KR20120077913A - Method for preparing aromatic carbonate from dialkyl carbonate - Google Patents
Method for preparing aromatic carbonate from dialkyl carbonate Download PDFInfo
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- KR20120077913A KR20120077913A KR1020100140043A KR20100140043A KR20120077913A KR 20120077913 A KR20120077913 A KR 20120077913A KR 1020100140043 A KR1020100140043 A KR 1020100140043A KR 20100140043 A KR20100140043 A KR 20100140043A KR 20120077913 A KR20120077913 A KR 20120077913A
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 27
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- -1 aromatic hydroxy compound Chemical class 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 239000003446 ligand Substances 0.000 claims abstract description 7
- AZLYZRGJCVQKKK-UHFFFAOYSA-N dioxohydrazine Chemical compound O=NN=O AZLYZRGJCVQKKK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 125000002723 alicyclic group Chemical group 0.000 claims description 13
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000010936 titanium Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- DOLVFFGLNYMIPV-UHFFFAOYSA-N 2,4-ditert-butyl-6-[3-[(3,5-ditert-butyl-2-hydroxyphenyl)methylideneamino]propyliminomethyl]phenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(C=NCCCN=CC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O DOLVFFGLNYMIPV-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 101100419874 Caenorhabditis elegans snr-2 gene Proteins 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- CHZCERSEMVWNHL-UHFFFAOYSA-N 2-hydroxybenzonitrile Chemical compound OC1=CC=CC=C1C#N CHZCERSEMVWNHL-UHFFFAOYSA-N 0.000 description 1
- 125000006290 2-hydroxybenzyl group Chemical group [H]OC1=C(C([H])=C([H])C([H])=C1[H])C([H])([H])* 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- GHWVXCQZPNWFRO-UHFFFAOYSA-N butane-2,3-diamine Chemical compound CC(N)C(C)N GHWVXCQZPNWFRO-UHFFFAOYSA-N 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inorganic Chemistry (AREA)
Abstract
본 발명의 디알킬 카보네이트로부터 방향족 카보네이트의 제조방법은 방향족 하이드록시 화합물과 디알킬 카보네이트를 하기 화학식 1로 표시되는 촉매의 존재하에서 반응시키는 단계를 포함하는 것을 특징으로 한다:
[화학식 1]
(L)Ti(OR) 2
(상기에서 R은 탄소수 1~10의 알킬기 또는 탄소수 6~30의 아릴기이고, LH2은
[Formula 1]
(L) Ti (OR) 2
(In the above, R is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms, and LH 2 is
Description
본 발명은 디알킬 카보네이트로부터 방향족 카보네이트의 제조방법에 관한 것이다. 보다 구체적으로 본 발명은 특정 촉매를 사용하여 안정적으로 방향족 카보네이트를 제조할 수 있는 방법에 관한 것이다.
The present invention relates to a process for the preparation of aromatic carbonates from dialkyl carbonates. More specifically, the present invention relates to a process for stably producing aromatic carbonates using specific catalysts.
방향족 카보네이트는 폴리카보네이트 제조에 유용한 모노머로 그 제조에 관한 많은 연구가 진행되고 있다. 종래에는 알칼리의 존재 하에 페놀과 포스겐을 반응시킴으로써 방향족 탄산 에스테르를 얻는 포스겐법에 의해 주로 제조되었다. 그러나, 상기 방법은 맹독성인 포스겐을 사용해야 하는 점과 반응에 의해 부생되는 중성염을 처리해야 한다는 문제점이 있다. Aromatic carbonates are useful monomers for the production of polycarbonates. Conventionally, it was mainly produced by the phosgene method of obtaining an aromatic carbonate by reacting phenol with phosgene in the presence of alkali. However, this method has a problem in that it is necessary to use toxic toxic genes and to deal with by-product neutral salts.
따라서 이러한 결점을 해소하기 위하여 디메틸 카보네이트 등의 지방족 탄산 에스테르와 페놀을 반응시켜 방향족 탄산 에스테르를 제조하는 에스테르 교환법이 개발되었다. 이와 같은 에스테르 교환법은 통상 촉매 존재하에서 진행되며 사용되는 촉매로는 PbO, TiX4 (X= 알콕시기 또는 아릴옥시기), SnR2(OPh)2 (R = 알킬기) 등이 알려져 있다. 그러나 PbO 촉매의 경우 안정성은 높으나 촉매의 활성이 낮아 반응속도가 매우 느리며 TiX4와 SnR2(OPh)2 는 활성은 PbO 촉매 보다는 높으나 안정성이 부족하고, 상당량의 에테르가 부산물로 얻어진다는 단점이 있다. Therefore, in order to alleviate this drawback, a transesterification method has been developed in which an aliphatic carbonate such as dimethyl carbonate is reacted with a phenol to produce an aromatic carbonate. Such transesterification is usually carried out in the presence of a catalyst and known catalysts include PbO, TiX4 (X = alkoxy group or aryloxy group), SnR2 (OPh) 2 (R = alkyl group) and the like. However, in the case of PbO catalyst, the reaction rate is very slow due to high stability but low activity of the catalyst. TiX4 and SnR2 (OPh) 2 have higher activity than PbO catalyst but lack stability, and a considerable amount of ether is obtained as a by-product.
한편, 일산화탄소 및 산소를 사용하여 방향족 하이드록시 화합물을 카보닐화 반응시켜 방향족 카보네이트를 제조하는 방법이 개발되었으나,이와 같이 일산화탄소를 반응원료로 하여 합성하는 방법은 반응성이 상당히 떨어질 뿐만 아니라, 고압 반응기 설계가 필요하는 등 아직까지 상업화하기에는 곤란한 문제점이 있다. Meanwhile, a method of preparing an aromatic carbonate by carbonylating an aromatic hydroxy compound using carbon monoxide and oxygen has been developed.However, the method of synthesizing carbon monoxide as a reaction raw material not only has a low reactivity but also a high pressure reactor design. There is a problem that it is difficult to commercialize yet.
따라서, 일산화탄소가 아닌 디알킬 카보네이트를 출발물질로 하여 안정적이고 고수율로 방향족 카보네이트를 제조할 수 있는 방법의 개발이 필요한 실정이다.
Therefore, there is a need for the development of a method for producing an aromatic carbonate in a stable and high yield using a dialkyl carbonate other than carbon monoxide as a starting material.
본 발명의 목적은 일산화탄소가 아닌 디알킬 카보네이트를 반응원료로 하는 방향족 카보네이트를 제조하는 방법을 제공하는 것이다.It is an object of the present invention to provide a process for producing aromatic carbonates using dialkyl carbonates other than carbon monoxide as a reactant.
본 발명의 다른 목적은 고수율로 방향족 카보네이트를 제조할 수 있는 방법을 제공하는 것이다.Another object of the present invention is to provide a process for producing aromatic carbonates in high yield.
본 발명의 또 다른 목적은 기존 촉매시스템 대비 높은 촉매활성을 가짐으로써 디알킬 카르보네이트의 에스테르화 반응의 속도를 빠르게 하여 효과적으로 디아릴카르보네이트를 생산할 수 있는 방법을 제공하는 것이다. Still another object of the present invention is to provide a method capable of effectively producing diaryl carbonates by having a high catalytic activity compared to the existing catalyst system to speed up the esterification reaction of dialkyl carbonates.
본 발명이 이루고자 하는 기술적 과제들은 이상에서 언급한 기술적 과제들로 제한되지 않으며, 언급되지 않은 또 다른 기술적 과제들은 아래의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.
Technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.
본 발명의 관점은 디알킬 카보네이트로부터 방향족 카보네이트의 제조방법에 관한 것이다. 상기 방법은 방향족 하이드록시 화합물과 디알킬 카보네이트를 하기 화학식 1로 표시되는 촉매의 존재하에서 반응시키는 단계를 포함한다:
An aspect of the invention relates to a process for the preparation of aromatic carbonates from dialkyl carbonates. The method comprises the step of reacting an aromatic hydroxy compound with a dialkyl carbonate in the presence of a catalyst represented by formula (1):
[화학식 1] [Formula 1]
(L)(L)
TiTi
((
OROR
))
22
(상기에서 R은 탄소수 1~10의 알킬기 또는 탄소수 6~30의 아릴기이고, LH2은
구체예에서, 상기 LH2은 살란형 또는 살렌형 리간드이다.In an embodiment, said LH 2 is a salland or salen ligand.
한 구체예에서는 상기 촉매는 하기 화학식 1-1로 표시될 수 있다:
In one embodiment, the catalyst may be represented by the following Formula 1-1:
[화학식 1-1] [Formula 1-1]
(상기에서 R은 탄소수 1~10의 알킬기 또는 탄소수 6~30의 아릴기이고, A는 0~1개의 이민결합을 포함하고; B는 탄소수 6~30의 지환족기, 불포화 지환족기, 또는 방향족기이고, n은 0~2의 정수이고; C는 0~1개의 이중결합을 포함하고; D는 C의 환 구조에 인접하며, 인접하는 2개의 탄소 원자를 공유하는 탄소수 6~30의 지환족기, 불포화 지환족기, 또는 방향족기이고, m은 0~1의 정수임).(Wherein R is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms, and A contains 0 to 1 imine bond; B is an alicyclic group, unsaturated alicyclic group, or aromatic group having 6 to 30 carbon atoms) N is an integer of 0 to 2, C is 0 to 1 double bond, D is an alicyclic group having 6 to 30 carbon atoms adjacent to the ring structure of C and sharing two adjacent carbon atoms, Unsaturated alicyclic group or aromatic group, and m is an integer of 0-1.
상기 촉매는 디알킬 카보네이트 1 몰에 대해 1 × 10-5 내지 5 × 10-1 몰로 사용할 수 있다.The catalyst may be used in 1 × 10 −5 to 5 × 10 −1 moles per mole of dialkyl carbonate.
구체예에서, 상기 반응은 100 내지 280 ℃의 온도에서 수행할 수 있다. In embodiments, the reaction may be carried out at a temperature of 100 to 280 ℃ .
구체예에서, 상기 반응은 분자체가 충진된 반응기에서 수행할 수 있다.In an embodiment, the reaction can be carried out in a reactor filled with molecular sieves.
구체예에서, 상기 방향족 하이드록시 화합물은 하기 화학식 2로 표시될 수 있다:
In an embodiment, the aromatic hydroxy compound may be represented by the following Chemical Formula 2:
[화학식 2][Formula 2]
Ar-OHAr-OH
(상기에서, Ar은 치환 또는 비치환된 아릴기임).(In the above, Ar is a substituted or unsubstituted aryl group).
구체예에서, 상기 디알킬 카보네이트는 하기 화학식 3으로 표시될 수 있다:
In embodiments, the dialkyl carbonate may be represented by the following formula (3):
[화학식 3] (3)
(상기에서, R1 및 R2는 각각 탄소수 1~6의 알킬기이며 서로 같거나 다름).
(In the above, R 1 and R 2 are each an alkyl group having 1 to 6 carbon atoms and the same or different from each other).
본 발명은 일산화탄소가 아닌 디알킬 카보네이트를 반응원료로 하여 낮은 반응온도에서도 고수율로 방향족 카보네이트를 제조할 수 있으며, 기존 촉매시스템 대비 높은 촉매활성을 가짐으로써 디알킬 카르보네이트의 에스테르화 반응의 속도를 빠르게 하여 효과적으로 디아릴카르보네이트를 생산할 수 있는 방법을 제공하는 발명의 효과를 갖는다.
The present invention can produce aromatic carbonate with high yield even at low reaction temperature using dialkyl carbonate rather than carbon monoxide as a raw material, and has higher catalytic activity than existing catalyst system, thereby speeding up the esterification of dialkyl carbonate. It has the effect of the invention to provide a method that can quickly produce a diaryl carbonate to speed up.
본 발명의 디알킬 카보네이트로부터 방향족 카보네이트의 제조방법은 방향족 하이드록시 화합물과 디알킬 카보네이트를 하기 화학식 1로 표시되는 촉매의 존재하에서 반응시키는 단계를 포함한다:
A method for preparing an aromatic carbonate from the dialkyl carbonate of the present invention includes reacting an aromatic hydroxy compound with a dialkyl carbonate in the presence of a catalyst represented by the following formula (1):
[화학식 1] [Formula 1]
(L)Ti(OR)(L) Ti (OR)
22
(상기에서 R은 탄소수 1~10의 알킬기 또는 탄소수 6~30의 아릴기이고, LH2은
구체예에서, 상기 LH2은 살란형 또는 살렌형 리간드이다.In an embodiment, said LH 2 is a salland or salen ligand.
한 구체예에서는 상기 촉매는 하기 화학식 1-1로 표시될 수 있다:In one embodiment, the catalyst may be represented by the following Formula 1-1:
[화학식 1-1] [Formula 1-1]
(상기에서 R은 탄소수 1~10의 알킬기 또는 탄소수 6~30의 아릴기이고, A는 0~1개의 이민결합을 포함하고; B는 탄소수 6~30의 지환족기, 불포화 지환족기, 또는 방향족기이고, n은 0~2의 정수이고; C는 0~1개의 이중결합을 포함하고; D는 C의 환 구조에 인접하며, 인접하는 2개의 탄소 원자를 공유하는 탄소수 6~30의 지환족기, 불포화 지환족기, 또는 방향족기이고, m은 0~1의 정수임).
(Wherein R is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms, and A contains 0 to 1 imine bond; B is an alicyclic group, unsaturated alicyclic group, or aromatic group having 6 to 30 carbon atoms) N is an integer of 0 to 2, C is 0 to 1 double bond, D is an alicyclic group having 6 to 30 carbon atoms adjacent to the ring structure of C and sharing two adjacent carbon atoms, Unsaturated alicyclic group or aromatic group, and m is an integer of 0-1.
상기 A가 이민결합을 포함하지 않을 경우 살란구조이며, 이민결합을 1개 포함할 경우 살렌구조이다. When A does not include an imine bond, it has a salane structure, and when it contains one imine bond, it has a salen structure.
또한 상기 A는 이중결합을 0~1개 포함할 수도 있다. In addition, A may include 0 to 1 double bond.
상기 B는 A의 환 구조에 인접하며, 인접하는 2개의 탄소 원자를 공유할 수 있다. 바람직하게는 B는 방향족 기이며, 복수의 환이 융합된 구조를 가질 수 있다. B is adjacent to the ring structure of A and may share two adjacent carbon atoms. Preferably, B is an aromatic group, and may have a structure in which a plurality of rings are fused.
바람직하게는 D는 지환족기이다. Preferably, D is an alicyclic group.
바람직하게는 R은 메킬기, 에틸기, n-프로필기, 이소프로필기, n-부틸기, 이소부틸기, tert-부틸기, 페닐기 등일 수 있다.Preferably, R may be a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, phenyl group or the like.
바람직하게는 n은 1~2의 정수이며, m은 0 또는 1이다.
Preferably n is an integer of 1-2, and m is 0 or 1.
구체예에서, 상기 촉매는 (Salan)Ti(OMe)2, (Ph-Salen)Ti(OMe)2, (Salan)Ti(O i Pr)2, (Ph-Salen)Ti(O i Pr)2, 등일 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용될 수 있다. In an embodiment, the catalyst is (Salan) Ti (OMe) 2 , (Ph-Salen) Ti (OMe) 2 , (Salan) Ti (O i Pr) 2 , (Ph-Salen) Ti (O i Pr) 2 , And the like. These can be used individually or in mixture of 2 or more types.
구체예에서, 상기 촉매는 디알킬 카보네이트 1 몰에 대해 1 × 10-5 내지 5 × 10-1 몰, 바람직하게는 5 × 10-5 내지 1 × 10- 2몰로 사용할 수 있다. 상기 범위에서 촉매 효율이 우수하며, 촉매의 회수면에서도 바람직하다. In an embodiment, the catalyst is from 1 × 10 −5 to 5 × 10 −1 moles , preferably with respect to 1 mole of dialkyl carbonate 5 × 10 -5 to 1 × 10 - may be 2 mol. It is excellent in catalyst efficiency in the said range, and it is preferable also from a catalyst recovery point.
상기 방향족 하이드록시 화합물은 하기 화학식 2로 표시될 수 있다:
The aromatic hydroxy compound may be represented by the following Formula 2:
[화학식 2][Formula 2]
Ar-OHAr-OH
(상기에서, Ar은 치환 또는 비치환된 아릴기임).(In the above, Ar is a substituted or unsubstituted aryl group).
상기 Ar은 페닐기 또는 나프틸기일 수 있으며, 치환기로는 탄소수 1-4의 알킬, 할로겐, 알콕시, 니트로, 시아노 등일 수 있다. Ar may be a phenyl group or a naphthyl group, the substituent may be alkyl having 1 to 4 carbon atoms, halogen, alkoxy, nitro, cyano and the like.
구체예에서 상기 방향족 하이드록시 화합물의 예로는 페놀, 나프톨, 크레졸, 클로로페놀, 알킬 페놀, 알콕시 페놀, 니트로 페놀, 시아노 페놀 등이 사용될 수 있으며, 반드시 이에 제한되는 것은 아니다. 이중 페놀이 바람직하게 사용될 수 있다. Specific examples of the aromatic hydroxy compound may include phenol, naphthol, cresol, chlorophenol, alkyl phenol, alkoxy phenol, nitro phenol, cyano phenol, and the like, but are not limited thereto. Double phenols can be preferably used.
상기 디알킬 카보네이트는 하기 화학식 3으로 표시될 수 있다:
The dialkyl carbonate may be represented by the following formula (3):
[화학식 3] (3)
(상기에서, R1 및 R2는 각각 탄소수 1~6의 알킬기이며 서로 같거나 다름).
(In the above, R 1 and R 2 are each an alkyl group having 1 to 6 carbon atoms and the same or different from each other).
상기 디알킬 카보네이트의 예로는 디메틸카보네이트, 디에틸카보네이트, 디프로필카보네이트, 디부틸카보네이트, 메틸에틸카보네이트, 메틸프로필카보네이트, 에틸프로필카보네이트 등이 사용될 수 있으며, 반드시 이에 제한되는 것은 아니다. 이중 디메틸카보네이트가 바람직하게 사용될 수 있다. Examples of the dialkyl carbonates include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, and the like, but are not necessarily limited thereto. Double dimethyl carbonate can be preferably used.
구체예에서는, 상기 반응은 100 내지 280 ℃의 온도, 바람직하게는 120 내지 250 ℃, 더욱 바람직하게는 180 내지 240 ℃에서 수행할 수 있다. 상기 범위에서 디아릴카르보네이트를 고수율로 얻을 수 있다. In embodiments, the reaction may be carried out at a temperature of 100 to 280 ℃, preferably 120 to 250 ℃, more preferably 180 to 240 ℃. Diaryl carbonate can be obtained in a high yield in the above range.
본 발명의 에스테르 교환 반응은 압력범위: 760 ~15000 mmHg 의 압력에서 진행될 수 있다. 바람직하게는 상기 에스테르 교환 반응은 760 ~ 7500 mmHg에서 진행할 수 있다. The transesterification reaction of the present invention can be carried out at a pressure range of 760-15000 mmHg. Preferably, the transesterification reaction may proceed at 760-7500 mmHg.
반응시간은 특별한 제한이 없으며, 통상 1초 내지 150 분으로 반응될 수 있다.
The reaction time is not particularly limited, and may be generally reacted with 1 second to 150 minutes.
이하, 본 발명의 바람직한 실시예를 통해 본 발명의 구성 및 작용을 더욱 상세히 설명하기로 한다. 다만, 이는 본 발명의 바람직한 예시로 제시된 것이며 어떠한 의미로도 이에 의해 본 발명이 제한되는 것으로 해석될 수는 없다. Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.
여기에 기재되지 않은 내용은 이 기술 분야에서 숙련된 자이면 충분히 기술적으로 유추할 수 있는 것이므로 그 설명을 생략하기로 한다.
Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.
실시예Example
실시예 1Example 1
외부 히터를 가진 내용적 200 ml의 오토클레이브 반응기에 페놀 (65.88g, 700mmol), 탄산디메틸 (31.53g, 350 mmol), 촉매로 N,N'-bis(2-hydroxybenzyl)-N,N'-dimethyl-1,2-diaminoethane과 Ti(O i Pr)4 의 티탄착물인 (Salan)Ti(O i Pr)2 (0.0102 g, 0.022 mmol)을 넣고 반응기내 산소를 질소로 치환한후 가열하여 230 ℃에 도달한후 15분간 유지하고, 냉각기를 이용하여 감온 후 가스크로마토그래피를 이용하여 수율과 전환율을 구하였다. Phenol in an autoclave reactor with a volume of 200 ml with an external heater (65.88g, 700mmol), dimethyl carbonate (31.53g, 350 mmol), N , N as the catalyst '-bis (2-hydroxybenzyl) - N, N' - Titanium complex of dimethyl-1,2-diaminoethane and Ti (O i Pr) 4 was added (Salan) Ti (O i Pr) 2 (0.0102 g, 0.022 mmol), and the oxygen in the reactor was replaced with nitrogen and heated to 230 After reaching 15 ° C., the resultant was maintained for 15 minutes, and the temperature and temperature were reduced by using a cooler.
실시예 2Example 2
분자체 (molecular sieve 4Å, Aldrich) 40 g이 채워진 실린더를 장착하고, 230 ℃에 도달한 후 30분 유지하는 것 이외에는 실시예 1과 동일하게 반응을 진행하였다.
The reaction was performed in the same manner as in Example 1 except that a cylinder filled with 40 g of a molecular sieve (Aldrich) was maintained for 30 minutes after reaching 230 ° C.
실시예 3Example 3
230 ℃에 도달한 후 120분 유지하는 것 이외에는 실시예 2와 동일하게 반응을 진행하였다.
The reaction was carried out in the same manner as in Example 2 except that the mixture was maintained at 230 ° C. for 120 minutes.
실시예 4Example 4
220 ℃에 도달한 후 120분 유지하는 것 이외에는 실시예 2와 동일하게 반응을 진행하였다.
The reaction was carried out in the same manner as in Example 2, except that the mixture was maintained at 220 ° C. for 120 minutes.
실시예 5Example 5
200 ℃에 도달한 후 120분 유지하는 것 이외에는 실시예 2와 동일하게 반응을 진행하였다.
The reaction was carried out in the same manner as in Example 2 except that the mixture was maintained at 200 ° C. for 120 minutes.
실시예 6Example 6
180 ℃에 도달한 후 120분 유지하는 것 이외에는 실시예 2과 동일하게 반응을 진행하였다.
The reaction proceeded in the same manner as in Example 2 except that the mixture was maintained at 180 ° C. for 120 minutes.
실시예 7Example 7
150 ℃에 도달한 후 120분 유지하는 것 이외에는 실시예 2와 동일하게 반응을 진행하였다.
The reaction proceeded in the same manner as in Example 2 except that the mixture was maintained at 120 ° C. for 120 minutes.
실시예 8Example 8
230 ℃에 도달한 후 120분 유지하는 것 이외에는 실시예 1과 동일하게 반응을 진행하였다.
The reaction was carried out in the same manner as in Example 1 except that the mixture was maintained at 230 ° C. for 120 minutes.
비교예 1Comparative Example 1
촉매로 n-Bu2SnO 를 사용하는 것 이외에는 실시예 1과 동일하게 반응을 진행하였다.
The reaction was carried out in the same manner as in Example 1, except that n- Bu 2 SnO was used as the catalyst.
비교예 2Comparative Example 2
230 ℃에 도달한 후 30분 유지하는 것 이외에는 비교예 1과 동일하게 반응을 진행하였다.
The reaction proceeded in the same manner as in Comparative Example 1 except that the mixture was maintained at 230 ° C. for 30 minutes.
비교예 3Comparative Example 3
촉매로 n-Bu2Sn(OAc)2 를 사용하는 것 이외에는 실시예 1과 동일하게 반응을 진행하였다.
The reaction was carried out in the same manner as in Example 1, except that n- Bu 2 Sn (OAc) 2 was used as the catalyst.
비교예 4Comparative Example 4
반응온도가 230 ℃에 도달한 후 30분 유지하는 것 이외에는 비교예 3과 동일하게 반응을 진행하였다
The reaction was carried out in the same manner as in Comparative Example 3 except that the reaction temperature reached 230 ° C. and maintained for 30 minutes.
비교예 5Comparative Example 5
촉매로 Zr(OBu)4 를 사용하는 것 이외에는 실시예 1과 동일하게 반응을 진행하였다.
The reaction was carried out in the same manner as in Example 1, except that Zr (OBu) 4 was used as the catalyst.
비교예 6Comparative Example 6
230 ℃에 도달한 후 30분 유지하는 것 이외에는 비교예 5와 동일하게 반응을 진행하였다.
The reaction proceeded in the same manner as in Comparative Example 5 except that the mixture was maintained at 230 ° C. for 30 minutes.
(oC)Reaction temperature
( o C)
yield (%)MPC
yield (%)
상기 표 1에 나타난 바와 같이, 실시예1이 비교예 1~6에 비해 우수한 전환율을 갖는 것을 확인할 수 있다.
As shown in Table 1, it can be confirmed that Example 1 has an excellent conversion rate compared to Comparative Examples 1-6.
(oC)Reaction temperature
( o C)
시
예room
city
Yes
상기 표 2에 나타난 바와 같이, 분자체 충진시 수율이 현저히 증가한 것을 확인할 수 있으며, 또한 반응온도가 높을 수록 보다 우수한 전환율을 갖는 것을 알 수 있다.
As shown in Table 2, it can be seen that the yield increased significantly when filling the molecular sieve, and also it can be seen that the higher the reaction temperature has a better conversion rate.
이상 첨부된 표를 참조하여 본 발명의 실시예들을 설명하였으나, 본 발명은 상기 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 제조될 수 있으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야 한다.
While the embodiments of the present invention have been described with reference to the accompanying tables, the present invention is not limited to the above embodiments, but may be manufactured in various forms, and having ordinary skill in the art to which the present invention pertains. It will be understood by those skilled in the art that the present invention may be embodied in other specific forms without changing the technical spirit or essential features of the present invention. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.
Claims (8)
[화학식 1]
(L) Ti ( OR ) 2
(상기에서 R은 탄소수 1~10의 알킬기 또는 탄소수 6~30의 아릴기이고, LH2은
A method for preparing an aromatic carbonate from a dialkyl carbonate comprising reacting an aromatic hydroxy compound with a dialkyl carbonate in the presence of a catalyst represented by the following formula (1):
[Formula 1]
(L) Ti ( OR ) 2
(In the above, R is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms, and LH 2 is
The method of claim 1, wherein the LH 2 is a sallan type or a salen type ligand.
[화학식 1-1]
(상기에서 R은 탄소수 1~10의 알킬기 또는 탄소수 6~30의 아릴기이고, A는 0~1개의 이민결합을 포함하고; B는 탄소수 6~30의 지환족기, 불포화 지환족기, 또는 방향족기이고, n은 0~2의 정수이고; C는 0~1개의 이중결합을 포함하고; D는 C의 환 구조에 인접하며, 인접하는 2개의 탄소 원자를 공유하는 탄소수 6~30의 지환족기, 불포화 지환족기, 또는 방향족기이고, m은 0~1의 정수임).
The method of claim 1, wherein the catalyst is represented by the following Chemical Formula 1-1:
[Formula 1-1]
(Wherein R is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms, and A contains 0 to 1 imine bond; B is an alicyclic group, unsaturated alicyclic group, or aromatic group having 6 to 30 carbon atoms) N is an integer of 0 to 2, C is 0 to 1 double bond, D is an alicyclic group having 6 to 30 carbon atoms adjacent to the ring structure of C and sharing two adjacent carbon atoms, Unsaturated alicyclic group or aromatic group, and m is an integer of 0-1.
The method of claim 1, wherein the catalyst is used in an amount of 1 × 10 −5 to 5 × 10 −1 moles with respect to 1 mole of dialkyl carbonate.
The method of claim 1, wherein the reaction is carried out at a temperature of 100 to 280 ℃.
The method of claim 1 wherein the reaction is carried out in a reactor filled with molecular sieves.
[화학식 2]
Ar-OH
(상기에서, Ar은 치환 또는 비치환된 아릴기임).
The method of claim 1, wherein the aromatic hydroxy compound is represented by the following Chemical Formula 2:
(2)
Ar-OH
(In the above, Ar is a substituted or unsubstituted aryl group).
[화학식 3]
(상기에서, R1 및 R2는 각각 탄소수 1~6의 알킬기이며 서로 같거나 다름).
The method of claim 1, wherein the dialkyl carbonate is represented by the following Chemical Formula 3:
(3)
(In the above, R 1 and R 2 are each an alkyl group having 1 to 6 carbon atoms and the same or different from each other).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017018A (en) * | 2014-05-02 | 2015-11-04 | 三星Sdi株式会社 | Method of preparing aromatic carbonate from dialkyl carbonate |
| CN105879914A (en) * | 2016-06-03 | 2016-08-24 | 湖南师范大学 | Temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst and preparation method thereof |
| WO2016137067A1 (en) * | 2015-02-27 | 2016-09-01 | 삼성에스디아이 주식회사 | Method for preparing dialkyl carbonate |
| CN106045804A (en) * | 2016-06-03 | 2016-10-26 | 湖南师范大学 | Method for realizing asymmetric oxidation reaction of thioether under aqueous-phase catalysis of chiral Salen Ti complex catalyst based on temperature-sensitive type ionic liquid |
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| ATE112547T1 (en) | 1990-06-29 | 1994-10-15 | Enichem Sintesi | PROCESS AND CATALYST FOR THE PRODUCTION OF ORGANIC CARBONATES. |
| JP3898246B2 (en) | 1995-12-18 | 2007-03-28 | 日本ジーイープラスチックス株式会社 | Method for producing aromatic carbonate |
| US6175033B1 (en) | 2000-02-22 | 2001-01-16 | General Electric Company | Method and catalyst system for producing aromatic carbonates |
| EP2112187A1 (en) | 2008-04-21 | 2009-10-28 | Stichting Dutch Polymer Institute | Process for the preparation of polycarbonates |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017018A (en) * | 2014-05-02 | 2015-11-04 | 三星Sdi株式会社 | Method of preparing aromatic carbonate from dialkyl carbonate |
| CN105017018B (en) * | 2014-05-02 | 2017-04-12 | 乐天尖端材料株式会社 | Method of preparing aromatic carbonate from dialkyl carbonate |
| WO2016137067A1 (en) * | 2015-02-27 | 2016-09-01 | 삼성에스디아이 주식회사 | Method for preparing dialkyl carbonate |
| CN105879914A (en) * | 2016-06-03 | 2016-08-24 | 湖南师范大学 | Temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst and preparation method thereof |
| CN106045804A (en) * | 2016-06-03 | 2016-10-26 | 湖南师范大学 | Method for realizing asymmetric oxidation reaction of thioether under aqueous-phase catalysis of chiral Salen Ti complex catalyst based on temperature-sensitive type ionic liquid |
| CN106045804B (en) * | 2016-06-03 | 2019-01-11 | 湖南师范大学 | A method of based on temperature sensitive type ionic liquid chirality Salen Ti composition catalyst aqueous catalysis thioether asymmetric oxidation reaction |
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