KR20200064457A - Method for Production of 5-Vinyl-2-Norbornene Using Zeolite Catalyst substituted with Sn - Google Patents
Method for Production of 5-Vinyl-2-Norbornene Using Zeolite Catalyst substituted with Sn Download PDFInfo
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- KR20200064457A KR20200064457A KR1020180150606A KR20180150606A KR20200064457A KR 20200064457 A KR20200064457 A KR 20200064457A KR 1020180150606 A KR1020180150606 A KR 1020180150606A KR 20180150606 A KR20180150606 A KR 20180150606A KR 20200064457 A KR20200064457 A KR 20200064457A
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- norbornene
- vinyl
- tin
- cyclopentadiene
- zeolite
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 48
- 239000010457 zeolite Substances 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 80
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 45
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 238000005698 Diels-Alder reaction Methods 0.000 abstract description 13
- 239000006227 byproduct Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 3
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 230000001939 inductive effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 8
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910017855 NH 4 F Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical group CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 description 1
- NWNPESVXYXCGLH-UHFFFAOYSA-N 4-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C=C)C2 NWNPESVXYXCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- -1 and the like Natural products 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- XDRPDDZWXGILRT-FDGPNNRMSA-L bis[[(z)-4-oxopent-2-en-2-yl]oxy]tin Chemical compound [Sn+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O XDRPDDZWXGILRT-FDGPNNRMSA-L 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- FLQHFAFLFQBLML-UHFFFAOYSA-N cyclohexene hex-1-ene Chemical compound C1=CCCCC1.C=CCCCC FLQHFAFLFQBLML-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/50—Diels-Alder conversion
- C07C2/52—Catalytic processes
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/39—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing seven carbon atoms
- C07C13/42—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing seven carbon atoms with a bicycloheptene ring structure
- C07C13/43—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing seven carbon atoms with a bicycloheptene ring structure substituted by unsaturated acyclic hydrocarbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/20—Use of additives, e.g. for stabilisation
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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Abstract
Description
본 발명은 5-비닐-2-노보넨(5-vinyl-2-norbornene, VNB)의 제조방법에 관한 것으로, 보다 상세하게는 제올라이트의 골격 구성 원소 중 하나인 알루미눔을 주석으로 치환한 제올라이트 촉매를 이용하여 5-비닐-2-노보넨을 제조하는 방법에 관한 것이다.The present invention relates to a method of producing 5-vinyl-2-norbornene (5-vinyl-2-norbornene, VNB), and more specifically, a zeolite catalyst in which one of the skeleton constituent elements of zeolite is replaced with tin. It relates to a method for producing 5-vinyl-2-norbornene using.
5-비닐-2-노보넨은 에틸렌-프로필렌-디엔 공중합체(ethylene-propylene-diene monomer, EPDM) 합성고무 제조 시 디엔으로 사용되는 5-에틸리덴-2-노보넨(5-ethylidene-2-norbornene, ENB)의 원료이며, 일반적으로 아래의 반응식 1과 같이 1,3-부타디엔(1,3-butadiene, BD)과 사이클로펜타디엔(cyclopentadiene, CPD)의 딜스-알더(Diels-Alder) 반응을 통해 제조한다.5-Vinyl-2-norbornene is 5-ethylidene-2-norbornene (5-ethylidene-2- used as diene in the manufacture of ethylene-propylene-diene monomer (EPDM) synthetic rubber. norbornene, ENB), and in general, Diels-Alder reaction of 1,3-butadiene (BD) and cyclopentadiene (CPD) as shown in Reaction Scheme 1 below. Is manufactured through.
[반응식 1] [Scheme 1]
딜스-알더 반응은 컨쥬게이티드 디엔(conjugated diene)과 알켄(alkene)의 유기화학반응으로, 컨쥬게이티드 디엔과 친디엔체(dienophile)의 혼합물에 열 등의 에너지를 가해주면, 고리 모양의 사이클로헥센(cyclohexene)이 형성되는 반응이다. 1,3-부타디엔과 사이클로펜타디엔의 딜스-알더 반응에서는 두 반응물이 모두 컨쥬게이티드 디엔과 알켄으로서 작용할 수 있어서 부산물이 많이 생성되는 문제가 있다. 상기와 같은 이유로 상용화된 5-비닐-2-노보넨 제조 공정에서도 반응에 참여한 사이클로펜타디엔의 50%가 올리고머 및 부산물로 전환되어 원단위가 증가하는 특징이 있다. 미국 특허 제4,219,688호에서도 무촉매 상태에서 1,3-부타디엔과 사이클로펜타디엔의 딜스-알더 반응을 통해 5-비닐-2-노보넨을 제조하는 경우 반응온도 170℃에서 반응시간이 3 내지 4시간으로 길며, 5-비닐-2-노보넨 선택도가 20 내지 35%로 낮음을 시사한다. The Diels-Alder reaction is an organic chemical reaction of conjugated diene and alkene. When energy such as heat is applied to a mixture of conjugated diene and dienophile, it is a cycle of a ring. It is a reaction in which hexene (cyclohexene) is formed. In the Diels-Alder reaction of 1,3-butadiene and cyclopentadiene, both reactants can act as conjugated dienes and alkenes, and there is a problem that many by-products are generated. For the above reasons, even in the commercialized 5-vinyl-2-norbornene production process, 50% of the cyclopentadiene participating in the reaction is converted into oligomers and by-products, thereby increasing the raw unit. In the case of preparing 5-vinyl-2-norbornene through a Diels-Alder reaction of 1,3-butadiene and cyclopentadiene in a non-catalytic state in US Patent No. 4,219,688, the reaction time is 3 to 4 hours at a reaction temperature of 170°C. It is long, suggesting that 5-vinyl-2-norbornene selectivity is as low as 20 to 35%.
이에 5-비닐-2-노보넨 선택도를 향상시키고자 시도된 다양한 방법들이 보고되었다. 예를 들어, 다양한 루이스산 촉매를 적용하는 방법이 있다. 이에 대하여, 대한민국 특허공보 제10-0258196호에서는 루이스산 특성을 부가하기 위한 방법으로 원소주기율 제1족의 알칼리 금속, 제2족의 알칼리 토금속, 또는 이들의 혼합물을 제올라이트에 담지하여 반응온도 200℃ 및 반응압력 400psig에서 5-비닐-2-노보넨을 제조하여 사이클로펜타디엔 전환율 80 내지 90% 및 5-비닐-2-노보넨 선택도 30 내지 50%를 달성한 바 있다. 그러나, 제올라이트에 존재하는 고유의 브뢴스테드산으로 인해 3a,4,7,7a-테트라하이드로인덴(3a,4,7,7a-tetrahydro-indene, THI) 및 올리고머와 같은 부산물의 생성을 수반하고 반응이 진행되는 동안 5-비닐-2-노보넨이 3a,4,7,7a-테트라하이드로인덴으로 전환되어 5-비닐-2-노보넨의 수율이 감소할 뿐만 아니라 끓는점이 비슷하여 증류로 5-비닐-2-노보넨을 분리할 때 어려움이 있다. Accordingly, various methods have been reported to attempt to improve 5-vinyl-2-norbornene selectivity. For example, there is a method of applying various Lewis acid catalysts. On the other hand, in Korean Patent Publication No. 10-0258196, as a method for adding Lewis acid characteristics, an element periodicity group 1 alkali metal,
또한, 대한민국 특허공보 제10-0652922호에서는 1,3-부타디엔과 사이클로펜타디엔의 딜스-알더 반응 시 부산물인 3a,4,7,7a-테트라하이드로인덴 및 올리고머의 생성을 감소시키고자 불화나트륨(NaF), 불화칼륨(KF), 불화세슘(CsF), 불화마그네슘(MgF2), 불화아연(ZnF2) 및 불화암모늄(NH4F) 중에서 선택된 불소 화합물 및 이들이 담지된 담지 촉매를 적용한 바 있다. 그 결과, 불화칼륨(KF)을 담지한 알루미나 촉매하에서 사이클로펜타디엔 전환율 99% 및 5-비닐-2-노보넨 선택도 60%를 달성하였다. 하지만, 상기 촉매의 경우, 불소 화합물이 금속염 형태로 사용되어 생성물과 촉매 분리가 어렵고 물질 자체의 독성에 따른 위험성이 존재한다.In addition, Korean Patent Publication No. 10-0652922 discloses sodium fluoride to reduce the production of byproducts 3a,4,7,7a-tetrahydroindene and oligomers during the Diels-Alder reaction of 1,3-butadiene and cyclopentadiene. Fluorine compounds selected from (NaF), potassium fluoride (KF), cesium fluoride (CsF), magnesium fluoride (MgF 2 ), zinc fluoride (ZnF 2 ) and ammonium fluoride (NH 4 F), and supported catalysts supported thereon have. As a result, a cyclopentadiene conversion rate of 99% and 5-vinyl-2-norbornene selectivity were achieved under alumina catalyst carrying potassium fluoride (KF). However, in the case of the catalyst, since the fluorine compound is used in the form of a metal salt, it is difficult to separate the product from the catalyst, and there is a risk according to the toxicity of the substance itself.
추가로, 대한민국 특허공보 제10-0652921호에서는 불화나트륨(NaF), 불화칼륨(KF), 불화세슘(CsF), 불화마그네슘(MgF2), 불화아연(ZnF2) 및 불화암모늄(NH4F) 중에서 선택된 불소 화합물이 담지된 담지촉매를 사용하여 사이클로펜타디엔과 1,3-부타디엔의 딜스-알더 반응을 수행하는 기술을 개시하면서 종래와 동등 이상의 전환율, 수율 및 5-비닐-2-노보넨 선택도를 유지하는 동시에 부산물인 3a,4,7,7a-테트라하이드로인덴과 올리고머의 선택도는 감소시키고, 목적물인 5-비닐-2-노보넨의 회수를 위한 정제공정이 용이하다고 언급하고 있다. 그러나, 불소 화합물이 금속염 형태로 담지되므로 상기 촉매를 반복 사용하면 촉매 성분의 유실에 의한 비활성화 가능성이 높다는 단점이 있다.Additionally, in Korean Patent Publication No. 10-0652921, sodium fluoride (NaF), potassium fluoride (KF), cesium fluoride (CsF), magnesium fluoride (MgF 2 ), zinc fluoride (ZnF 2 ) and ammonium fluoride (NH 4 F ) Using a supported catalyst having a fluorine compound selected from the above, discloses a technique for performing a Diels-Alder reaction of cyclopentadiene and 1,3-butadiene, and has a conversion rate, yield equal to or higher than that of the prior art, and 5-vinyl-2-norbornene While maintaining the selectivity, the selectivity of by-products 3a,4,7,7a-tetrahydroindene and oligomer is reduced, and it is mentioned that the purification process for the recovery of the target product, 5-vinyl-2-norbornene is easy. have. However, since the fluorine compound is supported in the form of a metal salt, there is a disadvantage that the possibility of deactivation due to loss of the catalyst component is high when the catalyst is repeatedly used.
본 발명의 목적은 종래 기술의 단점을 회피하면서 사이클로펜타디엔과 1,3-부타디엔으로부터 5-비닐-2-노보넨을 제조하는 새로운 방법을 제공하는 것이다.It is an object of the present invention to provide a new method for producing 5-vinyl-2-norbornene from cyclopentadiene and 1,3-butadiene while avoiding the disadvantages of the prior art.
상기 목적을 달성하기 위하여, 본 발명은 제올라이트의 골격 내 알루미눔을 주석으로 치환한 제올라이트 촉매(이하, 주석 치환 제올라이트 촉매)의 존재하에서 사이클로펜타디엔과 1,3-부타디엔의 딜스-알더 반응을 통해 5-비닐-2-노보넨을 제조하는 방법을 제공한다. In order to achieve the above object, the present invention through the Diels-Alder reaction of cyclopentadiene and 1,3-butadiene in the presence of a zeolite catalyst (hereinafter, a tin-substituted zeolite catalyst) in which aluminum in the skeleton of the zeolite is substituted with tin. A method for producing 5-vinyl-2-norbornene is provided.
본 발명에 따르면, 사이클로펜타디엔과 1,3-부타디엔의 딜스-알더 반응을 통한 5-비닐-2-노보넨의 제조에 주석 치환 제올라이트 촉매를 사용함으로써, 5-비닐-2-노보넨을 높은 선택도로 수득할 수 있다.According to the present invention, by using a tin-substituted zeolite catalyst for the production of 5-vinyl-2-norbornene through a Diels-Alder reaction of cyclopentadiene and 1,3-butadiene, 5-vinyl-2-norbornene is high. It can be obtained with selectivity.
도 1은 실시예 1에서 제조한 주석 치환 BEA 제올라이트의 X선 회절 패턴이다.
도 2는 실시예 1에서 제조한 주석 치환 BEA 제올라이트의 피리딘 흡착 적외선 분광 스펙트럼이다.
도 3은 주석 치환 제올라이트(Sn-BEA) 및 K 담지된 제올라이트(K/BEA)를 각각 5-비닐-2-노보넨 제조 반응에 촉매로 적용한 경우에 수득한 사이클로펜타디엔 전환율 및 생성물 선택도를 그래프로 나타낸 것이다.1 is an X-ray diffraction pattern of the tin-substituted BEA zeolite prepared in Example 1.
2 is a pyridine adsorption infrared spectral spectrum of the tin-substituted BEA zeolite prepared in Example 1.
FIG. 3 shows the cyclopentadiene conversion and product selectivity obtained when tin-substituted zeolite (Sn-BEA) and K-supported zeolite (K/BEA) were applied as catalysts to a 5-vinyl-2-norbornene production reaction, respectively. It is shown graphically.
이하, 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 다양한 변환을 가할 수 있고 여러 가지 실시양태를 가질 수 있는 바, 특정 실시양태들을 예시하고자 한다. 그러나, 이는 본 발명을 특정한 실시 형태로 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변환, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 본 발명을 설명함에 있어서 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우 그 상세한 설명을 생략한다.The present invention is intended to illustrate certain embodiments, as various transformations may be applied and various embodiments may be applied. However, this is not intended to limit the present invention to a specific embodiment, it should be understood to include all conversions, equivalents, or substitutes included in the spirit and scope of the present invention. In the description of the present invention, if it is determined that a detailed description of known technologies related to the present invention may obscure the subject matter of the present invention, the detailed description will be omitted.
본 발명은 5-비닐-2-노보넨 선택도를 증진시키는 제조방법에 관한 것으로, 주석 치환된 제올라이트 촉매의 존재하에서 사이클로펜타디엔을 1,3-부타디엔과 반응시켜 5-비닐-2-노보넨을 제조하는 방법을 제공한다.The present invention It relates to a method for improving 5-vinyl-2-norbornene selectivity, and reacting cyclopentadiene with 1,3-butadiene in the presence of a tin-substituted zeolite catalyst to produce 5-vinyl-2-norbornene. Provide a method.
본 발명에서 사용되는 사이클로펜타디엔은 종래의 방법인 디사이클로펜타디엔의 열분해 증류법으로 순도 95% 이상으로 제조된다.The cyclopentadiene used in the present invention is produced with a purity of 95% or more by the pyrolysis distillation method of dicyclopentadiene, which is a conventional method.
본 발명은 상기한 사이클로펜타디엔과 1,3-부타디엔의 반응이 주석 치환 제올라이트 촉매 존재하에서 수행되는 것이 특징이다. 상기 주석 치환 제올라이트 촉매는 제올라이트의 골격 내 알루미눔을 루이스산 금속인 주석으로 치환하여 제올라이트 고유의 구조적 특징을 유지하면서 루이스산 특성을 갖는 촉매이다. 바람직한 실시양태에 따르면, 본 발명의 촉매에서 Si/Sn의 몰 비는 10 내지 50, 바람직하게는 10 내지 30일 수 있다.The present invention is characterized in that the reaction of cyclopentadiene and 1,3-butadiene described above is carried out in the presence of a tin-substituted zeolite catalyst. The tin-substituted zeolite catalyst is aluminum in the framework of the zeolite It is a catalyst that has Lewis acid properties while maintaining the unique structural characteristics of zeolite by substituting with Lewis acid metal tin. According to a preferred embodiment, the molar ratio of Si/Sn in the catalyst of the present invention may be 10 to 50, preferably 10 to 30.
본 발명에서, 상기 주석 치환 제올라이트 촉매는 골격 내 알루미눔이 제거된 제올라이트 분말을 주석 전구체와 혼합하고 소성하여 주석이 골격에 포함된 제올라이트로서 얻는다. 상기 주석 전구체로는 염화주석(II)(tin(II) chloride), 아세트산주석(II)(tin(II) acetate), 옥살산주석(II)(tin(II) oxalate), 아세틸아세톤산주석(II)(tin(II) acetylacetonate) 등을 사용할 수 있다.In the present invention, the tin-substituted zeolite catalyst is obtained by mixing and calcining a zeolite powder from which aluminum is removed in the skeleton with a tin precursor, and thus, as a zeolite containing tin in the skeleton. The tin precursors include tin(II) chloride, tin(II) acetate, tin oxalate (II), tin acetylacetonate (II) )(tin(II) acetylacetonate).
본 발명에서, 상기 주석 치환 제올라이트 촉매는 반응물인 사이클로펜타디엔과 1,3-부타디엔의 중량 합계에 대하여 0.1 내지 15중량%로 사용할 수 있는데, 상기 촉매의 사용량이 0.1중량% 미만이면 촉매 효과가 뚜렷하지 않고 상기 촉매의 사용량이 15중량%를 초과해도 반응 수율이 증가되지는 않는다. 바람직하게는, 주석 치환 제올라이트 촉매는 사이클로펜타디엔과 1,3-부타디엔의 중량 합계에 대하여 5 내지 15중량%로 사용할 수 있다.In the present invention, the tin-substituted zeolite catalyst can be used in an amount of 0.1 to 15% by weight based on the total weight of the reactants cyclopentadiene and 1,3-butadiene, and when the amount of the catalyst used is less than 0.1% by weight, the catalyst effect is obvious However, even if the amount of the catalyst used exceeds 15% by weight, the reaction yield does not increase. Preferably, the tin-substituted zeolite catalyst can be used in an amount of 5 to 15% by weight based on the total weight of cyclopentadiene and 1,3-butadiene.
본 발명에서, 사이클로펜타디엔 1몰에 대하여 1,3-부타디엔을 1 내지 5몰, 바람직하게는 사이클로펜타디엔 1몰에 대하여 1,3-부타디엔을 1 내지 3몰 투입시킬 수 있다.In the present invention, 1 to 3 moles of 1,3-butadiene may be added to 1 mole of cyclopentadiene, preferably 1 to 3 moles of 1,3-butadiene to 1 mole of cyclopentadiene.
본 발명에서, 상기 반응은 160 내지 250℃의 온도 범위에서 수행할 수 있다. 반응 온도가 160℃ 미만이면 사이클로펜타디엔의 이량화에 의한 디사이클로펜타디엔 생성이 증가하며, 반응 온도가 250℃를 초과하게 되면 5-비닐-2-노보넨의 이성질화에 의해 3a,4,7,7a-테트라하이드로인덴 생성이 증가하고 올리고머의 생성량도 증가한다. In the present invention, the reaction can be carried out in a temperature range of 160 to 250 ℃. When the reaction temperature is less than 160°C, dicyclopentadiene production by dimerization of cyclopentadiene increases, and when the reaction temperature exceeds 250°C, 3a,4, by isomerization of 5-vinyl-2-norbornene, 7,7a-tetrahydroindene production increases and the amount of oligomer production increases.
본 발명에서, 상기 반응은 1400 내지 3500kPa의 압력 범위에서 수행할 수 있다. 또한, 상기 반응은 질소, 아르곤 등과 같은 불활성 기체를 이용하여 가압할 수 있다.In the present invention, the reaction can be carried out in a pressure range of 1400 to 3500kPa. In addition, the reaction may be pressurized using an inert gas such as nitrogen or argon.
본 발명에서, 상기 반응은 5 내지 30분 동안 수행할 수 있고, 바람직하게는 10분 정도가 좋다. 반응 시간이 30분을 초과하게 되면 생성된 5-비닐-2-노보넨이 3a,4,7,7a-테트라하이드로인덴으로 이성질화되어 5-비닐-2-노보넨 선택도가 감소하고 부산물이 증가하는 단점이 있다.In the present invention, the reaction can be carried out for 5 to 30 minutes, preferably about 10 minutes. When the reaction time exceeds 30 minutes, the resulting 5-vinyl-2-norbornene isomerizes to 3a,4,7,7a-tetrahydroindene to reduce 5-vinyl-2-norbornene selectivity and by-products. This has the disadvantage of increasing.
본 발명에서, 상기 제올라이트로는 BEA, FAU, MOR, FER, MFI 및 LTL형 제올라이트로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있다. 바람직하게는, 상기 제올라이트는 BEA형일 수 있다.In the present invention, as the zeolite, one or more selected from the group consisting of BEA, FAU, MOR, FER, MFI and LTL type zeolite may be used. Preferably, the zeolite may be BEA type.
본 발명에서, 상기 반응은 지방족 탄화수소 및 방향족 탄화수소 용매로 이루어진 군으로부터 선택된 1종 이상의 용매를 사용하여 수행할 수 있다. 상기 탄화수소 용매로는 극성이 낮고 생성물과의 끓는점 차이가 커서 분리한 용이한 용매를 사용할 수 있다. 이러한 용매로는, 예를 들어, 사이클로헥산, 펜탄, 헥산, 헵탄, 사염화탄소(CCl4), 이황화탄소(CS2), p-자일렌(p-xylene), 톨루엔, 벤젠, 디에틸에테르, 메틸 t-부틸 에테르(MTBE), 디에틸아민 등이 있고, n-헥산 및 톨루엔이 바람직하다.In the present invention, the reaction may be performed using one or more solvents selected from the group consisting of aliphatic hydrocarbons and aromatic hydrocarbon solvents. As the hydrocarbon solvent, a low polarity and a large difference in boiling point from the product may be used to facilitate separation of the solvent. Such solvents include, for example, cyclohexane, pentane, hexane, heptane, carbon tetrachloride (CCl 4 ), carbon disulfide (CS 2 ), p-xylene, toluene, benzene, diethyl ether, methyl t-butyl ether (MTBE), diethylamine, and the like, and n-hexane and toluene are preferred.
본 발명에서, 상기 반응은 사이클로펜타디엔 1중량부에 대하여 20중량부 이하의 용매 중에서 수행할 수 있다.In the present invention, the reaction may be carried out in a solvent of 20 parts by weight or less based on 1 part by weight of cyclopentadiene.
본 발명의 반응은 종래 사이클로펜타디엔과 1,3-부타디엔으로부터 5-비닐-2-노보넨을 합성하는 데 사용되는 반응기를 사용하여 수행할 수 있고, 특별히 한정되지는 않는다. The reaction of the present invention can be carried out using a reactor used to synthesize 5-vinyl-2-norbornene from conventional cyclopentadiene and 1,3-butadiene, and is not particularly limited.
실시예Example
이하, 본 발명의 구체적인 실시예를 통해 발명의 작용, 효과를 보다 구체적으로 설명하기로 한다. 다만, 이는 본 발명의 예시로서 제시된 것으로 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며, 실시예에 의해 본 발명의 권리범위가 어떠한 의미로든 한정되는 것은 아니다.Hereinafter, the operation and effects of the invention will be described in more detail through specific examples of the present invention. However, this is provided as an example of the present invention, and the present invention may be implemented in various different forms, and the scope of the present invention is not limited in any sense by examples.
제조예 1: 주석 치환 제올라이트 촉매의 제조 Preparation Example 1 : Preparation of tin-substituted zeolite catalyst
BEA 제올라이트(25g)를 7M의 질산 수용액(500mL)에 분산시킨 후 100℃, 환류 조건에서 밤새 처리하여 골격 내 알루미눔을 제거하였다. 이어서 제올라이트를 증류수로 세척하여 잔존 질산 수용액을 완전히 제거하고 상온에서 24시간 동안 건조시킨 후 110℃에서 2시간 동안 완전히 건조시켰다. 건조된 제올라이트 분말(20g)을 주석 전구체로서 염화주석(II)(6.5g)과 균일하게 혼합한 후 500℃, 공기 분위기에서 4시간 동안 소성하여 골격 내 알루미눔이 주석으로 치환된 BEA 제올라이트 촉매를 얻었다(Si/Sn 몰 비 = 20). 이를 X선 회절 분석한 결과, 도 1에 나타낸 바와 같이, 주석 치환 BEA 제올라이트의 골격 구조를 유지하고 있었다. BEA zeolite (25 g) was dispersed in a 7 M aqueous nitric acid solution (500 mL), and then treated at 100° C. under reflux overnight to remove aluminum in the skeleton. Subsequently, the zeolite was washed with distilled water to completely remove the residual aqueous nitric acid solution, dried at room temperature for 24 hours, and then completely dried at 110°C for 2 hours. The dried zeolite powder (20 g) was uniformly mixed with tin chloride (II) (6.5 g) as a tin precursor, and then calcined at 500° C. for 4 hours in an air atmosphere to obtain a BEA zeolite catalyst in which aluminum in the skeleton was replaced with tin. Obtained (Si/Sn molar ratio = 20). As a result of X-ray diffraction analysis, as shown in Fig. 1, the skeleton structure of the tin-substituted BEA zeolite was maintained.
추가로, 주석 치환 BEA 제올라이트에 피리딘을 흡착시켜 적외선 분광분석한 결과, 도 2에 나타낸 바와 같이, 파수(wavenumber) 1450cm-1 영역의 흡수 밴드가 루이스산에 공유결합된 피리딘의 적외선 흡수 밴드를 나타내는 것으로부터, 주석이 제올라이트 골격 내 치환됨으로써 루이스산점이 형성되었음을 확인할 수 있었다.In addition, as a result of infrared spectroscopy by adsorbing pyridine to a tin-substituted BEA zeolite, as shown in FIG. 2, the absorption band in the wavenumber 1450 cm -1 region represents the infrared absorption band of pyridine covalently bound to Lewis acid. From this, it was confirmed that the Lewis acid point was formed by substitution of tin in the zeolite skeleton.
실시예 1: 주석 치환 제올라이트 촉매를 이용한 딜스-알더 반응 Example 1 : Diels-Alder reaction using a tin-substituted zeolite catalyst
500mL의 고압 반응기에 용매인 톨루엔 270mL(234.09g), 1,3-부타디엔 23.4g(0.433몰), 사이클로펜타디엔 14.9g(0.225몰) 및 제조예 1에서 제조한 주석 치환 BEA 제올라이트 촉매(Sn-BEA) 4.5g을 질소 분위기하에서 투입하였다. 질소로 가압하여 반응기 압력을 2700kPa까지 증가시킨 후 200℃에서 10분 동안 반응을 수행하였다. 반응 종료 후, 반응기 온도를 상온까지 급냉시키고, 생성물을 샘플링하여 기체 크로마토그래피와 아래 식을 이용하여 사이클로펜타디엔 전환율 및 생성물 선택도를 계산하였다.In a high pressure reactor of 500 mL, 270 mL (234.09 g) of toluene, 23.4 g (0.433 mol) of 1,3-butadiene, 14.9 g (0.225 mol) of cyclopentadiene and tin-substituted BEA zeolite catalyst prepared in Preparation Example 1 (Sn- BEA) 4.5g was added under a nitrogen atmosphere. After pressurizing with nitrogen to increase the reactor pressure to 2700 kPa, the reaction was performed at 200°C for 10 minutes. After the reaction was completed, the reactor temperature was rapidly cooled to room temperature, and the product was sampled to calculate cyclopentadiene conversion and product selectivity using gas chromatography and the following formula.
사이클로펜타디엔 전환율(%) = (생성물로 전환된 사이클로펜타디엔의 몰 수/반응에 공급된 사이클로펜타디엔의 몰 수) x 100Cyclopentadiene conversion (%) = (number of moles of cyclopentadiene converted to product/number of moles of cyclopentadiene supplied to the reaction) x 100
생성물 선택도(%) = (사이클로펜타디엔으로부터 전환된 특정 생성물의 몰 수/사이클로펜타디엔으로부터 전환된 모든 생성물의 몰 수 x 100Product selectivity (%) = (molar number of specific products converted from cyclopentadiene/mole number of all products converted from
분석 결과를 아래 표 1에 나타냈다.Table 1 shows the results of the analysis.
제조예 2: 알칼리 금속 담지 제올라이트 촉매의 제조 Preparation Example 2 : Preparation of alkali metal-supported zeolite catalyst
질산칼륨 6.9g을 증류수 50mL에 완전히 용해시킨 후 건조된 BEA 제올라이트 50g에 함침하였다. 110℃에서 2시간 동안 건조시킨 후, 500℃, 공기 분위기에서 4시간 동안 소성하여 K가 담지된 BEA 제올라이트(K/BEA) 촉매를 제조하였다. 제조된 촉매의 성분 분석 결과, K의 함량은 5중량%였다.6.9 g of potassium nitrate was completely dissolved in 50 mL of distilled water and then impregnated with 50 g of dried BEA zeolite. After drying at 110° C. for 2 hours, calcination was performed at 500° C. for 4 hours in an air atmosphere to prepare a K-supported BEA zeolite (K/BEA) catalyst. As a result of component analysis of the prepared catalyst, the content of K was 5% by weight.
비교예 1: 알칼리 금속 담지 제올라이트 촉매를 이용한 딜스-알더 반응 Comparative Example 1 : Diels-Alder reaction using an alkali metal-supported zeolite catalyst
제조예 2에서 제조한 알칼리 금속 K가 담지된 BEA 제올라이트(K/BEA)를 촉매로서 사용하는 것을 제외하고는 실시예 1과 동일하게 반응을 수행하여 생성물을 수득하고, 실시예 1에 기재된 식을 이용하여 사이클로펜타디엔 전환율 및 생성물 선택도를 계산하였다. 분석 결과를 아래 표 1에 나타냈다.The reaction was performed in the same manner as in Example 1, except that the BEA zeolite (K/BEA) loaded with the alkali metal K prepared in Preparation Example 2 was used as a catalyst to obtain a product, and the formula described in Example 1 was obtained. Cyclopentadiene conversion and product selectivity were calculated. Table 1 shows the results of the analysis.
선택도(%)product
Selectivity (%)
또한, 위의 표 1의 분석 결과에 따른 사이클로펜타디엔 전환율 및 생성물 선택도를 도 3에 그래프로 나타냈다.In addition, the cyclopentadiene conversion and product selectivity according to the analysis results in Table 1 above are shown graphically in FIG. 3.
위의 표 1 및 도 3으로부터, 주석 치환 BEA 제올라이트(Sn-BEA)를 5-비닐-2-노보넨 제조 반응에 촉매로 적용할 경우, K 담지된 BEA 제올라이트(K/BEA)에 비해 5-비닐-2-노보넨 선택도가 증가하고 부산물인 올리고머 선택도가 감소함을 확인할 수 있다.From Table 1 and FIG. 3, when tin-substituted BEA zeolite (Sn-BEA) is applied as a catalyst to the 5-vinyl-2-norbornene production reaction, it is 5-compared to K-supported BEA zeolite (K/BEA). It can be seen that the selectivity of vinyl-2-norbornene increases and the selectivity of by-product oligomer decreases.
이상의 내용을 근거로 할 때, 본 발명에 의하면 주석 치환 제올라이트 촉매의 존재하에 1,3-부타디엔과 사이클로펜타디엔의 딜스-알더 반응을 진행하는 경우 5-비닐-2-노보넨 선택도를 개선할 수 있으며, 부산물인 올리고머의 생성을 감소시킬 수 있다. Based on the above, according to the present invention, 5-vinyl-2-norbornene selectivity is improved when the Diels-Alder reaction of 1,3-butadiene and cyclopentadiene is performed in the presence of a tin-substituted zeolite catalyst. Can reduce the production of by-product oligomers.
또한, 본 발명에서 개발한 촉매를 사용하여 딜스-알더 반응을 진행하는 경우 생성물과 촉매의 분리가 용이하며, 촉매 금속 성분의 유출 없이 안정적으로 반응성을 유지할 수 있다.In addition, when the Diels-Alder reaction is performed using the catalyst developed in the present invention, the separation of the product and the catalyst is easy, and the reactivity can be stably maintained without leaking the catalyst metal component.
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시 양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.Since the specific parts of the present invention have been described in detail above, it is obvious to those skilled in the art that this specific technique is only a preferred embodiment, and the scope of the present invention is not limited thereby. something to do. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.
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| KR100258196B1 (en) | 1997-08-25 | 2000-06-01 | 남창우 | Method for preparing 5-vinyl-2-norbornene using a ununiform catalyst |
| KR100652921B1 (en) | 2005-12-07 | 2006-12-04 | 한국과학기술연구원 | Preparation method of 5-vinyl-2-norbornene using supported catalysts containg fluoride compound |
| KR100652922B1 (en) | 2005-12-07 | 2006-12-04 | 한국과학기술연구원 | A process for preparing 5-vinyl-2-norbornene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100258196B1 (en) | 1997-08-25 | 2000-06-01 | 남창우 | Method for preparing 5-vinyl-2-norbornene using a ununiform catalyst |
| KR100652921B1 (en) | 2005-12-07 | 2006-12-04 | 한국과학기술연구원 | Preparation method of 5-vinyl-2-norbornene using supported catalysts containg fluoride compound |
| KR100652922B1 (en) | 2005-12-07 | 2006-12-04 | 한국과학기술연구원 | A process for preparing 5-vinyl-2-norbornene |
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