KR20040061898A - Method for preparing of Diphenyl Carbonate - Google Patents
Method for preparing of Diphenyl Carbonate Download PDFInfo
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- KR20040061898A KR20040061898A KR1020020088200A KR20020088200A KR20040061898A KR 20040061898 A KR20040061898 A KR 20040061898A KR 1020020088200 A KR1020020088200 A KR 1020020088200A KR 20020088200 A KR20020088200 A KR 20020088200A KR 20040061898 A KR20040061898 A KR 20040061898A
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- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
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- C—CHEMISTRY; METALLURGY
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- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
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Abstract
Description
본 발명은 디페닐카보네이트의 제조방법에 관한 것으로서, 더욱 상세하게는 디메틸카보네이트와 페놀을 촉매 존재 하에서 반응시켜 디페닐카보네이트를 제조하는 방법을 수행함에 있어, 상기 반응 촉매로는 다음 화학식 1로 표시되는 바와 같이, 황산유도체를 리간드로 가진 유기주석화합물을 사용하여 종래 일반적 촉매 사용방법에 비해 넓은 온도범위에서 그리고 단시간 내에 높은 수율로 디페닐카보네이트를 제조할 뿐만 아니라 통상의 부반응물의 생성을 최소화하는 디페닐카보네이트의 제조방법에 관한 것이다.The present invention relates to a method for preparing diphenyl carbonate, and more particularly, in the process for preparing diphenyl carbonate by reacting dimethyl carbonate and phenol in the presence of a catalyst, the reaction catalyst is represented by the following formula (1) As described above, the organotin compound having a sulfuric acid derivative as a ligand is used to prepare diphenyl carbonate at a high yield in a wide temperature range and within a short time as compared with a conventional method of using a catalyst, and to minimize the production of conventional side reactions. A method for producing phenyl carbonate.
[화학식 1][Formula 1]
상기 화학식에서, R은 C1∼C6의 알킬기 또는 페닐기(C6H5-) 이고, R1은 할로겐 원자,C1∼C6의 알킬기, C1∼C6의 할로 알킬기, 또는 톨릴기(CH3C6H5-) 이고, n은 1 또는 2 이다.In the above formula, R is C 1 -C 6 alkyl group or phenyl group (C 6 H 5- ), R 1 is a halogen atom, C 1 -C 6 alkyl group, C 1 -C 6 halo alkyl group, or tolyl group (CH 3 C 6 H 5- ) and n is 1 or 2.
폴리카보네이트는 내충격성과 같은 우수한 기계적 성질, 우수한 내열성 및 투명성 때문에 여러 용도로 사용되고 있다. 상기 폴리카보네이트는 종래 포스겐과 비스페놀-A를 계면 중합시켜 제조되어 왔으나 포스겐의 맹독성, HCl과 같은 부산물의 생성, 계면 중합 시 과량의 메틸렌클로라이드의 사용, 그리고 세척과정에서 발생되는 다량의 폐수문제로 인하여 점차 포스겐 대신 디페닐카보네이트를 원료로 사용하는 방법이 개발되고 있다.Polycarbonates are used in many applications because of their excellent mechanical properties such as impact resistance, good heat resistance and transparency. The polycarbonate has been prepared by interfacial polymerization of phosgene and bisphenol-A, but due to the toxic toxicity of phosgene, the generation of by-products such as HCl, the use of excess methylene chloride in the interfacial polymerization, and the large amount of wastewater generated in the washing process. Increasingly, a method of using diphenyl carbonate as a raw material instead of phosgene has been developed.
일반적으로 디페닐카보네이트는 다음의 반응식 1에서 보여지는 바와 같이, 디메틸카보네이트(DMC)와 페놀을 반응시켜 메틸페닐카보네이트를 거치는 2 단계 평형반응으로 제조될 수 있으나 상기 평형이 반응물에 치우쳐 있고 반응속도가 느리기 때문에 디페닐카보네이트의 수율을 향상시키기 위해서 다양한 촉매계가 제안되었다.In general, diphenyl carbonate can be prepared in a two-step equilibrium reaction of methyl carbonate by reacting dimethyl carbonate (DMC) with phenol, as shown in Scheme 1 below, but the equilibrium is biased to the reactant and the reaction rate is slow. Therefore, various catalyst systems have been proposed to improve the yield of diphenyl carbonate.
상기 다양한 촉매계를 사용하여 디페닐카보네이트를 제조하는 방법의 예로는, 높은 표면적을 갖는 산화티타늄을 촉매로 사용하는 방법[미국특허 제 5,354,923호]과 각각 활성탄에 지지된 티타늄[일본공개특허 평8-231471호]이나 실리카에 지지된 몰리브덴을 촉매로 사용하는 법[일본공개특허 평8-231472호] 등이 있다. 상기 촉매는 모두 불균일계로서 반응 후 반응물과 촉매를 분리하기 쉽다는 이점이 있으나, 160 ∼ 200 ℃의 온도에서 3 ∼ 5시간의 조건에서 반응시켰을 때 생성물인 디페닐카보네이트의 수율이 1 ∼ 3 % 정도로 낮은 문제가 있다.Examples of a method for producing diphenyl carbonate using the various catalyst systems include a method using titanium oxide having a high surface area as a catalyst [US Pat. No. 5,354,923] and titanium supported on activated carbon, respectively. 231471] or a method using molybdenum supported on silica as a catalyst (Japanese Patent Laid-Open No. 8-231472). All of the catalysts are heterogeneous and have an advantage in that the reactants and the catalysts are easily separated after the reaction, but the yield of diphenyl carbonate as a product is 1 to 3% when the reaction is carried out at a temperature of 160 to 200 ° C. for 3 to 5 hours. There is a problem as low as that.
또한 PbO2촉매 존재하에서 메틸페닐카보네이트를 불균등화 반응(disproportionation) 시켜 190 ℃의 온도에서 50 % 정도의 수율로 디페닐카보네이트를 제조하는 방법[미국특허 제 5,166,393호]이 있다. 그러나 원료인 메틸페닐카보네이트가 고가이고 제조방법이 마땅하지 않아 경제성이 떨어지는 단점이 있다.In addition, there is a method for producing diphenyl carbonate in a yield of about 50% at a temperature of 190 ℃ by disproportionation of methylphenyl carbonate in the presence of a PbO 2 catalyst (US Pat. No. 5,166,393). However, there is a disadvantage in that the economic efficiency of the methylphenyl carbonate is expensive and the manufacturing method is not suitable.
또 다른 촉매 사용의 방법으로, 디메틸카보네이트와 페놀의 에스테르 교환반응에 각각 Fe(OPh)3나 Ti(OPh)4와 같은 촉매를 이용[일본공개특허 평7-033714호, 미국특허 제 4,182,726호]하는 방법도 있으나, 디페닐카보네이트의 전구체인 메틸페닐카보네이트의 제조에 관해서만 언급하고 있을 뿐만 아니라 그 수율도 10 ∼ 30 % 정도로 낮다.As another method of using a catalyst, a catalyst such as Fe (OPh) 3 or Ti (OPh) 4 is used for the transesterification reaction of dimethyl carbonate and phenol, respectively [JP-A-7-033714, U.S. Patent 4,182,726]. There is also a method of making, but not only mentions the production of methylphenyl carbonate, which is a precursor of diphenyl carbonate, but also a low yield of about 10 to 30%.
또한 여러 가지 유기티타늄과 유기주석을 이용하여 디메틸카보네이트로부터 디페닐카보네이트를 제조하는 방법[미국특허 제 4,410,464호]이 있다. 상기제조법은 에스테르 교환반응을 통하여 메틸페닐카보네이트를 먼저 제조하고 이를 분리한 후 불균등화 반응을 통하여 디페닐카보네이트를 제조하는 방법을 제안하고 있으나 별개의 2 단계 반응을 거쳐야 하므로 분리 및 장치비가 많이 드는 단점이 있다.In addition, there is a method for preparing diphenyl carbonate from dimethyl carbonate using various organotitanium and organotin (US Patent No. 4,410,464). The above manufacturing method proposes a method of preparing methylphenyl carbonate first through a transesterification reaction and then separating it, and then preparing a diphenyl carbonate through disproportionation reaction, but it requires a separate two-step reaction, which leads to a high separation and device cost. have.
상기 일반적 촉매 존재하에서 디페닐카보네이트의 제조방법을 수행하게 되면 생성물의 수율이 낮고 부반응으로 인한 부산물이 생성되는 등의 문제가 있는 바, 이를 해결하기 위하여 반응 촉매로서는 황산유도체를 리간드로 가진 유기주석화합물을 선택 사용하므로써 반응속도를 크게 향상시켜 단시간내에 반응을 완결시키고, 부반응을 최대한 억제하여 목적물에 대한 수율을 크게 향상시키는 디페닐카보네이트의 새로운 제조방법을 개발함으로써 본 발명을 완성하게 되었다.When the production method of diphenyl carbonate is carried out in the presence of the general catalyst, there is a problem that the yield of the product is low and by-products are generated due to side reactions. To solve this problem, an organic tin compound having a sulfate derivative as a ligand is used as a reaction catalyst. The present invention has been completed by developing a new method for producing diphenyl carbonate, which greatly improves the reaction rate by shortening the reaction by shortly using, and suppressing side reactions as much as possible, thereby greatly improving the yield of the target product.
본 발명은 디메틸카보네이트와 페놀을 촉매 존재 하에서 반응하여 디페닐카보네이트를 제조하는 방법에 있어서, 상기 반응 촉매로는 다음 화학식 1로 표시되는 황산유도체를 리간드로 가진 유기주석산화물을 사용하는 것을 그 특징으로 한다.The present invention provides a method for producing diphenyl carbonate by reacting dimethyl carbonate and phenol in the presence of a catalyst, wherein the reaction catalyst is characterized in that an organic tin oxide having a sulfate derivative represented by the following formula (1) as a ligand do.
[화학식 1][Formula 1]
상기 화학식에서, R은 C1∼C6의 알킬기 또는 페닐기(C6H5-) 이고, R1은 할로겐 원자, C1∼C6의 알킬기, C1∼C6의 할로 알킬기, 또는 톨릴기(CH3C6H5-) 이고, n은 1 또는 2 이다.In the above formula, R is a C 1 -C 6 alkyl group or a phenyl group (C 6 H 5- ), R 1 is a halogen atom, C 1 -C 6 alkyl group, C 1 -C 6 halo alkyl group, or tolyl group (CH 3 C 6 H 5- ) and n is 1 or 2.
이와 같은 본 발명을 상세히 설명하면 다음과 같다.The present invention will be described in detail as follows.
본 발명은 황산유도체를 리간드로 가진 유기주석화합물의 촉매 존재하에서, 디메틸카보네이트와 페놀을 반응시키는 것을 특징으로 하는 것으로, 기존의 촉매를 사용하는 방법보다 단시간 내에 넓은 온도범위에서 디페닐카보네이트의 생성율을 크게 향상시키며, 부반응을 억제하여 경제적으로 유용한 디페닐카보네이트의 제조방법에 관한 것이다.The present invention is characterized in that the reaction of dimethyl carbonate and phenol in the presence of a catalyst of an organotin compound having a sulfate derivative as a ligand, the production rate of diphenyl carbonate in a wider temperature range within a shorter time than the method using a conventional catalyst The present invention relates to a method for producing diphenyl carbonate which is greatly improved and suppresses side reactions and is economically useful.
본 발명에서 디페닐카보네이트를 제조하는 반응에 사용되는 촉매는 상기 화학식 1로 표시되는 황산유도체를 리간드로 가진 유기주석화합물로, 반응물인 디메틸카보네이트에 대하여 0.1 ∼ 10 몰% 범위내에서 사용한다. 촉매의 사용량이 0.1 몰% 미만으로 소량이면 반응속도가 너무 느리고, 10 몰%를 초과하면 한계선 이상으로 반응속도와 선택성이 향상되지 않는 문제점이 있다. 상기 화학식 1로 표시되는 촉매를 구체적으로 예시하면, Bu2Sn(OH)(OSO2Me), (CH3)2Sn(OH)(OSO2CF3),(C2H5)2Sn(OH)(OSO2C6H5CH3), (C3H7)2Sn(OH)(OSO2F), (C5H12)2Sn(OH)(OSO2Cl), (C6H14)2Sn(OH)(OSO2CH3), Ph2Sn(OH)(OSO2CF3), [Ph2Sn(OSO2CF3)]2O, [(CH3)2Sn(OSO2CF3)]2O, [(C2H5)2Sn(OSO2C6H5CH3)]2O, [(C3H7)2Sn(OH)(OSO2F)]2O, [(C5H12)2Sn(OH)(OSO2Cl)]2O, [(C6H14)2Sn(OH)(OSO2CH3)]2O, [Ph2Sn(OH)(OSO2CF3)]2O 등이 포함되며, 이들 촉매는 1종 이상이 사용될 수 있다.The catalyst used in the reaction for preparing diphenyl carbonate in the present invention is an organotin compound having a sulfuric acid derivative represented by Chemical Formula 1 as a ligand, and is used within the range of 0.1 to 10 mol% based on the reactant dimethyl carbonate. If the amount of the catalyst is less than 0.1 mol%, the reaction rate is too slow, and if it exceeds 10 mol%, there is a problem that the reaction rate and selectivity are not improved beyond the limit line. Specific examples of the catalyst represented by Chemical Formula 1 include Bu 2 Sn (OH) (OSO 2 Me), (CH 3 ) 2 Sn (OH) (OSO 2 CF 3 ), (C 2 H 5 ) 2 Sn ( OH) (OSO 2 C 6 H 5 CH 3 ), (C 3 H 7 ) 2 Sn (OH) (OSO 2 F), (C 5 H 12 ) 2 Sn (OH) (OSO 2 Cl), (C 6 H 14 ) 2 Sn (OH) (OSO 2 CH 3 ), Ph 2 Sn (OH) (OSO 2 CF 3 ), [Ph 2 Sn (OSO 2 CF 3 )] 2 O, [(CH 3 ) 2 Sn ( OSO 2 CF 3 )] 2 O, [(C 2 H 5 ) 2 Sn (OSO 2 C 6 H 5 CH 3 )] 2 O, [(C 3 H 7 ) 2 Sn (OH) (OSO 2 F)] 2 O, [(C 5 H 12 ) 2 Sn (OH) (OSO 2 Cl)] 2 O, [(C 6 H 14 ) 2 Sn (OH) (OSO 2 CH 3 )] 2 O, [Ph 2 Sn (OH) (OSO 2 CF 3 )] 2 O and the like, and one or more of these catalysts may be used.
본 발명에서 사용된 촉매의 역할은 반응의 활성화 에너지를 낮춤으로써 반응을 용이하게 일어날 수 있게 해주는 것이다. 즉, 반응시에 황산 유도체가 먼저 유기주석 화합물과 반응하여 주석의 전자 밀도를 감소시키므로써 주석이 더 강한 루이스산(lewis acidic)의 성질을 갖게 되고, 반응물인 페놀 및 디메틸카보네이트는 촉매에 더 쉽게 배위된다. 결과적으로 반응이 더 용이하게 일어나므로써 목적으로 하는 생성물의 수율을 높이며 또한 부반응의 생성도 억제하는 효과를 나타낸다.The role of the catalyst used in the present invention is to make the reaction easy by lowering the activation energy of the reaction. That is, during the reaction, the sulfuric acid derivative first reacts with the organotin compound to reduce the electron density of tin, thereby making tin have a stronger Lewis acidic property, and the reactants phenol and dimethyl carbonate are easier to catalyze. To be coordinated. As a result, the reaction occurs more easily, thereby increasing the yield of the desired product and suppressing the formation of side reactions.
또한 본 발명은 디메틸카보네이트와 페놀의 몰비([페놀]/[디메틸카보네이트])를 2 ∼ 20으로 조절하여 반응시키는 것에 기술구성상의 특징이 있는 것으로, 상기 반응식 1에서 보여지는 바와 같이 디메틸카보네이트 한 분자에 페놀 두 분자가 반응하여 디페닐카보네이트가 생성되므로 페놀의 양은 디메틸카보네이트 양에 대하여 적어도 2 몰비 이상이 되어야 한다. 그러나 상기 사용량이 2 ∼ 20 몰비의 범위에서는 증가하지만 20 몰비를 초과하면 반응물의 양에 관계없이 생성되는 디페닐카보네이의 증가량은 거의 일정하게 나타내었다.In addition, the present invention is characterized by the technical configuration in the reaction by adjusting the molar ratio ([phenol] / [dimethyl carbonate]) of dimethyl carbonate and phenol to 2 to 20, one molecule of dimethyl carbonate as shown in Scheme 1 Since two molecules of phenol react to form diphenyl carbonate, the amount of phenol should be at least 2 molar ratio based on the amount of dimethyl carbonate. However, the amount of use increased in the range of 2 to 20 molar ratio, but if the amount exceeds 20 molar ratio, the amount of diphenylcarbonei produced regardless of the amount of reactants was almost constant.
본 발명은 상기와 같이 디메틸카보네이트와 페놀의 반응물에 촉매로 황산유도체를 리간드로 가진 유기주석화합물을 사용하여 디페닐카보네이트를 제조하는 것으로, 상기 반응온도는 130 ∼ 250 ℃이며, 반응시간은 1 ∼ 24시간이다. 상기 반응온도가 130 ℃ 미만이면 반응속도가 느려지고, 250 ℃를 초과하는 고온에서는 반응물인 디메틸카보네이트가 분해되거나 목적 생성물 외에 부산물의 생성이 증가되어 선택성이 나빠지는 문제가 발생한다.The present invention is to prepare a diphenyl carbonate using an organotin compound having a sulfuric acid derivative as a ligand to the reactant of dimethyl carbonate and phenol as described above, the reaction temperature is 130 ~ 250 ℃, the reaction time is 1 ~ 24 hours. If the reaction temperature is less than 130 ℃ reaction rate is slow, at a high temperature of more than 250 ℃ dimethyl carbonate, which is a reactant, or the production of by-products in addition to the target product increases the problem that the selectivity worsens.
또한 상기 반응은 회분식 또는 연속식의 반응기를 이용하여 실시할 수 있다. 상기 반응기가 회분식인 경우 반응시 생성되는 메탄올은 반응기 윗쪽에 충진된 분자체(molecular sieve)층을 통과시켜 제거할 수 있다.The reaction can also be carried out using a batch or continuous reactor. When the reactor is a batch, methanol generated during the reaction may be removed by passing through a molecular sieve layer filled on the reactor.
본 발명은 황산유도체를 리간드로 가진 유기주석화합물을 촉매로 이용하여 디메틸카보네이트와 페놀을 상기와 같은 특정조건으로 반응을 실시하였고 그 결과 디페닐카보네이트의 수율을 향상시키고 부반응을 감소시켰다.In the present invention, the reaction was carried out using the organotin compound having a sulfate derivative as a catalyst as a catalyst for dimethyl carbonate and phenol under specific conditions as described above. As a result, the yield of diphenyl carbonate was improved and side reactions were reduced.
이하, 본 발명을 다음의 실시예에 의하여 더욱 상세하게 설명하겠는 바, 본 발명이 실시예에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, which are not intended to limit the present invention.
실시예 1Example 1
1 단계 : Bu2Sn(OH)(OSO2Me) 촉매제조Step 1: Manufacture Bu 2 Sn (OH) (OSO 2 Me) Catalyst
250 ml 플라스크에 디부틸틴옥사이드(2.48 g, 10 mmol)과 메탄설폰산(0.96g, 10 mmol)과 용매로 디클로로메탄(CH2Cl250 ml)를 혼합하여 실온에서 2시간 교반시켰다. 상기 교반 초기에는 뿌연 용액을 형성하다가 디부틸틴옥사이드와 메탄설폰산이 CH2Cl2에 시간이 지나면서 완전히 투명한 용액으로 바뀌었다. 상기 제조된 화합물에서 디클로로메탄(CH2Cl2)을 제거하고 진공 건조시켜 3.44 g의 흰색 파우더를 얻었다. 상기 제조된 파우더의 원소 분석 결과는 다음과 같다.In a 250 ml flask, dichloromethane (2.48 g, 10 mmol), methanesulfonic acid (0.96 g, 10 mmol), and dichloromethane (CH 2 Cl 2 50 ml) were mixed with a solvent and stirred at room temperature for 2 hours. At the beginning of the stirring, a cloudy solution was formed, and dibutyltin oxide and methanesulfonic acid were changed to a completely clear solution over time in CH 2 Cl 2 . Dichloromethane (CH 2 Cl 2 ) was removed from the compound prepared in vacuo to give 3.44 g of a white powder. Elemental analysis of the prepared powder is as follows.
측정값 (이론값)-C : 32.1 % (31.2 %), H : 6.43 % (6.38 %), S : 9.22 % (9.28 %)Measured value (theoretical value) -C: 32.1% (31.2%), H: 6.43% (6.38%), S: 9.22% (9.28%)
2 단계 : 디페닐카보네이트 제조Step 2: preparing diphenyl carbonate
100 ml의 고압 반응기에 디메틸카보네이트(3.6 g, 40 mmol)와 페놀(18.8 g, 200 mmol)을 벤젠(40 ml)에 용해시킨 후 상기 1 단계에서 제조한 황산유도체를 리간드로 가진 유기주석화합물 촉매(0.138 g, 0.4 mmol)를 첨가한다. 반응기 윗쪽에 장착된 실린더에 분자체(molecular sieve 4A) 30 g을 채우고, 반응기를 진공펌프와 연결하여 반응기 내부의 공기를 제거한다. 반응기의 온도를 10 ℃/min의 속도로 180 ℃까지 올린 후 3시간 반응시킨다. 반응 후 혼합물은 가스크로마토그래피를 이용하여 분석하여, 그 결과 메틸페닐카보네이트가 37.3 %, 디페닐카보네이트가 21.9 %의 수율로 생성된 것을 확인할 수 있었다.Organotin compound catalyst having a sulfuric acid derivative prepared in step 1 as a ligand after dissolving dimethyl carbonate (3.6 g, 40 mmol) and phenol (18.8 g, 200 mmol) in benzene (40 ml) in a 100 ml high pressure reactor. (0.138 g, 0.4 mmol) is added. A cylinder mounted on the top of the reactor is filled with 30 g of molecular sieve 4A, and the reactor is connected to a vacuum pump to remove air inside the reactor. The temperature of the reactor was raised to 180 ° C. at a rate of 10 ° C./min and reacted for 3 hours. After the reaction, the mixture was analyzed using gas chromatography. As a result, it was confirmed that methylphenyl carbonate was produced in a yield of 37.3% and diphenyl carbonate in 21.9%.
본 발명의 각 생성물의 수율은 다음 수학식 1과 같은 방법으로 계산하였다.The yield of each product of the present invention was calculated by the same method as in Equation 1.
실시예 2Example 2
상기 실시예 1과 같은 방법으로 제조하되, 여러 가지 유기주석산화물과 황산유도체를 반응시켜 제조한 촉매를 이용하여 실시하였다. 상기 제조된 혼합물을 가스크로마토그래피로 분석하여 다음 표 1에 나타내었다.Prepared in the same manner as in Example 1, using a catalyst prepared by reacting various organic tin oxide and sulfuric acid derivatives. The prepared mixture was analyzed by gas chromatography and shown in Table 1 below.
실시예 3Example 3
1 단계 : [Ph2Sn(OSO2CF3)]2O 촉매제조Step 1: Preparation of [Ph 2 Sn (OSO 2 CF 3 )] 2 O Catalyst
딘스탁(Dean Stark) 장치에 연결되어 있는 250 ml 플라스크에 디페닐틴옥사이드(2.89 g, 10 mmol)와 트리플루오로메탄설폰산(1.50 g, 10 mmol)를 용매인 톨루엔 100 ml에 넣어 혼합하였다. 상기 혼합물을 24시간 동안 반응 후 약 0.18 g의 생성물을 얻었다. 상기 제조된 화합물의 톨루엔을 제거하고 진공에서 건조시켜 약 4.29 g의 흰색 파우더를 얻었다. 상기 제조된 파우더의 원소 분석 결과는 다음과 같다.In a 250 ml flask connected to a Dean Stark apparatus, diphenyltin oxide (2.89 g, 10 mmol) and trifluoromethanesulfonic acid (1.50 g, 10 mmol) were added to 100 ml of toluene as a solvent and mixed. . The mixture was reacted for 24 hours, yielding about 0.18 g of product. Toluene of the prepared compound was removed and dried in vacuo to yield about 4.29 g of white powder. Elemental analysis of the prepared powder is as follows.
측정값 (이론값)-C : 37.2 % (36.3 %), H : 2.33 % (2.32 %), S : 7.48 % (7.44 %)Measured value (theoretical value) -C: 37.2% (36.3%), H: 2.33% (2.32%), S: 7.48% (7.44%)
2 단계 : 디페닐카보네이트 제조Step 2: preparing diphenyl carbonate
상기 1 단계와 동일한 방법으로 여러 가지 유기주석산화물과 황산유도체를 반응시켜 제조한 촉매를 실시예 1과 동일 방법으로 제조하였다. 상기 제조된 혼합물을 가스크로마토그래피로 분석하여 다음 표 2에 나타내었다.A catalyst prepared by reacting various organotin oxides and sulfate derivatives in the same manner as in step 1 was prepared in the same manner as in Example 1. The prepared mixture was analyzed by gas chromatography and shown in Table 2 below.
실시예 4Example 4
상기 실시예 1에서 제조한 Bu2Sn(OH)(OSO2CF3) 촉매를 동일한 방법으로 실시하되, 그 양을 변화시키며 제조하였다. 상기 제조된 혼합물을 가스크로마토그래피로 분석하여 다음 표 3에 나타내었다.Bu 2 Sn (OH) (OSO 2 CF 3 ) catalyst prepared in Example 1 was carried out in the same manner, but was prepared by changing the amount. The prepared mixture was analyzed by gas chromatography and shown in Table 3 below.
실시예 5Example 5
상기 실시예 1에서 제조한 [Bu2Sn(OSO2F)]2O 촉매를 동일한 방법으로 실시하되, 디메틸카보네이트에 대한 페놀의 몰비([페놀]/[디메틸카보네이트])를 변화시키면서 실시하였다. 상기 제조된 혼합물을 가스크로마토그래피로 분석하여 표 4에 나타내었다.[Bu 2 Sn (OSO 2 F)] 2 O catalyst prepared in Example 1 was carried out in the same manner, while changing the molar ratio ([phenol] / [dimethyl carbonate]) of phenol to dimethyl carbonate. The prepared mixture is shown in Table 4 by gas chromatography.
실시예 6Example 6
상기 실시예 1와 동일한 방법으로 Ph2Sn(OH)(OSO2CH3)촉매를 사용하여 디페닐카보네이트를 제조하되, 반응온도를 변화시키면서 실시하여 그 결과를 다음 표 5에 나타내었다.In the same manner as in Example 1 to prepare a diphenyl carbonate using a Ph 2 Sn (OH) (OSO 2 CH 3 ) catalyst, the reaction was carried out while changing the reaction temperature is shown in Table 5 below.
비교예Comparative example
상기 실시예 1과 동일 방법으로 제조하되, 촉매로 티타늄이소프로폭사이드(Ti[OCH(CH3)2]4)를 0.113 g (0.4 mmol)사용하여 수행하였다. 상기 제조된 화합물의 분석한 결과 디페닐카보네이트 15.3 %, 메틸페닐카보네이트 33.1 % 그리고 부산물로 메틸이소프로필카보네이트 2.2 %, 디이소프로필카보네이트 0.5 %가 생성됨을 확인하였다.Prepared in the same manner as in Example 1, but performed using 0.113 g (0.4 mmol) of titanium isopropoxide (Ti [OCH (CH 3 ) 2 ] 4 ) as a catalyst. As a result of analysis of the prepared compound, it was confirmed that 15.3% of diphenyl carbonate, 33.1% of methylphenyl carbonate, and 2.2% of methyl isopropyl carbonate and 0.5% of diisopropyl carbonate were produced as by-products.
상기 실시예 1 ∼ 6, 비교예에서 알 수 있듯이, 실시예가 비교예에 비하여 목적으로 하는 디페닐카보네이트의 수율이 4배 이상 향상되었으며, 반응 중간체인 메틸카보네이트의 수율도 향상되었다.As can be seen from the above Examples 1 to 6 and Comparative Examples, the yield of the target diphenyl carbonate was improved by four times or more as compared with the Comparative Example, and the yield of methyl carbonate as the reaction intermediate was also improved.
본 발명의 황산유도체를 리간드로 가진 유기주석화합물을 촉매로 사용한 실시예 1과 기존의 촉매인 티타늄이소프로폭사이드를 사용한 비교예를 보면, 실시예 1이 생성물의 수율이 높을 뿐만 아니라 메틸이소프로필카보네이트, 디이소프로필카보네이트 등의 부산물도 생성되지 않았다.Example 1 using an organic tin compound having a sulfate derivative as a ligand of the present invention as a catalyst and a comparative example using titanium isopropoxide, which is an existing catalyst, show that Example 1 has a high yield of the product as well as methyl isopropyl. No by-products such as carbonate and diisopropyl carbonate were produced.
또한 상기 실시예 2는 화학식 1로 표현되는 촉매의 종류에 따른 생성물의 수율 변화, 실시예 3은 화학식 3으로 표현되는 촉매의 종류에 따른 생성물의 수율 변화, 실시예 4는 반응물인 디메틸카보네이트에 대한 촉매량의 변화에 따른 생성물의수율변화, 실시예 5는 디메틸카보네이트에 대한 페놀량의 변화에 따른 생성물의 수율변화 그리고 실시예 6은 반응온도에 따른 생성물의 수율변화를 나타낸 것으로 상기의 실시예는 본 발명의 범위내에서 우수한 효과를 보였다.In addition, Example 2 is a change in the yield of the product according to the type of catalyst represented by Formula 1, Example 3 is a change in the yield of the product according to the type of catalyst represented by Formula 3, Example 4 for the reactant dimethyl carbonate Yield change of the product according to the change in the amount of catalyst, Example 5 shows a change in the yield of the product according to the change in the amount of phenol relative to dimethyl carbonate and Example 6 shows a change in the yield of the product according to the reaction temperature. It showed excellent effects within the scope of the invention.
이상에서 설명한 바와 같이, 본 발명에 따른 제조방법에 의하면 기존의 방법보다 넓은 온도 범위에서 단시간 내에 부반응 없이 높은 수율로 산업적으로 유용한 폴리카보네이트의 원료인 디페닐카보네이트를 효과적으로 제조할 수 있다.As described above, according to the production method according to the present invention it is possible to effectively prepare diphenyl carbonate which is a raw material of the industrially useful polycarbonate in a high yield without a side reaction in a short time in a wider temperature range than the conventional method.
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