CN109535197A - A kind of method and its application of stabilizing phosphite ligands - Google Patents

A kind of method and its application of stabilizing phosphite ligands Download PDF

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Publication number
CN109535197A
CN109535197A CN201811553420.7A CN201811553420A CN109535197A CN 109535197 A CN109535197 A CN 109535197A CN 201811553420 A CN201811553420 A CN 201811553420A CN 109535197 A CN109535197 A CN 109535197A
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phosphite ligands
reaction
cyclodextrin
stabilizing
phosphite
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CN109535197B (en
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黄高峰
牛广文
赵德胜
严宏岳
张留升
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SHANDONG XINHECHENG PHARMACEUTICAL CO Ltd
Shandong Xin He Cheng Vitamin Co Ltd
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SHANDONG XINHECHENG PHARMACEUTICAL CO Ltd
Shandong Xin He Cheng Vitamin Co Ltd
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Priority to PCT/CN2019/095104 priority patent/WO2020124996A1/en
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    • 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
    • C07F9/025—Purification; Separation; Stabilisation; Desodorisation of organo-phosphorus compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C07C45/505—Asymmetric hydroformylation
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids
    • C07F9/142—Esters of phosphorous acids with hydroxyalkyl compounds without further substituents on alkyl
    • 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
    • C07F9/06—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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention discloses a kind of method and its application of stabilizing phosphite ligands, cyclodextrin compounds are added in the reaction system existing for phosphite ligands, to inhibit the degradation of ligand；In the reaction system, the phosphite ligands are as the catalyst reacted or the catalyst reacted is collectively constituted with transition metal.The decomposition that reaction system phosphite ligand can effectively be inhibited by this method, improves the service life of phosphite ligands, further achievees the purpose that improve reaction efficiency.

Description

A kind of method and its application of stabilizing phosphite ligands
Technical field
The invention belongs to field of catalytic reactions, and in particular to a method of it improves catalysis reaction and matches body life time, especially relate to And a kind of method that the phosphite ligands service life is improved in catalysis reaction.
Background technique
The catalyst that phosphite ligands are formed with transition metal is widely used.Such as public affairs in US 4464515 and 4503196 It opens in the hydrogenation process for unsaturated compound conjugated diene, discloses in European patent application 366212 and 177999 for alkene In the oligomeric or dimerization of hydrocarbon, disclosed in US 911518 in the synthesis process for optics drugs, US4810815 and It is disclosed in 4714773 during being adiponitrile for butadiene hydrocyanation；It is public in US 5103033 and European application 459464 It opens and burns silanization for the silane of alkene.US 3499933, which is disclosed, is used for carbonyl for a kind of phosphite complex of rhodium-containing Change reaction.
During the reaction, phosphite ligands can gradually degrade.US 4599206 and 4717775 discloses a kind of phosphorous The mechanism of degradation of hydrochlorate ligand.In this mechanism, which is slowly hydrolyzed in the presence of water in the reactive mixture.It should Decomposition product then in reaction mixture aldehyde product and additional water, through series of steps react generate hydroxyalkyl phosphine Acid.The acid is further catalyzed ligand hydrolysis.This inevitably " chain " effect makes to remain in the phosphorous in reaction solution The hydrolysis of hydrochlorate ligand becomes very quickly.
There are three ways to solving phosphite ligands degradation at present: it proposes tertiary amine being added to reactant in US 4567306 In system, the hydroxyalkylphosphonic acids of generation are neutralized in time and are quenched, avoids that self-catalysis degradation reaction occurs.But the tertiary amine being added can urge Polymerization reaction occurs for aldehyde compound in change system, and heel rate is caused to be significantly increased；It proposes to mix reaction in US 4712775 Object is removed the phosphoric acid by-product that autocatalysis generates by weak-base ion-exchange resin from the system containing ligand, and will Processed mixture is recycled in reactor.But this mode will lead to the loss of noble metal catalyst, and need to increase Oil (gas) filling device investment；B.Costisella, H.Gross (JPrakt.Chem., 317 (5), 798-806) report epoxides Phosphate compounds are formed to inhibit ligand hydrolysis with phosphoric acid, but likewise, epoxy also can be with the aldehyde product shape in system At by-product and it is necessary to constantly add to maintain suitable concentration.
Cyclodextrin is big ring supermolecule, is the oligomer of cyclic annular glucose.The characteristic that cyclodextrin has inner cavity hydrophobic, can Inclusion compound and molecular assembly are formed by host-guest identification with many organic and inorganic molecule, to form microreactor. Nakamura A, (Inoue Y.J.Am.Chem.Soc., 2003,125 (4): 966) using cyclodextrin as microreactor into During row asymmetry [4+4] cyclization dimerization reaction, the presence (see attached drawing 1) of cyclodextrin inclusion compound is confirmed by characterization. But it is intended merely to improve the spatial selectivity of certain class reaction using cyclodextrin in article, not have anti-using its cavity hydrophobic performance The only report of phosphite hydrolysis (see attached drawing 1).
Summary of the invention
Present invention is generally directed to the above problems, provide a kind of method of new stabilizing phosphite ligands, and this method passes through Disposably to the cyclodextrin super molecular compound of hydroformylation reaction system addition 0.01wt%-5wt%, Asia is efficiently solved The problem of phosphate ligand degradation.
A kind of method of stabilizing phosphite ligands, comprising: ring is added in the reaction system existing for phosphite ligands Dextrin class compound, to inhibit the degradation of ligand.
In the reaction system, the phosphite ligands as reaction catalyst or with common group of transition metal At the catalyst of reaction.
Preferably, the reaction system is hydroformylation reaction system.
Preferably, the cyclodextrin compounds are to be added at one time, with the total restatement of reaction mixture, additive amount is 0.01wt%-5wt%；Preferably 0.1wt%-2wt%.
Preferably, the cyclodextrin compounds are cyclodextrin or derivatives thereof.
Preferably, the cyclodextrin compounds are that cyclodextrin and its derivative contain 6~12 D- glucopyranoses Unit, the preferably molecule containing 6,7,8 glucose units, i.e. α, β and γ cyclodextrin and its derivative.
The various phosphite ligands that method in the present invention is previously mentioned suitable for CN 1092058A, preferably, institute The phosphite ligands stated are selected from one of three organic phosphite ligands or more phosphite ligands；
The structure of the three organic phosphite ligands is shown below:
Wherein, R ' is alkyl, including alkyl or aryl；Preferably C1~C6Alkyl, substitution or unsubstituted phenyl, Replacing the substituent group on the perhaps unsubstituted naphthalene phenyl or naphthyl can be methyl, methoxyl group or halogen etc., example Such as:
Preferably, the three organic phosphite ligands are not when the cyclodextrin compounds are beta cyclodextrin Including
The structure of more phosphite ligands is shown below:
Wherein, Ar is for substitution or unsubstituted aryl, including phenyl and condensed-nuclei aromatics, preferably naphthalene；X is independently For numerical value 0 or 1；Y is the alkyl for representing m valence, and m 2-6, Y are more preferably alkylidene (i.e. m=2), more preferably C1~C10 Alkylidene；A independently indicate a divalent abutment (such as :-CR1R2-、-O-、-S-、-NR3-、-SiR4R5Or-CO- etc., wherein R1And R2Respectively indicate H, C1~C12Alkyl, phenyl, tolyl or anisyl, R3、R4Or R5Respectively indicate H or-CH3), n 0 Or 1.Such as:
The present invention also provides a kind of methods for carrying out hydroformylation reaction, comprising: phosphorous acid is added in reaction dissolvent Salt ligand and rhodium catalyst, are then added the cyclodextrin compounds, and stirring forms cyclodextrin with phosphite ligands Inclusion compound, then heating is passed through olefin feedstock and gaseous mixture (carbon monoxide and hydrogen) carries out hydroformylation reaction, and reaction terminates After obtain hydroformylation product.
Wherein, the temperature of the hydroformylation reaction is generally 70-140 DEG C, preferably 80-120 DEG C.
The olefin feedstock and gaseous mixture do not have ratio limitation；Gaseous mixture ratio (carbon monoxide: hydrogen) is also without special limit System, generally about 70:30~30:70, preferably 50:50.
The reaction dissolvent has no particular/special requirement, as long as reaction raw materials can be dissolved and catalyst is formed homogeneously, and boiling point is high In product in favor of rectifying separation, preferably tetraethyleneglycol dimethyl ether, tetraethylene glycol dimethyl ether, dimethylformamide, dimethyl sulfoxide.
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
(1) added cyclodextrin will not be catalyzed formylation reaction system generation side reaction, especially aldehydes in the present invention The polymerization side reactions of product；
(2) added cyclodextrin property is stablized in the present invention, and the increase with the reaction time is without adding and can maintain Imitate concentration；
(3) required cyclodextrin additive is simple and easy to get in the present invention, low in cost, is conducive to answer on a large scale in production With.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of cyclodextrin inclusion compound in the prior art；
Fig. 2 is just different than the result figure that changes with time for the carbonylation conversion ratio and product of embodiment 2；
Fig. 3 is the result of variations figure of the average conversion of 30 days different solvents and average just different ratio in embodiment 2~6；
Fig. 4 is the result of variations figure of the average conversion of 30 days different materials and average just different ratio in embodiment 7~10；
Fig. 5 is the result of variations figure of the average conversion of 30 days different ligands and average just different ratio in embodiment 11~14.
Specific embodiment
Following embodiment is conducive to that present invention is further described in detail, but does not limit the invention.
Embodiment 1
With reference to the method for evaluating ligand stability in US 5364950, the solution of hydroformylation reaction is simulated.The solution contains There is a 72ppm rhodium, the ligand A of 0.6wt% (6,6 '-[3,3 ', 5,5 '-four (1,1- dimethyl ethyl) 1,1 '-diphenyl -2,2 ' - Diyl] dioxy] two-dibenzo [d, f] [1,3,2]-diphosphine oxygen ligand), about 84wt% butyraldehyde, about 8.2wt% tetraethylene glycol diformazan Ether is as solvent and about 7.1wt% xenol.The solution filling of five equal portions is assigned in the container cleaned with nitrogen.It leaves Sample A is constant, as control.0.2wt% Hydroxy pentyl phosphonic acids is added in sample B to E and 0.6wt% water (is based on container The total weight of middle content).It no longer adds any substance in sample B, is added the tert-butylamine of 5wt% in sample C, in sample D The styrene oxide of 5wt% is added and 1wt% beta cyclodextrin is added in sample E.Under same experimental conditions, sample is taken out in timing The measurement of product solution remains on the amount of the ligand in solution.Table l remaining initial ligand percentage after showing 24 hours.Pass through ratio Relatively illustrate that the present invention realizes improved purpose.
Table 1
Sample Ligand remains percentage %
1A 100
1B 0
1C 67
1D 33
1E 99
Ligand A concrete structure formula is as follows:
Embodiment 2
With reference to the method for utilizing two kettles series connection carbonylation evaluation ligand stability in 5364950 embodiment 12 of US, use Beta cyclodextrin (accounting for total mixture quality 0.7wt%) replaces 1,2- Epoxydodecane.Reaction continues 124 days, compared to 1, the 2- Epoxydodecane of a 0.2wt% is added described in US5364950 every three days, does not carry out ligand in this reaction process With adding for cyclodextrin, other conditions are consistent with US 5364950.Fig. 2 is showing carbonylation conversion ratio and product just Different ratio changes with time, and sampling is primary every three days, tests 124 days altogether.As shown in Figure 2, it in 124 days reaction process, urges The activity of agent does not change, and (high just different ratio may be due to cyclodextrin than being basically stable at 95 or so for product just different Cavity has shape-selective effect).This constant activity shows to degrade there is no excessive ligand during the reaction.
Embodiment 3
In addition to reaction dissolvent tetraethyleneglycol dimethyl ether is changed to dimethyl imide in equal volume, runing time is changed to 30 It, other process conditions are consistent with embodiment 2.
Embodiment 4:
In addition to reaction dissolvent tetraethyleneglycol dimethyl ether is changed to dimethyl sulfoxide in equal volume, runing time is changed to 30 days, Other process conditions are consistent with embodiment 2.
Embodiment 5:
In addition to reaction dissolvent tetraethyleneglycol dimethyl ether is changed to ethylene glycol in equal volume, runing time is changed to 30 days, other Process conditions are consistent with embodiment 2.
Embodiment 6:
In addition to reaction dissolvent tetraethyleneglycol dimethyl ether is changed to Isononyl benzoate in equal volume, runing time is changed to 30 It, other process conditions are consistent with embodiment 2.
Comparing embodiment 2~6, by calculating separately 30 days average conversions and being averaged just different than carrying out more several differences The difference of solvent, shown in result figure 3:
The effect of dimethylformamide and dimethyl sulfoxide is slightly good molten with other it can be seen from the result of variations figure of Fig. 3 Agent.
Embodiment 7
In addition to reaction raw materials are become propylene, runing time is changed to 30 days, other process conditions and embodiment 2 keep one It causes.
Embodiment 8
In addition to reaction raw materials are become 1- octene, runing time is changed to 30 days, other process conditions and embodiment 2 keep one It causes.
Embodiment 9
In addition to reaction raw materials are become styrene, runing time is changed to 30 days, other process conditions and embodiment 2 keep one It causes.
Embodiment 10
In addition to reaction raw materials are become isobutene, runing time is changed to 30 days, other process conditions and embodiment 2 keep one It causes.
Comparing embodiment 7-10 carrys out this method to difference by the average conversion and average just different ratio that calculate separately 30 days The usable condition of raw material, shown in result figure 4:
This method has a preferable applicability to alkene described in embodiment it can be seen from Fig. 4 result of variations figure, and 30 It average conversion and just different more stable than；And the just different ratio of product can be significantly improved to different alkene.
Embodiment 11
In addition to becoming ligand with flowering structure, runing time is changed to 30 days, other process conditions and embodiment 2 keep one It causes.
Embodiment 12
In addition to replacing with ligand with flowering structure, runing time is changed to 30 days, other process conditions and embodiment 2 keep one It causes.
Embodiment 13
In addition to replacing with ligand with flowering structure, runing time is changed to 30 days, other process conditions and embodiment 2 keep one It causes.
Embodiment 14
In addition to replacing with ligand with flowering structure, runing time is changed to 30 days, other process conditions and embodiment 2 keep one It causes.
Comparing embodiment 11-14 carrys out this method to not by the average conversion and average just different ratio that calculate separately 30 days With the usable condition of raw material, as a result as shown in Figure 5:
This method has general applicability, embodiment 11 to phosphite ligands it can be seen from Fig. 5 result of variations figure It may be to cause protecting effect to occur poor since the group on ligand is mismatched with selected cyclodextrin cavity size It is different.

Claims (10)

1. a kind of method of stabilizing phosphite ligands, which is characterized in that add in the reaction system existing for phosphite ligands Enter cyclodextrin compounds, to inhibit the degradation of ligand.
2. the method for stabilizing phosphite ligands according to claim 1, which is characterized in that the cyclodextrin chemical combination Object is cyclodextrin or derivatives thereof.
3. the method for stabilizing phosphite ligands according to claim 1, which is characterized in that the cyclodextrin chemical combination Object contains 6~12 D- glucopyranose units；Preferably contain 6~8 glucose units.
4. the method for stabilizing phosphite ligands according to claim 1, which is characterized in that the reaction system is hydrogen first Acylation reaction system.
5. the method for stabilizing phosphite ligands according to claim 2, which is characterized in that in the reaction system, The phosphite ligands are as the catalyst reacted or the catalyst reacted is collectively constituted with transition metal.
6. the method for stabilizing phosphite ligands according to claim 1, which is characterized in that the cyclodextrin chemical combination Object is to be added at one time, with the total restatement of reaction mixture, additive amount 0.01wt%-5wt%；Preferably 0.1wt%-2wt%.
7. the method for stabilizing phosphite ligands according to claim 1, which is characterized in that the phosphite ligands Selected from one of three organic phosphite ligands or more phosphite ligands；
The structure of the three organic phosphite ligands is shown below:
Wherein, R ' is alkyl；
The structure of more phosphite ligands is shown below:
Wherein, Ar is for substitution or unsubstituted aryl；X independently is 0 or 1；Y is the alkyl for representing m valence, m 2-6；A is only It is vertical to indicate that a divalent abutment, n are 0 or 1.
8. the method for stabilizing phosphite ligands according to claim 1, which is characterized in that the phosphite ligands For with one of flowering structure:
9. a kind of method for carrying out hydroformylation reaction characterized by comprising phosphite ligands are added in reaction dissolvent And rhodium catalyst, then cyclodextrin is added in the method for stabilizing phosphite ligands according to any one of claims 1 to 8 Compound, stirring makes cyclodextrin compounds and phosphite ligands form inclusion compound, and then heating is passed through olefin feedstock and mixes It closes gas and carries out hydroformylation reaction, obtain hydroformylation product after reaction；
The gaseous mixture is carbon monoxide and hydrogen.
10. the method according to claim 8 for carrying out hydroformylation reaction, which is characterized in that the olefin feedstock packet Include ethylene, propylene, 1- octene, styrene or isobutene.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020124996A1 (en) * 2018-12-19 2020-06-25 浙江新和成股份有限公司 Method for stabilizing phosphite ligand and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3553298A (en) * 1967-10-20 1971-01-05 Hooker Chemical Corp Hydrolytic stabilized phosphite esters
SI9300506A (en) * 1992-09-29 1994-06-30 Union Carbide Chem Plastic Process for stabilizing phosphite ligands
CN1092075A (en) * 1992-10-05 1994-09-14 希巴-盖吉股份公司 Method with stabilizing trivalent phosphorus compounds with amines
CN104955568A (en) * 2012-09-25 2015-09-30 陶氏技术投资有限责任公司 Process for stabilizing a phosphite ligand against degradation

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109535197B (en) * 2018-12-19 2020-04-21 山东新和成维生素有限公司 Method for stabilizing phosphite ligand and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3553298A (en) * 1967-10-20 1971-01-05 Hooker Chemical Corp Hydrolytic stabilized phosphite esters
SI9300506A (en) * 1992-09-29 1994-06-30 Union Carbide Chem Plastic Process for stabilizing phosphite ligands
CN1092058A (en) * 1992-09-29 1994-09-14 联合碳化化学品及塑料技术公司 The method of stabilizing phosphite ligands
CN1092075A (en) * 1992-10-05 1994-09-14 希巴-盖吉股份公司 Method with stabilizing trivalent phosphorus compounds with amines
CN104955568A (en) * 2012-09-25 2015-09-30 陶氏技术投资有限责任公司 Process for stabilizing a phosphite ligand against degradation
CN104955568B (en) * 2012-09-25 2017-05-03 陶氏技术投资有限责任公司 Process for stabilizing a phosphite ligand against degradation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020124996A1 (en) * 2018-12-19 2020-06-25 浙江新和成股份有限公司 Method for stabilizing phosphite ligand and application thereof

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