CN101835786A - Method of inhibiting metal precipitation from transition metal complex - Google Patents
Method of inhibiting metal precipitation from transition metal complex Download PDFInfo
- Publication number
- CN101835786A CN101835786A CN200880112475A CN200880112475A CN101835786A CN 101835786 A CN101835786 A CN 101835786A CN 200880112475 A CN200880112475 A CN 200880112475A CN 200880112475 A CN200880112475 A CN 200880112475A CN 101835786 A CN101835786 A CN 101835786A
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- CN
- China
- Prior art keywords
- transition metal
- acid ester
- reaction
- phosphorous acid
- metal complex
- 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.)
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 98
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 98
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 53
- 239000002184 metal Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000001556 precipitation Methods 0.000 title abstract 3
- 230000002401 inhibitory effect Effects 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 88
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 125000003118 aryl group Chemical group 0.000 claims abstract description 24
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 204
- -1 aromatic series phosphorous acid ester Chemical class 0.000 claims description 129
- 229910052763 palladium Inorganic materials 0.000 claims description 76
- 125000004432 carbon atom Chemical group C* 0.000 claims description 42
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 35
- 238000006317 isomerization reaction Methods 0.000 claims description 27
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 20
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 18
- 125000000746 allylic group Chemical group 0.000 claims description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 150000008300 phosphoramidites Chemical class 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
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- 238000005649 metathesis reaction Methods 0.000 claims description 4
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- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
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- 238000005937 allylation reaction Methods 0.000 claims description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- SXADIBFZNXBEGI-UHFFFAOYSA-N phosphoramidous acid Chemical group NP(O)O SXADIBFZNXBEGI-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- MWPAAGZZENKROJ-UHFFFAOYSA-N n,n-dimethyl-2-phosphanylaniline Chemical compound CN(C)C1=CC=CC=C1P MWPAAGZZENKROJ-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- APVDIAOSUXFJNU-UHFFFAOYSA-N rhodium(3+) phosphite Chemical compound [Rh+3].[O-]P([O-])[O-] APVDIAOSUXFJNU-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
- B01J31/186—Mono- or diamide derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
-
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/60—Quinoline or hydrogenated quinoline ring systems
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657154—Cyclic esteramides of oxyacids of phosphorus
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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Abstract
A method by which a liquid reaction mixture resulting from a reaction conducted using a transition metal complex catalyst containing an organophosphorus ligand is inhibited from undergoing precipitation of the transition metal therein and the transition metal complex catalyst is efficiently taken out of the reaction system as a liquid containing the catalyst therein. The method is characterized in that a solution containing a complex which is a complex of a transition metal selected among transition metals of Groups 8 to 10 and has a ligand comprising a trivalent organophosphorus compound is brought into contact with an aromatic phosphite different from the trivalent organophosphorus compound to thereby inhibit the transition metal complex from causing metal precipitation in the solution.
Description
Technical field
The present invention relates in the solution that contains transition metal complex, suppress the method that this transition metal is separated out with transition metal and organic ligand.In detail, the present invention relates in reacted solution such as ligand complex catalyzed dose the hydrogenation that uses transition metal-contain organophosphorus, isomerization reaction, suppress the method that transition metal is separated out from this transition metal complex catalyst.
Background technology
Contain the complex compound catalyst that the part of organophosphorus forms by transition metal and phosphite ester ligand etc. and be used to a large amount of reaction process, as such reaction process, for example hydrogenation formaldehyde glycosylation reaction of the hydrogenation of known unsaturated compound, isomerization reaction, alkene, the dimerization reaction of alkene etc.In addition, during hydrogenation formaldehyde glycosylation reaction, if constituting the phosphite ester ligand of rhodium-phosphite ester ligand complex compound catalyst partly is decomposed owing to the effect of acidic by-products that produces or hydrolysis etc., then complex compound becomes unstable, the metal of complex compound catalyst precipitate in the reaction soln, therefore, the known acidic by-products (referring to patent documentation 1) that will remove generation.The transition metal (for example rhodium (the 8th family), palladium (the 10th family) etc.) that is used for the complex compound catalyst of these reactions is from reacted reaction soln Separation and Recovery.
But in the actual reaction process, metal is not only the loss of catalyst metal, but also is a reason of device internal contamination when complex compound catalyst is separated out in reaction process, causes the problem of quiet run aspects such as for example thermal conductivity reduction.
For metal separating out from metal complex catalyst, to cause the complex compound instability that becomes be one of reason of separating out to its part because of decomposition takes place parts such as oxidation when the separation of when reaction or purpose resultant etc.-recoverys, therefore, stabilization is sought in the decomposition of the part of requirement prevention complex compound catalyst etc., suppress the separating out of metal in the technique process, and be fetched into outside the reaction system with the form of the liquid that contains metal complex catalyst.
Patent documentation 1: Japanese Unexamined Patent Application Publication 2000-501712
Summary of the invention
The invention provides separating out of transition metal in the reacted reaction solution that suppress to use the transition metal complex catalyst that contains organophosphor ligand, and effectively transition metal complex catalyst is fetched into the outer method of reaction system with the liquid form that contains this catalyzer.
For separating out of transition metal in the reaction solution that prevents to use the transition metal complex catalyst that contains phosphite ester ligand etc. that is used to various reactions, the inventor furthers investigate the state of this transition metal complex in the reacted reaction solution, found that one of its reason is: some decomposes parts such as the phosphite ester ligand of these transition metal complex catalysts because of oxidation etc. in reaction or in the separation-recovery, cause complex compound to become unstable thus, the metal of complex compound becomes and separates out easily.Also find in addition,, can make this transition metal complex stabilization, prevent separating out of transition metal by the transition metal complex in the reaction solution being contacted processing with the antioxidant phosphorous acid ester.The present invention is based on that above-mentioned cognition finishes.
That is, main points of the present invention are following every technical scheme.
1: a kind ofly suppress the method that metal is separated out from transition metal complex, it is characterized in that, the solution that contains transition metal complex is contacted with the aromatic series phosphorous acid ester, thereby suppress the transition metal complex precipitating metal from this solution, described transition metal complex has the part that is made of 3 valency organo phosphorous compoundss, described transition metal is selected from group VIII, and described aromatic series phosphorous acid ester is different from this 3 valency organo phosphorous compounds.
2:, it is characterized in that described aromatic series phosphorous acid ester is the material shown in the following formula (I) as above-mentioned scheme 1 described method.
In the formula (I), 3 R represent to have substituting group independently of one another or do not have substituent alkyl, and at least 1 R is an aryl.
3: scheme 1 or scheme 2 described methods as described is characterized in that for described aromatic series phosphorous acid ester, at least 1 aryl in the formula (I) has substituting group at its ortho position.
4:, it is characterized in that for described aromatic series phosphorous acid ester, at least 1 aryl in the formula (I) is by tertiary carbon atom or quaternary carbon atom bonded substituting group at the substituting group that the ortho position had as above-mentioned scheme 3 described methods.
5:, it is characterized in that for described aromatic series phosphorous acid ester, 3 R in the formula (I) are identical and be to have at the ortho position by tertiary carbon atom or the substituent phenyl of quaternary carbon atom bonded as above-mentioned scheme 4 described methods.
6:, it is characterized in that described aromatic series phosphorous acid ester is a monodentate phosphite as above-mentioned scheme 1～5 each described method.
7:, it is characterized in that described 3 valency organo phosphorous compoundss are at least a compounds that select in the group that free phosphine, phosphorous acid ester and phosphoramidite form as above-mentioned scheme 1～6 each described method.
8:, it is characterized in that described 3 valency organo phosphorous compoundss are at least a compounds that are selected from the group of being made up of multiple tooth phosphine, phosphorous acid ester and phosphoramidite as above-mentioned scheme 1～7 each described method.
9:, it is characterized in that described group VIII transition metal is palladium or platinum as above-mentioned scheme 1～8 each described method.
10: as above-mentioned scheme 1～9 each described method; it is characterized in that the described solution of transition metal complex that contains the part that is made of 3 valency organo phosphorous compoundss and be selected from the transition metal of group VIII transition metal is to carry out arbitrary reacted solution in isomerization reaction, hydrogenation, hydrogenation formyl reaction, dehydrogenation reaction, oligomerization, metathesis, linked reaction or the allylation reaction with this transition metal complex as catalyzer.
11: as above-mentioned scheme 10 described methods, it is characterized in that the solution that contains the allylic cpd derivative different after the isomerization reaction that the described solution that contains the part that is made of 3 valency organo phosphorous compoundss and the transition metal complex of the transition metal that is selected from group VIII transition metal is raw material allylic cpd derivative with raw material.
12: as above-mentioned scheme 10 or 11 described methods, it is characterized in that the reaction solution after the isomerization reaction that the described solution of transition metal complex that contains the part that is made of 3 valency organo phosphorous compoundss and be selected from the transition metal of group VIII transition metal is the acetoxyl group allylic cpd.
13: as above-mentioned scheme 12 described methods, it is characterized in that, described acetoxyl group allylic cpd be the oxidation diacetoxy resultant of reaction by divinyl obtain contain 3,4-diacetoxy-1-butylene is as the liquid of principal constituent.
The method according to this invention, contain in the reacted reaction solution of transition metal complex catalyst of organophosphor ligand in use, suppressed separating out of transition metal, stablized complex compound, so can not produce the metal loss in the reaction system, the form of this transition metal complex catalyst with the liquid that contains this catalyzer can be fetched into outside the reaction system efficiently the pollution in can restraining device, the reduction of thermal conductivity etc.
Description of drawings
Fig. 1 is the molten survival rate time history plot of depositing of Pd in explanation embodiment 9 and the comparative example 7.Wherein, the longitudinal axis is represented the molten survival rate (%) of depositing of Pd, and transverse axis is represented the time (h), and DBPO is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.
Embodiment
Below the present invention will be described in more detail.
Transition metal complex catalyst among the present invention constitutes by containing part that is made of 3 valency organo phosphorous compoundss and the transition metal complex that is selected from the transition metal of group VIII transition metal, and this part has P-C key, P-O key or P-N key.Such transition metal complex catalyst is the known transition metal complex catalyst that hydrocyanation many manufacturing processes such as (adiponitrileizations of divinyl) of oligomerization, metathesis, linked reaction, the diene of hydroformylation, dehydrogenation, the alkene of hydrogenation, the alkene of the isomerization that is used for allylic cpd derivative for example, unsaturated compound use.
The part that is made of 3 valency organo phosphorous compoundss that transition metal complex catalyst among the present invention contains is the compound with P-C key, P-O key or P-N key, comprises the monodentate and the polydentate ligand that are selected from phosphine, phosphorous acid ester and phosphoramidite.
As phosphine, can enumerate trialkyl phosphine, alkyl diaryl phosphine, dialkyl aryl phosphine, bicyclic alkyl aryl phosphine, cycloalkyl diaryl phosphine, tris(aralkyl)phosphine, tricyclic alkyl phosphine and triaryl phosphine etc., the compound shown in for example following general formula (i).
In the above-mentioned formula (i), 3 R ' are independent separately, can be the same or different, and be the alkyl or aryl that replaces or do not have replacement.
As aryl, can enumerate phenyl, naphthyl, xenyl etc., as alkyl, can enumerate carbonatoms and be 1～10 alkyl, for example methyl, ethyl, propyl group, butyl, cyclohexyl etc.In addition, as the substituting group that these groups can have, can enumerate alkyl, alkoxyl group, silyl, amino, acyl group, carboxyl, halogen atom, alkylsulfonyl, sulfonic group, cyano group, trifluoromethyl etc.Among these, aryl such as preferred phenyl, naphthyl.
As the concrete example of described phosphine, can enumerate triphenylphosphine, three-p-methylphenyl phosphine, three-p-methoxyphenyl phosphine, three-to fluorophenyl phosphine, three-rubigan phosphine, three (dimethylamino phenyl) phosphine, propyl group diphenylphosphine, tert-butyl diphenyl phosphine, normal-butyl diphenylphosphine, n-hexyl diphenylphosphine, cyclohexyl diphenylphosphine, dicyclohexyl Phenylphosphine, tricyclohexyl phosphine, trimethyl-phosphine, triethyl phosphine, tributylphosphine, tri octyl phosphine etc.
As described phosphorous acid ester, can enumerate following formula (1-1) and (2-1) shown in monodentate and the part of 2 teeth.
As described phosphoramidite, can enumerate following formula (1-2), (2-2), (2-3), (2-4) and (2-5) shown in monodentate and the part of 2 teeth.
In the above-mentioned formula, Y
1, Y
2, Y
3, Y
4, Y
5, Y
6, Y
7, Y
8And Y
9Represent chain or cyclic alkyl, aryl or heterocyclic radical independently of one another, these groups can further have substituting group.In addition, Y
2And Y
3, Y
4And Y
5, Y
6And Y
7And Y
8And Y
9All can be interconnected to form ring.N represents methene chain (CH
2-) length, n is 1～10, is preferably 1～5, is preferably 2～4 especially.M represents the length of methene chain, and m is 1～5, is preferably 1～3.
R
1And R
5Representing hydrogen atom independently of one another, having substituting group or do not have substituent carbonatoms is 3～20 the second month in a season or tertiary hydrocarbon base, R
2, R
3, R
6, R
7, R
9And R
10Expression independently of one another has substituting group or do not have substituent carbonatoms is 1～20 alkyl or to have substituting group or do not have substituent carbonatoms be 1～10 alkoxyl group, R
4And R
8Represent that independently of one another hydrogen atom, carbonatoms are that 1～4 alkyl, halogen atom or carbonatoms are 1～4 alkoxyl group.
The alkyl skeleton part of above-mentioned chain or cyclic alkyl and alkoxyl group carbonatoms usually is 1～20, is preferably 1～14.As its concrete example, for example can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, octyl group, decyl, cyclohexyl, cyclopentyl etc.In addition, as the substituting group that alkyl can have, can enumerate carbonatoms and be 1～10 alkoxyl group, carbonatoms and be 6～10 aryl, amino, cyano group, carbonatoms and be 2～10 ester group, hydroxyl, halogen atom etc.
The carbonatoms of above-mentioned aryl is generally 6～20, is preferably 6～14.Concrete example as aryl, can enumerate phenyl, naphthyl, as the substituting group that these groups can have, can enumerate hydrogen atom, carbonatoms is 1～20 alkyl, carbonatoms is 1～10 alkoxyl group, carbonatoms is 3～20 cycloalkyl, carbonatoms is 6～20 aryl, carbonatoms is 6～20 aryloxy, carbonatoms is 6～20 alkylaryl, carbonatoms is 6～20 alkyl-aryloxy, carbonatoms is 6～20 aralkyl, carbonatoms is 6～20 alkoxy aryl, cyano group, ester group, hydroxyl, and chlorine, halogen atoms such as fluorine etc.
Y
1～Y
9Be to have substituting group or do not have under the situation of substituent aryl, as concrete example, can enumerate phenyl, the 2-aminomethyl phenyl, the 3-aminomethyl phenyl, the 4-aminomethyl phenyl, 2, the 3-3,5-dimethylphenyl, 2, the 4-3,5-dimethylphenyl, 2, the 5-3,5-dimethylphenyl, 2, the 6-3,5-dimethylphenyl, the 2-ethylphenyl, the 2-isopropyl phenyl, the 2-tert-butyl-phenyl, 2, the 4-di-tert-butyl-phenyl, the 2-chloro-phenyl-, the 3-chloro-phenyl-, the 4-chloro-phenyl-, 2, the 3-dichlorophenyl, 2, the 4-dichlorophenyl, 2, the 5-dichlorophenyl, 3, the 4-dichlorophenyl, 3, the 5-dichlorophenyl, the 4-trifluoromethyl, the 2-p-methoxy-phenyl, the 3-p-methoxy-phenyl, the 4-p-methoxy-phenyl, 3, the 5-Dimethoxyphenyl, the 4-cyano-phenyl, the 4-nitrophenyl, trifluoromethyl, pentafluorophenyl group and following group (C-1)～(C-8) etc.
Enumerate below above-mentioned formula (1-1), (1-2), (2-1), (2-2), (2-3), (2-4) and (2-5) shown in the concrete example of part.
As the transition metal of the group VIII in the transition metal complex catalyst among the present invention, preferred ruthenium, rhodium, nickel, palladium, platinum etc. are preferably palladium especially.This transition metal is supplied with the form of compound, as concrete compound, can enumerate for example acetate, vitriol, nitrate, halide salts, organic salt, inorganic salt, acetylacetonate complex, alkene coordination compound, amine coordination compound, pyridine coordination compound, carbon monoxide coordination compound, phosphine coordination compound, phosphorous acid ester coordination compound etc.
As concrete palladium compound, can enumerate metallic palladium, palladium, trifluoracetic acid palladium, palladous sulfate, Palladous nitrate, Palladous chloride, palladium bromide, palladium iodide, two (acetyl acetone) palladium, dichloro cyclooctadiene palladium, dichloro two (triphenylphosphine) palladium, tetrakis triphenylphosphine palladium, two (dibenzyl acetone) palladium, tetrachloro-palladium potassium chlorate, tetrachloro-palladium acid sodium, dichloro two (benzonitrile) palladium, dichloro two (acetonitrile) palladium and other carbonate, contain olefin(e) compound, contain organic phosphorus compound, chlorination Allylpalladium dipolymer etc.Particularly, preferably use palladium, trifluoracetic acid palladium, two (acetyl acetone) palladium, tetrakis triphenylphosphine palladium etc. from aspects such as price and easy processing.
The addition of the above-mentioned part in the relevant transition metal complex of the present invention, the phosphorus atom in the preferred part is 0.1～1000 with respect to the mol ratio of 1 mole of transition metal in the transition metal complex, more preferably 1～100, be preferably 1～10 especially.In addition, part can be one or more part.Preparation method to transition metal complex is not particularly limited, for example can be when this complex compound be reacted as catalyzer, by heating, transistion metal compound and ligand compound are reacted in solvent with desired ratio make the liquid that contains catalyzer.
Among the present invention, the solution that contains above-mentioned transition metal complex (this complex compound contain the part that is made of 3 valency organo phosphorous compoundss and the transition metal of group VIII) is contacted with the aromatic series phosphorous acid ester, but the aromatic series phosphorous acid ester is different from 3 valency organo phosphorous compoundss as part.
One of reason that the metal of transition metal complex catalyst is separated out is that the phosphite ester ligand of this metal complex catalyst is oxidized and make complex compound become unstable in reaction or in the separation-recovery.Therefore, the aromatic series phosphorous acid ester that is used to contact needs only the function that can bring into play as himself oxidized composition, prevent that the part oxidation that is made of 3 valency organo phosphorous compoundss that above-mentioned metal complex catalyst has from getting final product, and can enumerate the aromatic series phosphorous acid ester shown in the following formula (I).
In the above-mentioned formula (I), 3 R represent to have substituting group independently of one another or do not have substituent alkyl, and at least 1 R is an aryl.
Alkyl in the formula (I) is selected from alkyl or aryl.
Alkyl is that carbonatoms is generally 1～20, is preferably 1～14 the straight chain or the alkyl or the cyclic alkyl of side chain, as concrete alkyl, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, octyl group, decyl, cyclohexyl, cyclopentyl etc.In addition, as the substituting group that alkyl can have, can enumerate carbonatoms and be 1～10 alkoxyl group, carbonatoms and be 6～10 aryl, amino, cyano group, carbonatoms and be 2～10 ester group, hydroxyl, halogen atom etc.
The carbonatoms of aryl is generally 6～20, is preferably 6～14.As the concrete example of aryl, can enumerate phenyl, naphthyl.As the substituting group that these groups can have, can enumerate hydrogen atom, carbonatoms and be 1～20 alkyl, carbonatoms and be 1～10 alkoxyl group, carbonatoms and be 3～20 cycloalkyl, carbonatoms and be 6～10 aryl, carbonatoms and be 6～20 aryloxy, carbonatoms and be 6～20 alkylaryl, carbonatoms and be 6～20 alkyl-aryloxy, carbonatoms and be 6～20 aralkyl, carbonatoms and be halogen atoms such as 6～20 alkoxy aryl, cyano group, ester group, hydroxyl and chlorine, fluorine etc.As substituting group, preferred sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl, cyclohexyl etc., special preferred tertiary butyl.
As the aromatic series phosphorous acid ester, (2 or 6) have substituting group at least 1 aryl in the preferred formula (I) at its ortho position, and the substituting group that preferred ortho position is had is by tertiary carbon atom or quaternary carbon atom and aryl bonded substituting group.3 R that the aromatic series phosphorous acid ester particularly preferably is in the formula (I) are identical, and the ortho position has by tertiary carbon atom or the substituent phenyl of quaternary carbon atom bonded.In addition, the optimization aromatic phosphorous acid ester is a monodentate phosphite.Special preferably ortho position has the monodentate phosphite of the phenyl of the tertiary butyl.
As the aromatic series phosphorous acid ester, specifically can enumerate triphenyl phosphite, three (o-tolyl) phosphorous acid ester, three (o-isopropyl phenyl) phosphorous acid ester, three (2-tert-butyl-phenyl) phosphorous acid ester, three (isobutyl phenenyl) phosphorous acid ester, three (isopropyl phenyl) phosphorous acid ester, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, three (2, the 5-di-tert-butyl-phenyl) phosphorous acid ester, three (2, the 6-di-tert-butyl-phenyl) phosphorous acid ester, three (2, the 3-di-tert-butyl-phenyl) phosphorous acid ester, three (2, the 4-diisopropyl phenyl) phosphorous acid ester, three (2, the 5-diisopropyl phenyl) phosphorous acid ester, three (2, the 6-diisopropyl phenyl) phosphorous acid ester, three (2, the 3-diisopropyl phenyl) phosphorous acid ester, propyl group two (2-tert-butyl-phenyl) phosphorous acid ester, the tertiary butyl two (2-tert-butyl-phenyl) phosphorous acid ester, normal-butyl two (2-tert-butyl-phenyl) phosphorous acid ester, n-hexyl phenylbenzene phosphorous acid ester, the tertiary butyl two (2, the 4-tert-butyl-phenyl) phosphorous acid ester, normal-butyl-two (2, the 4-tert-butyl-phenyl) phosphorous acid ester, two (2, the 4-tert-butyl-phenyl) cyclohexyl phosphorous acid ester, three (2-tert-butylcyclohexyl) phosphorous acid ester, two (2-tert-butylcyclohexyl) phenyl phosphites etc.Among these, preferred three (2-tert-butyl-phenyl) phosphorous acid ester, three (isobutyl phenenyl) phosphorous acid esters, three (isopropyl phenyl) phosphorous acid ester, three (2,4-two-tert-butyl-phenyl) phosphorous acid ester, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester etc., preferred especially three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.
Comprise the solution of the transition metal complex of the part that constitutes by 3 valency organo phosphorous compoundss and group VIII transition metal, the specifically reaction solution that obtains by the reaction of using this transition-metal catalyst as containing among the present invention.As the reaction of using this transition metal complex catalyst, for example can enumerate oligomerization, metathesis, the linked reaction of hydroformylation, dehydrogenation, the alkene of hydrogenation, the alkene of isomerization, the unsaturated compound of allylic cpd derivative, the hydrocyanation (adiponitrileization of divinyl) of diene etc.Especially, be reaction solution after the isomerization reaction of allylic cpd derivative of catalyzer preferably among the present invention with this transition metal complex, the acetoxyl group allylic cpd that the acetic oxide oxygen glycosylation reaction of preferred especially divinyl obtains, promptly 3,4-diacetoxy-1-butylene is to 1, the reaction solution of 4-diacetoxy-2-butylene isomerization reaction.
In the method for the present invention, the reaction solution that reaction by above-mentioned this transition-metal catalyst of use is obtained contacts with the aromatic series phosphorous acid ester, but reaction solution can be a reacted reaction solution itself, also can be the reaction solution that contains catalyzer after removing the debris behind the resultant or isolate catalyzer from reaction solution, reacted reaction solution is contacted.Contacting specifically of reaction solution and aromatic series phosphorous acid ester can contact by adding the solution that contains the aromatic series phosphorous acid ester to reacted reaction solution.The aromatic series phosphorous acid ester can be a solid itself, also can be solution, with the contact efficiency consideration of reaction solution, preferably makes its uniform dissolution in advance when adding.
Thus, after the reaction process, in the reaction solution, transition metal complex catalyst and aromatic series phosphorous acid ester form uniform solution, be sent in the pipe arrangement of in-process, in the device such as distillation tower, so, suppressed in the pipe arrangement and device such as distillation tower in separating out in the metal loss that causes, the operation system of catalyst metal produce pollution.In addition, catalyst metal can be with this dissolving metal the form of solution be fetched into outside the system, carry out catalyst treatment (catalyst recovery or discarded) for the solution that takes out.Can carry out following operation in the catalyst treatment operation: the solution that takes out is directly burnt; Transfer to the elsewhere in order to reclaim metal; Perhaps utilize the submerged combustion device be arranged in the factory etc. with the recovery of calx form etc.
If necessary, the mixture to reaction solution and aromatic series phosphorous acid ester carries out heat treated.The heat treated temperature is generally 20 ℃～200 ℃, is preferably 80 ℃～180 ℃.Surpass this scope, when high temperature was handled, thermolysis took place in aromatic series phosphorous acid ester self, and temperature is crossed when hanging down, and the solubleness of aromatic series phosphorous acid ester in reaction solution reduces, and the effect that the inhibition metal is separated out reduces.
Choice criteria as the aromatic series phosphorous acid ester, the anti-oxidant function that is had in order farthest to bring into play this phosphorous acid ester, need avoid the decomposition that causes because of the factor beyond the oxygen, specifically, it is not preferred using the phosphorous acid ester that thermolysis or decomposition take place easily.Therefore, the heat stable aromatic series phosphorous acid ester of preferred use, in addition, in order to improve chemical stability, the optimization aromatic ring has the substituent phosphorous acid ester of large volume at the ortho position of its P-O key, to prevent that the P-O key is because of ftractureing with other the reaction of chemical ingredients.In addition, usually the cost of monodentate phosphite is lower than the cost of multidentate phosphite, so on function and the angle of cost, preferred monodentate aromatic series phosphorous acid ester.
Under the situation that interpolation aromatic series phosphorous acid ester contacts in the reaction solution that obtains by the reaction of using transition-metal catalyst, the ratio of aromatic series phosphorous acid ester and reaction solution is different because of the kind of the transition-metal catalyst that reaction solution contained, amount etc., but common 1 mole metal with respect to transition-metal catalyst, the aromatic series phosphorous acid ester that adds is 1 molar equivalent～1000 molar equivalents, preferred 2 molar equivalents～50 molar equivalents.The molar equivalent of the aromatic series phosphorous acid ester that adds surpasses this ratio, and when its addition was very few, the effect that the metal that can not be inhibited is separated out, and addition is when too much can not obtain the effect that conforms to addition, so be not preferred on the cost.
The concentration of the aromatic series phosphorous acid ester solution that adds is different because of the kind of this aromatic series phosphorous acid ester, is generally 50 ppm by weight～1 weight %, is preferably 100 ppm by weight～5000 ppm by weight.
Below, the reaction solution after the isomerization reaction that makes the acetoxyl group allylic cpd of having used transition metal complex catalyst is described with the method that the aromatic series phosphorous acid ester contacts.
Make as 3 of acetoxyl group allylic cpd by the oxidation diacetoxy reaction of divinyl equiconjugate dienes, 4-diacetoxy-1-butylene class and/or 1, the method for 4-diacetoxy-2-butylene class is known.Usual method is; in the presence of palladium series catalyst; make divinyl, acetic acid and oxygen reaction; make 1; 4-diacetoxy-2-butylene and 3; 4-diacetoxy-1-butylene, and this reaction solution also contains 1-acetoxyl group-4-hydroxyl-2-butylene as the hydrolyzate of these diacetoxy butylene classes, 3-hydroxyl-4-acetoxyl group-1-butylene, 4-hydroxyl-3-acetoxyl group-1-butylene etc. usually.
As in the isomerization reaction as 3 of raw material supplying, 4-diacetoxy-1-butylene except pure product, also can directly use the reacted reaction solution of diacetoxyization of above-mentioned divinyl; Perhaps wait and remove boiling points such as acetic acid, water than 3, the reaction solution after at least a portion of the by product that 4-diacetoxy-1-butylene is low by distillation; Perhaps wait and remove boiling point than 3, the reaction solution behind part or all of the by product that 4-diacetoxy-1-butylene is high by distillation; Even can use removed part or all of low-boiling by-products and high boiling point by-products produced after reaction solution etc.In the method for the present invention, these are used as " contain 3,4-diacetoxy-1-butylene is as the liquid of principal constituent ".Usually, " containing 3; 4-diacetoxy-1-butylene is as the liquid of principal constituent " that the present invention uses also contains 1,4-diacetoxy-2-butylene, in addition, can also contain as 3,3-hydroxyl-4-acetoxyl group-the 1-butylene of the hydrolyzate of 4-diacetoxy-1-butylene, 4-hydroxyl-3-acetoxyl group-1-butylene and/or 3,4-dihydroxyl-1-butylene and as 1,1-acetoxyl group-4-hydroxyl-the 2-butylene and/or 1 of the hydrolyzate of 4-diacetoxy-2-butylene, 4-dihydroxyl-2-butylene.
In the isomerization reaction of above-mentioned acetoxyl group allylic cpd etc., the transition metal complex that uses as catalyzer is preferably with phosphorous acid ester or phosphoramidite, preferred especially with the complex compound catalyst of phosphoramidite as part and palladium formation.With respect to the acetoxyl group allylic cpd as reaction raw materials, the consumption of transition metal complex is 0.001 ppm by weight～1000 ppm by weight, and more preferably 0.001～100 ppm by weight is preferably 0.01～100 ppm by weight especially.
The temperature of implementing isomerization reaction is generally 20～200 ℃, is preferably 80～180 ℃, is preferably 100 ℃～160 ℃ especially.When temperature of reaction was too high, the metallization of transition metal complex catalyst caused taking place aging, caused active the disappearance; In addition, reaction temperature is spent when low, and speed of response reduces, and needs not only long but also big reactor.
The pressure of implementing isomerization reaction is generally 1 air pressure, carries out but also can under reduced pressure or add to depress, and is preferably 1 air pressure～10 air pressure, is preferably 1～3 air pressure especially.Reaction pressure is crossed when low, and along with the reduction of temperature of reaction, catalyst activity reduces, and reaction pressure is when too high, and reactor cost increases.
Isomerization reaction is carried out in liquid phase usually, and this isomerization reaction both can be implemented in the presence of solvent, also can implement not existing under the solvent.Use under the situation of solvent, as preferred solvent, if can catalyst-solvent and starting compound just can use, be not particularly limited.As the concrete example of solvent, can enumerate ethers such as diglyme, diphenyl ether, dibenzyl ether, diallyl ether, tetrahydrofuran (THF) (THF), dioxane; N-N-methyl-2-2-pyrrolidone N-, N, amidess such as dinethylformamide, N,N-dimethylacetamide; Ketones such as pimelinketone; Ester classes such as n-butyl acetate, gamma-butyrolactone, phthalandione two (n-octyl) ester; Toluene, dimethylbenzene, dodecylbenzene etc. are aromatic hydrocarbon based; Aliphatic hydrocarbons such as Skellysolve A, normal hexane, normal heptane, octane; The by product itself that isomerization reaction generates; Allylic cpd derivative itself as raw material; Allylic cpd itself as resultant; The compound that the leavings group of raw material allylic cpd forms etc.As particularly preferred solvent, can enumerate allylic cpd itself, as allylic cpd itself of resultant etc. as raw material.
Consumption to solvent has no particular limits, but because isomerization reaction is mainly carried out with intramolecular reaction, reacts so preferably use than still less quantity of solvent in the past.Usually, with respect to the gross weight as the allylic cpd derivative of raw material, the amount of solvent is 0～10 times of weight, is preferably 0～5 times of weight, most preferably is 0～1 times of weight.Under the too much situation of quantity of solvent, speed of response reduces.
Reactive mode when implementing isomerization reaction can be used complete, the plug flow type reactor of stirring-type, in a continuous manner, semicontinuous mode or batch mode carry out.Preferably except the steam that solvent, starting compound, resultant of reaction, byproduct of reaction, catalyst decomposes thing etc. form, the gas phase portion in the reactor is formed by rare gas elementes such as argon, nitrogen.Particularly because entering of air waits that to cause sneaking into of oxygen be the reason of catalyst aging (being that the phosphorus compound oxidation disappears), so the preferred amount that reduces oxygen as far as possible.
The supplying opening that is provided with near the pipe arrangement reactor outlet is to the solution that injects the aromatic series phosphorous acid ester from the continuous effusive reaction solution of isomerization reactor.The injection of aromatic series phosphorous acid ester solution can be a successive, also can be step, but preferably supply with continuously.Supply has the reaction solution of aromatic series phosphorous acid ester to be transferred to separation circuit (distillation tower), carry out fractionation by distillation, this separation circuit is used for 3, and the resultant that the isomerization reaction of 4-diacetoxy-1-butylene obtains (1,4-diacetoxy-2-butylene) is separated from isomerization reaction liquid.The separation of resultant can be adopted habitual lock out operation, specifically, except distillation procedures such as no column plate distillation, underpressure distillation, thin film distillation, wet distillation, can also enumerate gas-liquid separation, evaporation (vaporization), stripping, gas absorption, extraction etc. and separate operation.Each lock out operation can carry out with separate operation, also can carry out the separation of composition more than 2 kinds simultaneously.In addition, the raffinate after resultant and raw material allylic cpd etc. are isolated can carry out above-mentioned catalyst treatment.
As the reaction example beyond the above-mentioned isomerization reaction, can enumerate the hydrogenation formaldehyde glycosylation reaction of alkene.The hydrogenation formaldehyde glycosylation reaction of alkene usually uses the metal complex catalyst of the part that contains transition metal (for example Rh, Pd etc.) and be made of organo phosphorous compounds, in the presence of solvent or do not exist alkene and oxygen-containing gas (mixed gas of carbon monoxide and hydrogen) reaction are carried out.With respect to 1 molar reactive matrix, catalyst consumption is generally more than the 0.1ppm mole, be preferably more than the 1ppm mole, and be 0.2 mole of % following, be preferably 0.1 mole below the %.Temperature of reaction is generally-20 ℃～150 ℃, is preferably 0 ℃～100 ℃, and reaction pressure is generally 0.01MPa～30MPa, is preferably 0.05MPa～20MPa.
In addition, as other reaction example, can also enumerate the hydrogenation of the alkene that used above-mentioned transition metal complex catalyst, carbonyl compound, group with imine moiety etc.With respect to 1 molar reactive matrix, this catalyst consumption in the hydrogenation is generally more than the 0.1ppm mole, is preferably more than the 1ppm mole, and is 0.2 mole below the %, is preferably 0.1 mole below the %.Temperature of reaction is generally-20 ℃～150 ℃, is preferably 0 ℃～100 ℃, and the hydrogen dividing potential drop is generally 0.001MPa～30MPa, is preferably 0.01MPa～20MPa.
During reaction solution that method of the present invention is used for obtaining through above-mentioned reaction example, can successfully take out the solution that contain transition metal from reaction solution.
Embodiment
Below by embodiment and comparative example method of the present invention is described in detail, but the invention is not restricted to these embodiment.
Reference example 1
In the presence of 1kg Pd-Te catalyzer, circulation 0.21kg/hr divinyl, 2.94kg/hr the mixed gas of acetic acid and 0.34kg/hr 6 volume % oxygen/94 volume % nitrogen, at 80 ℃, the condition of 6MPa is carried out the acetoxylation reaction, obtain mixed solution, this mixed solution contains 81 weight %1,4-diacetoxy-2-butylene, 9 weight %3,4-diacetoxy-1-butylene, 2 weight %3-hydroxyl-4-acetoxyl group-1-butylene, 3 weight % acetic acid, and 3 weight % boiling point than 3, composition that 4-diacetoxy-1-butylene is low and 2 weight % boiling points are than 3, the composition that 4-diacetoxy-1-butylene is high.
Reference example 2
By continuous still battery the mixed solution that obtains in the 11L reference example 1 is separated into and contains 3, the liquid of 4-diacetoxy-1-butylene and contain 1, the liquid of 4-diacetoxy-2-butylene.In addition, 40 sections Oldershaw distillation tower is used in distillation.During continuous still battery, tower top pressure remains that 20mmHg, reflux ratio remain 3, tower top temperature remains 95 ℃, column bottom temperature and remains 151 ℃, and import mixed solution continuously with the flow of 150cc/hr 20 sections position at the bottom of the distance tower, distillate continuously from the flow of top of tower with 27cc/hr, the flow with 123cc/hr at the bottom of the tower carries out continuous drawing.By this continuous still battery, the form with the jar fluid at the bottom of the tower obtains containing 1, and the liquid of 4-diacetoxy-2-butylene obtains containing 3, the liquid of 4-diacetoxy-1-butylene from cat head with the form of distillate.What obtain contains 3, the liquid of 4-diacetoxy-1-butylene is mixed solution, wherein contain 3,4-diacetoxy-1-butylene is 45 weight %, 3-hydroxyl-4-acetoxyl group-1-butylene be 11 weight %, acetic acid be 22 weight %, as the boiling point of other compositions than 3, the composition that 4-diacetoxy-1-butylene is low be 20 weight % and boiling point than 3, the composition that 4-diacetoxy-1-butylene is high is 2 weight %.In addition, this contains 3, and 1 of the liquid of 4-diacetoxy-1-butylene, 4-diacetoxy-2-butylene content are below the 1 weight %.
Reference example 3
By carrying out continuous still battery, contain 3 from what 300kg reference example 2 obtained, isolate boiling point than 3 in the liquid of 4-diacetoxy-1-butylene, the major part of the composition that 4-diacetoxy-1-butylene is low.Need to prove that the packed tower (HETP140mm/NTP) that is filled with 5m rule weighting material TM-700M (MC filling) is used in distillation.In the continuous still battery, tower top pressure remains that 100mmHg, reflux ratio remain 3, tower top temperature remains 77 ℃, column bottom temperature and remains 144 ℃ temperature, import 300kg continuously with the position of flow 2610mm at the bottom of the distance tower of 20kg/hr and contain 3, the liquid of 4-diacetoxy-1-butylene, distillate continuously from the flow of top of tower with 7.6kg/hr, the position of 580mm is carried out continuous drawing with the form of effluent with the flow of 11.4kg/hr at the bottom of the distance tower, and the flow with 1kg/hr carries out continuous drawing at the bottom of the tower.By this continuous still battery, obtained boiling point than 3 from cat head, the composition that 4-diacetoxy-1-butylene is low with the form of distillate.The acetic acid that contains in this distillate is 71 weight %, 3,4-diacetoxy-1-butylene is that 0.18 weight % (is equivalent to import 3 of distillation tower, 0.17 weight % of 4-diacetoxy allylic cpd amount), and other boiling point than 3, the composition that 4-diacetoxy-1-butylene is low is 21 weight %.In addition, contain the liquid that extracts at the bottom of the tower 3,4-diacetoxy-1-butylene is that 70 weight %, 3-hydroxyl-4-acetoxyl group-1-butylene are that 9 weight %, the boiling point that reaches other are than 3, the composition that 4-diacetoxy-1-butylene is low be 3 weight %, boiling point than 3, the composition that 4-diacetoxy-1-butylene is high is 18 weight %.In addition, the liquid that extracts from effluent, obtained refining 3,4-diacetoxy-1-butylene, its contain 3,4-diacetoxy-1-butylene is that 69 weight %, 3-hydroxyl-4-acetoxyl group-1-butylene are 15 weight %, reach other boiling points than 3, the composition that 4-diacetoxy-1-butylene is low be 4 weight %, boiling point than 3, the composition that 4-diacetoxy-1-butylene is high is 12 weight %.
Embodiment 1
Under nitrogen atmosphere, in the glass flask, add part (the part 31.2mg shown in the above-mentioned formula (B-3) shown in palladium (3.2mg), the following formula (1), with respect to metallic palladium is 2 molar equivalents) and reference example 3 in contain 3 from what effluent obtained, the liquid of 4-diacetoxy-1-butylene (75g), 80 ℃ of heated and stirred 1 hour, make its dissolving, preparation palladium catalyst solution.Measure the molten metallic palladium concentration of depositing in this palladium catalyst solution by ICP-MS (InductivelyCoupled Plasma Mass Spectrometry), the result: palladium metal concentration is 20 ppm by weight.Add DBPO[three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester shown in following formula (2) to this palladium catalyst liquid of 2cc] (5.0mg, be 20 molar equivalents with respect to metallic palladium), under the normal pressure, in 175 ℃ of heating 27 hours.Using the eyelet rugosity is the strainer of 8 μ m, and the catalyst solution after the heating is filtered, and utilizes ICP-MS that the concentration that is dissolved in the remaining palladium in the filtrate is measured.Consequently, the remaining dissolved metallic palladium concentration after the heating and filtering is 20 ppm by weight.According to heating the molten survival rate of depositing that preceding initial stage concentration and remaining concentration of ordinary dissolution calculate metallic palladium.Consequently, the molten survival rate of depositing of metallic palladium is 100%, and Pd metal eduction rate is 0%.
Molten survival rate (the %)=remaining concentration of ordinary dissolution/initial stage concentration of depositing
Pd metallization amount (ppm by weight)=initial stage concentration-remaining concentration of ordinary dissolution
Pd metal eduction rate (%)=[Pd metallization amount]/[initial stage concentration]
Comparative example 1
(blank test)
As above-mentioned embodiment 1, wherein, do not add DBPO to palladium catalyst solution, in 175 ℃ of heating, implement similarly to Example 1 in addition under the normal pressure.Consequently, the remaining dissolving metallic palladium concentration after the heating and filtering is 6 ppm by weight, and Pd metal eduction rate is 70%.
Comparative example 2
(effect of DBPO and triphenylphosphine relatively)
As above-mentioned embodiment 1, wherein, not to add DBPO, but add triphenylphosphine (4 molar equivalents of 0.4mg, metallic palladium) to palladium catalyst solution, in 175 ℃ of heating, in addition, implement similarly to Example 1 under the normal pressure.Consequently, the remaining dissolving metallic palladium concentration after the heating and filtering is 2 ppm by weight, and Pd metal eduction rate is 90%.
Embodiment 2
(triphenylphosphine 1000 ppm by weight existence conditions)
Under nitrogen atmosphere, in part (2 molar equivalents of 78.8mg, metallic palladium), triphenylphosphine (triphenylphosphine concentration 1000 ppm by weight in 76.5mg, the catalyst solution) and the 75g reference example 3 shown in glass flask interpolation palladium (7.9mg), the formula (1), contain 3 from what effluent obtained, the liquid of 4-diacetoxy-1-butylene, 80 ℃ of heated and stirred 1 hour, make its dissolving, preparation palladium catalyst solution.Utilize ICP-MS that the molten metallic palladium concentration of depositing in this palladium catalyst solution is measured the result: palladium metal concentration is 54 ppm by weight.Add the DBPO[three shown in the described formula (2) (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester to this palladium catalyst liquid of 2cc] (20 molar equivalents of 12.6mg, metallic palladium), under the normal pressure, in 175 ℃ of heating 10 hours.Using the eyelet rugosity is the strainer of 8 μ m, and the catalyst solution after the heating is filtered, and utilizes ICP-MS that the concentration that is dissolved in palladium remaining in the filtrate is measured.Consequently, the remaining dissolved metallic palladium concentration after the heating and filtering is 52 ppm by weight.According to heating the molten survival rate of depositing that preceding initial stage concentration and remaining densitometer are calculated metallic palladium.Consequently, the molten survival rate of depositing of metallic palladium is 96%, and Pd metal eduction rate is 4%.
Embodiment 3
As above-mentioned embodiment 2, wherein, the DBPO addition is that 6.3mg (in addition, implement similarly to Example 2 by 10 molar equivalents of metallic palladium.Consequently, the remaining dissolving metallic palladium concentration after the heating and filtering is 50 ppm by weight, and Pd metal eduction rate is 7%.
Embodiment 4
As above-mentioned embodiment 2, wherein, add triphenyl phosphite [P (OPh) to palladium catalyst solution
3] (4 molar equivalents of 5 μ l, metallic palladium) replacement DBPO, in 175 ℃ of heating, in addition, implement similarly to Example 2 under the normal pressure.Consequently, the remaining dissolving metallic palladium concentration after the heating and filtering is 23 ppm by weight, and Pd metal eduction rate is 57%.
Embodiment 5
Under nitrogen atmosphere, in part (2 molar equivalents of 48.4mg, metallic palladium), triphenylphosphine (triphenylphosphine concentration 500 ppm by weight in 12.4mg, the catalyst solution) and the 24g reference example 3 shown in glass flask interpolation palladium (5.0mg), the above-mentioned formula (1), contain 3 from what effluent obtained, the liquid of 4-diacetoxy-1-butylene, 80 ℃ of heated and stirred 1 hour, make its dissolving, preparation palladium catalyst solution.Add 1.8g (20 molar equivalents of metallic palladium) to this palladium catalyst liquid of 3cc and contain 3, the liquid of 4-diacetoxy-1-butylene (wherein contain the DBPO[three shown in the above-mentioned formula of 1 weight % (2) (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester]).Utilize ICP-MS that the molten metallic palladium concentration of depositing in this palladium catalyst solution is measured the result: palladium metal concentration is 59 ppm by weight.This palladium catalyst solution was heated 10 hours in 175 ℃ under normal pressure.Using the eyelet rugosity is the strainer of 8 μ m, and the catalyst solution after the heating is filtered, and utilizes ICP-MS that the concentration that is dissolved in palladium remaining in the filtrate is measured.Consequently, the remaining dissolved metallic palladium concentration after the heating and filtering is 55 ppm by weight.According to heating the molten survival rate of depositing that preceding initial stage concentration and remaining densitometer are calculated metallic palladium.Consequently, the molten survival rate of depositing of metallic palladium is 93%, and Pd metal eduction rate is 7%.
Comparative example 3
As above-mentioned embodiment 2, wherein, do not add DBPO to palladium catalyst solution, in addition, implement similarly to Example 2.Consequently, the remaining dissolving metallic palladium concentration after the heating and filtering is 4 ppm by weight, and Pd metal eduction rate is 93%.
Comparative example 4
As above-mentioned embodiment 2, wherein, add three (normal-butyl) phosphorous acid ester [P (On-Bu) to palladium catalyst solution
3] (4 molar equivalents of 5 μ l, metallic palladium) replacement DBPO, in addition, implement similarly to Example 2.Consequently, the remaining dissolving metallic palladium concentration after the heating and filtering is 2 ppm by weight, and Pd metal eduction rate is 96%.
The result of the foregoing description 1～5 and comparative example 1～4 sums up and is shown in table 1.
Embodiment 6
Under nitrogen atmosphere, in part (2 molar equivalents of 19.5mg, metallic palladium) shown in glass flask interpolation palladium (2.2mg), the formula (3) and 20g reference example 3, contain 3 from what effluent obtained, the liquid of 4-diacetoxy-1-butylene, 80 ℃ of heated and stirred 1 hour, make its dissolving, preparation palladium catalyst solution.Utilize ICP-MS that the molten metallic palladium concentration of depositing in this palladium catalyst solution is measured the result: palladium metal concentration is 42 ppm by weight.Add the DBPO[three shown in the above-mentioned formula (2) (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester to this palladium catalyst liquid of 3cc] (20 molar equivalents of 19mg, metallic palladium), under the normal pressure, in 175 ℃ of heating 10 hours.Using the eyelet rugosity is the strainer of 8 μ m, and the catalyst solution after the heating is filtered, and utilizes ICP-MS that the concentration that is dissolved in the remaining palladium in the filtrate is measured.Consequently, the remaining dissolved metallic palladium concentration after the heating and filtering is 41 ppm by weight.According to heating the molten survival rate of depositing that preceding initial stage concentration and remaining densitometer are calculated metallic palladium.Consequently, the molten survival rate of depositing of metallic palladium is 98%, and Pd metal eduction rate is 2%.
Comparative example 5
As above-mentioned embodiment 6, wherein, do not add DBPO to palladium catalyst solution, in addition, implement similarly to Example 6.Consequently, the remaining dissolving metallic palladium concentration after the heating and filtering is 0 ppm by weight, and Pd metal eduction rate is 100%.
Embodiment 7
Under nitrogen atmosphere, in part (2 molar equivalents of 19.5mg, metallic palladium), triphenylphosphine (triphenylphosphine concentration 1000 ppm by weight in 20mg, the catalyst solution) and the 20g reference example 3 shown in glass flask interpolation palladium (2.2mg), the formula (3), contain 3 from what effluent obtained, the liquid of 4-diacetoxy-1-butylene, 80 ℃ of heated and stirred 1 hour, make its dissolving, preparation palladium catalyst solution.Utilize ICP-MS that the molten metallic palladium concentration of depositing in this palladium catalyst solution is measured the result: palladium metal concentration is 42 ppm by weight.Add the DBPO[three shown in the described formula (2) (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester to this palladium catalyst liquid of 2cc] (20 molar equivalents of 19mg, metallic palladium), under the normal pressure, in 175 ℃ of heating 10 hours.Using the eyelet rugosity is the strainer of 8 μ m, and the catalyst solution after the heating is filtered, and utilizes ICP-MS that the concentration that is dissolved in the remaining palladium in the filtrate is measured.Consequently, the remaining dissolved metallic palladium concentration after the heating and filtering is 40 ppm by weight.According to heating the molten survival rate of depositing that preceding initial stage concentration and remaining densitometer are calculated metallic palladium.Consequently, the molten survival rate of depositing of metallic palladium is 96%, and Pd metal eduction rate is 4%.
Comparative example 6
As above-mentioned embodiment 7, wherein, do not add DBPO to palladium catalyst solution, in addition, implement similarly to Example 7.Consequently, the remaining dissolving metallic palladium concentration after the heating and filtering is 0 ppm by weight, and Pd metal eduction rate is 100%.
Embodiment 8
Under nitrogen atmosphere, in part (2 molar equivalents of 46.2mg, metallic palladium), triphenylphosphine (triphenylphosphine concentration 500 ppm by weight in 12.7mg, the catalyst solution) and the 24g reference example 3 shown in glass flask interpolation palladium (5.1mg), the above-mentioned formula (3), contain 3 from what effluent obtained, the liquid of 4-diacetoxy-1-butylene, 80 ℃ of heated and stirred 1 hour, make its dissolving, preparation palladium catalyst solution.Add 1.8g (20 molar equivalents of metallic palladium) to this palladium catalyst liquid of 3cc and contain 3, the liquid of 4-diacetoxy-1-butylene (wherein contain the DBPO[three shown in the above-mentioned formula of 1 weight % (2) (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester]).Utilize ICP-MS that the molten metallic palladium concentration of depositing in this palladium catalyst solution is measured the result: palladium metal concentration is 58 ppm by weight.This palladium catalyst solution was heated 10 hours in 175 ℃ under normal pressure.Using the eyelet rugosity is the strainer of 8 μ m, and the catalyst solution after the heating is filtered, and utilizes ICP-MS that the concentration that is dissolved in the remaining palladium in the filtrate is measured.Consequently, the remaining dissolved metallic palladium concentration after the heating and filtering is 56 ppm by weight.According to heating the molten survival rate of depositing that preceding initial stage concentration and remaining densitometer are calculated metallic palladium.Consequently, the molten survival rate of depositing of metallic palladium is 97%, and Pd metal eduction rate is 3%.
The result of the foregoing description 6～8 and comparative example 5～6 sums up and is shown in table 2.
Table 2
| Embodiment 6 | Comparative example 5 | Embodiment 7 | Comparative example 6 | Embodiment 8 | |
| The molten Pd concentration wtppm that deposits of stock liquid | ?42 | ??42 | ??42 | ??42 | ?58 |
| Additive is mol ratio vs Pd metal 1. | ?DBPO/Pd＝?20 | ??- | ??DBPO/Pd＝??20 | ??- | ?DBPO/Pd＝?20 |
| Additive is wtppm 2. | ?- | ??- | ??PPh3：??1000wtppm | ??PPh3：??1000wtppm | ?PPh3：?500wtppm |
| Temperature ℃ | ?175 | ??175 | ??175 | ??175 | ?175 |
| Time h | ?10 | ??10 | ??10 | ??10 | ?10 |
| The molten Pd concentration wtppm that deposits after the heating and filtering | ?41 | ??0 | ??40 | ??0 | ?56 |
| The molten Pd survival rate % that deposits | ?98 | ??0 | ??96 | ??0 | ?97 |
| Pd metal eduction rate % | ?2 | ??100 | ??4 | ??100 | ?3 |
Embodiment 9
(metal to metallic palladium that is produced by DBPO under the reduced pressure is separated out inhibition)
Under nitrogen atmosphere, contain 3 at reference example 3 by what effluent obtained to pack into the part shown in palladium (21mg), the formula (1) (2 molar equivalents of 200mg, metallic palladium), triphenylphosphine (the triphenylphosphine concentration in 49mg, the catalyst solution is 10 ppm by weight) and 400cc of glass flask, the liquid of 4-diacetoxy-1-butylene, 80 ℃ of heated and stirred 1 hour, the preparation catalyst solution obtains the reaction solution that palladium metal concentration is 50 ppm by weight.With reaction solution and the DBPO shown in the formula (2) (20 molar equivalents of 1.22g, the metallic palladium) container with cover of packing into that obtains, close the lid carry out airtight after, down (300～380torr) are warmed up to 165 ℃ in decompression.Keep this temperature, and when reaching 165 ℃ the palladium concentration of (time=0) beginning every specified time assaying reaction liquid, observe over time.It the results are shown in Figure 1.
In addition, palladium concentration is measured by IPC-MS.In addition, the molten survival rate (%) of depositing of palladium is a ratio with respect to the initial stage concentration in the reaction solution.
Comparative example 7
As above-mentioned embodiment 7, wherein, do not add DBPO, in addition, observe palladium concentration similarly to Example 9 over time, it the results are shown in Figure 1.
Utilizability on the industry
For industrial reactions of carrying out such as the isomerization reaction of carrying out take transition metal complex as catalyst, hydrogenations, method of the present invention can suppress in the pipe arrangement or the device such as destilling tower in the generation of separating out the dirt that the metal loss that causes and the interior catalyst metals of operation system cause of catalyst metals, and can effectively catalyst metals be fetched into outside the system with the liquid form that is dissolved with catalyst metals, method of the present invention is method useful on the industry.
In addition, at this full content of quoting Japanese patent application 2007-288508 number specification sheets, claims, accompanying drawing and summary proposing on November 6th, 2007,, count this specification sheets as the disclosed content of specification sheets of the present invention.
Claims (13)
1. one kind is suppressed the method that metal is separated out from transition metal complex, it is characterized in that, the solution that contains transition metal complex is contacted with the aromatic series phosphorous acid ester, thereby suppress the transition metal complex precipitating metal from this solution, described transition metal complex has the part that is made of 3 valency organo phosphorous compoundss, described transition metal is selected from group VIII, and described aromatic series phosphorous acid ester is different from this 3 valency organo phosphorous compounds.
2. the method for claim 1 is characterized in that, described aromatic series phosphorous acid ester is the material shown in the following formula (I),
In the formula (I), 3 R represent to have substituting group independently of one another or do not have substituent alkyl, and at least 1 R is an aryl.
3. method as claimed in claim 1 or 2 is characterized in that, for described aromatic series phosphorous acid ester, at least 1 aryl in the formula (I) has substituting group at its ortho position.
4. method as claimed in claim 3 is characterized in that, for described aromatic series phosphorous acid ester, at least 1 aryl in the formula (I) is by tertiary carbon atom or quaternary carbon atom bonded substituting group at the substituting group that the ortho position had.
5. method as claimed in claim 4 is characterized in that, for described aromatic series phosphorous acid ester, 3 R in the formula (I) are identical and be to have at the ortho position by tertiary carbon atom or the substituent phenyl of quaternary carbon atom bonded.
6. as each described method of claim 1～5, it is characterized in that described aromatic series phosphorous acid ester is a monodentate phosphite.
7. as each described method of claim 1～6, it is characterized in that described 3 valency organo phosphorous compoundss are at least a compounds that select in the group that free phosphine, phosphorous acid ester and phosphoramidite form.
8. as each described method of claim 1～7, it is characterized in that described 3 valency organo phosphorous compoundss are at least a compounds that are selected from the group of being made up of multiple tooth phosphine, phosphorous acid ester and phosphoramidite.
9. as each described method of claim 1～8, it is characterized in that described group VIII transition metal is palladium or platinum.
10. as each described method of claim 1～9; it is characterized in that; the described solution that contains transition metal complex is as catalyzer with this transition metal complex; carry out the arbitrary reacted solution in isomerization reaction, hydrogenation, hydrogenation formyl reaction, dehydrogenation reaction, oligomerization, metathesis, linked reaction or the allylation reaction, described transition metal complex contains the part that is made of 3 valency organo phosphorous compoundss and is selected from the transition metal of group VIII transition metal.
11. method as claimed in claim 10, it is characterized in that, solution after the isomerization reaction that the described solution that contains transition metal complex is raw material allylic cpd derivative, that contain the allylic cpd derivative different with raw material, described transition metal complex contain the part that is made of 3 valency organo phosphorous compoundss and are selected from the transition metal of group VIII transition metal.
12. as claim 10 or 11 described methods, it is characterized in that, reaction solution after the isomerization reaction that the described solution that contains transition metal complex is the acetoxyl group allylic cpd, described transition metal complex contain the part that is made of 3 valency organo phosphorous compoundss and are selected from the transition metal of group VIII transition metal.
13. method as claimed in claim 12 is characterized in that, described acetoxyl group allylic cpd be the oxidation diacetoxy resultant of reaction by divinyl obtain contain 3,4-diacetoxy-1-butylene is as the liquid of principal constituent.
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| JP2007288508 | 2007-11-06 | ||
| JP2007-288508 | 2007-11-06 | ||
| PCT/JP2008/070069 WO2009060840A1 (en) | 2007-11-06 | 2008-11-04 | Method of inhibiting metal precipitation from transition metal complex |
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| KR (1) | KR20100084519A (en) |
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| CN110290872A (en) * | 2017-02-27 | 2019-09-27 | 株式会社可乐丽 | The manufacturing method of catalyst liquid |
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| US7928267B1 (en) * | 2009-06-22 | 2011-04-19 | Eastman Chemical Company | Phosphite containing catalysts for hydroformylation processes |
| KR101811102B1 (en) | 2015-07-13 | 2017-12-20 | 주식회사 엘지화학 | Catalyst composition comprising phosphorus-based ligands and hydroformylation process using the same |
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| FR1603513A (en) * | 1967-11-06 | 1971-05-03 | ||
| DE3505654A1 (en) * | 1985-02-19 | 1986-08-21 | Degussa Ag, 6000 Frankfurt | METHOD FOR PRODUCING 2-ALKYL-1,4-BUTANDIAL |
| JPH08295683A (en) * | 1995-04-28 | 1996-11-12 | Mitsui Toatsu Chem Inc | Production of 3-formyltetrahydrofuran |
| EP0839794A1 (en) * | 1996-11-04 | 1998-05-06 | Dsm N.V. | Process for the continuous preparation of an alkyl 5-formylvalerate compound |
| JP3948792B2 (en) * | 1997-08-11 | 2007-07-25 | 三井化学株式会社 | Method for producing 3-formyltetrahydrofuran |
| JP3903575B2 (en) * | 1998-03-09 | 2007-04-11 | 三菱化学株式会社 | Method for producing aldehydes |
| JP4085566B2 (en) * | 2000-09-29 | 2008-05-14 | 三菱化学株式会社 | Method for producing allyl compounds |
| JP4328080B2 (en) * | 2002-10-30 | 2009-09-09 | 三菱化学株式会社 | Solid supported organophosphorus compound, transition metal complex, and catalytic reaction method |
| JP4292960B2 (en) * | 2002-12-10 | 2009-07-08 | 三菱化学株式会社 | Method of storing Group VIII metal-organic phosphite complex catalyst solution |
| US7015360B2 (en) * | 2003-03-28 | 2006-03-21 | Dow Global Technologies, Inc. | Asymmetric catalysts prepared from optically active bisphosphites bridged by achiral diols |
| JP2007039490A (en) * | 2005-08-01 | 2007-02-15 | Mitsubishi Rayon Co Ltd | Fluidity improver, aromatic polycarbonate resin composition and molded product |
| CN1986055B (en) * | 2006-12-22 | 2012-06-27 | 中国科学院上海有机化学研究所 | Catalyst system and catalyzing method of propylene hydrogenation and formylation |
| CN101835786A (en) * | 2007-11-06 | 2010-09-15 | 三菱化学株式会社 | Method of inhibiting metal precipitation from transition metal complex |
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| CN110290872A (en) * | 2017-02-27 | 2019-09-27 | 株式会社可乐丽 | The manufacturing method of catalyst liquid |
| US11628430B2 (en) | 2017-02-27 | 2023-04-18 | Kuraray Co., Ltd. | Method for manufacturing catalyst liquid |
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| JP2014169346A (en) | 2014-09-18 |
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| WO2009060840A1 (en) | 2009-05-14 |
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