KR20080007941A - Manufacturing method of high purity sorbitan - Google Patents
Manufacturing method of high purity sorbitanDownload PDFInfo
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- KR20080007941A KR20080007941AKR1020060067206AKR20060067206AKR20080007941AKR 20080007941 AKR20080007941 AKR 20080007941AKR 1020060067206 AKR1020060067206 AKR 1020060067206AKR 20060067206 AKR20060067206 AKR 20060067206AKR 20080007941 AKR20080007941 AKR 20080007941A
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- JNYAEWCLZODPBN-JGWLITMVSA-N(2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diolChemical compoundOC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1OJNYAEWCLZODPBN-JGWLITMVSA-N0.000titleclaimsabstractdescription26
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- JOXIMZWYDAKGHI-UHFFFAOYSA-Ntoluene-4-sulfonic acidChemical compoundCC1=CC=C(S(O)(=O)=O)C=C1JOXIMZWYDAKGHI-UHFFFAOYSA-N0.000claimsabstractdescription16
- FBPFZTCFMRRESA-FSIIMWSLSA-ND-GlucitolNatural productsOC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)COFBPFZTCFMRRESA-FSIIMWSLSA-N0.000claimsabstractdescription11
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- 125000003178carboxy groupChemical group[H]OC(*)=O0.000description1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/20—Oxygen atoms
- 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
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Abstract
Description
Translated fromKorean도 1은 본 발명의 방법에 의해 실험실에서 제조된 1,4-솔비탄의 합성결과를 나타낸 그래프.1 is a graph showing the results of the synthesis of 1,4-sorbitan prepared in the laboratory by the method of the present invention.
도 2는 본 발명의 방법에 의해 파일롯 실험에서 제조된 1,4-솔비탄의 합성결과를 나타낸 그래프.Figure 2 is a graph showing the synthesis results of 1,4-sorbitan prepared in a pilot experiment by the method of the present invention.
도 3은 본 발명의 방법에 의해 파일롯 실험에서 제조된 1,4-솔비탄의 합성결과를 나타낸 그래프.Figure 3 is a graph showing the synthesis results of 1,4-sorbitan prepared in a pilot experiment by the method of the present invention.
도 4는 본 발명의 방법에 의해 플랜트 실험에서 제조된 1,4-솔비탄의 합성결과를 나타낸 그래프.Figure 4 is a graph showing the results of the synthesis of 1,4-sorbitan prepared in the plant experiment by the method of the present invention.
도 5는 본 발명의 방법에 의해 플랜트 실험에서 제조된 1,4-솔비탄과 일본 중앙화성 제품의 외관 색상을 비교한 사진.Figure 5 is a photograph comparing the appearance color of 1,4-sorbitan and Japanese centralized product produced in the plant experiment by the method of the present invention.
도 6은 145℃, 460torr 조건에서 제조된 1,4-솔비탄의 합성결과를 나타낸 그래프.Figure 6 is a graph showing the synthesis results of 1,4-sorbitan prepared at 145 ℃, 460torr conditions.
도 7은 145℃, 460torr 조건에서 제조된 1,4-솔비탄과 일본 중앙화성 제품의 외관 색상을 비교한 사진.Figure 7 is a photograph comparing the appearance color of 1,4-sorbitan and Japan Centralized Products produced at 145 ℃, 460torr conditions.
본 발명은 솔비탄(Sorbitan)의 제조방법에 관한 것으로, 더욱 상세하게는 1,4-솔비탄을 고순도로 제조할 수 있는 방법을 제공하는 것이다.The present invention relates to a manufacturing method of sorbitan (Sorbitan), and more particularly, to provide a method for producing 1,4-sorbitan in high purity.
PE, EVA, PVC필름으로 식품을 포장하거나 온상 피복하는 경우 필름 내면에 물방울이 맺혀서 식품의 보관 시나 작물 생육 시 나쁜 영향을 미치고 있다. 이를 개선하기 위해 플라스틱 필름의 표면장력을 증가시켜 물과의 친화력을 향상시키기 위해 비이온계 계면활성제의 일종인 AF(Antifogging)제를 첨가하고 있다. 특히 온상필름용 첨가제로의 사용이 두드러지고 있는데 AF제가 필름표면으로 접촉하면서 발생되는 물방울을 퍼져 흐르게 하는 동안에 같이 소모되기 때문이다. AF제의 소모량은 필름재질과의 상호친화성, 온상주변의 온도와 온상내부의 수증기 증발량 등과 깊은 관계가 있으므로 무적지속성(無敵持續性)을 일정하게 유지시키기는 매우 어렵다.When packaging or hot-bed coating of foods with PE, EVA and PVC films, water droplets form on the inner surface of the film, which adversely affects food storage and crop growth. In order to improve this, the AF (Antifogging) agent, which is a kind of nonionic surfactant, is added to increase the surface tension of the plastic film to improve affinity with water. In particular, the use as an additive for hot-phase film is prominent because it is consumed while the AF agent is spreading and flowing water droplets generated by contact with the film surface. Consumption of the AF agent has a strong relationship with the film material material compatibility, the temperature around the hotbed and the vapor evaporation amount inside the hotbed, and thus it is very difficult to maintain a constant invincibility.
이 AF제 중에서 가장 많이 사용되고 있는 물질은 Span(Sorbitan monofatty acid ester)계열이다. 당 분자의 수산기가 지방산의 카르복실기와 아실화 하여 에스테르 결합을 이룬 당 지방산 에스테르(Sugar Fatty acid ester)는 식품 및 의약품 등을 비롯한 다양한 용도의 계면활성제와 첨가제로 이용할 수 있고, 기능성 관능기를 당 분자의 다양한 입체적 결합 방식으로 배당화 하면 고기능성 복합소재를 필요로 하는 외용공학 분야의 광학재료와 생체분야도 이용이 가능하다. 당 알콜인 솔비톨을 이용한 솔비탄 지방산 에스테르를 합성할 경우 부산물을 만들게 되어 모노-, 디-, 트리 지방산 에스테르의 혼합물을 생성하게 된다. 이렇게 되면 필름내에서의 무적초기성, 무적지속성, 무적저온성 등의 데이타가 일정치 못하기 때문에 농민들로부터 빈번한 클레임을 불러 일으키게 된다.The most commonly used substance among these AF agents is Span (Sorbitan monofatty acid ester) family. Sugar fatty acid ester, in which the hydroxyl group of the sugar molecule is acylated with the carboxyl group of the fatty acid to form an ester bond, can be used as a surfactant and additive for various uses, including food and pharmaceuticals. Dividing by various three-dimensional coupling methods, it is possible to use optical materials and biological fields in the field of external engineering requiring high functional composite materials. Synthesis of sorbitan fatty acid esters using sorbitol, a sugar alcohol, produces by-products, resulting in a mixture of mono-, di- and tri-fatty acid esters. This results in frequent claims from farmers because the data of invincible initial, invincible persistence, and invincible low temperature in film are inconsistent.
일반적인 span의 제조과정은 솔비톨과 지방산을 혼합하여 230℃ 정도의 고온에서 탈수반응(Dehydration)시켜 솔비탄을 제조하는데, 이때 솔비탄으로의 전환율은 50% 넘기기가 매우 어렵고 일반적으로 약 40%가 된다. 여기에 촉매를 투입하여 span을 제조한다.In general, the manufacturing process of sorbitol is mixed with sorbitol and fatty acid and dehydrated at a high temperature of about 230 ° C. to produce sorbitan. The conversion to sorbitan is very difficult to exceed 50%, and is generally about 40%. . The catalyst is added thereto to prepare a span.
따라서, 본 발명의 목적은 고순도 1,4-솔비탄을 제조하는 방법을 제공하는 것이다.Accordingly, it is an object of the present invention to provide a method for producing high purity 1,4-sorbitan.
본 발명의 다른 목적은 고순도 1,4-솔비탄으로 Span을 합성, 농업용 필름의 품질을 향상시키는 것이다.Another object of the present invention is to synthesize Span with high purity 1,4-sorbitan to improve the quality of agricultural films.
상기 본 발명의 목적은, 솔비톨로부터 p-툴루엔술폰산, H3PO2로부터 선택되는 하나 이상의 산촉매를 0.1-2중량% 부가하여, 반응온도 110-135℃에서, 40 내지 120torr의 압력으로 1 내지 20 시간 반응시키는 것으로 구성되는 1,4-솔비탄의 제조방법에 의해 달성된다.The object of the present invention is to add 0.1-2% by weight of at least one acid catalyst selected from sorbitol with p-toluenesulfonic acid and H3 PO2 , at a reaction temperature of 110-135 ° C. at a pressure of 40-120 torr. It is achieved by the method for producing 1,4-sorbitan consisting of reacting for 20 hours.
온도조건은 135℃ 이상에서는 반응속도는 빠르지만 제품의 탄화를 촉진시켜 전반적인 색상에 나쁜 영향을 끼치게 되고 110℃ 이하에서는 반응이 잘 일어나지 않으므로 110-135℃, 특히 110-120℃가 바람직하다.The temperature is faster than 135 ℃ reaction rate is fast but promotes the carbonization of the product has a bad effect on the overall color and less than 110 ℃ 110-135 ℃, especially 110-120 ℃ is preferable because the reaction does not occur well.
압력은 낮을수록 반응온도를 떨어뜨려 제품의 품질을 향상시키기는 하나, 반응속도가 느려지는 문제가 있으므로 40 내지 120torr가 바람직하다.The lower the pressure, the lower the reaction temperature to improve the quality of the product, but the reaction rate is slow, so 40 to 120 torr is preferable.
본 발명의 제조방법에 의해 제조된 1,4-솔비탄의 순도는 85% 이상이고, 수 율은 90% 이상이다.Purity of 1,4-sorbitan prepared by the production method of the present invention is 85% or more, the yield is 90% or more.
이하 실시예에 의해 본 발명을 보다 상세하게 설명한다.The present invention will be described in more detail with reference to the following Examples.
실시예 1Example 1
솔비톨 1kg을 4구 플라스크에 넣고 약 100℃까지 승온시켰다. 용융이 완료된 후 p-툴루엔술폰산, H3PO2혼합촉매를 0.2% 첨가하였다. 온도를 125℃로 승온시키고 진공을 걸어 압력을 120torr로 조절하여 반응시켰다. 그 결과를 도 1에 도시하였다.1 kg of sorbitol was placed in a four neck flask and heated to about 100 ° C. After melting was complete, 0.2% of a p-toluenesulfonic acid and H3 PO2 mixed catalyst was added. The temperature was raised to 125 ° C. and vacuum was applied to adjust the pressure to 120 torr. The results are shown in FIG.
순도 85%이상의 1,4-솔비탄을 얻었으며, 색상 역시 매우 안정하였다.Purity 1,4- sorbitan of more than 85% was obtained, the color was also very stable.
실시예 2Example 2
솔비톨 6kg을 SUS 304 재질로 제작된 파일롯 장치에 넣고 약 100℃까지 승온시켰다. 용융이 완료된 후 p-툴루엔술폰산, H3PO2혼합촉매를 0.2% 첨가하였다. 온도를 123℃로 승온시키고 진공을 걸어 압력을 110torr로 조절하여 반응시켰다. 그 결과를 도 2에 도시하였다.6 kg of sorbitol was placed in a pilot device made of SUS 304 and heated to about 100 ° C. After melting was complete, 0.2% of a p-toluenesulfonic acid and H3 PO2 mixed catalyst was added. The temperature was raised to 123 ° C. and vacuum was applied to adjust the pressure to 110 torr. The results are shown in FIG.
반응은 5시간 전후가 가장 양호한 반응진행상태를 보였다. 순도 85%이상의 1,4-솔비탄을 얻었으며, 색상 역시 매우 안정하였다.The reaction was best after 5 hours. Purity 1,4- sorbitan of more than 85% was obtained, the color was also very stable.
실시예 3Example 3
솔비톨 60kg을 SUS 304 재질로 제작된 파일롯 장치에 넣고 약 100℃까지 승온시켰다. 용융이 완료된 후 p-툴루엔술폰산, H3PO2혼합촉매를 0.2% 첨가하였다. 온도를 125℃로 승온시키고 진공을 걸어 압력을 40torr로 조절하여 반응시켰다. 그 결과를 도 3에 도시하였다.60 kg of sorbitol was placed in a pilot device made of SUS 304 and heated to about 100 ° C. After melting was complete, 0.2% of a p-toluenesulfonic acid and H3 PO2 mixed catalyst was added. The temperature was raised to 125 ° C. and vacuum was applied to adjust the pressure to 40 torr. The results are shown in FIG.
반응물 용량이 실시예 2에 비해 10배나 커진데 비해 반응속도는 별 차이가 없다. 이것은 70torr 정도 더 감압상태에서 반응시킨 결과이다. 순도와 색상 모두 양호하였다.The reaction rate is 10 times larger than that of Example 2, but the reaction rate is not much different. This is the result of the reaction under reduced pressure about 70torr. Both purity and color were good.
실시예 4Example 4
솔비톨 1500kg을 SUS 316L 재질로 제작된 플랜트 장치에 넣고 약 100℃까지 승온시켰다. 용융이 완료된 후 p-툴루엔술폰산, H3PO2혼합촉매를 0.2% 첨가하였다. 온도를 115℃로 승온시키고 진공을 걸어 압력을 45torr로 조절하여 반응시켰다. 그 결과를 도 4 및 도 5에 도시하였다.1500 kg of sorbitol was placed in a plant device made of SUS 316L and heated up to about 100 ° C. After melting was complete, 0.2% of a p-toluenesulfonic acid and H3 PO2 mixed catalyst was added. The temperature was raised to 115 ° C. and vacuum was applied to adjust the pressure to 45 torr. The results are shown in FIGS. 4 and 5.
수율은 90.2%, 순도는 87.65%였고 색상도 가장 양호하였다.The yield was 90.2%, purity was 87.65%, and color was the best.
일본 중앙화성의 시판제품과의 품질을 비교한 결과를 하기 표 1에 게시하였다.The results of comparing the quality with the commercially available products of Central Japan of Japan are published in Table 1 below.
표1Table 1
비교예 1Comparative Example 1
실시예 1과 동일한 반응을 진행하되 온도 및 압력조건을 145℃, 460torr로 하여 반응시켰다. 그 결과를 도 6 및 도 7에 게시하였다.The reaction was carried out in the same manner as in Example 1, but the reaction was performed at 145 ° C. and 460 torr. The results are posted in FIGS. 6 and 7.
순도 및 수율은 우수하나, 색상이 도 7에 나타난 것처럼 갈색으로 문제가 있었다.Purity and yield were good, but there was a problem with the color brown as shown in FIG.
상기 본 발명의 제조 방법에 따라 현재까지 시판되는 제품보다 고순도이고 외관도 우수한 1,4-솔비탄을 제조하게 되었다. 따라서, 고순도의 span 제조 또한 가능하게 되어 고품질의 농업용 필름을 제공할 수 있다.According to the manufacturing method of the present invention, it is possible to produce 1,4-sorbitan having a higher purity and better appearance than commercially available products. Therefore, high-purity span production is also possible to provide a high quality agricultural film.
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| CN103483347A (en)* | 2012-06-13 | 2014-01-01 | 第一毛织株式会社 | Crude reaction product comprising dianhydro sugar alcohol and method for preparing the same |
| US9100743B2 (en) | 2013-03-15 | 2015-08-04 | Vocollect, Inc. | Method and system for power delivery to a headset |
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| CN103483347A (en)* | 2012-06-13 | 2014-01-01 | 第一毛织株式会社 | Crude reaction product comprising dianhydro sugar alcohol and method for preparing the same |
| US9100743B2 (en) | 2013-03-15 | 2015-08-04 | Vocollect, Inc. | Method and system for power delivery to a headset |
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