WO2023070760A1 - 一种催化进行烯烃羰基化的方法 - Google Patents
一种催化进行烯烃羰基化的方法 Download PDFInfo
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- propylene
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- olefin
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 16
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 230000006315 carbonylation Effects 0.000 title claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 11
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 6
- -1 ethylene, propylene, butene Chemical class 0.000 claims abstract description 5
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 101150034699 Nudt3 gene Proteins 0.000 claims abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 21
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 19
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 14
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 229910018286 SbF 6 Inorganic materials 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 238000007037 hydroformylation reaction Methods 0.000 description 13
- 229910052703 rhodium Inorganic materials 0.000 description 9
- 239000010948 rhodium Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- VUFNLQXQSDUXKB-DOFZRALJSA-N 2-[4-[4-[bis(2-chloroethyl)amino]phenyl]butanoyloxy]ethyl (5z,8z,11z,14z)-icosa-5,8,11,14-tetraenoate Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(=O)OCCOC(=O)CCCC1=CC=C(N(CCCl)CCCl)C=C1 VUFNLQXQSDUXKB-DOFZRALJSA-N 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 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 1
- UZOOFOAVJQHYEU-UHFFFAOYSA-N C(=O)=[RhH].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C(=O)=[RhH].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 UZOOFOAVJQHYEU-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CNXSPTPPLUUKDE-UHFFFAOYSA-K [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O.C1CCC=CC=CC1 Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O.C1CCC=CC=CC1 CNXSPTPPLUUKDE-UHFFFAOYSA-K 0.000 description 1
- NENDHUHGFRLXEN-UHFFFAOYSA-N acetic acid;rhodium Chemical compound [Rh].CC(O)=O NENDHUHGFRLXEN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- KGQCLZJFUIPDGS-UHFFFAOYSA-N dioxaphospholane Chemical compound C1CPOO1 KGQCLZJFUIPDGS-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- GNPXKHTZVDUNOY-UHFFFAOYSA-N oxomethylidenerhodium Chemical compound O=C=[Rh] GNPXKHTZVDUNOY-UHFFFAOYSA-N 0.000 description 1
- BDDWSAASCFBVBK-UHFFFAOYSA-N rhodium;triphenylphosphane Chemical compound [Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BDDWSAASCFBVBK-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
-
- 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
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
-
- 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
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
- B01J2531/0233—Aza-Cp ligands, i.e. [CnN(5-n)Rn]- in which n is 0-4 and R is H or hydrocarbyl, or analogous condensed ring systems
-
- 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
Definitions
- the invention relates to the field of carbonylation reactions, in particular to a method for carbonylation of olefins with a catalyst.
- butanol and octanol are bulk chemical raw materials with a wide range of uses. At present, butanol is synthesized industrially mainly through propylene hydroformylation to produce n-butyraldehyde and isobutyraldehyde, and then use this as raw material for subsequent reactions. Propylene hydroformylation is a key step in the synthesis of butanol.
- WO0200583, EP3712126A1, and CN102826967A use triphenylphosphine-rhodium as a catalyst; JP2002047294 uses cyclooctadiene acetate-rhodium as a catalyst; CN110156580 uses 6,6'-((3,3'-di-tert-butyl-5 ,5'-Dimethoxy-[1,1'-biphenyl]-2,bis(oxy))dibenzo[d,f][1,3,2]dioxaphospholane Alkene-rhodium is a catalyst; CN103896748A uses acetylmorpholine-rhodium as a catalyst; EP3770144A1 uses acetic acid-rhodium as a catalyst; CN111348995A uses three [2,4-di-tert-butylphenyl] phosphite-rhodium as a catalyst; US9550179 uses long
- Rhodium has relatively high catalytic activity for propylene hydroformylation reaction, and the reaction conditions of the reaction system using this as catalyst are generally relatively mild, with a typical reaction temperature between 90-132°C and a typical reaction pressure between 1.6-5MPa (see Table 1).
- the first object of the present invention is to provide a method for carbonylation of olefins with a catalyst.
- the method further adjusts the performance of the catalyst by coordinating metal iridium with highly active carbene ligands, and endows the catalyst with good catalytic activity.
- the reaction temperature can be lowered, the energy consumption can be reduced, and the cost can be reduced.
- the invention provides a method for carbonylation of olefins with a catalyst, comprising the following steps: using cyclic alkylcarbene iridium as a catalyst, and olefins as raw materials for carbonylation reaction to generate aldehydes, and the structural formula of the cyclic alkylcarbene iridium is:
- Dipp is 2,6-diisopropylbenzene
- R 1 and R 2 are methyl or ethyl
- X is Cl, Br, CH 3 CO 2 , NO 3 , BF 4 , PF 6 or SbF 6 ;
- the olefins include one or more of ethylene, propylene, butene and higher olefins.
- the above catalyst can be better applied in the olefin carbonylation reaction process, and compared with the previous rhodium catalyst, it has low cost, good activity and good catalytic effect.
- the reaction solvent includes one or a mixture of n-butyraldehyde, isobutyraldehyde, toluene, benzene and tetrahydrofuran.
- the catalyst is used in an amount of 0.005-2 wt%, preferably 0.05-1 wt%, of the amount of the reaction solvent.
- the olefin propylene, other raw materials include carbon monoxide and hydrogen
- the total reaction pressure is between 0.5-5.0 MPa, preferably between 1.0-3.0 MPa.
- the total reaction pressure can be 0.6MPa, 0.7MPa, 0.7MPa, 0.9MPa, 1.0MPa and so on.
- the reaction temperature is between 60°C and 180°C, preferably between 80°C and 140°C.
- the reaction temperature may be 60°C, 70°C, 80°C, or 90°C.
- the scheme of the present invention is more suitable for the hydroformylation reaction of propylene, and can obtain better reaction effect at 60-180° C. and a pressure of 0.5-5.0 MPa. At the same time, the price of metal iridium is only about one-third of metal rhodium. It is equivalent to that the present invention provides an economical and mild new method for synthesizing n-butyraldehyde and isobutyraldehyde through propylene hydroformylation reaction.
- the partial pressure ratio of propylene to carbon monoxide is between 1:1-1:10, preferably between 1:2-1:5.
- the partial pressure ratio of propylene to hydrogen is between 1:1-1:10, preferably between 1:2-1:5.
- Controlling each operating parameter in the above reaction process within an appropriate ratio range can significantly improve the effect of the reaction.
- the carbonylation reaction method of the present invention has a high activity carbene ligand in coordination with metal iridium, and uses a coordination anion to further adjust the performance of the catalyst, which endows the catalyst with good catalytic activity;
- Fig. 1 is the catalyst CAAC (C 2 C 2 )-Ir-Cl carbon nuclear magnetic resonance spectrogram that the embodiment 1 of the present invention provides;
- Fig. 2 is the H NMR spectrum of the catalyst CAAC(C 2 C 2 )-Ir-Cl provided in Example 1 of the present invention.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种催化进行烯烃羰基化的方法，包括如下步骤：以环状烷基卡宾铱为催化剂，烯烃为原料羰基化反应生成醛，所述环状烷基卡宾铱的结构式为：其中，Dipp为2,6-二异丙基苯，R 1、R 2为甲基或乙基，X为Cl、Br、CH 3CO 2、NO 3、BF 4 、PF 6或SbF 6；所述烯烃包括乙烯、丙烯、丁烯以及高碳烯烃中的一种或几种。所述烯烃羰基化的方法通过采用铱催化剂，催化活性好，降低反应能耗，充分降低了反应温度。
Description
本发明涉及羰基化反应领域，具体而言，涉及一种催化剂进行烯烃羰基化的方法。
丁醇和辛醇是用途非常广泛的大宗化工原料。目前，工业上合成丁辛醇主要通过丙烯氢甲酰化反应制得正丁醛和异丁醛，然后以此为原料进行后续反应而得。丙烯氢甲酰化反应是合成丁辛醇的关键步骤。
至今，已有许多关于丙烯氢甲酰化合成正丁醛和异丁醛的专利报道，这些专利以及目前工业方法普遍采用基于金属铑的催化剂。比如，WO0200583、EP3712126A1、CN102826967A使用三苯基磷-铑为催化剂；JP2002047294使用环辛二烯醋酸-铑为催化剂；CN110156580使用6,6'-((3,3'-二-叔丁基-5,5'-二甲氧基-[1,1'-联苯]-2,双(氧基))二苯并[d,f][1,3,2]二氧杂磷杂环戊二烯-铑为催化剂；CN103896748A使用乙酰吗啉-铑为催化剂；EP3770144A1使用醋酸-铑为催化剂；CN111348995A使用三[2，4-二叔丁基苯基]亚磷酸酯-铑为催化剂；US9550179使用长链羧酸-铑为催化剂；CN102826973A使用乙酰丙酮羰基-铑为催化剂；EP2417094B1使用三苯基膦羰基氢化铑为催化剂；EP2417093B1使用二聚醋酸铑+三苯基磷三间磺酸钠盐。由于金属铑具有较高的丙烯氢甲酰化反应催化活性，以此为催化剂的反应体系反应条件普遍比较温和，典型的反应温度在90-132℃间，典型的反应压力在1.6-5MPa间(见表1)。
尽管铑金属在丙烯氢甲酰化反应中可以多次循环利用，但反应过程中的缓慢流失和失活不可避免。由于国际铑金属价格快速上涨，使得相应工艺过程催化剂成本也快速增加。
表1 现有技术的反应压力
有鉴于此，特提出本发明。
发明内容
本发明的第一目的在于提供一种催化剂进行烯烃羰基化的方法，该方法通过高活性卡宾配体配合金属铱、并采用配位阴离子来进一步调节催化剂性能，赋予了催化剂很好的催化活性。且能够降低反应的温度，降低能耗，且降低了成本。
为了实现本发明的上述目的，特采用以下技术方案：
本发明提供了一种催化剂进行烯烃羰基化的方法，包括如下步骤：以环状烷基卡宾铱为催化剂，烯烃为原料羰基化反应生成醛，所述环状基卡宾铱的结构式为：
其中，Dipp为2,6-二异丙基苯，R
1、R
2为甲基或乙基，X为Cl、Br、CH
3CO
2、NO
3、BF
4、PF
6或SbF
6；
所述烯烃包括乙烯、丙烯、丁烯以及高碳烯烃中的其中一种或几种。
上述催化剂可以较好的应用在烯烃羰基化反应过程中，而且相比于以往的铑催化剂，其成本低，活性好，催化效果好。
优选地，作为进一步可实施的方案，反应溶剂包括正丁醛、异丁醛、甲苯、苯以及四氢呋喃中的一种或几种的混合。
优选地，作为进一步可实施的方案，所述催化剂的用量为反应溶剂用量的0.005-2wt％，优选地为0.05-1wt％。
优选地，作为进一步可实施的方案，所述烯烃丙烯，其他原料包括一氧化碳、氢气，反应总压力为0.5-5.0MPa之间，优选地为1.0-3.0MPa之间。反应总压力可以为0.6MPa、0.7MPa、0.7MPa、0.9MPa、1.0MPa等等。
优选地，作为进一步可实施的方案，反应温度在60～180℃之间，优选在80℃～140℃之间。该反应温度为可以为60℃、70℃、80℃、90℃均可。
本发明的方案更为适用于丙烯氢甲酰化反应，且能在60～180℃之间和0.5-5.0MPa压力下获得较好的反应效果。同时，金属铱价格只有金属铑的三分之一左右。相当于本发明提供了一种经济、温和的通过丙烯氢甲酰化反应合成正丁醛和异丁醛的新方法。
优选地，作为进一步可实施的方案，丙烯与一氧化碳的分压比在1:1-1:10之间，优选地为1:2-1:5之间。
优选地，作为进一步可实施的方案，丙烯与氢气的分压比在1:1-1:10之间，优选地为1:2-1:5之间。
将上述反应过程中的各个操作参数均控制在适宜的比例范围内，能够显著提高反应的效果。
与现有技术相比，本发明的有益效果在于：
(1)本发明的羰基化反应方法过高活性卡宾配体配合金属铱、并采用配位阴离子来进一步调节催化剂性能，赋予了催化剂很好的催化活性；
(2)本发明的催化反应温度低、能耗低，采用的催化剂成本也低。
通过阅读下文优选实施方式的详细描述，各种其他的优点和益处对于本领域普通技术人员将变得清楚明了。附图仅用于示出优选实施方式的目的，而并不认为是对本发明的限制。而且在整个附图中，用相同的参考符号表示相同的部件。在附图中：
图1为本发明实施例1提供的催化剂CAAC(C
2C
2)-Ir-Cl核磁共振碳谱图；
图2为本发明实施例1提供的催化剂CAAC(C
2C
2)-Ir-Cl核磁共振氢谱图。
下面将结合实施例对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限制本发明的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
实施例1
在50ml高压反应釜中，加入含0.25wt％CAAC(C
2C
2)-Ir-Cl的甲苯溶液10ml，通入氢气置换三次后，依次通入3bar丙烯、8bar一氧化碳、8bar氢气，搅拌下升温至90℃。在此温度下搅拌反应8h，将反应液冷却至0℃。缓慢泄压后，取样进行气相色谱分析，结果显示丙烯转化率为92.1％，正、异丁醛选择性为99.9％(正丁醛：异丁醛＝3.3:1)，具体该实施例所采用催化剂的确认图谱核磁共振氢谱图以及核磁共振碳谱图参见图1-2所示。
实施例2-7
采用实施例1的丙烯氢甲酰化反应方法，改变CAAC(C
2C
2)-Ir-X的配位阴离子，结果如表2所示：
表2.CAAC(C
2C
2)-Ir-X的配位阴离子对丙烯氢甲酰化反应影响
实施例8-12
采用实施例1的丙烯氢甲酰化反应方法，改变不同温度进行反应，结果如表3所示：
表3 温度对丙烯氢甲酰化反应影响
实施例13-16
采用实施例1的丙烯氢甲酰化反应方法，改变气体压力，结果如表4所示：
表4 压力对丙烯氢甲酰化反应影响
从上表中也可以看出，通过采用铱催化剂进行催化反应过程中，即使在低温低压的条件下依然具有良好的反应选择性以及反应转化率，所以本发明通过采用了新型的催化剂进行催化反应，并对反应条件进行摸索后，实现了在低能耗的条件下进行反应，且反应效率高。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (7)
- 一种催化剂进行烯烃羰基化的方法，其特征在于，包括如下步骤：以环状烷基卡宾铱为催化剂，烯烃为原料羰基化反应生成醛，所述环状基卡宾铱的结构式为：
其中，Dipp为2,6-二异丙基苯，R 1、R 2为甲基或乙基，X为Cl、Br、CH 3CO 2、NO 3、BF 4、PF 6或SbF 6；所述烯烃包括乙烯、丙烯、丁烯以及高碳烯烃中的其中一种或几种。 - 根据权利要求1所述的方法，其特征在于，反应溶剂包括正丁醛、异丁醛、甲苯、苯以及四氢呋喃中的一种或几种的混合。
- 根据权利要求2所述的方法，其特征在于，所述催化剂的用量为反应溶剂用量的0.005-2wt％，优选地为0.05-1wt％。
- 根据权利要求1所述的方法，其特征在于，所述烯烃丙烯，其他原料包括一氧化碳、氢气，反应总压力为0.5-5.0MPa之间，优选地为1.0-3.0MPa之间。
- 根据权利要求4所述的方法，其特征在于，丙烯与一氧化碳的分压比在1:1-1:10之间，优选地为1:2-1:5之间。
- 根据权利要求4所述的方法，其特征在于，丙烯与氢气的分压比在1:1-1:10之间，优选地为1:2-1:5之间。
- 根据权利要求4所述的方法，其特征在于，反应温度在60～180℃之间，优选在80℃～140℃之间。
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