CN100496736C - Water soluble ligand rhodium complex catalyst used for preparing aldehyde with dicyclopentadiene hydroformylation - Google Patents
Water soluble ligand rhodium complex catalyst used for preparing aldehyde with dicyclopentadiene hydroformylation Download PDFInfo
- Publication number
- CN100496736C CN100496736C CNB2007100230183A CN200710023018A CN100496736C CN 100496736 C CN100496736 C CN 100496736C CN B2007100230183 A CNB2007100230183 A CN B2007100230183A CN 200710023018 A CN200710023018 A CN 200710023018A CN 100496736 C CN100496736 C CN 100496736C
- Authority
- CN
- China
- Prior art keywords
- water soluble
- catalyst
- rhodium
- hydroformylation
- dicyclopentadiene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 239000010948 rhodium Substances 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 26
- 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 title claims abstract description 18
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 17
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000003446 ligand Substances 0.000 title claims abstract description 12
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 5
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 239000011734 sodium Substances 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- -1 sodium sulfonates Chemical class 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 239000012062 aqueous buffer Substances 0.000 claims 1
- 150000001805 chlorine compounds Chemical group 0.000 claims 1
- 239000000306 component Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- MYAJTCUQMQREFZ-UHFFFAOYSA-K tppts Chemical compound [Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC(P(C=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=C(C=CC=2)S([O-])(=O)=O)=C1 MYAJTCUQMQREFZ-UHFFFAOYSA-K 0.000 abstract description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 abstract description 6
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 150000001299 aldehydes Chemical class 0.000 description 9
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 4
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 3
- SUCYXRASDBOYGB-UHFFFAOYSA-N cobalt rhodium Chemical compound [Co].[Rh] SUCYXRASDBOYGB-UHFFFAOYSA-N 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- GBZQODYDRJQFHG-UHFFFAOYSA-N manganese rhodium Chemical compound [Mn].[Rh] GBZQODYDRJQFHG-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Abstract
A catalyst for preparing aldehyde by dicyclopentadiene hydroformylation reaction is composed of an active component as a water soluble salt of rhodium, an auxiliary agent as a water soluble salt of cobalt or manganese, a water soluble ligand as sodium triphenylphosphino-3-sulphonate (TPPTS) and a phase transfer agent as hexadecyl trimethyl ammonium bromide (CTAB), wherein the concentration of Rh3+ in the active component is 5.0x10-4M~4.0x10-3M, the mol ratio of Co2 or Mn2 of the auxiliary agent with Rh3 is 0.2~1. The catalyst is simple in preparing method, easy for separating from reaction product and is reusable, which selectivity is greatly increased by adding the auxiliary agent, and the catalyst is also applicable for preparing various aldehydes, which carbon atomic number add one, by olefin hydroformylation.
Description
One, technical field
The present invention relates to a kind of water soluble ligand rhodium complex catalyst, especially relate to the water soluble ligand rhodium complex catalyst, water soluble ligand rhodium cobalt and the rhodium manganese duplex metal complexes catalyst that are used for preparing aldehyde with dicyclopentadiene hydroformylation.
Two, background technology
Germany scientist Roelen Otto found hydroformylation of olefin (Hydroformylation in 1938; claim OXO-Synthesis again) since; its research and development are contained for a long time always and are not waned; it becomes the most important organic chemical industry's production technology in the world today with annual 700-800 ten thousand tons output, and employed raw material is from C
2Cut ethene begins until chain length C
17Alkene.Dicyclopentadiene (DCPD) is the important component in the C5 fraction; can obtain unsaturated single aldehyde and dialdehyde through hydroformylation reaction; single aldehyde and derivative thereof are the important source material of synthetic perfume, and dialdehyde and derivative thereof then can be used for preparing high molecular polymer and plasticizer.Less about the report of dicyclopentadiene hydroformylation reaction in the document at present, Luigi etc. (LuigiG.., Mario M.J.Mol.Catal.1991,68,7) have studied homogeneous catalyst HRh (CO) (PPh
3)
3Performance in dicyclopentadiene hydroformylation reaction thinks that P/Rh comparison product is single aldehyde or dialdehyde plays an important role.Zhao Ming etc. (Zhao Ming, Yuan Gang. fine chemistry industry .1996,13,32) (HRh (CO) is (TPPTS) to have studied the water-soluble rhodium phosphine composition
3) be used for dicyclopentadiene hydroformylation and prepare unsaturated single aldehyde, but product does not have dialdehyde to generate.The used rhodium precursor of present most of olefin hydroformylation rhodium catalyst is rhodium carbonyl or rhodium-and-phosphine composition; it is less to be with the rhodium inorganic salts that catalyst is used for the document of hydroformylation reaction, (Ali E, BassamCatal.Comm.2003 such as Ali; 4,621) reported first use RhCl
33H
2O is a catalyst, P (OPh)
3Be part, be used for the styrene hydroformylation reaction.(HRh (CO) (TPPTS) with the water-soluble rhodium phosphine composition since Kuntz in 1976 etc.
3) be used for since the catalyzed alkene hydroformylation reaction; because this method has solved the separation problem of catalyst and product in the homogeneous catalytic reaction preferably; therefore be that the water/oily biphasic catalysis system of catalyst becomes the focus that the researcher pays close attention to rapidly with the water-soluble rhodium phosphine composition; but with the rhodium inorganic salts is catalyst; three sodium sulfonates of triphenylphosphine (TPPTS) are water soluble ligand, are used for hydroformylation reaction and do not appear in the newspapers.Simultaneously, people such as Li (Li C.Z., Widjaja E.D., Garland M.J.Am.Chem.Soc.2003,125,5540.) find HMn (CO)
5Auxiliary agent exists down, can significantly improve Rh
4(CO)
12The catalytic performance of catalyst in the homogeneous phase hydroformylation reaction.(HRh (CO) (TPPTS) and manganese or cobalt inorganic salts are to the water-soluble rhodium phosphine composition
3) document of facilitation of catalyst also do not appear in the newspapers.
Three, summary of the invention
The invention provides a kind of efficient catalyst that aldehyde is produced in the dicyclopentadiene hydroformylation reaction that is used for.It is simple and convenient that this catalyst has synthetic method; and at cheap Co or Mn chloride under the condition as auxiliary agent; improved the activity of hydroformylation reaction and the selectivity of target product aldehyde significantly, and the catalyst water is easy to separate with product oil phase, the catalyst water is reusable.
The invention is characterized in that the water soluble salt with rhodium is an active component, with cobalt or manganese water soluble salt is auxiliary agent, adding water soluble ligand three sodium sulfonates of triphenylphosphine (TPPTS), is consisting of phase-transferring agent with softex kw (CTAB), and catalyst is at synthesis gas (H
2/ CO=1) pressure 4.0-6.0Mpa uses under the temperature 100-120 ℃ of condition, and this catalyst is in the dicyclopentadiene hydroformylation reaction; conversion ratio is near 100%; the dialdehyde selectivity is near 90%, and under cobalt or manganese auxiliary agent existence condition, the dialdehyde selectivity reaches more than 99%.
Feature of the present invention also is: Rh content has considerable influence to catalyst performance, and suitable rhodium content is (with Rh
3+Ionometer) be 1.0 * 10
-4M～1.0 * 10
-2M is preferably 5.0 * 10
-4M～4.0 * 10
-3M, the mol comparison catalyst performance influence of cobalt rhodium or manganese rhodium is bigger, and suitable cobalt rhodium mol ratio is 0～1, is preferably 0.2～1.The water soluble salt of rhodium can be RhCl
3, Rh (NO
3)
3Or Rh
2(SO
4)
3Cobalt and manganese water soluble salt are all chloride.
Catalyst among the present invention is used for the dicyclopentadiene hydroformylation reaction, is reflected in the stainless steel autoclave and carries out, and product is analyzed with gas chromatograph.
Four, the specific embodiment
Embodiment 1: earlier with 190.0ml buffer solution (PH is about 7.3), 10.0ml dicyclopentadiene, RhCl
3(concentration is 1.0 * 10
-3M), three sodium sulfonates of 0.328g triphenylphosphine (TPPTS) and 0.603g consisting of phase-transferring agent softex kw (CTAB) mixing join mixed liquor in the autoclave then, use N earlier
2(1.0MPa) displacement is three times, removes air in the still, uses synthesis gas (H then
2/ CO=1 1.0MPa) cleans 1 time, and pressurising starts agitator and is warming up to and set 110 ℃ of reactions of reaction temperature 3.0h to the required pressure 4.8Mpa of reaction.Reaction finishes back water flowing cooling, takes out the reactor material, leave standstill 1.0h after, isolate catalyst water and product oil phase, the catalyst water recycles, product oil phase is analyzed with gas chromatograph.Reaction result sees Table 1.
Embodiment 2: earlier with 190.0ml buffer solution (pH is about 7.3), 10.0ml dicyclopentadiene, RhCl
3And CoCl
2(the metal ion total concentration is 1.0 * 10
-3M, wherein the Co/Rh mol ratio is 0.5), three sodium sulfonates of 0.328g triphenylphosphine (TPPTS) and 0.603g consisting of phase-transferring agent softex kw (CTAB) mixing join mixed liquor in the autoclave then, use N earlier
2(1.0MPa) displacement is three times, removes air in the still, uses synthesis gas (H then
2/ CO=1.0 1.0MPa) cleans 1 time, and pressurising starts agitator and is warming up to and set 110 ℃ of reactions of reaction temperature 3.0h to the required pressure 4.8MPa of reaction.Reaction result sees Table 1.
Embodiment 3: earlier with 190.0ml buffer solution (pH is about 7.3), 10.0ml dicyclopentadiene, RhCl
3And MnCl
2(the metal ion total concentration is 1.0 * 10
-3M, wherein the Mn/Rh mol ratio is 0.5), three sodium sulfonates of 0.328g triphenylphosphine (TPPTS) and 0.6025g consisting of phase-transferring agent softex kw (CTAB) mixing join mixed liquor in the autoclave then, use N earlier
2(1.0MPa) displacement is three times, removes air in the still, uses synthesis gas (H then
2/ CO=1.0 1.0MPa) cleans 1 time, and pressurising starts agitator and is warming up to and set 110 ℃ of reactions of reaction temperature 3.0h to the required pressure 4.8MPa of reaction.Reaction result sees Table 1.
Several catalyst dicyclopentadiene hydroformylation of table 1 performance comparison result
A only uses the Rh molal quantity when calculating space-time yield, and the Co molal quantity does not count
B only uses the Rh molal quantity when calculating space-time yield, and the Mn molal quantity does not count
Embodiment 4: as the catalyst system of embodiment 1, isolated catalyst water is added autoclave react next time, other conditions are with embodiment 1, and reaction result sees Table 2.
Table 2 catalyst stability evaluation result
By above-mentioned result as can be known; utilize the synthetic aqueous phase catalyst system of one-step method original position of the present invention; in autoclave, carry out the dicyclopentadiene hydroformylation reaction in gap; the catalytic activity height, the highest near 100%, selectivity is good; greater than 99%; the Preparation of catalysts method is simple, and catalyst just can be realized separating by simple separatory through leaving standstill the back, and catalyst is reusable.The synthetic aqueous phase catalyst system of this one-step method original position can be used for producing all kinds of aldehyde that carbon number increases by olefin hydroformylation in the industrial production.
Claims (2)
1, a kind of water soluble ligand rhodium complex catalyst that is used for preparing aldehyde with dicyclopentadiene hydroformylation; it is characterized in that this catalyst comprises active component, auxiliary agent, water soluble ligand and consisting of phase-transferring agent four parts; active component is the water soluble salt of rhodium; auxiliary agent is cobalt or manganese water soluble chloride; water soluble ligand is three sodium sulfonates of triphenylphosphine; consisting of phase-transferring agent is a softex kw, and the concentration of active component is 5.0 * 10
-4M～4.0 * 10
-3M, auxiliary agent Co
2+Or Mn
2+With Rh
3+Mol ratio be 0.2～1, catalyst is at synthesis gas H
2/ CO=1, pressure 4.8MPa, pH are 7.3 aqueous buffer solution, use under 110 ℃ of conditions of temperature.
2, according to the described water soluble ligand rhodium complex catalyst that is used for preparing aldehyde with dicyclopentadiene hydroformylation of claim 1, the water soluble salt that it is characterized in that rhodium is chloride, nitrate or sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100230183A CN100496736C (en) | 2007-05-31 | 2007-05-31 | Water soluble ligand rhodium complex catalyst used for preparing aldehyde with dicyclopentadiene hydroformylation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100230183A CN100496736C (en) | 2007-05-31 | 2007-05-31 | Water soluble ligand rhodium complex catalyst used for preparing aldehyde with dicyclopentadiene hydroformylation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101053843A CN101053843A (en) | 2007-10-17 |
| CN100496736C true CN100496736C (en) | 2009-06-10 |
Family
ID=38793994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100230183A Expired - Fee Related CN100496736C (en) | 2007-05-31 | 2007-05-31 | Water soluble ligand rhodium complex catalyst used for preparing aldehyde with dicyclopentadiene hydroformylation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100496736C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617311B (en) * | 2012-02-27 | 2014-01-08 | 中国科学院新疆理化技术研究所 | Method for synthesizing tricyclic decane unsaturated monoaldehyde |
| CN103521268B (en) * | 2012-07-03 | 2016-01-20 | 中国科学院大连化学物理研究所 | A kind of heterogeneous catalyst being applied to hydroformylation of olefin and preparation method thereof |
| CN104387233B (en) * | 2014-11-29 | 2016-01-06 | 中国科学院新疆理化技术研究所 | A kind of method of synthesizing tricyclic decane dimethanol |
| CN110330421B (en) * | 2019-08-26 | 2021-09-28 | 重庆化工职业学院 | Method for preparing tricyclodecanedicarboxylic acid by taking dicyclopentadiene as raw material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106374A (en) * | 1993-09-09 | 1995-08-09 | 赫彻斯特股份公司 | Acidification of 1,3-butadiene |
| CN1131138A (en) * | 1994-11-17 | 1996-09-18 | Dsm有限公司 | Process for preparing aldehyde |
| CN1149043A (en) * | 1995-09-02 | 1997-05-07 | 赫彻斯特股份公司 | Process for hydroformylation of olefinically unsaturated compounds |
| EP1529769A1 (en) * | 2003-11-08 | 2005-05-11 | Celanese Chemicals Europe GmbH | Process for the preparation of TCD-dialdehyde |
| CN1781603A (en) * | 2004-11-30 | 2006-06-07 | 四川大学 | Loaded complex catalyst for isobutylene hydrogen formylation reaction |
-
2007
- 2007-05-31 CN CNB2007100230183A patent/CN100496736C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106374A (en) * | 1993-09-09 | 1995-08-09 | 赫彻斯特股份公司 | Acidification of 1,3-butadiene |
| CN1131138A (en) * | 1994-11-17 | 1996-09-18 | Dsm有限公司 | Process for preparing aldehyde |
| CN1149043A (en) * | 1995-09-02 | 1997-05-07 | 赫彻斯特股份公司 | Process for hydroformylation of olefinically unsaturated compounds |
| EP1529769A1 (en) * | 2003-11-08 | 2005-05-11 | Celanese Chemicals Europe GmbH | Process for the preparation of TCD-dialdehyde |
| CN1781603A (en) * | 2004-11-30 | 2006-06-07 | 四川大学 | Loaded complex catalyst for isobutylene hydrogen formylation reaction |
Non-Patent Citations (2)
| Title |
|---|
| 双环戊二烯在水溶性铑膦络合催化体系中的氢甲酰化反应. 赵明，袁刚.精细化工，第13卷第4期. 1996 |
| 双环戊二烯在水溶性铑膦络合催化体系中的氢甲酰化反应. 赵明，袁刚.精细化工，第13卷第4期. 1996 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101053843A (en) | 2007-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cornils et al. | Introducing TPPTS and related ligands for industrial biphasic processes | |
| Overett et al. | Organometallic chemistry and surface science: mechanistic models for the Fischer–Tropsch synthesis | |
| CN103483381B (en) | The preparation of one class phosphine functionalized ion liquid and the application in hydroformylation reaction thereof | |
| CN101293818B (en) | Two-stage reaction method for mixed butylene hydroformylation | |
| CN109456154A (en) | A method of fatty aldehyde is prepared by hydroformylation reaction | |
| CN109806911A (en) | A kind of highly selective catalyst for preparing linear chain aldehyde and its preparation and application | |
| Kalck | Homo-and heterobimetallic complexes in catalysis | |
| Farnetti et al. | Homogeneous and heterogeneous catalysis | |
| CN106008184B (en) | The method that isobutene prepares 3 methylbutyraldehyds | |
| CN100496736C (en) | Water soluble ligand rhodium complex catalyst used for preparing aldehyde with dicyclopentadiene hydroformylation | |
| CN102056872A (en) | Method for separating 1-butene from C4-containing hydrocarbon streams by hydroformylation | |
| CN109836318A (en) | A kind of method that hydroformylation of olefin prepares aldehyde | |
| CN106083551A (en) | A kind of hydroformylation of propene prepares the method for butyraldehyde | |
| CN101565353A (en) | Preparation method for 2-propyl enanthol | |
| CN104870086B (en) | Catalyst composition for hydroformylation reaction and method for hydroformylation of olefin using same | |
| CN106608816A (en) | Method for preparing C4-C8 aldehydes | |
| CN1171981A (en) | Catalyst ststems based on rhodium complexes containing diphosphine ligands and their use preparation of aldehydes | |
| JP2004506032A (en) | Manufacture of oxygenated products | |
| CN107597192A (en) | A kind of catalyst and hydroformylation reaction method for hydroformylation reaction | |
| CN107497493A (en) | Ethylene synthase methyl propionate carbon monoxide-olefin polymeric and its synthetic method | |
| Parshall | Organometallic chemistry in homogeneous catalysis | |
| CN114522739B (en) | Method for preparing 1, 3-propylene glycol from vinyl acetate | |
| CN112898122A (en) | Method for preparing isononyl alcohol from mixed octenes | |
| CN107089900A (en) | A kind of preparation method of β benzyl carbinols | |
| TW466231B (en) | Process for preparing aldehydes by hydroformylation of olefinic compounds having from 3 to 5 carbon atoms in the presence of an aqueous catalyst phase |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: JIANG SOVIET LIANDONG CHEMICAL INDUSTRY CO., LTD. Free format text: FORMER OWNER: NANJING UNIVERSITY Effective date: 20091016 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20091016 Address after: No. two, No. 1 North Ring Road, Jiangsu, Danyang Patentee after: JiangSu Liandong Chemical Co., Ltd. Address before: No. 22, Hankou Road, Nanjing, Jiangsu Patentee before: Nanjing University |
|
| DD01 | Delivery of document by public notice |
Addressee: JiangSu Liandong Chemical Co., Ltd. Document name: Notification of Termination of Patent Right |
|
| DD01 | Delivery of document by public notice | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090610 Termination date: 20160531 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |