature (℃) 촉매catalyst 시간time 수득율(%)Yield (%) 실시예2-1Example 2-1 증류수Distilled water 2828 TBAB / NaOHTBAB / NaOH 22 6565 비교예2-1Comparative Example 2-1 아세톤Acetone 2828 TBAB / NaOHTBAB / NaOH 22 -- 비교예2-2Comparative Example 2-2 에틸아세테이트Ethyl acetate 2828 TBAB / NaOHTBAB / NaOH 22 -- 비교예2-3Comparative Example 2-3 톨루엔toluene 2828 TBAB / NaOHTBAB / NaOH 22 -- 비교예2-4Comparative Example 2-4 아이소파-GIsopha-G 2828 TBAB / NaOHTBAB / NaOH 22 -- 비교예2-5Comparative Example 2-5 THFTHF 2828 TBAB / NaOHTBAB / NaOH 22 -- 비교예2-6Comparative Example 2-6 에틸아세테이트Ethyl acetate 2828 TBABTBAB 22 -- 비교예2-7Comparative Example 2-7 톨루엔toluene 2828 TBABTBAB 22 -- 비교예2-8Comparative Example 2-8 아이소파-GIsopha-G 2828 TBABTBAB 22 -- 비교예2-9Comparative Example 2-9 THFTHF 2828 TBABTBAB 22 --

<실험예2-2> 반응온도에 따른 노나노일록시벤젠술포네이트의 수득율 비교<Experimental Example 2-2> Comparison of the yield of nonanoyl oxybenzene sulfonate according to the reaction temperature

실험예2-1에서 반응이 진행되지 않은 용매를 이용하여, 온도 조건과 촉매조건을 표 9와 같이 달리하여 반응을 진행하였다. 또한 증류수에서 온도조건을 달리하여 반응을 진행하고 수득율을 확인하였다.In Example 2-1, the reaction was carried out by using a solvent in which the reaction did not proceed, and the temperature conditions and the catalyst conditions were changed as shown in Table 9. In addition, the reaction was performed by varying the temperature conditions in distilled water and the yield was confirmed.

표 9는 반응온도에 따른 노나노일록시벤젠술포네이트의 수득율이다. 비교예2-10 내지 비교예2-14에서 유기용매(아세톤, 에틸아세테이트, 톨루엔, 아이소파-G, THF)에서 반응온도를 올려 60 내지 150℃에서 수행하였으나, 반응이 진행되지 않음을 확인하였다. 또한 증류수인 비교예2-15 내지 비교예2-17을 보면 60℃에서 반응시, 수득율은 30%로 나타났으며, 반응 온도가 100℃로 증가함에 따라 수득율이 10%로 감소하였다. 또한 150℃에서는 반응이 진행되지 않음을 확인하였다.Table 9 shows the yield of nonanoyloxybenzenesulfonate according to the reaction temperature. In Comparative Examples 2-10 to 2-14, the reaction temperature was raised in an organic solvent (acetone, ethyl acetate, toluene, isopa-G, THF), and the reaction was performed at 60 to 150°C, but it was confirmed that the reaction did not proceed. . In addition, when looking at Comparative Examples 2-15 to Comparative Examples 2-17, which are distilled water, when reacting at 60°C, the yield was 30%, and as the reaction temperature increased to 100°C, the yield was reduced to 10%. Also, it was confirmed that the reaction did not proceed at 150°C.

구분division 반응용매 혼합비율
(중량비)Reaction solvent mixing ratio
(Weight ratio) 온도(℃)Temperature (℃) 촉매catalyst 시간time 수득율(%)Yield (%) 비교예2-10Comparative Example 2-10 아세톤Acetone 6060 p-TSAp-TSA 22 -- 비교예2-11Comparative Example 2-11 에틸아세테이트Ethyl acetate 6060 H2SO4 H 2 SO 4 22 -- 비교예2-12Comparative Example 2-12 톨루엔toluene 100100 p-TSAp-TSA 22 -- 비교예2-13Comparative Example 2-13 아이소파-GIsopha-G 150150 p-TSAp-TSA 22 -- 비교예2-14Comparative Example 2-14 THFTHF 6060 H2SO4H2SO4 22 -- 비교예2-15Comparative Example 2-15 증류수Distilled water 6060 TBAB / NaOHTBAB / NaOH 22 3030 비교예2-16Comparative Example 2-16 증류수Distilled water 100100 TBAB / NaOHTBAB / NaOH 22 1010 비교예2-17Comparative Example 2-17 증류수Distilled water 150150 TBAB / NaOHTBAB / NaOH 22 --

<실험예2-3> 유기용매 종류 및 혼합비율에 따른 노나노일록시벤젠술포네이트의 수득율 비교<Experimental Example 2-3> Comparison of the yield of nonanoyloxybenzenesulfonate according to the type and mixing ratio of the organic solvent

다음으로 증류수와 유기용매의 혼합용매에서 수득율을 분석하였다. 유기용매는 아세톤, 에틸아세테이트, 톨루엔, 아이소파-G, 테트라하이트로퓨란(tetrahydrofuran, THF)을 사용하였다. Next, the yield was analyzed in a mixed solvent of distilled water and an organic solvent. As the organic solvent, acetone, ethyl acetate, toluene, isopa-G, and tetrahydrofuran (THF) were used.

아세톤Acetone

표 10은 아세톤 혼합비율에 따른 노나노일록시벤젠술포네이트 수득율의 수득율을 비교한 결과이다. 실시예2-1에서 증류수만 이용하였을 때 65%의 수득율을 보였으나, 증류수 90%, 아세톤 10%의 혼합용액(실시예2-4)에서는 수득율이 73%로 증가하였으며, 증류수 80%, 아세톤 20%의 혼합용액(실시예2-2) 사용시 77%로 아세톤을 20%가 포함된 용액을 반응용매로 사용시 수득율이 가장 높음을 확인하였다. 반면 증류수 60%, 아세톤40%의 용액에서는 수득율이 52%로 증류수만 이용하였을 때보다 수득율이 감소되는 것을 확인하였다(비교예2-18-1).Table 10 is a result of comparing the yield of the nonanoyloxybenzenesulfonate yield according to the acetone mixing ratio. When only distilled water was used in Example 2-1, the yield was 65%, but in a mixed solution of 90% distilled water and 10% acetone (Example 2-4), the yield increased to 73%, 80% distilled water, acetone When using a 20% mixed solution (Example 2-2), it was confirmed that the yield was highest when using a solution containing 20% acetone as 77% as a reaction solvent. On the other hand, it was confirmed that in the solution of 60% distilled water and 40% acetone, the yield was 52%, which was lower than when only distilled water was used (Comparative Example 2-18-1).

또한 실시예2-2와 동일한 조건에서 촉매를 사용하지 않고 반응을 수행하였을 때, 반응이 진행되지 않음을 확인하였다. In addition, when the reaction was performed without using a catalyst under the same conditions as in Example 2-2, it was confirmed that the reaction did not proceed.

구분division 반응용매 혼합비율
(중량비)Reaction solvent mixing ratio
(Weight ratio) 온도(℃)Temperature (℃) 촉매catalyst 시간time 수득율(%)Yield (%) 실시예2-2Example 2-2 증류수(8) / 아세톤(2)Distilled water (8) / Acetone (2) 2828 TBAB / NaOHTBAB / NaOH 22 7777 실시예2-3Example 2-3 증류수(7) / 아세톤(3)Distilled water (7) / Acetone (3) 2828 TBAB / NaOHTBAB / NaOH 22 7575 비교예2-18-1Comparative Example 2-18-1 증류수(6) / 아세톤(4)Distilled water (6) / Acetone (4) 2828 TBAB / NaOHTBAB / NaOH 22 5252 실시예2-4Example 2-4 증류수(9) / 아세톤(1)Distilled Water (9) / Acetone (1) 2828 TBAB / NaOHTBAB / NaOH 22 7373 비교예2-18-2Comparative Example 2-18-2 증류수(8) / 아세톤(2)Distilled water (8) / Acetone (2) 2828 -- 22 --

에틸아세테이트Ethyl acetate

표 11은 증류수와 에틸아세테이트 혼합비율에 따른 노나노일록시벤젠술포네이트의 수득율을 나타낸 것이다. 실시예2-1에서 증류수만 이용하였을 때 65%의 수득율을 보였고, 에틸아세테이트를 10 내지 40%로 혼합한 용매에서는 수득율이 45 내지 61%로 증류수만 사용하였을 때 보다 감소하였다. 또한, 증류수 80%, 에틸아세테이트 20%의 혼합용액 비교예2-19와 동일한 조건에서 촉매를 사용하지 않고 반응을 수행하였을 때, 반응이 진행되지 않음을 확인하였다. Table 11 shows the yield of nonanoyloxybenzenesulfonate according to the mixing ratio of distilled water and ethyl acetate. In Example 2-1, when only distilled water was used, a yield of 65% was exhibited, and in a solvent mixed with ethyl acetate at 10 to 40%, the yield was 45 to 61%, which was lower than when only distilled water was used. In addition, it was confirmed that the reaction did not proceed when the reaction was performed without using a catalyst under the same conditions as Comparative Example 2-19 in a mixed solution of distilled water 80% and ethyl acetate 20%.

구분division 반응용매 혼합비율
(중량비)Reaction solvent mixing ratio
(Weight ratio) 온도(℃)Temperature (℃) 촉매catalyst 시간time 수득율(%)Yield (%) 비교예2-19Comparative Example 2-19 증류수(8) / 에틸아세테이트(2)Distilled water (8) / Ethyl acetate (2) 2828 TBAB / NaOHTBAB / NaOH 22 6161 비교예2-20Comparative Example 2-20 증류수(7) / 에틸아세테이트(3)Distilled water (7) / ethyl acetate (3) 2828 TBAB / NaOHTBAB / NaOH 22 5757 비교예2-21Comparative Example 2-21 증류수(6) / 에틸아세테이트(4)Distilled water (6) / ethyl acetate (4) 2828 TBAB / NaOHTBAB / NaOH 22 4545 비교예2-22Comparative Example 2-22 증류수(9) / 에틸아세테이트(1)Distilled Water (9) / Ethyl Acetate (1) 2828 TBAB / NaOHTBAB / NaOH 22 5555 비교예2-23Comparative Example 2-23 증류수(8) / 에틸아세테이트(2)Distilled water (8) / Ethyl acetate (2) 2828 -- 22 --

톨루엔toluene

표 12는 증류수와 톨루엔 혼합비율에 따른 노나노일록시벤젠술포네이트의 수득율을 나타낸 것이다. 실시예2-1에서 증류수만 이용하였을 때 65%의 수득율을 보였고, 톨루엔을 10 내지 40%로 혼합한 용매에서는 수득율이 50 내지 60%로 증류수 만 사용하였을 때 보다 감소하였다. 또한, 증류수 80%, 톨루엔 20%의 혼합용액 실시예2-24와 동일한 조건에서 촉매를 사용하지 않고 반응을 수행하였을 때, 반응이 진행되지 않음을 확인하였다. Table 12 shows the yield of nonanoyloxybenzenesulfonate according to the mixing ratio of distilled water and toluene. When only distilled water was used in Example 2-1, the yield was 65%, and in the solvent mixed with toluene at 10 to 40%, the yield was 50 to 60%, which was lower than when only distilled water was used. In addition, it was confirmed that when the reaction was performed without using a catalyst under the same conditions as in Example 2-24, a mixed solution of 80% distilled water and 20% toluene, the reaction did not proceed.

구분division 반응용매 혼합비율
(중량비)Reaction solvent mixing ratio
(Weight ratio) 온도(℃)Temperature (℃) 촉매catalyst 시간time 수득율(%)Yield (%) 비교예2-24Comparative Example 2-24 증류수(8) / 톨루엔(2)Distilled water (8) / Toluene (2) 2828 TBAB / NaOHTBAB / NaOH 22 6060 비교예2-25Comparative Example 2-25 증류수(7) / 톨루엔(3)Distilled water (7) / Toluene (3) 2828 TBAB / NaOHTBAB / NaOH 22 5555 비교예2-26Comparative Example 2-26 증류수(6) / 톨루엔(4)Distilled water (6) / Toluene (4) 2828 TBAB / NaOHTBAB / NaOH 22 5050 비교예2-27Comparative Example 2-27 증류수(9) / 톨루엔 (1)Distilled Water (9) / Toluene (1) 2828 TBAB / NaOHTBAB / NaOH 22 5353 비교예2-28Comparative Example 2-28 증류수(8) / 톨루엔(2)Distilled water (8) / Toluene (2) 2828 -- 22 --

아이소파GIsopa G

표 13은 증류수와 아이소파G의 혼합비율에 따른 노나노일록시벤젠술포네이트의 수득율을 나타낸 것이다. 실시예2-1에서 증류수만 이용하였을 때 65%의 수득율을 보였고, 아이소파G을 10 내지 40%로 혼합한 용매에서는 수득율이 50 내지 63%로 증류수만 사용하였을 때 보다 감소하였다. 또한, 증류수 80%, 아이소파G 20%의 혼합용액 실시예2-29와 동일한 조건에서 촉매를 사용하지 않고 반응을 수행하였을 때, 반응이 진행되지 않음을 확인하였다. Table 13 shows the yield of nonanoyloxybenzenesulfonate according to the mixing ratio of distilled water and isopar G. In Example 2-1, when only distilled water was used, a yield of 65% was exhibited, and in the solvent mixed with isopar G at 10 to 40%, the yield was 50 to 63%, which was lower than when only distilled water was used. In addition, when the reaction was performed without using a catalyst under the same conditions as in Example 2-29, a mixed solution of 80% distilled water and 20% isopa G, it was confirmed that the reaction did not proceed.

구분division 반응용매 혼합비율
(중량비)Reaction solvent mixing ratio
(Weight ratio) 온도(℃)Temperature (℃) 촉매catalyst 시간time 수득율(%)Yield (%) 비교예2-29Comparative Example 2-29 증류수(8) / 아이소파G(2)Distilled water (8) / Isopha G (2) 2828 TBAB / NaOHTBAB / NaOH 22 6161 비교예2-30Comparative Example 2-30 증류수(7) / 아이소파G(3)Distilled water (7) / Isopha G (3) 2828 TBAB / NaOHTBAB / NaOH 22 6363 비교예2-31Comparative Example 2-31 증류수(6) /아이소파G (4)Distilled water (6) / Isopha G (4) 2828 TBAB / NaOHTBAB / NaOH 22 5050 비교예2-32Comparative Example 2-32 증류수(9) / 아이소파G(1)Distilled water(9) / Isopar G(1) 2828 TBAB / NaOHTBAB / NaOH 22 5757 비교예2-33Comparative Example 2-33 증류수(8) / 아이소파G(2)Distilled water (8) / Isopha G (2) 2828 -- 22 --

테트라하이트로퓨란(tetrahydrofuran, THF)Tetrahydrofuran (THF)

표 14는 증류수와 THF의 혼합비율에 따른 노나노일록시벤젠술포네이트의 수득율을 나타낸 것이다. 실시예2-1에서 증류수만 이용하였을 때 65%의 수득율을 보였고, THF를 10 내지 40%로 혼합한 용매에서는 수득율이 49 내지 63%로 증류수만 사용하였을 때 보다 감소하였다. 또한, 증류수 80%, THF 20%의 혼합용액 실시예2-34과 동일한 조건에서 촉매를 사용하지 않고 반응을 수행하였을 때, 반응이 진행되지 않음을 확인하였다. Table 14 shows the yield of nonanoyloxybenzenesulfonate according to the mixing ratio of distilled water and THF. In Example 2-1, when only distilled water was used, a yield of 65% was shown, and in a solvent in which THF was mixed with 10 to 40%, the yield was 49 to 63%, which was lower than when only distilled water was used. In addition, when the reaction was performed without using a catalyst under the same conditions as in Example 2-34, a mixed solution of distilled water 80% and THF 20%, it was confirmed that the reaction did not proceed.

구분division 반응용매 혼합비율
(중량비)Reaction solvent mixing ratio
(Weight ratio) 온도(℃)Temperature (℃) 촉매catalyst 시간time 수득율(%)Yield (%) 비교예2-34Comparative Example 2-34 증류수(8) / THF(2)Distilled Water(8) / THF(2) 2828 TBAB / NaOHTBAB / NaOH 22 6363 비교예2-35Comparative Example 2-35 증류수(7) / TFH(3)Distilled water (7) / TFH (3) 2828 TBAB / NaOHTBAB / NaOH 22 5858 비교예2-36Comparative Example 2-36 증류수(6) / THF (4)Distilled Water (6) / THF (4) 2828 TBAB / NaOHTBAB / NaOH 22 4949 비교예2-37Comparative Example 2-37 증류수(9) / THF (1)Distilled Water (9) / THF (1) 2828 TBAB / NaOHTBAB / NaOH 22 6060 비교예2-38Comparative Example 2-38 증류수(8) / THF (2)Distilled Water (8) / THF (2) 2828 -- 22 --

Claims (11)

하기 반응식Ⅰ과 같이 아실클로라이드와 소듐하이드록시벤젠술포네이트를 반응용매(solvent) 하에서 반응시키는 단계를 포함하는, 화학식1로 표시되는 소듐 아실옥시벤젠술포네이트를 제조하는 방법;
[화학식1]
Figure pat00003

[반응식Ⅰ]
Figure pat00004

상기 반응식Ⅰ 및 화학식1의 상기 R은 C6 내지 C22의 직쇄상 또는 분쇄상의 포화 알킬기이고,
상기 반응용매(solvent)는 물과 아세톤이 10:0 내지 6.5:3.5의 중량비로 혼합된 것이다.A method of preparing sodium acyloxybenzenesulfonate represented by Chemical Formula 1, comprising reacting acyl chloride and sodium hydroxybenzenesulfonate under a reaction solvent as shown in Scheme I below;
[Formula 1]
Figure pat00003

[Scheme I]
Figure pat00004

R in Reaction Scheme I and Formula 1 is a C6 to C22 linear or branched saturated alkyl group,
The reaction solvent is a mixture of water and acetone in a weight ratio of 10:0 to 6.5:3.5. 제 1항에 있어서,
상기 반응시키는 단계는 반응기에 상기 반응용매를 첨가하는 단계;
소듐하이드록시벤젠술포네이트를 첨가하는 단계;
소듐하이드록사이드 수용액을 첨가하는 단계;
촉매를 첨가하고 교반하는 단계; 및
상기 아실클로라이드를 첨가하여 반응을 진행하는 단계를 포함하는 것인, 제조하는 방법.According to claim 1,
The step of reacting includes adding the reaction solvent to a reactor;
Adding sodium hydroxybenzenesulfonate;
Adding an aqueous sodium hydroxide solution;
Adding and stirring the catalyst; And
The method of manufacturing, comprising the step of proceeding the reaction by adding the acyl chloride. 제 2항에 있어서
상기 반응용매 800 내지 1200g 기준으로, 상기 소듐하이드록시벤젠술포네이트 0.5 내지 1.5몰(mol), 20 내지 80% 소듐하이드록사이드 수용액 50 내지 100g 및 상기 아실클로라이드 0.5 내지 1.5몰(mol)을 첨가하는 것을 특징으로 하는, 제조하는 방법.The method of claim 2
Based on 800 to 1200 g of the reaction solvent, 0.5 to 1.5 mol (mol) of the sodium hydroxybenzenesulfonate, 50 to 100 g of 20 to 80% sodium hydroxide aqueous solution, and 0.5 to 1.5 mol (mol) of the acyl chloride are added. Characterized in that, the method of manufacturing. 제 2항에 있어서
상기 촉매는 상기 반응시키는 단계에서 첨가된 상기 반응용매, 상기 소듐하이드록시벤젠술포네이트, 상기 소듐하이드록사이드 수용액 및 상기 아실클로라이드의 전체중량 기준으로 0.1 내지 1.5 중량%로 첨가하는 것을 특징으로 하는, 제조하는 방법.The method of claim 2
The catalyst is characterized in that 0.1 to 1.5% by weight based on the total weight of the reaction solvent, the sodium hydroxybenzenesulfonate, the sodium hydroxide aqueous solution and the acyl chloride added in the reaction step, How to manufacture. 제 2항에 있어서,
상기 반응시키는 단계는 상기 반응기의 온도를 10 내지 40℃로 유지하는 단계를 더 포함하는 것인, 제조하는 방법.According to claim 2,
The reacting step further comprises maintaining the temperature of the reactor at 10 to 40°C. 제 2항에 있어서,
상기 반응시키는 단계는 pH를 7 내지 9로 유지하는 단계를 더 포함하는 것인, 제조하는 방법.According to claim 2,
The reacting step further comprises maintaining the pH at 7 to 9. 제 1항에 있어서,
상기 반응시키는 단계에서 상기 아실클로라이드와 상기 소듐하이드록시벤젠술포네이트가 0.8 내지 1.0: 1.0 내지 1.2의 몰비로 첨가하여 반응시키는 것인, 제조하는 방법.According to claim 1,
In the reacting step, the acyl chloride and the sodium hydroxybenzenesulfonate are added in a molar ratio of 0.8 to 1.0: 1.0 to 1.2 to react. 제 2항에 있어서,
상기 촉매는 산 화합물, 염기 화합물, 금속 화합물 및 암모늄 염 화합물으로 이루어진 군에서 선택되는 1종 이상인 것인, 제조하는 방법.According to claim 2,
The catalyst is one or more selected from the group consisting of an acid compound, a base compound, a metal compound, and an ammonium salt compound. 제 8항에 있어서,
상기 산 화합물은 파라톨루엔술포닉산, 인산, 차아인산, 차아인산소다 및 황산 중에서 선택된 1종 이상이고, 상기 염기 화합물은 알칼리금속수산화물이며, 상기 금속 화합물은 Fe, Cu, Co, Ti, Sn 및 Mn 중에서 선택된 1종 이상의 금속을 함유하는 화합물이며, 상기 암모늄염은 4급 암모늄염인 것인, 제조하는 방법. The method of claim 8,
The acid compound is at least one selected from paratoluenesulfonic acid, phosphoric acid, hypophosphorous acid, sodium hypophosphite, and sulfuric acid, the base compound is an alkali metal hydroxide, and the metal compound is Fe, Cu, Co, Ti, Sn, and Mn It is a compound containing one or more metals selected from, and the ammonium salt is a quaternary ammonium salt. 제 9항에 있어서,
상기 암모늄염은 세틸트리메닐암모늄 클로라이드(Cetyltrimethylammonium chloride), (3-클로로-2-하이드록시프로필)트리메틸암모늄 클로라이드((3-Chloro-2-hydroxypropyl)trimethylammonium chloride), 디아릴디메틸암모늄 클로라이드(Diallyldimethylammonium chloride), 디도데실디메틸암모늄 브로마이드(Didodecyldimethylammonium bromide), 디메틸옥타데실[2-(트리메톡실란)프로필]암모늄 클로라이드(Dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride), (하이드라지노카르보닐메틸)트리메틸암모늄 클로라이드((Hydrazinocarbonylmethyl)trimethylammonium chloride), 글리시틸트리메틸암모늄 클로라이드(Glycidyltrimethylammonium chloride), 헥사데실(2-하이드록시에틸)디메틸암모늄 디하이드로젠 포스페이트(Hexadecyl(2-hydroxyethyl)dimethylammonium dihydrogen phosphate), 헥사데실트리메틸암모늄 브로마이드(Hexadecyltrimethylammonium bromide), 미리스틸트리메틸암모늄 브로마이드(Myristyltrimethylammonium bromide), 테트라뷰틸암모늄 바이설페이트(Tetrabutylammonium bisulfate), 테트라뷰틸암모늄 브로마이드(Tetrabutylammonium bromide), 테트라뷰틸암모늄 클로라이드(Tetrabutylammonium chloride), 테트라뷰틸암모늄 헥사플로오로포스페이트(Tetrabutylammonium hexafluorophosphate), 테트라뷰틸암모늄 하이드로젠설페이트(Tetrabutylammonium hydrogensulfate), 테트라뷰틸암모늄 퍼클로레이트(Tetrabutylammonium perchlorate), 테트라뷰틸암모늄 셀페이트(Tetrabutylammonium sulfate), 메틸트리옥틸암모늄 클로라이드(Methyltrioctylammonium chloride), 테트라뷰틸암모늄 트리브로마이드(Tetrabutylammonium tribromide), 테트라뷰틸암모늄 아세테이트(Tetraethylammonium acetate), 테트라에틸암모늄 브로마이드(Tetraethylammonium bromide), 테트라에틸암모늄 클로라이드(Tetraethylammonium chloride), 테트라에틸암모늄 아이오다이드(Tetraethylammonium iodide), 테트라메틸암모늄 브로마이드(Tetramethylammonium bromide), 테트라메틸암모늄 클로라이드(Tetramethylammonium chloride), 테트라메틸암모늄 포르메이트(Tetramethylammonium formate), 테트라메틸암모늄 아이오다이드(Tetramethylammonium iodide), 테트라메틸암모늄 실리케이트(Tetramethylammonium silicate), 테트라프로필암모늄 브로마이드(Tetrapropylammonium bromide), 트리뷰틸메틸암모늄 클로라이드(Tributylmethylammonium chloride), 트리뷰틸메틸암모늄 브로마이드(Tributylmethylammonium bromide), 트리에틸메틸암모늄 클로라이드(Triethylmethylammonium chloride), 트리메틸페닐암모늄 브로마이드(Trimethylphenylammonium bromide), 트리메틸페닐암모늄 클로라이드(Trimethylphenylammonium chloride) 및 (비닐벤질)트리메틸암모늄 클로라이드((Vinylbenzyl)trimethylammonium chloride)로 이루어진 군에서 선택되는 1종 이상인 것인, 제조하는 방법.The method of claim 9,
The ammonium salt is cetyltrimethylammonium chloride, (3-chloro-2-hydroxypropyl) trimethylammonium chloride ((3-Chloro-2-hydroxypropyl)trimethylammonium chloride), diaryldimethylammonium chloride. ), didodecyldimethylammonium bromide, dimethyloctadecyl[2-(trimethoxysilyl)propyl]ammonium chloride, (hydrazinocarbonylmethyl)trimethyl Ammonium chloride ((Hydrazinocarbonylmethyl)trimethylammonium chloride), Glycidyltrimethylammonium chloride, Hexadecyl (2-hydroxyethyl) dimethylammonium dihydrogen phosphate, Hexadecyl Trimethylammonium bromide (Hexadecyltrimethylammonium bromide), Myristyltrimethylammonium bromide (Myristyltrimethylammonium bromide), Tetrabutylammonium bisulfate (Tetrabutylammonium bisulfate), Tetrabutylammonium bromide (Tetrabutylammonium butylmonium chloride), Tetrabutylammonium bromide Fluorophosphate (Tetrabutylammonium hexafluorophosphate), Tetrabutylammonium hydrogensulfate, Tetrabutylammonium perchlorate, Tetrabutyl Ammonium sulfate (Tetrabutylammonium sulfate), Methyltrioctylammonium chloride, Tetrabutylammonium tribromide, Tetraethylammonium acetate, Tetraethylammonium bromide, Tetraethylammonium bromide, tetraethylammonium bromide (Tetraethylammonium chloride), Tetraethylammonium iodide, Tetramethylammonium bromide, Tetramethylammonium chloride, Tetramethylammonium formate, Tetramethylammonium iodide (Tetramethylammonium iodide), Tetramethylammonium silicate, Tetrapropylammonium bromide, Tributylmethylammonium chloride, Tributylmethylammonium bromide, Triethylmethylammonium bromide (Triethylmethylammonium chloride), trimethylphenylammonium bromide (Trimethylphenylammonium bromide), trimethylphenylammonium chloride (Trimethylphenylammonium chloride) and (vinylbenzyl) trimethylammonium chloride ((Vinylbenzyl)trimethylammonium chloride) is one or more selected from the group consisting of How to. 제 1항에 있어서,
상기 화학식1로 표시되는 화합물은 소듐 노나노일록시벤젠술포네이트 또는 소듐 라우로일록시벤젠술포네이트인 것인, 제조하는 방법.According to claim 1,
The compound represented by Chemical Formula 1 is sodium nonanoyloxybenzenesulfonate or sodium lauroyloxybenzenesulfonate.
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