KR20150064499A - A Method for Preparation of Solketal - Google Patents
A Method for Preparation of Solketal Download PDFInfo
- Publication number
- KR20150064499A KR20150064499A KR1020130149301A KR20130149301A KR20150064499A KR 20150064499 A KR20150064499 A KR 20150064499A KR 1020130149301 A KR1020130149301 A KR 1020130149301A KR 20130149301 A KR20130149301 A KR 20130149301A KR 20150064499 A KR20150064499 A KR 20150064499A
- Authority
- KR
- South Korea
- Prior art keywords
- solketal
- glycerol
- comparative example
- yield
- acetone
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings 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
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
본 발명은 솔케탈의 제조방법에 관한 것으로서, 보다 상세하게는 아세톤을 이용하여 글리세롤로부터 솔케탈을 제조하는 제조방법에 관한 것이다.The present invention relates to a method for producing a solketal, and more particularly, to a method for producing a solketal from glycerol using acetone.
솔케탈은 (2,2-Dimethyl-1,3-dioxolan-4-yl) methanol로 표시되는 1,3-디옥소란-4-메탄올 화합물로서, 의약, 농약 등의 합성 중간체로 다양하게 응용되고 있다. Solketal is a 1,3-dioxolane-4-methanol compound represented by (2,2-Dimethyl-1,3-dioxolan-4-yl) methanol and is widely applied as a synthetic intermediate such as medicines and agricultural chemicals have.
이러한 솔케탈의 제조방법으로서, 종래에는 Comparison of glycerol ketals, glycerol acetates and branched alcohol-derived fatty esters as cold-flow improvers for palm biodiesel; Fuel 108, 2013, p709-714 에서와 같이, p-toluene sulfonic acid와 같은 고가의 산 촉매를 이용하여 솔케탈을 합성하고 있다.As a method for producing such a sorbitol, there has heretofore been used a composition of glycerol ketals, glycerol acetates and branched alcohol-derived fatty esters as cold-flow improvers for palm biodiesel; As in Fuel 108, 2013, p. 709-714, salkatals are synthesized using expensive acid catalysts such as p-toluene sulfonic acid.
그러나, 종래의 방법에 의하면, 사용되는 산 촉매의 가격이 너무 비싸서, 경제성이 떨어지는 등의 문제가 많이 발생하였다.However, according to the conventional method, the cost of the acid catalyst to be used is too high, resulting in a problem of poor economical efficiency.
따라서, 일반적으로 사용되는 저렴한 산 촉매를 사용하면서도 특수한 합성 조건을 사용하여 수율을 크게 높일 수 있는, 새로운 솔케탈의 합성방법에 대한 연구가 필요한 실정이다.
Therefore, it is necessary to study the synthesis method of a novel sorbitol which can increase the yield by using special synthesis conditions while using a generally used inexpensive acid catalyst.
상기와 같은 종래기술의 문제점을 해결하고자, In order to solve the above problems of the prior art,
본 발명은 저렴한 산 촉매를 사용하면서도 특수한 합성 조건을 사용하여 수율을 크게 높일 수 있는, 새로운 솔케탈의 제조방법을 제공하는 것을 목적으로 한다.
It is an object of the present invention to provide a novel method for producing a sourcetal using a cheap acid catalyst, which can greatly increase the yield by using special synthesis conditions.
상기의 목적을 달성하기 위하여, In order to achieve the above object,
본 발명은 pKa 값이 -3 이하인 산 촉매 하에서, 글리세롤과 아세톤을 반응시켜여, 솔케탈을 제조하는 솔케탈의 제조방법을 제공한다.
The present invention provides a method for producing a solketal by reacting glycerol with acetone under an acid catalyst having a pKa value of not more than -3.
또한, 본 발명은 상기 제조방법에 의하여 제조된 솔케탈을 제공한다.
In addition, the present invention provides a solketal produced by the above-mentioned production method.
본 발명의 솔케탈의 제조방법에 따르면, According to the method for producing a socetal of the present invention,
저렴한 산 촉매를 사용하면서도 특수한 합성 조건을 사용하여 수율을 크게 높일 수 있다는 장점이 있다.It is advantageous in that the yield can be greatly increased by using a special synthesis condition while using an inexpensive acid catalyst.
이하 본 발명의 솔케탈의 제조방법 및 상기 제조방법에 의하여 제조된 솔케탈에 대하여 상세하게 설명한다.
Hereinafter, the method for producing the sorketal of the present invention and the solketal prepared by the method will be described in detail.
본 발명은 기존과 같이 p-toluene sulfonic acid와 같은 고가의 산 촉매 사용하여 솔케탈을 제조하는 것이 아니라, 저가의 산 촉매를 사용하여 글리세롤과 아세톤을 반응시켜 솔케탈을 제조하는 방법에 관한 것이다. 따라서, 솔케탈의 제조 공정이 기존에 비해 적은 비용으로도 솔케탈의 수율을 향상시킬 수 있다.
The present invention relates to a method for producing a sol-gel by reacting glycerol with acetone using a low-cost acid catalyst, instead of preparing a sol-gel using an expensive acid catalyst such as p-toluene sulfonic acid. Therefore, the manufacturing process of the socetal can improve the yield of the socetal with less cost than the conventional process.
이를 위하여, 본 발명의 솔케탈의 제조방법은 하기의 반응식 1과 같이, pKa 값이 -3 이하인 산 촉매 하에서, 글리세롤과 아세톤을 반응시켜, 솔케탈, 즉 (2,2-Dimethyl-1,3-dioxolan-4-yl) methanol을 제조한다.To this end, the process for preparing a sorbitol of the present invention comprises reacting glycerol with acetone under the presence of an acid catalyst having a pKa value of not more than -3 as shown in Reaction Scheme 1 below to obtain a sorbitan, ie, (2,2-Dimethyl- dioxolan-4-yl) methanol.
[반응식 1][Reaction Scheme 1]
상기 반응식 1과 같이, 본 발명의 솔케탈 제조방법에 의하여 글리세롤과 아세톤을 반응시키면, (2,2-Dimethyl-1,3-dioxolan-4-yl) methanol과 2,2-Dimethyl-1,3-dioxan-5-ol이 생성된다. 본 발명의 솔케탈 제조방법은 상기 반응식 1에서 생성되는 솔케탈, 즉 (2,2-Dimethyl-1,3-dioxolan-4-yl) methanol의 선택도 및 최종 수율을 향상시키기 위하여, 다음과 같은 특징을 갖는다.
As shown in Scheme 1, when glycerol and acetone are reacted with each other according to the production method of the present invention, 2,2-Dimethyl-1,3-dioxolan-4-yl methanol and 2,2- -dioxan-5-ol. < / RTI > In order to improve the selectivity and final yield of the (2, 2-dimethyl-1,3-dioxolan-4-yl) methanol produced in the above reaction scheme 1, the sol- .
본 발명의 솔케탈의 제조방법에 있어서, 상기 글리세롤은 솔케탈 제조에 사용 가능한 것이라면, 통상의 구입 가능한 것을 특별한 제한 없이 사용할 수 있으며, 바람직하게는 순도 60 내지 99.5%의 글리세롤을 사용할 수 있다.
In the method for producing the sorbitol of the present invention, the glycerol can be used without any particular limitation, and glycerol having a purity of 60 to 99.5% can be used.
본 발명의 솔케탈의 제조방법에 있어서, 아세톤은 글리세롤 반응에 사용하는 것이라면 통상의 구입 가능한 것을 특별한 제한 없이 사용할 수 있으며, 바람직하게는 순도 40 내지 99.5%의 아세톤을 사용할 수 있다. 본 발명에 있어서, 상기 아세톤은 글리세롤을 기준으로 3 내지 15 당량비로 투입하여 사용할 수 있다. 상기 아세톤이 3 당량비 미만으로 사용되면 글리세롤의 전환률 및 솔케탈의 선택도가 떨어질 수 있고, 15 당량비를 초과하여 사용하더라고, 추가에 따른 특별한 효과의 상승이 없다.
In the production method of the present invention, acetone is not particularly limited as long as it is used for glycerol reaction, and acetone having a purity of 40 to 99.5% can be used. In the present invention, acetone may be used in an amount of 3 to 15 equivalents based on glycerol. If the acetone is used in an amount less than 3 equivalents, the conversion of glycerol and the selectivity of the sorbitol may be lowered, and even if the acetone is used in an amount exceeding 15 equivalents, there is no increase in the specific effect.
본 발명의 솔케탈의 제조방법에 있어서, 상기 Ka 값이 -3 이하인 산 촉매는, pKa 값이 -3 이하인 것이라면 통상의 구입 가능한 것을 특별한 제한 없이 사용할 수 있으나, 바람직하게는 저가의 HCl 또는 H2SO4를 사용할 수 있다.In the method for producing a sorbitan according to the present invention, the acid catalyst having a Ka value of -3 or less can be used without any particular limitation if it has a pKa value of -3 or less, but it is preferably an inexpensive HCl or H 2 SO 4 can be used.
상기 pKa 값이 -3 이하인 산 촉매는 글리세롤을 기준으로 0.001 내지 0.03 당량비로 투입하여 촉매로 사용할 수 있다. 상기 pKa 값이 -3 이하인 산 촉매가 상기 당량비에서 사용되면 촉매로서의 기능을 최적으로 수행할 수 있다.
The acid catalyst having a pKa value of -3 or less may be added in an amount of 0.001 to 0.03 equivalents based on glycerol and used as a catalyst. When the acid catalyst having the pKa value of -3 or less is used in the above-mentioned equivalent ratio, the function as a catalyst can be optimally performed.
본 발명의 솔케탈의 제조방법에 있어서, 상기 글리세롤과 아세톤의 반응은 10~50℃의 반응온도에서 수행할 수 있다. 상기 반응온도가 10℃ 미만이면 반응성이 떨어져 수율에 문제가 있고, 50℃ 초과이면 추가의 에너지 제공에 따라 경제성이 떨어지는 문제가 있다.
In the method for producing the sorbitol of the present invention, the reaction of glycerol with acetone may be carried out at a reaction temperature of 10 to 50 ° C. If the reaction temperature is lower than 10 ° C, the reactivity tends to be low to yield. If the reaction temperature is higher than 50 ° C, there is a problem that economical efficiency is deteriorated due to provision of additional energy.
본 발명은 상기의 제조방법에 의하여 제조된 솔케탈을 제공한다.The present invention provides a solketal produced by the above-mentioned production method.
상기의 제조방법에 의하여 제조된 본 발명의 솔케탈은 솔케탈의 수율이 98% 이상, 바람직하게는 솔케탈의 수율이 99% 이상이기 때문에, 경제성이 뛰어나다.
The sol-gel of the present invention produced by the above-mentioned production method is excellent in economical efficiency because the yield of the sol-gel process is 98% or more, and the yield of the sol-gel process is preferably 99% or more.
이하 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변경 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.
실시예Example
솔케탈의Sorbetal
제조 Produce
[실시예 1] 플라스크 반응기에 글리세롤 9.21g (0.10 mol), 아세톤 29.0 0g (0.50 mol, 5 eq), 황산(pKa 값: -3.0) 0.098g (0.001 mol, 0.015 eq)을 투입한 후, 25℃에서 15시간 동안 교반하여 솔케탈을 제조하였다.Example 1 Into a flask reactor were charged 9.21 g (0.10 mol) of glycerol, 29.0 g (0.50 mol, 5 eq) of acetone and 0.098 g (0.001 mol, 0.015 eq) of sulfuric acid (pKa value: RTI ID = 0.0 > C < / RTI > for 15 hours.
[실시예 2][Example 2]
아세톤을 58.0g (1.0 mol, 10 eq) 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 솔케탈을 제조하였다.Solketal was prepared in the same manner as in Example 1 except that 58.0 g (1.0 mol, 10 eq) of acetone was used.
[실시예 3][Example 3]
황산을 0.020g (0.0002 mol, 0.003 eq) 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 솔케탈을 제조하였다.(0.0002 mol, 0.003 eq) of sulfuric acid was used as the solvent.
[실시예 4][Example 4]
황산 대신 염산을 동일한 당량비로 사용한 것을 제외하고는 실시예 3과 동일한 방법으로 솔케탈을 제조하였다.Solketal was prepared in the same manner as in Example 3 except that hydrochloric acid was used in the same equivalent ratio instead of sulfuric acid.
[비교예 1][Comparative Example 1]
아세톤을 5.80g (0.1 mol) 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 솔케탈을 제조하였다.Solketal was prepared in the same manner as in Example 1 except that 5.80 g (0.1 mol) of acetone was used.
[비교예 2][Comparative Example 2]
황산을 0.490g (0.005 mol, 0.05 eq) 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 솔케탈을 제조하였다.Solketal was prepared in the same manner as in Example 1, except that 0.490 g (0.005 mol, 0.05 eq) of sulfuric acid was used.
[비교예 3][Comparative Example 3]
황산을 1.455g (0.015 mol, 0.15 eq) 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 솔케탈을 제조하였다.(0.015 mol, 0.15 eq) of sulfuric acid was used as the solvent.
[비교예 4][Comparative Example 4]
황산 대신 MSA(methansulfornic acid)를 동일한 당량비로 사용한 것을 제외하고는 실시예 3과 동일한 방법으로 솔케탈을 제조하였다.Solketal was prepared in the same manner as in Example 3, except that MSA (methansulfornic acid) was used in the same equivalent ratio instead of sulfuric acid.
[비교예 5][Comparative Example 5]
황산 대신 질산을 동일한 당량비로 사용한 것을 제외하고는 실시예 3과 동일한 방법으로 솔케탈을 제조하였다.Solketal was prepared in the same manner as in Example 3 except that nitric acid was used in the same equivalent ratio instead of sulfuric acid.
[비교예 6][Comparative Example 6]
황산 대신 인산을 동일한 당량비로 사용한 것을 제외하고는 실시예 3과 동일한 방법으로 솔케탈을 제조하였다.Solketal was prepared in the same manner as in Example 3, except that phosphoric acid instead of sulfuric acid was used in the same equivalent ratio.
[비교예 7][Comparative Example 7]
황산 대신 포름산을 동일한 당량비로 사용한 것을 제외하고는 실시예 3과 동일한 방법으로 솔케탈을 제조하였다.Solketal was prepared in the same manner as in Example 3, except that formic acid was used in the same equivalent ratio instead of sulfuric acid.
[비교예 8][Comparative Example 8]
황산 대신 아세트산을 동일한 당량비로 사용한 것을 제외하고는 실시예 3과 동일한 방법으로 솔케탈을 제조하였다.
Solketal was prepared in the same manner as in Example 3, except that acetic acid instead of sulfuric acid was used in the same equivalent ratio.
상기 실시예 1 내지 실시예 4 및 비교예 1 내지 비교예 8의 반응 조건을 하기 표 1에 나타내었다.
The reaction conditions of Examples 1 to 4 and Comparative Examples 1 to 8 are shown in Table 1 below.
실험예Experimental Example
상기 실시예 및 비교예에서 제조한 솔케탈 반응물에 대하여, 가스 크로마토그래피(GC 6890N, agilent)를 이용하여, 미반응 글리세롤, 솔케탈을 GC area % 분석을 통하여 분석하였다. 글리세롤 전환율 및 솔케탈 선택도, 솔케탈 수율을 하기 식 1 내지 3을 이용하여 계산하였으며, 그 결과를 표 2에 나타내었다.The non-reacted glycerol and sorketal were analyzed by GC area% analysis using the gas chromatography (GC 6890N, agilent) for the sol-gel reaction products prepared in the examples and comparative examples. Glycerol conversion, solketal selectivity and solketal yield were calculated using the following formulas 1 to 3, and the results are shown in Table 2.
[식 1][Formula 1]
글리세롤 전환율 (conversion, %) = 100- 반응 후 글리세롤 GC area%Glycerol conversion (conversion,%) = 100- Glycerol GC area after reaction%
[식 2][Formula 2]
솔케탈 선택도 (selectivity, %) = 100ⅹ(생성된 솔케탈 GC area%)/(글리세롤 전환율)Solketal selectivity (selectivity,%) = 100 × (produced sol-ketal GC area%) / (glycerol conversion)
[식 3][Formula 3]
솔케탈 수율 (yield, %) = (글리세롤 전환율 ⅹ 솔케탈 선택도)/(100)
Solketal yield (yield,%) = (glycerol conversion x Solketal selectivity) / (100)
상기 표 2에서 나타낸 바와 같이, 본 발명의 솔케탈의 제조방법에 의하여 제조한 실시예 1 내지 실시예 4의 경우, 모두 98% 이상의 수율을 갖는 것으로 나타나, 비교예 1 내지 비교예 8의 경우에 비하여 수율이 높게 나타나는 것을 알 수 있었다. 비교예 중 일부의 솔케탈의 선택도가 높았으나, 글리세롤의 전환율이 낮아 전체적인 솔케탈의 수율은 실시예 1 내지 4보다 낮게 나타났다. 따라서, 본 발명의 실시예 1 내지 4의 제조 방법으로 솔케탈을 제조하는 경우, 저렴한 산 촉매를 사용하면서도 우수한 수율을 나타낸다는 것을 확인할 수 있었다.
As shown in Table 2, all of Examples 1 to 4 produced by the method of producing the present invention showed a yield of 98% or more, and compared to Comparative Examples 1 to 8 And the yield was high. The selectivity of some of the comparative examples was high, but the conversion rate of glycerol was low, and the yield of the overall sorbitan was lower than those of Examples 1 to 4. Therefore, it was confirmed that when producing the solketal by the production methods of Examples 1 to 4 of the present invention, an excellent yield was obtained while using an inexpensive acid catalyst.
Claims (8)
상기 pKa 값이 -3 이하인 산 촉매는 HCl 또는 H2SO4인 것을 특징으로 하는 솔케탈의 제조방법.The method according to claim 1,
Wherein the acid catalyst having the pKa value of -3 or less is HCl or H 2 SO 4 .
상기 반응은 10~50℃의 반응온도로 반응시키는 것을 특징으로 하는 솔케탈의 제조방법.The method according to claim 1,
Wherein the reaction is carried out at a reaction temperature of 10 to 50 ° C.
상기 아세톤은 글리세롤을 기준으로 3 내지 15 당량비로 투입하는 것을 특징으로 하는 솔케탈의 제조방법.The method according to claim 1,
Wherein the acetone is added in an amount of 3 to 15 equivalents based on glycerol.
상기 pKa 값이 -3 이하인 산 촉매는 글리세롤을 기준으로 0.001 내지 0.03 당량비로 첨가되는 것을 특징으로 하는 솔케탈의 제조방법.The method according to claim 1,
Wherein the acid catalyst having a pKa value of -3 or less is added in an amount of 0.001 to 0.03 equivalents based on glycerol.
상기 솔케탈의 수율이 98% 이상인 것을 특징으로 하는 솔케탈의 제조방법.The method according to claim 1,
Wherein the yield of the sorbent is 98% or more.
상기 솔케탈의 수율이 99% 이상인 것을 특징으로 하는 솔케탈의 제조방법.The method according to claim 1,
Wherein the yield of the sorbent is 99% or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130149301A KR101703159B1 (en) | 2013-12-03 | 2013-12-03 | A Method for Preparation of Solketal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130149301A KR101703159B1 (en) | 2013-12-03 | 2013-12-03 | A Method for Preparation of Solketal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20150064499A true KR20150064499A (en) | 2015-06-11 |
| KR101703159B1 KR101703159B1 (en) | 2017-02-06 |
Family
ID=53503045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020130149301A KR101703159B1 (en) | 2013-12-03 | 2013-12-03 | A Method for Preparation of Solketal |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101703159B1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020025154A (en) * | 2002-03-09 | 2002-04-03 | 김용래 | Method for preparing highly pure glyceryl monoester |
| JP2005514354A (en) * | 2001-11-13 | 2005-05-19 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Conversion of tetrahydroxybutane to tetrahydrofuran. |
-
2013
- 2013-12-03 KR KR1020130149301A patent/KR101703159B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005514354A (en) * | 2001-11-13 | 2005-05-19 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Conversion of tetrahydroxybutane to tetrahydrofuran. |
| KR20020025154A (en) * | 2002-03-09 | 2002-04-03 | 김용래 | Method for preparing highly pure glyceryl monoester |
Non-Patent Citations (3)
| Title |
|---|
| 10th Green Chemistry Conference. AN INTERNATIONAL EVENT Barcelona - Spain, 2013* * |
| Comparison of glycerol ketals, glycerol acetates and branched alcohol-derived fatty esters as cold-flow improvers for palm biodiesel; Fuel 108, 2013, p709-714 |
| Microporous and Mesoporous Materials 179 (2013) 182-190 * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101703159B1 (en) | 2017-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113372302A (en) | 2, 5-tetrahydrofuran dimethanol diacid ester and preparation method and application thereof | |
| KR101679717B1 (en) | A Method for Preparation of Allyl alcohol and the Allyl alcohol Prepared by the Same | |
| KR101703159B1 (en) | A Method for Preparation of Solketal | |
| KR101307559B1 (en) | Synthesis of glycerol carbonate using high active catalysts | |
| CN102531897B (en) | Method for preparing alpha-replacing malonic acid diacetoxyiodo derivative | |
| WO2005077874A1 (en) | Method for producing 2,7-dimethyl-octa-2,4,6-trienedial | |
| CN110894183A (en) | Alkyl levulinate and preparation method thereof | |
| KR101514379B1 (en) | Method for preparing 5-hydroxymethyl-2-furfural using acid catalyst under biomass-derived ethylene glycol-based solvent | |
| KR101559532B1 (en) | Method for preparing levulinic acid using solid acid catalyst under biomass-derived ethylene glycol-based solvent | |
| CN110878025B (en) | Method for reducing aromatic nitro compound into aromatic amine compound | |
| CN113979970A (en) | Preparation method of cationic epoxy resin 3, 4-epoxy cyclohexyl methyl-3 ',4' -epoxy cyclohexyl formate | |
| KR101709670B1 (en) | A Method for Preparation of Ester Compound which Improve the Yield by Using an Acetone | |
| KR102025601B1 (en) | A method for preparation of anhydrosugar alcohols usint a catalyst that is heteropoly aci salt substituted with ammonium | |
| KR101316608B1 (en) | Method for preparing glycerol carbonate using Zn catalysts and acid | |
| CN107522661B (en) | Preparation method of 2-mercapto-1-alkyl imidazole | |
| KR101293818B1 (en) | METHOD FOR PREPARING α, β-UNSATURATED ALDEHYDE | |
| CN109096240B (en) | Preparation method of macrolide precursor | |
| KR101634220B1 (en) | A Method for Preparation of Ester Compound and the Ester Compound manufactured by the Same | |
| CN110734373B (en) | Method for preparing perfluoro isobutyryl fluoride by reaction kettle liquid phase method | |
| KR20150131515A (en) | A Method for Preparation of Allyl Formate | |
| CN114874078B (en) | Synthesis method of propylene glycol phenyl ether with high isomer content | |
| CN113861014B (en) | Levulinic acid (ACA)13C, preparation method and application | |
| KR102071898B1 (en) | Method for preparing highly enantio-enriched gingerols | |
| CN108191732B (en) | Synthesis method of N-methylpyrrole | |
| CN110563568B (en) | Preparation method of trifluoroacetylacetone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| FPAY | Annual fee payment |
Payment date: 20200116 Year of fee payment: 4 |