CN114149464B - Ligand for polyketone polymerization catalyst and preparation method thereof - Google Patents
Ligand for polyketone polymerization catalyst and preparation method thereof Download PDFInfo
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- CN114149464B CN114149464B CN202111533705.6A CN202111533705A CN114149464B CN 114149464 B CN114149464 B CN 114149464B CN 202111533705 A CN202111533705 A CN 202111533705A CN 114149464 B CN114149464 B CN 114149464B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
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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 System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
- C07F9/5072—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure P-H
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- C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
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Abstract
The invention provides a ligand for a polyketone polymerization catalyst and a preparation method thereof; the preparation method comprises the following steps: a) Reacting bis (2-methoxyphenyl) phosphine oxide with 1,1 '-dibromo dimethyl ether in a solvent to obtain 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether; b) And c), carrying out reduction reaction on the 1,1 '-bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether obtained in the step a) in a solvent to obtain the 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether. Compared with the prior art, the ligand for the polyketone polymerization catalyst is prepared by selecting specific raw materials according to specific process steps to realize better overall interaction; the ligand has novel structure, high catalytic activity, simpler structure and lower molecular weight; meanwhile, the preparation method has the advantages of simple process route, low cost, high product yield and good quality, and is beneficial to the industrialization of polyketone.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a ligand for a polyketone polymerization catalyst and a preparation method thereof.
Background
Polyketone (POK) is a novel green polymer material synthesized from carbon monoxide, olefins (ethylene, propylene, styrene), has photodegradation and biodegradation properties, and can be further chemically modified, and has excellent and wide performance, so that the polyketone is a 'natural' thermoplastic engineering plastic. The synthesis of polyketones has undergone the development of three main catalytic systems: the main group of the system consists of a transition metal compound, a bidentate ligand, strong acid and anions thereof, an oxidant, a cocatalyst, a solvent and the like. Initially, palladium acetate/1, 3-bis [ bis (2-methoxyphenyl) phosphino ] propane/trifluoroacetic acid catalyst system developed by shell company has higher catalytic activity on ethylene and carbon monoxide polyketone, and development of novel bidentate ligand in polymerization catalyst system has important function on improving polymerization catalytic activity of polyketone. Thereafter, ST pharmaceutical co.ltd successively developed bidentate ligands such as 2, 2-dimethyl-1, 3-bis [ bis (2-methoxyphenyl) phosphino ] propane, 3-bis [ bis- (2-methoxyphenyl) phosphinomethyl ] -1, 5-dioxa-spiro [5,5] undecane and ((2, 2-dimethyl-1, 3-dioxane-5, 5-diyl) bis (methylene)) bis (2-methoxyphenyl) phosphine), which all exhibit higher catalytic activity during polyketide synthesis than 1, 3-bis [ bis (2-methoxyphenyl) phosphino ] propane. However, these ligands have long synthetic routes, low yields and complex structures.
Therefore, developing a ligand of a novel polyketone catalyst and a preparation method thereof, which have the advantages of simple synthetic route, high yield, low cost, novel ligand structure, high catalytic activity, simpler structure and lower molecular weight, become technical problems to be solved by the technicians in the field.
Disclosure of Invention
In view of the above, the invention aims to provide a novel ligand for a polyketone polymerization catalyst and a preparation method thereof, wherein the ligand has novel structure, high catalytic activity, simpler structure and lower molecular weight, and meanwhile, the preparation method has the advantages of simple process route, low cost, high product yield and good quality, and is beneficial to polyketone industrialization.
The invention provides a ligand for a polyketone polymerization catalyst, which has a structure shown in a formula (I):
the invention also provides a preparation method of the ligand for the polyketone polymerization catalyst, which comprises the following steps:
a) Reacting bis (2-methoxyphenyl) phosphine oxide with 1,1 '-dibromo dimethyl ether in a solvent to obtain 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether;
b) And c), carrying out reduction reaction on the 1,1 '-bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether obtained in the step a) in a solvent to obtain the 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether.
Preferably, the reaction in step a) is carried out under the action of a hydrogen-withdrawing reagent; the hydrogen drawing reagent comprises one or more of potassium tert-butoxide, sodium hydride and n-butyllithium.
Preferably, the molar ratio of the bis (2-methoxyphenyl) phosphine oxide, 1' -dibromodimethyl ether and the hydrogen drawing reagent in the step a) is (2-4): 1: (2-6).
Preferably, the step a) specifically includes:
a1 Adding the bis (2-methoxyphenyl) phosphine oxide into a solvent, and stirring until the bis (2-methoxyphenyl) phosphine oxide is completely dissolved to obtain a bis (2-methoxyphenyl) phosphine oxide solution; the stirring speed is 100 r/min-400 r/min;
a2 Adding a hydrogen-extracting reagent into the bis (2-methoxyphenyl) phosphine oxide solution obtained in the step a 1) to react, so as to obtain a bis (2-methoxyphenyl) phosphine oxide salt reaction solution;
a3 Adding 1,1 '-dibromodimethyl ether into the bis (2-methoxyphenyl) phosphine oxide salt reaction solution obtained in the step a 2) to react to obtain 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether.
Preferably, the temperature of the 1,1' -dibromodimethyl ether added in the step a 3) is controlled to be-40 ℃ to-10 ℃, the reaction is carried out for 1h to 2h after the addition is finished and the reaction is carried out for 14h to 20h after the temperature is raised to 20 ℃ to 35 ℃.
Preferably, the reduction reaction in step b) is carried out in the presence of a reducing agent and triethylamine; the reducing agent comprises HSiCl 3 One or more of lithium aluminum hydride and sodium borohydride.
Preferably, the molar ratio of 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether, triethylamine and reducing agent in step b) is 1: (6-10): (6-10).
Preferably, the step b) specifically includes:
b1 Mixing 1,1 '-bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether, triethylamine and a solvent to obtain a1, 1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether mixed solution;
b2 Adding a reducing agent into the 1,1 '-bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether mixed solution obtained in the step b 1) for reduction reaction to obtain the 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether.
Preferably, the temperature of the reducing agent added in the step b 2) is controlled to be 0-40 ℃, the temperature is raised to a reflux state after the addition is completed, and the reaction is kept for 4-10 hours.
The invention provides a ligand for a polyketone polymerization catalyst and a preparation method thereof; the preparation method comprises the following steps: a) Reacting bis (2-methoxyphenyl) phosphine oxide with 1,1 '-dibromo dimethyl ether in a solvent to obtain 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether; b) And c), carrying out reduction reaction on the 1,1 '-bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether obtained in the step a) in a solvent to obtain the 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether. Compared with the prior art, the ligand for the polyketone polymerization catalyst is prepared by selecting specific raw materials according to specific process steps to realize better overall interaction; the ligand has novel structure, high catalytic activity, simpler structure and lower molecular weight; meanwhile, the preparation method has the advantages of simple process route, low cost, high product yield and good quality, and is beneficial to the industrialization of polyketone. Experimental results show that the purity of the product is more than 98%, the yield is more than 85% by adopting the preparation method provided by the invention, and meanwhile, the ligand is used for carrying out polymerization reaction, and the catalytic activity is as high as 25.37 kg/(g-Pd.h).
Drawings
FIG. 1 is a process route diagram for preparing polyketone ligand 1,1' -bis [ bis (2-methoxyphenyl) phosphino ] dimethyl ether according to the embodiment of the invention;
FIG. 2 is a schematic illustration of a polyketone ligand 1,1' -bis [ bis (2-methoxyphenyl) phosphino group provided in an embodiment of the invention]Dimethyl ether 31 P NMR；
FIG. 3 is an embodiment of the present inventionExample provided polyketide ligand 1,1' -bis [ bis (2-methoxyphenyl) phosphino ]]Dimethyl ether 1 HNMR。
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a ligand for a polyketone polymerization catalyst, which has a structure shown in a formula (I):
the ligand can be named as 1,1' -bis [ bis (2-methoxyphenyl) phosphino ] dimethyl ether, and has novel structure, high catalytic activity, simpler structure and lower molecular weight. Experimental results show that the ligand carries out polymerization reaction, the catalytic activity is as high as 25.37 kg/(g-Pd.h), and the technical requirements of polyketone production in the market are met.
The invention also provides a preparation method of the ligand for the polyketone polymerization catalyst, which comprises the following steps:
a) Reacting bis (2-methoxyphenyl) phosphine oxide with 1,1 '-dibromo dimethyl ether in a solvent to obtain 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether;
b) And c), carrying out reduction reaction on the 1,1 '-bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether obtained in the step a) in a solvent to obtain the 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether.
Firstly, reacting bis (2-methoxyphenyl) phosphine oxide with 1,1 '-dibromo dimethyl ether in a solvent to obtain 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether.
In the present invention, the bis (2-methoxyphenyl) phosphine oxide has the following formula:
the 1,1' -dibromodimethyl ether has the following formula structure:
the source of the bis (2-methoxyphenyl) phosphine oxide and 1,1' -dibromodimethyl ether is not particularly limited and commercially available products known to those skilled in the art may be used.
In the present invention, the solvent is preferably tetrahydrofuran or diethyl ether; the source of the present invention is not particularly limited.
In the present invention, the reaction is preferably carried out under the action of a hydrogen-withdrawing reagent; the hydrogen extracting reagent preferably comprises one or more of potassium tert-butoxide, sodium hydride and n-butyllithium, and more preferably potassium tert-butoxide, sodium hydride or n-butyllithium. The source of the hydrogen extracting reagent is not particularly limited, and commercially available products known to those skilled in the art can be used.
In the present invention, the molar ratio of the bis (2-methoxyphenyl) phosphine oxide, 1' -dibromodimethyl ether and the hydrogen drawing reagent is preferably (2-4): 1: (2-6).
On this basis, the step a) is preferably specifically:
a1 Adding the bis (2-methoxyphenyl) phosphine oxide into a solvent, and stirring until the bis (2-methoxyphenyl) phosphine oxide is completely dissolved to obtain a bis (2-methoxyphenyl) phosphine oxide solution;
a2 Adding a hydrogen-extracting reagent into the bis (2-methoxyphenyl) phosphine oxide solution obtained in the step a 1) to react, so as to obtain a bis (2-methoxyphenyl) phosphine oxide salt reaction solution;
a3 Adding 1,1 '-dibromodimethyl ether into the bis (2-methoxyphenyl) phosphine oxide salt reaction solution obtained in the step a 2) to react to obtain 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether.
In the present invention, the stirring speed is preferably 100r/min to 400r/min, more preferably 200r/min to 300r/min.
In the invention, in order to avoid the excessive violent reaction, the temperature of the hydrogen drawing reagent is preferably controlled to be-40 ℃ to-5 ℃, the reaction temperature is allowed to be increased to 20 ℃ to 35 ℃ after the completion of the addition, and the reaction time is 1h to 3h.
In the invention, the reaction is avoided to be too severe, impurities are controlled, the temperature of the added 1,1' -dibromodimethyl ether is preferably controlled to be-40 ℃ to-10 ℃, the reaction is carried out for 1h to 2h after the addition is finished, and the reaction is carried out for 14h to 20h after the temperature is raised to 20 ℃ to 35 ℃; and (5) tracking and detecting the completion of the reaction.
In the present invention, after the completion of the tracking detection reaction, the method preferably further comprises:
slowly dripping the reaction solution into 20-40 ml of water under stirring to quench the reaction, wherein the dripping time is 20-30 min, separating the solution after fully stirring, washing with water, drying, removing the solvent under reduced pressure, recrystallizing the ethanol and petroleum ether, and drying to obtain the 1,1' -bis [ bis (2-methoxyphenyl) phosphoryl ] dimethyl ether.
After the 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether is obtained, the obtained 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether is subjected to reduction reaction in a solvent to obtain the 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether.
In the present invention, the solvent is preferably acetonitrile, toluene or xylene; the source of the present invention is not particularly limited.
In the present invention, the reduction reaction is preferably carried out in the presence of a reducing agent and triethylamine; the reducing agent preferably comprises HSiCl 3 One or more of lithium aluminum hydride, sodium borohydride, more preferably HSiCl 3 Lithium aluminum hydride or sodium borohydride. The sources of the reducing agent and triethylamine are not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the molar ratio of the 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether, triethylamine and the reducing agent is preferably 1: (6-10): (6-10).
On this basis, the step b) is preferably specifically:
b1 Mixing 1,1 '-bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether, triethylamine and a solvent to obtain a1, 1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether mixed solution;
b2 Adding a reducing agent into the 1,1 '-bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether mixed solution obtained in the step b 1) for reduction reaction to obtain the 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether.
In the invention, the temperature of the reducing agent is preferably controlled to be 0-40 ℃, the temperature is raised to a reflux state after the reducing agent is added, and the temperature is kept for reaction for 4-10 hours; the follow-up detection reaction was complete.
In the present invention, after the completion of the tracking detection reaction, the method preferably further comprises:
cooling, adding 6-10 times of HSiCl 3 Quenching reaction with 20-40 wt% molar equivalent sodium hydroxide water solution, standing to separate liquid, separating out organic phase, acetonitrile extraction twice, merging organic phase, water washing with saturated saline water once, drying, decompression to eliminate solvent, methanol re-crystallization to obtain 1,1' -bis [ bis (2-methoxy phenyl) phosphino radical]Dimethyl ether.
The invention provides a preparation method of a ligand of a novel polyketone catalyst, which takes bis (2-methoxyphenyl) phosphine oxide as an initial raw material, firstly reacts with 1,1 '-dibromodimethyl ether to obtain an intermediate product, and then 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether is synthesized by reduction; the preparation method has the advantages of simple process route, high product yield, good quality and novel ligand structure, and the ligand is used for carrying out polymerization reaction, has the catalytic activity as high as 25.37 kg/(g-Pd.h), has a simpler structure and lower molecular weight, reduces the production cost of polyketone, and is more beneficial to the industrialization of polyketone.
The invention provides a ligand for a polyketone polymerization catalyst and a preparation method thereof; the preparation method comprises the following steps: a) Reacting bis (2-methoxyphenyl) phosphine oxide with 1,1 '-dibromo dimethyl ether in a solvent to obtain 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether; b) And c), carrying out reduction reaction on the 1,1 '-bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether obtained in the step a) in a solvent to obtain the 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether. Compared with the prior art, the ligand for the polyketone polymerization catalyst is prepared by selecting specific raw materials according to specific process steps to realize better overall interaction; the ligand has novel structure, high catalytic activity, simpler structure and lower molecular weight; meanwhile, the preparation method has the advantages of simple process route, low cost, high product yield and good quality, and is beneficial to the industrialization of polyketone. Experimental results show that the purity of the product is more than 98%, the yield is more than 85% by adopting the preparation method provided by the invention, and meanwhile, the ligand is used for carrying out polymerization reaction, and the catalytic activity is as high as 25.37 kg/(g-Pd.h).
In order to further illustrate the present invention, the following examples are provided. The raw materials used in the following examples of the present invention are all commercially available.
Example 1
The preparation method of the ligand 1,1 '-bis [ bis (2-methoxyphenyl) phosphino ] dimethyl ether of the novel polyketone polymerization catalyst is shown in a process route shown in figure 1, and figure 1 is a process route diagram of the preparation process of the polyketone ligand 1,1' -bis [ bis (2-methoxyphenyl) phosphino ] dimethyl ether provided by the embodiment of the invention; the method comprises the following specific steps:
(1) Preparation of 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether:
2.35g of bis (2-methoxyphenyl) phosphine oxide is added into 30mL of tetrahydrofuran under anhydrous and anaerobic conditions, stirring is carried out until the bis (2-methoxyphenyl) phosphine oxide is dissolved, the stirring speed is 200r/min, the temperature is reduced to minus 20 ℃, wen Dijia 11.2.2 mL of 1.6M/Ln-BuLi solution is controlled, after 20min, dropwise adding is finished, the temperature is slowly increased to 30 ℃ and stirring is carried out for 1h (the stirring speed is unchanged), the temperature is reduced to minus 20 ℃, wen Dijia.61 g of 1 '-dibromodimethyl ether is controlled, after 20min, dropwise adding is finished, the temperature is kept for 1h, the temperature is increased to 30 ℃, the temperature is kept for 15h, the follow-up detection reaction is finished, the reaction solution is slowly dropwise added into 30mL of water under stirring, the dropwise adding time is 25min, after full stirring, liquid separation, water washing, drying, decompression removing the solvent, ethanol and petroleum ether recrystallization are carried out, and the white 1.60g of 1,1' -bis [ 2-methoxyphenyl ] phosphono ] dimethyl ether is obtained after drying, the yield is 93.14%.
(2) 1,1' -bis [ bis (2-methoxyphenyl) phosphino ] dimethyl ether:
under anhydrous and anaerobic conditions, 1' -bis [ bis (2-methoxyphenyl) phosphono]Dimethyl ether 2.60g and triethylamine 3.62g are added into acetonitrile 20mL, the temperature is controlled at 20 ℃, and HSiCl is added dropwise 3 4.88g, after 15min, heating to reflux state, after 6h of reaction, tracking and detecting that the reaction is complete, cooling, adding 8 times of HSiCl 3 Quenching reaction with 30wt% molar equivalent sodium hydroxide water solution, standing to separate liquid, separating out organic phase, acetonitrile extraction twice, combining organic phase, water washing with saturated saline water once, drying, decompression eliminating solvent, methanol re-crystallization to obtain 1,1' -bis [ bis (2-methoxy phenyl) phosphino group]2.18g of dimethyl ether with the purity of 99.23 percent and the yield of 90.13 percent.
Example 2
The preparation process of ligand 1,1' -bis [ bis (2-methoxy phenyl) phosphino ] dimethyl ether as one new kind of polyketone polymerization catalyst has the technological path shown in figure 1; the method comprises the following specific steps:
(1) Preparation of 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether:
under the condition of no water and no oxygen, 1.96g of bis (2-methoxyphenyl) phosphine oxide is added into 30mL of tetrahydrofuran, stirred until the bis (2-methoxyphenyl) phosphine oxide is dissolved, the stirring speed is 250r/min, the temperature is reduced to minus 40 ℃, wen Dijia 7.00.00 mL of 1.6M/Ln-BuLi solution is controlled, the dropwise addition is completed after 20min, the temperature is slowly increased to 30 ℃ and stirred for 1.5h, the temperature is reduced to minus 10 ℃, wen Dijia.61 g of 1 '-dibromodimethyl ether is controlled, 20min is started, the dropwise addition is completed after the heat preservation reaction is carried out for 1h, the temperature is increased to 30 ℃ and the heat preservation reaction is carried out for 17h, the reaction liquid is slowly dripped into 30mL of water under stirring, the dropwise addition time is 25min, after full stirring, liquid separation, water washing, drying, decompression and solvent removal are carried out, ethanol and petroleum ether recrystallization are carried out, and white 1.61g of 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether is obtained after drying, the purity is 98.2%, and the yield is 93.44%.
(2) 1,1' -bis [ bis (2-methoxyphenyl) phosphino ] dimethyl ether:
under anhydrous and anaerobic conditions, 1' -bis [ bis (2-methoxyphenyl) phosphono]Dimethyl ether 2.60g and triethylamine 4.07g are added into acetonitrile of 20mL, the temperature is controlled to 20 ℃, and HSiCl is added dropwise 3 After 5.49g and 15min are added dropwise, the temperature is raised to a reflux state, after 6h of reaction, the reaction is tracked and detected to be complete, and the mixture is cooled and added with 8 times of HSiCl 3 Quenching reaction with 30wt% molar equivalent sodium hydroxide water solution, standing to separate liquid, separating out organic phase, acetonitrile extraction twice, combining organic phase, water washing with saturated saline water once, drying, decompression eliminating solvent, methanol re-crystallization to obtain 1,1' -bis [ bis (2-methoxy phenyl) phosphino group]2.23g of dimethyl ether with the purity of 98.6 percent and the yield of 91.62 percent.
Example 3
The preparation process of ligand 1,1' -bis [ bis (2-methoxy phenyl) phosphino ] dimethyl ether as one new kind of polyketone polymerization catalyst has the technological path shown in figure 1; the method comprises the following specific steps:
(1) Preparation of 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether:
2.35g of bis (2-methoxyphenyl) phosphine oxide is added into 20mL of tetrahydrofuran under anhydrous and anaerobic conditions, stirring is carried out until the bis (2-methoxyphenyl) phosphine oxide is dissolved, the stirring speed is 200r/min, the temperature is reduced to minus 10 ℃, 3.44g of tertiary sodium butoxide is slowly added in 5 batches, the temperature is slowly increased to 30 ℃ after 15min is finished, the temperature is reduced to minus 20 ℃ after stirring for 3 hours, wen Dijia 1,1 '-dibromodimethyl ether is started to be 0.61g, the dropwise adding is finished after 20min, the temperature is kept for 1 hour, the temperature is increased to 30 ℃ after the heat preservation reaction is carried out for 19 hours, the reaction liquid is slowly dripped into 30mL of water after tracking detection reaction is finished, the dropwise adding time is 25 minutes under stirring, after full stirring, liquid separation, water washing, drying, decompression and solvent removal are carried out, ethanol and petroleum ether recrystallization are carried out, and the white 1.56g of 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether is obtained after drying, and the yield is 90.45%.
(2) 1,1' -bis [ bis (2-methoxyphenyl) phosphino ] dimethyl ether:
under the anhydrous and anaerobic condition, adding 2.60g of 1,1 '-bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether and 2.72g of triethylamine into 30mL of acetonitrile, controlling the temperature to be 30 ℃, slowly adding 1.54g of lithium aluminum hydride in 3 batches, heating to a reflux state after finishing the addition, reacting for 10 hours, tracking and detecting completely, cooling, adding 30wt% sodium hydroxide water solution with the molar equivalent of 8 times of lithium aluminum hydride for quenching the reaction, standing and separating liquid, separating out an organic phase, extracting the organic phase twice by acetonitrile, merging the organic phase, washing the organic phase once by saturated saline water, drying, removing a solvent by decompression, recrystallizing the methanol to obtain 2.16g of 1,1' -bis [ bis (2-methoxyphenyl) phosphino ] dimethyl ether with the purity of 98.0 percent and the yield of 88.2 percent.
Through the above examples, a ligand 1,1' -bis [ bis (2-methoxyphenyl) phosphino ] dimethyl ether of a novel polyketone polymerization catalyst can be obtained, and the specific structure is as follows:
the spectra are shown in fig. 2 to 3.
Application examples
The ligand 1,1' -bis [ bis (2-methoxyphenyl) phosphino ] dimethyl ether is used for carrying out polymerization reaction, and the specific steps are as follows:
250mL of methanol, 9.7mg of p-benzoquinone, 1% by mass of trifluoromethanesulfonic acid based on the mass of methanol, 1.68mg of palladium acetate, and 4.01mg of 1,1' -bis [ bis (2-methoxyphenyl) phosphino were charged into a 500mL autoclave]Dimethyl ether; after the substances are added, the autoclave is filled with nitrogen for pressure maintaining and replacement, then 15g of propylene is filled, and CO and C are filled 2 H 4 The mass ratio is 1:1.1 to 5MPa, starting to heat, setting the temperature to 85 ℃, stirring at 400r/min, and continuously supplementing CO and C when the temperature is raised to 85 DEG C 2 H 4 The mass ratio is 1:1.1, maintaining the reaction pressure at 5.0MPa, and reacting for 6 hours; the mass of the treated and dried product was 121g, and the catalytic activity was 25.37 kg/(g-Pd. H).
Comparative example 1
The ligand 3, 3-bis- [ bis- (2-methoxyphenyl) phosphinomethyl ] -1, 5-dioxa-spiro [5,5] undecane is used for carrying out polymerization reaction, and the specific steps are as follows:
250mL of methanol, 9.7mg of p-benzoquinone, 1.68mg of palladium acetate, 5, and triflic acid accounting for 1% of the mass of the methanol were added into a 500mL autoclave04mg3, 3-bis- [ bis- (2-methoxyphenyl) phosphinomethyl ]]-1, 5-dioxa-spiro [5,5]]Undecane; after the substances are added, the autoclave is filled with nitrogen for pressure maintaining and replacement, then 15g of propylene is filled, and CO and C are filled 2 H 4 The mass ratio is 1:1.1 to 5MPa, starting to heat, setting the temperature to 85 ℃, stirring at 400r/min, and continuously supplementing CO and C when the temperature is raised to 85 DEG C 2 H 4 The mass ratio is 1:1.1, maintaining the reaction pressure at 5.0MPa, and reacting for 6 hours; the mass of the treated and dried product was 104g, and the catalytic activity was 21.80 kg/(g-Pd.h).
Comparative example 2
The ligand 1, 3-bis [ di (2-methoxyphenyl) phosphino ] propane (BDOMPP) is used for carrying out polymerization reaction, and the specific steps are as follows:
250mL of methanol, 9.7mg of p-benzoquinone, 1% by mass of trifluoromethanesulfonic acid, 1.68mg of palladium acetate, 3.99mg of 1, 3-bis [ di (2-methoxyphenyl) phosphino ] are added into a 500mL autoclave]Propane; after the substances are added, the autoclave is filled with nitrogen for pressure maintaining and replacement, then 15g of propylene is filled, and CO and C are filled 2 H 4 The mass ratio is 1:1.1 to 5MPa, starting to heat, setting the temperature to 85 ℃, stirring at 400r/min, and continuously supplementing CO and C when the temperature is raised to 85 DEG C 2 H 4 The mass ratio is 1:1.1, maintaining the reaction pressure at 5.0MPa, and reacting for 6 hours; the mass of the treated and dried product was 86g, and the catalytic activity was 18.03 kg/(g-Pd.h).
Experimental results show that under the same polymerization conditions, the catalytic activity of the ligand 1,1' -bis [ bis (2-methoxyphenyl) phosphino ] dimethyl ether provided by the invention is 25 kg/(g-Pd.h), which is higher than that of the existing known ligand preparation catalyst.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A ligand for a polyketone polymerization catalyst having a structure represented by formula (I):
2. A method for preparing the ligand for polyketone polymerization catalyst according to claim 1, comprising the steps of:
a) Reacting bis (2-methoxyphenyl) phosphine oxide with 1,1 '-dibromo dimethyl ether in a solvent to obtain 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether;
b) And c), carrying out reduction reaction on the 1,1 '-bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether obtained in the step a) in a solvent to obtain the 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether.
3. The process according to claim 2, wherein the reaction in step a) is carried out under the action of a hydrogen-withdrawing reagent; the hydrogen drawing reagent is one or more selected from potassium tert-butoxide, sodium hydride and n-butyllithium.
4. A process according to claim 3, wherein the molar ratio of bis (2-methoxyphenyl) phosphine oxide, 1' -dibromodimethyl ether and hydrogen withdrawing reagent in step a) is (2-4): 1: (2-6).
5. A method according to claim 3, wherein step a) is specifically:
a1 Adding the bis (2-methoxyphenyl) phosphine oxide into a solvent, and stirring until the bis (2-methoxyphenyl) phosphine oxide is completely dissolved to obtain a bis (2-methoxyphenyl) phosphine oxide solution; the stirring speed is 100 r/min-400 r/min;
a2 Adding a hydrogen-extracting reagent into the bis (2-methoxyphenyl) phosphine oxide solution obtained in the step a 1) to react, so as to obtain a bis (2-methoxyphenyl) phosphine oxide salt reaction solution;
a3 Adding 1,1 '-dibromodimethyl ether into the bis (2-methoxyphenyl) phosphine oxide salt reaction solution obtained in the step a 2) to react to obtain 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether.
6. The preparation method according to claim 5, wherein the temperature of adding 1,1' -dibromodimethyl ether in the step a 3) is controlled to be-40 ℃ to-10 ℃, the reaction is carried out for 1h to 2h after the addition is completed while keeping the temperature unchanged, and the temperature is raised to 20 ℃ to 35 ℃ for 14h to 20h.
7. The process according to claim 2, wherein the reduction reaction in step b) is carried out in the presence of a reducing agent and triethylamine; the reducing agent is selected from HSiCl 3 One or more of lithium aluminum hydride and sodium borohydride.
8. The process according to claim 7, wherein the molar ratio of 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether, triethylamine and reducing agent in step b) is 1: (6-10): (6-10).
9. The method according to claim 7, wherein the step b) is specifically:
b1 Mixing 1,1 '-bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether, triethylamine and a solvent to obtain a1, 1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether mixed solution;
b2 Adding a reducing agent into the 1,1 '-bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether mixed solution obtained in the step b 1) for reduction reaction to obtain the 1,1' -bis [ bis (2-methoxyphenyl) phosphono ] dimethyl ether.
10. The preparation method according to claim 9, wherein the temperature of the reducing agent added in the step b 2) is controlled to be 0-40 ℃, the temperature is raised to a reflux state after the addition is completed, and the reaction is maintained for 4-10 hours.
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| CN108290913A (en) * | 2015-12-07 | 2018-07-17 | St制药株式会社 | The method for preparing the ligand for polyketone polymerization catalyst |
| CN110590837A (en) * | 2019-10-10 | 2019-12-20 | 黄河三角洲京博化工研究院有限公司 | Synthesis method of bis (2-methoxyphenyl) phosphine oxide |
| CN110669071A (en) * | 2019-10-10 | 2020-01-10 | 黄河三角洲京博化工研究院有限公司 | Synthetic method of polyketone ligand 1, 3-bis [ bis (2-methoxyphenyl) phosphino ] propane |
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| CN108290913A (en) * | 2015-12-07 | 2018-07-17 | St制药株式会社 | The method for preparing the ligand for polyketone polymerization catalyst |
| CN110590837A (en) * | 2019-10-10 | 2019-12-20 | 黄河三角洲京博化工研究院有限公司 | Synthesis method of bis (2-methoxyphenyl) phosphine oxide |
| CN110669071A (en) * | 2019-10-10 | 2020-01-10 | 黄河三角洲京博化工研究院有限公司 | Synthetic method of polyketone ligand 1, 3-bis [ bis (2-methoxyphenyl) phosphino ] propane |
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