KR101060624B1 - Method for preparing acrylate monomer - Google Patents
Method for preparing acrylate monomer Download PDFInfo
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- KR101060624B1 KR101060624B1 KR1020110032049A KR20110032049A KR101060624B1 KR 101060624 B1 KR101060624 B1 KR 101060624B1 KR 1020110032049 A KR1020110032049 A KR 1020110032049A KR 20110032049 A KR20110032049 A KR 20110032049A KR 101060624 B1 KR101060624 B1 KR 101060624B1
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- acrylate
- alcohol solution
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 6
- 239000000178 monomer Substances 0.000 title abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 150000003333 secondary alcohols Chemical class 0.000 claims abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- 150000003624 transition metals Chemical class 0.000 claims abstract description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims abstract description 3
- 125000000075 primary alcohol group Chemical group 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- VFAHXTJRZRHGDN-UHFFFAOYSA-N [Ru].[C]=O Chemical compound [Ru].[C]=O VFAHXTJRZRHGDN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 2
- YACTZEZVNPAVGJ-UHFFFAOYSA-N P.C(=O)(O)C=C.C(=O)(O)C=C.C(=O)(O)C=C Chemical compound P.C(=O)(O)C=C.C(=O)(O)C=C.C(=O)(O)C=C YACTZEZVNPAVGJ-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 8
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- -1 acrylic ester Chemical class 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CKLONJANQGBREW-UHFFFAOYSA-N 2,2-difluoropropan-1-ol Chemical compound CC(F)(F)CO CKLONJANQGBREW-UHFFFAOYSA-N 0.000 description 1
- GGDYAKVUZMZKRV-UHFFFAOYSA-N 2-fluoroethanol Chemical compound OCCF GGDYAKVUZMZKRV-UHFFFAOYSA-N 0.000 description 1
- 238000005602 Reppe reaction Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
- C07C67/40—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of primary alcohols
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/14—Rubidium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/825—Osmium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
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- Crystallography & Structural Chemistry (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
본 발명은 아크릴레이트 단량체의 제조방법으로, 비양성자성 극성 유기용매에 용해된 1급 또는 2급 알코올 용액을 준비하는 단계; 전이금속 촉매 분말을 상기 알코올 용액에 분산시키는 단계; 이산화탄소, 아세틸렌과 수소 가스를 상기 알코올 용액에 혼입하여 반응시키는 단계; 및 상기 전 단계에서 생성된 반응 액상 혼합물을 증류하여 아크릴레이트를 분리하는 단계로 이루어지는 아크릴레이트의 제조방법을 제공한다.
본 발명에 의하여 상압과 상온 또는 가온상태의 온후한 상태에서 원료로서 값싼 이산화탄소 등을 사용하여 용매 내에 목적 화합물인 아크릴레이트가 고효율로 하나의 반응 단계에 의하여 얻어짐으로써 연속식 또는 배치식으로 소량 또는 대량의 아크릴레이트를 환경 문제 없이 경제적으로 제조하는 것이 가능하다.The present invention provides a method for preparing an acrylate monomer, comprising: preparing a primary or secondary alcohol solution dissolved in an aprotic polar organic solvent; Dispersing a transition metal catalyst powder in the alcohol solution; Reacting carbon dioxide, acetylene and hydrogen gas by mixing the alcohol solution; And it provides a method for producing an acrylate consisting of distilling the reaction liquid mixture produced in the previous step to separate the acrylate.
According to the present invention, by using a cheap carbon dioxide or the like as a raw material in a gentle state of normal pressure and normal temperature or a warm state, an acrylate as a target compound is obtained in one solvent in a continuous or batch manner by obtaining a single reaction step with high efficiency. It is possible to produce large quantities of acrylates economically without environmental problems.
Description
본 발명은 아크릴레이트 단량체의 제조방법, 특히, 비양성자성 용매 내에서 촉매를 사용하여 알코올 용액과 아세틸렌 가스로부터 아크릴레이트 단량체를 제조하는 방법에 관한 것이다.The present invention relates to a process for the preparation of acrylate monomers, in particular to the preparation of acrylate monomers from alcohol solutions and acetylene gases using catalysts in aprotic solvents.
아크릴레이트 단량체는 고분자 중합의 단량체로 사용되는 등 용도가 대단히 넓은 매우 중요한 화합물로서 일반적으로 아크릴산과 알코올을 축합 반응시켜 제조한다. 이러한 아크릴산은 프로필렌 가스를 고상 촉매에서 부분산화하여 아크롤레인을 만들고 이를 다시 산화하여 제조한다. 초기에는 이크릴산 또는 아크릴에스테르의 공업적 제조는 아세틸렌 화학 소위 말하는 레페(Reppe) 반응으로 고상 Ni 촉매에 각각 고압의 아세틸렌+CO+H2O 또는 아세틸렌+CO+ROH를 통과시켜 제조하였다. 그러나 석유화학의 발달로 프로필렌 가스의 수급이 용이해짐에 따라 프로필렌의 촉매적 산화에 의하여 아크릴산을 제조하고 이를 알코올과 축합 반응시켜 아크릴에스테르를 제조하는 공정이 널리 사용되게 되었다. 그러나 상기 반응은 두 단계의 화학 반응이 필요하며 특히 산을 이용한 에스테르화(esterification) 반응은 고온의 반응 조건을 필요로 하고 효율성이 떨어지는 문제점이 있다. 또한, 레페 합성법은 고압과 고온 환경에서 진행되고 가격적으로 비싼 CO gas를 사용하기 때문에 제조장치의 설비가 커지고 제조비가 상승하는 문제점이 있다.An acrylate monomer is a very important compound having a wide range of uses, such as being used as a monomer for polymer polymerization, and is generally prepared by condensation reaction of acrylic acid and alcohol. This acrylic acid is produced by partial oxidation of propylene gas in a solid catalyst to form acrolein and oxidation again. Initially, the industrial production of iscrylic acid or acrylic esters was prepared by passing acetylene + CO + H 2 O or acetylene + CO + ROH at high pressure through a solid Ni catalyst, respectively, by acetylene chemical so-called Reppe reaction. However, with the development of petrochemicals, the supply and demand of propylene gas is facilitated, so that acrylic acid is prepared by the catalytic oxidation of propylene and condensation reaction with alcohol to produce acrylic ester. However, the reaction requires a two-step chemical reaction, and in particular, an esterification reaction using an acid requires a high temperature reaction condition and has a problem of low efficiency. In addition, the repe synthesis method proceeds in a high pressure and high temperature environment and uses a costly expensive CO gas, there is a problem that the equipment of the manufacturing apparatus increases and the manufacturing cost increases.
본 발명은 비교적 온후한 조건에서 이산화탄소, 아세틸렌과 수소 가스를 사용하여 아크릴레이트를 제조하는 방법을 제공하기 위한 것이다.The present invention is to provide a method for producing an acrylate using carbon dioxide, acetylene and hydrogen gas in relatively mild conditions.
본 발명에 의하여, 비양성자성 극성 유기용매에 용해된 1급 또는 2급 알코올 용액을 준비하는 단계; 전이금속 촉매 분말을 상기 알코올 용액에 분산시키는 단계; 이산화탄소, 아세틸렌과 수소 가스를 상기 알코올 용액에 혼입하여 반응시키는 단계; 상기 전 단계에서 생성된 반응 액상 혼합물을 증류하여 아크릴레이트를 분리하는 단계로 이루어지는 아크릴레이트의 제조방법이 제공된다. 상기 제조방법은 배치 또는 연속식으로 이루어질 수 있다. 연속식일 때는 분리된 목적 화합물을 제외하고 촉매, 미반응 알코올과 용매는 환류될 수 있다.According to the present invention, preparing a primary or secondary alcohol solution dissolved in an aprotic polar organic solvent; Dispersing a transition metal catalyst powder in the alcohol solution; Reacting carbon dioxide, acetylene and hydrogen gas by mixing the alcohol solution; There is provided a method for producing an acrylate consisting of distilling the reaction liquid mixture produced in the previous step to separate the acrylate. The manufacturing method may be batch or continuous. When in continuous mode, the catalyst, unreacted alcohol and solvent may be refluxed except for the isolated desired compound.
본 발명의 제조방법에서 나타나는 반응식을 표시하면 다음과 같다.If the reaction scheme represented by the production method of the present invention is shown.
식 1Equation 1
상기 비양성자성 극성 유기용매는 양자기를 내지 않으면서 극성을 띄는 유기용매로서, 예를 들면, N,N-디메틸포름아미드(DMF), N,N-디메틸아세트아미드(DMAc), N-메틸피롤리돈(NMP), 테트라메틸우레아(TMU) 또는 디메틸술폭사이드(DMSO) 등이 있다. 이러한 비양성자성 극성 유기용매는 출발물질인 알코올을 용해하고 촉매를 분산하며 가스상태의 다른 출발 물질인 이산화탄소, 아세틸렌와 수소 가스를 용해하는 역할을 한다.The aprotic polar organic solvent is a polar organic solvent which does not emit a proton group and is, for example, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methylpi Ralidone (NMP), tetramethylurea (TMU) or dimethyl sulfoxide (DMSO). Such an aprotic polar organic solvent dissolves the starting material alcohol, disperses the catalyst and dissolves other starting materials carbon dioxide, acetylene and hydrogen gas.
본 발명의 출발물질인 1급 또는 2급 알코올은 목적하는 아크릴레이트에 따라 다양하게 선택될 수 있는 데 바람직하게는 수소가 치환되거나 치환되지 않은 탄소수 1 내지 10 의 1급 또는 2급 알킬 알코올이다. 탄소수가 2인 경우, 예를 들면, 에탄올, 2-플루오르에탄올, 2,2-디플루오르프로판올 또는 2,2,2-트리플루오르에탄올 등이다. The primary or secondary alcohol which is the starting material of the present invention may be variously selected according to the desired acrylate, and is preferably a primary or secondary alkyl alcohol having 1 to 10 carbon atoms which is substituted or unsubstituted. When carbon number is 2, it is ethanol, 2-fluoroethanol, 2, 2- difluoro propanol, 2, 2, 2- trifluoro ethanol, etc., for example.
상기 전이금속 촉매는, 바람직하게는, 백금족인 루테늄(Ru), 오스뮴(Os), 로듐(Rh), 이리듐(Ir), 팔라듐(Pd), 백금(Pt) 촉매, 가장 바람직하게는, 하기 식2로 표시되는 카르보닐루테늄계열 촉매이다. Preferably, the transition metal catalyst is ruthenium (Ru), osmium (Os), rhodium (Rh), iridium (Ir), palladium (Pd), platinum (Pt) catalyst which is a platinum group, and most preferably, Carbonyl ruthenium series catalyst represented by 2.
식2 Ru(CO)aXb(PPh3)c 2 Ru (CO) a X b (PPh 3 ) c
상기 식2에서 a는 1 또는 2이고 c는 0 내지 3의 정수이고 a+b+c는 5이고 X는 O2CCF3, HCL 또는 H2이다.In Formula 2, a is 1 or 2, c is an integer of 0 to 3, a + b + c is 5 and X is O 2 CCF 3, HCL or H 2 .
본 발명에 의하여 상압과 상온 또는 가온상태의 온후한 상태에서 원료로서 값싼 이산화탄소 등을 사용하여 용매 내에 목적 화합물인 아크릴레이트가 고효율로 하나의 반응 단계에 의하여 얻어짐으로써 연속식 또는 배치식으로 소량 또는 대량의 아크릴레이트를 환경 문제 없이 경제적으로 제조하는 것이 가능하다.According to the present invention, by using a cheap carbon dioxide or the like as a raw material in a gentle state of normal pressure and normal temperature or a warm state, an acrylate as a target compound is obtained in one solvent in a continuous or batch manner by obtaining a single reaction step with high efficiency. It is possible to produce large quantities of acrylates economically without environmental problems.
이하, 본 발명을 실시예에 의하여 상세히 설명한다. 이러한 설명은 본 발명을 예시하여 설명하기 위한 것으로 본 발명의 보호범위를 제한하기 위한 것으로 해석되어서는 아니 된다.Hereinafter, the present invention will be described in detail with reference to examples. This description is intended to illustrate the invention and should not be construed as limiting the protection scope of the invention.
비교예1Comparative Example 1
반응용기인 플라스크에 2,2,2-트리플루오르에탄올 (100 mL, 100 mol%), N,N-디메칠포름아마이드 (250 mL), 촉매 Ni(O2CCH3)2·4H2O (2.5 mol%l)를 넣고, 아세틸렌 가스 (1 atm), 이산화탄소 가스 (1 atm), 수소 가스 (1 atm)를 가한 후, 50 ℃에서 48시간 동안 교반 시켰다. 이산화탄소, 아세틸렌, 수소 가스를 각각 다른 풍선에 충진하여 충진한 각각의 풍선에 바늘을 연결하고 바늘의 끝을 반응 용기 내 용매에 잠기도록 설치하여 가스 상의 원료가 상압 하에서 공급되도록 한다. 반응 후 가스크로마토그래피-질량 분석법에 의해 목적 화합물 아크릴트리플루오르아세테이트의 수득률은 트리플루오르에탄올 기준으로 2몰%이었다. 2,2,2-trifluoroethanol (100 mL, 100 mol%), N, N-dimethylformamide (250 mL), catalyst Ni (O 2 CCH 3 ) 2 .4H 2 O ( 2.5 mol% l) was added, acetylene gas (1 atm), carbon dioxide gas (1 atm), and hydrogen gas (1 atm) were added, followed by stirring at 50 ° C. for 48 hours. Carbon dioxide, acetylene, and hydrogen gas are filled in different balloons, respectively, and a needle is connected to each balloon filled and the tip of the needle is installed to be immersed in a solvent in the reaction vessel so that the gaseous raw material is supplied under normal pressure. The yield of the target compound acryltrifluoroacetate by gas chromatography-mass spectrometry after the reaction was 2 mol% based on trifluoroethanol.
실시예1 Example 1
반응용기인 플라스크에 2,2,2-트리플루오르에탄올(100 mL, 100 mol%), N,N-디메칠포름아마이드 (250 mL), 촉매 Ru(CO)(H2)(PPh3)3 (2.5 mol%l)를 넣고, 아세틸렌 가스 (1 atm), 이산화탄소 가스 (1 atm), 수소가스 (1 atm)를 가한 후, 50 ℃에서 48시간 동안 교반 시켰다. 반응 후 가스크로마토그래피-질량 분석법(GC-MS)에 의해 목적 화합물 아크릴트리플루오르아세테이트의 수득률은 트리플루오르에탄올 기준으로 32몰%이었다. 가스크로마토그래피-질량 분석법(GC-MS)의 적용은 반응 중간에 주사기를 이용하여 일정량의 용액을 바이얼에 덜어낸 후 기준물질인 도데칸 (dodecane, 10 mol%)와 혼합한 후 바로 GC-MS 분석기에 주입하여 초기 온도는 30 oC로 세팅하고 1분당 5 oC 온도를 증가시키면 기준인 도데칸의 피크와 목적하는 아크릴산 또는 아크릴레이트 화합물이 각각 분리되어 나오고 각각의 피크들의 분자량은 자동계산하여 생성된 화합물을 확인한다.2,2,2-trifluoroethanol (100 mL, 100 mol%), N, N-dimethylformamide (250 mL), catalyst Ru (CO) (H 2 ) (PPh 3 ) 3 (2.5 mol% l) was added, acetylene gas (1 atm), carbon dioxide gas (1 atm), and hydrogen gas (1 atm) were added thereto, followed by stirring at 50 ° C. for 48 hours. After reaction, the yield of the target compound acryltrifluoroacetate was 32 mol% based on trifluoroethanol by gas chromatography-mass spectrometry (GC-MS). The application of gas chromatography-mass spectrometry (GC-MS) involves dispensing a certain amount of solution in a vial using a syringe in the middle of the reaction and mixing it with the reference material dodecane (10 mol%) and immediately following the GC- When injected into the MS analyzer, the initial temperature is set to 30 o C and the temperature increased by 5 o C per minute, the peaks of the reference dodecane and the desired acrylic acid or acrylate compound are separated and the molecular weights of the individual peaks are automatically calculated. Check the produced compound.
실시예2Example 2
촉매로 Ru(CO)(H2)(PPh3)3 대신에Ru(CO)ClH(PPh3)3 를 사용하는 것을 제외하고는 실시예1와 같이 실시하였다. 반응 후 가스크로마토그래피-질량 분석법에 의해 목적 화합물 아크릴트리플루오르아세테이트의 수득률은 트리플루오르에탄올 기준으로 33몰%이었다.The reaction was carried out as in Example 1, except that Ru (CO) ClH (PPh 3 ) 3 was used instead of Ru (CO) (H 2 ) (PPh 3 ) 3 as a catalyst. The yield of the target compound acryltrifluoroacetate by gas chromatography-mass spectrometry after the reaction was 33 mol% based on trifluoroethanol.
실시예3Example 3
촉매로 Ru(CO)ClH(PPh3)3 대신에 Ru(CO)(O2CCF3)2·CH3OH를 사용하는 것을 제외하고는 실시예1와 같이 실시하였다. 반응 후 가스크로마토그래피-질량 분석법에 의해 목적 화합물 아크릴트리플루오르아세테이트의 수득률은 트리플루오르에탄올 기준으로 52몰%이었다.The reaction was carried out as in Example 1, except that Ru (CO) (O 2 CCF 3 ) 2 .CH 3 OH was used instead of Ru (CO) ClH (PPh 3 ) 3 as a catalyst. The yield of the target compound acryltrifluoroacetate by gas chromatography-mass spectrometry after the reaction was 52 mol% based on trifluoroethanol.
Claims (7)
식2 Ru(CO)aXb(PPh3)c
상기 식2에서 a는 1 또는 2이고 c는 0 내지 3의 정수이고 a+b+c는 5이고 X는 O2CCF3, HCL 또는 H2이다.
식3 Ru(CO)(O2CCF3)2·CH3OHPreparing a primary or secondary alcohol solution having 1 to 4 carbon atoms dissolved in an aprotic polar organic solvent; Dispersing a carbonylruthenium-based transition metal catalyst powder of Formula 2 or Formula 3 in the alcohol solution; Reacting carbon dioxide, acetylene and hydrogen gas by mixing the alcohol solution; And distilling the reaction liquid mixture generated in the previous step to separate the acrylate.
2 Ru (CO) a X b (PPh 3 ) c
In Formula 2, a is 1 or 2, c is an integer of 0 to 3, a + b + c is 5 and X is O 2 CCF 3, HCL or H 2 .
Formula 3 Ru (CO) (O 2 CCF 3 ) 2 CH 3 OH
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