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
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- 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
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Abstract
一种用于双环戊二烯氢甲酰化制醛的催化剂，该催化剂由活性组分、助剂、水溶性配体以及相转移剂四部分组成，活性组分是铑的水溶性盐，助剂是钴或锰水溶性盐，水溶性配体是三苯基膦三间磺酸钠(TPPTS)，相转移剂是十六烷基三甲基溴化铵(CTAB)，活性组分Rh3+的浓度为5.0×10-4M～4.0×10-3M，助剂Co2+或Mn2+与Rh3+的摩尔比为0.2～1。该催化剂制备方法简单，催化剂易与反应产物分离且可重复使用，助剂的加入大大提高了催化剂的选择性，该催化剂还可用于通过烯烃氢甲酰化制取碳原子数增加一个的各类醛。A kind of catalyst that is used for the hydroformylation of dicyclopentadiene to aldehyde, this catalyst is made up of active component, assistant, water-soluble ligand and phase transfer agent four parts, and active component is the water-soluble salt of rhodium, helps The agent is a water-soluble salt of cobalt or manganese, the water-soluble ligand is sodium triphenylphosphine triisosulfonate (TPPTS), the phase transfer agent is cetyltrimethylammonium bromide (CTAB), and the active component Rh 3 The concentration of + is 5.0×10 -4 M～4.0×10 -3 M, and the molar ratio of Co 2+ or Mn 2+ to Rh 3+ is 0.2～1. The preparation method of the catalyst is simple, the catalyst is easy to separate from the reaction product and can be reused, and the addition of the auxiliary agent greatly improves the selectivity of the catalyst. aldehyde.
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.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102617311B (en) * | 2012-02-27 | 2014-01-08 | 中国科学院新疆理化技术研究所 | A method for synthesizing tricyclodecane 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 * |
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