CN116217624B - Cobalt-based catalyst composition and method for preparing polyester by catalyzing copolymerization of epoxy and carbon monoxide - Google Patents

Cobalt-based catalyst composition and method for preparing polyester by catalyzing copolymerization of epoxy and carbon monoxide Download PDF

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CN116217624B
CN116217624B CN202211025062.9A CN202211025062A CN116217624B CN 116217624 B CN116217624 B CN 116217624B CN 202211025062 A CN202211025062 A CN 202211025062A CN 116217624 B CN116217624 B CN 116217624B
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wenphos
cobalt
reaction
carbon monoxide
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CN116217624A (en
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李苏华
文远
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Sun Yat Sen University
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Sun Yat Sen University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
    • C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Catalysts (AREA)

Abstract

The application belongs to the field of degradable plastics, and particularly relates to a cobalt-based catalyst composition and a method for preparing polyester by catalyzing copolymerization of epoxy and carbon monoxide; the cobalt-based catalyst composition provided by the application comprises a cobalt catalyst and a ligand, wherein the ligand is selected from the oxidation, vulcanization or selenide of biphosphine, dinitrogen or nitrogen phosphine, and compared with the catalyst used in the prior art, the ligand in the catalyst composition provided by the application has a simple and novel structure, is a novel cobalt-based catalyst composition, and has higher yield and molecular weight of polyhydroxycarboxylate synthesized by catalysis, thereby solving the technical problem of complex polyhydroxycarboxylate catalytic system in the prior art.

Description

Cobalt-based catalyst composition and method for preparing polyester by catalyzing copolymerization of epoxy and carbon monoxide
Technical Field
The application belongs to the field of degradable plastics, and particularly relates to a cobalt-based catalyst composition and a method for preparing polyester by catalyzing copolymerization of epoxy and carbon monoxide.
Background
The types of the existing degradable plastics mainly comprise ester compounds such as polylactic acid, poly (adipic acid)/poly (butylene terephthalate) or poly (lactic acid)/poly (adipic acid)/poly (butylene terephthalate) with starch.
Compared with degradable plastics such as polylactic acid, poly (adipic acid)/poly (butylene terephthalate) or ester compounds such as polylactic acid+poly (adipic acid)/poly (butylene terephthalate) added with starch, the polyhydroxyalkanoate obtained by copolymerizing industrial waste gas and an epoxy compound is a way for synthesizing the degradable plastics at low cost, has lower factors limited by raw material sources and capacity, and provides possibility for large-scale popularization of the degradable plastics; at present, a two-step one-pot method is an important way for catalytically synthesizing polyhydroxyalkanoate with high molecular weight, for example, an aluminum porphyrin-cobalt carbonyl bimetallic catalyst and a beta-diimine zinc complex catalyst are used for synergistically catalyzing an epoxy compound and carbon monoxide to synthesize polyhydroxyalkanoate, the aluminum porphyrin-cobalt carbonyl bimetallic catalyst is used for firstly catalyzing the epoxy compound and the carbon monoxide to copolymerize, an intermediate product beta-butyrolactone is firstly synthesized, then the beta-diimine zinc complex is used for catalyzing beta-butyrolactone to carry out ring-opening polymerization, however, the catalyst composition used in the method has a complex structure, the route for catalytically synthesizing polyhydroxyalkanoate degradable plastics is longer, and the catalytic system of the method is complex.
Disclosure of Invention
In view of the above, the application provides a cobalt-based catalyst composition and a method for preparing polyester by catalyzing copolymerization of epoxy and carbon monoxide, which are used for solving the technical problem of complex polyhydroxycarboxylate catalytic system in the prior art.
In a first aspect, the application provides an active ligand having a structure represented by formula WenPhos or formula WenPhos oxide:
preferably, the preparation method of the active ligand WenPhos comprises the following steps:
step 1, dropwise adding n-hexane solution of n-butyllithium into a reaction container containing tetrahydrofuran solution of 2, 6-tetramethylpiperidine, and mixing by first stirring;
step 2, dropwise adding a tetrahydrofuran solution of the diphenyl sulfone derivative into the reaction container, and stirring and mixing the mixture for the second time;
step 3, dropwise adding tetrahydrofuran solution of diphenyl phosphine chloride into the reaction container, stirring and mixing in sequence for the third time, stirring and reacting overnight, and quenching the reaction to obtain a ligand WenPhos;
In the step 1, the temperature of the n-hexane solution dripping process of the n-butyllithium is-78 ℃, and the temperature of the first stirring process is-78 ℃;
In the step2, the temperature of the tetrahydrofuran solution dripping process of diphenyl sulfone is-78 ℃, and the temperature of the second stirring process is zero ℃;
In the step 3, the temperature of the tetrahydrofuran solution dropwise adding process of the dimethyl dichlorosilane is zero ℃, the temperature of the third stirring process is zero ℃, and the temperature of the stirring reaction is room temperature;
the structural formula of the diphenyl sulfone derivative is as follows:
preferably, the reaction vessel is a Schlenk bottle.
Preferably, the solvent used for the quenching reaction is dilute hydrochloric acid.
The quenching reaction with dilute hydrochloric acid gives a stable ligand WenPhos.
Preferably, after the quenching reaction, before obtaining the intermediate compound, the method further comprises the steps of: sequentially extracting, concentrating, and cooling.
The ligand WenPhos was obtained by extracting, concentrating, and cooling to separate out impurities, the solution used for extraction was methylene chloride, the solution used for cooling was methylene chloride, the cooling temperature was-20 ℃, and the yield of the ligand WenPhos was 45%.
Preferably, the preparation method of the active ligand WenPhos oxide comprises the following steps:
Step 1, adding a tert-butyl alcohol peroxide decane solution into an anhydrous toluene solution of a ligand WenPhos, and stirring overnight at room temperature to obtain a ligand WenPhos oxide solution;
step 2, spin-drying the ligand WenPhos oxide solution, and adding n-hexane for ultrasonic treatment to obtain ligand WenPhos oxide suspension;
step 3, filtering the ligand WenPhos oxide suspension to obtain the ligand WenPhos oxide.
Preferably, in step 3, the filtering includes the steps of:
Step 3.1, filtering the ligand WenPhos oxide suspension in a glove box to obtain a ligand WenPhos oxide solid crude product;
step 3.2, pumping the ligand WenPhos oxide solid crude product under a strong vacuum oil pump to obtain the ligand WenPhos oxide.
After the solvent was drained from WenPhos oxide solid crude product, ligand WenPhos oxide was obtained as a white powder in a yield of 72%.
Preferably, the preparation method of the diphenyl sulfone derivative comprises the following steps:
step 1, dropwise adding n-hexane solution of n-butyllithium into a reaction container containing tetrahydrofuran solution of 2, 6-tetramethylpiperidine, and fourth stirring and mixing;
Step 2, dropwise adding a tetrahydrofuran solution of diphenyl sulfone into the reaction container, and fifth stirring and mixing;
Step 3, dropwise adding a tetrahydrofuran solution of dimethyl dichlorosilane into the reaction container, sequentially and sixth stirring and mixing, stirring and reacting overnight, and quenching the reaction to obtain diphenyl sulfone derivatives;
in the step 1, the temperature of the normal hexane solution dripping process of the n-butyl lithium is-78 ℃, and the temperature of the fourth stirring process is-78 ℃;
In the step 2, the temperature of the tetrahydrofuran solution dripping process of diphenyl sulfone is-78 ℃, and the temperature of the fifth stirring process is zero ℃;
In the step 3, the temperature of the tetrahydrofuran solution dropwise adding process of the dimethyl dichlorosilane is zero ℃, the temperature of the sixth stirring process is zero ℃, and the temperature of the stirring reaction is room temperature;
preferably, the reaction vessel is a Schlenk bottle.
Preferably, the solvent used for the quenching reaction is dilute hydrochloric acid.
The dilute hydrochloric acid quenching reaction can obtain stable diphenyl sulfone derivative.
Preferably, after the quenching reaction, before obtaining the intermediate compound, the method further comprises the steps of: sequentially extracting, concentrating, and passing through column.
The extract was concentrated and passed through a column to separate out impurities, to obtain a diphenyl sulfone derivative, wherein the solution used for the extract was methylene chloride, the eluent used for the pass through the column was PE: ea=5:1, and the yield of the diphenyl sulfone derivative obtained by the pass through the column was 26%.
In a second aspect, the application provides a cobalt-based catalyst composition comprising a cobalt catalyst and a ligand;
The ligand is selected from any one or at least two of biphosphine, dinitrogen or oxidation, sulfuration or selenide of the nitrogen phosphine;
or the ligand is selected from the group consisting of a biphosphine, a dinitrogen or a combination of a nitrogen phosphine and an oxidizing agent;
The oxide of a biphosphine comprising the active ligand WenPhos oxide of claim 1;
the biphosphine comprising the active ligand WenPhos of claim 1.
Preferably, the oxidant is air, oxygen, anhydrous hydrogen peroxide, carbamide peroxide, peroxyalcohol, oxone, peroxyacid, sulfur, selenium.
Preferably, the peroxyl alcohol is tert-butyl peroxy alcohol.
The diphosphine, the dinitrogen or the nitrogen phosphine can generate the oxidation, the sulfuration or the selenide of the diphosphine, the dinitrogen or the nitrogen phosphine under the action of the oxidant, so that the diphosphine, the dinitrogen or the combination of the nitrogen phosphine and the oxidant can be copolymerized into the polyhydroxycarboxylate by adding the oxidation, the sulfuration or the selenide of the diphosphine, the dinitrogen or the nitrogen phosphine and the cobalt catalyst into a reaction system of carbon monoxide and the epoxy compound, and the cobalt-based catalyst composition can be selected according to actual needs.
Preferably, the ligand is 4, 5-bis-diphenylphosphine-9, 9-dimethyl xanthene Xantphos;
the cobalt-based catalyst composition further comprises an additive;
The additive is selected from BnCl, bnBr or sulfur chloride.
It should be noted that, the additives such as BnCl, bnBr or sulfur chloride can promote the oxidation reaction of 4, 5-bis-diphenylphosphine-9, 9-dimethyl xanthene Xantphos to generate oxide, thereby being beneficial to improving the molecular weight and yield of the polymerized polyhydroxycarboxylate.
Preferably, the cobalt catalyst is selected from the group consisting of Co 2(CO)8、Co4(CO)12, cobalt salts, and M x[Co(CO)4]y;
The cobalt salt is a positive monovalent, divalent or trivalent cobalt salt;
M is alkali metal or alkaline earth metal;
the alkali metal is lithium, sodium or potassium;
The alkaline earth metal is beryllium, magnesium or calcium.
Preferably, the segment of any organic segment linking two coordinating groups is an alkyl, fluoroalkyl, substituted alkyl, aralkyl, ether, aromatic ring, heteroaromatic ring, heterocyclic ring, or directly linked.
Preferably, the optionally substituted nitrogen heterocycle is a substituted and unsubstituted pyridine, a substituted and unsubstituted quinoline, a substituted and unsubstituted oxazoline, a substituted and unsubstituted oxazole, a substituted and unsubstituted imidazole, a substituted or unsubstituted triazole.
Preferably, the ligand in the cobalt-based catalyst composition may be selected from the group consisting of WenPhos and WenPhos oxide in addition to: xantphos (O 2)、BINAP(O2)、DPPF(O2), 1, 8-bis (diphenylphosphino) naphthalenedioxy, iPr-Phox (O) and Phen (O) have the following structures:
Preferably, in the cobalt-based catalyst composition, the molar ratio of the ligand to the cobalt catalyst is 0.1:1 to 5:1.
Preferably, the molar ratio of the ligand to the cobalt catalyst is 1:1-2:1.
In a third aspect, the application provides a method for preparing polyester by catalyzing copolymerization of epoxy and carbon monoxide by a cobalt-based catalyst composition.
The catalytic process is as follows:
preferably, the preparation of the polyester by copolymerizing the catalytic epoxy and the carbon monoxide specifically comprises the following steps:
step 1, adding the cobalt-based catalyst composition, an epoxy compound and a solvent into an autoclave, and stirring and mixing;
Step2, replacing air in the autoclave with carbon monoxide to obtain a reaction kettle;
Step 3, adding a carbon monoxide reactant into the reaction kettle to perform catalytic copolymerization reaction;
The temperature of the catalytic copolymerization reaction is 60-150 ℃ and the time is 5-60 hours.
Preferably, the method further comprises a post-treatment step 4: and after the carbon monoxide is slowly released, adding an aqueous hydrogen peroxide solution, stirring at room temperature for 2 hours until the system is colorless, adding dichloromethane or ethyl acetate, washing cobalt salt with water, concentrating, and removing residual solvent under high vacuum to obtain a polyester product.
Preferably, the temperature of the catalytic copolymerization reaction is 80-120 ℃ and the time is 5-15 hours.
Preferably, the pressure of carbon monoxide in the reaction kettle is 10 bar to 500 bar.
Preferably, the pressure of carbon monoxide is from 40 bar to 100 bar.
Preferably, the pressure of carbon monoxide is 50 bar to 80 bar.
Preferably, in step 1, the ligand is 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene oxide Xantphos (O 2) or WenPhos oxide;
in the step 3, the reaction kettle contains 0-22 milliliters of air.
Preferably, the reaction kettle contains 0-2 milliliters of air.
The volume of the air is 1 atmosphere under the condition of using the diphosphine ligand, and meanwhile, when 0.7-2 milliliters of air is contained in the reaction kettle, the conversion rate, the yield and the selectivity of the reactant are higher than those of a reaction system without air in the reactant.
Preferably, in step 3, the reaction vessel contains 0 to 0.06 millimoles of water.
Preferably, in step 3, the reaction kettle contains an additional oxidizing agent, and the structural formula of the additional oxidizing agent is as follows:
preferably, the epoxy compound is selected from PO, BO or PGE.
Preferably, in step 1, the cobalt-based catalyst composition is a cobalt catalyst and a ligand;
the ligand is biphosphine, dinitrogen or oxidation, sulfuration or selenide of the nitrogen phosphine;
The molar ratio of the cobalt catalyst to the ligand to the additive is 1:0.5:0-1:5:5.
Preferably, the molar ratio of the cobalt catalyst, the ligand and the additive is 1:1:0-1:2:1.
It should be noted that the conversion of the reactants in the cobalt catalyst, ligand and additive ratio was 100% in a short period of time, with yields up to 84%, and a product selectivity of 93%.
Preferably, in step 1, the cobalt-based catalyst composition is a cobalt catalyst and a ligand;
the ligand is a combination of biphosphine, dinitrogen or nitrogen phosphine and an oxidant;
The ratio of the cobalt catalyst, (biphosphine, dinitrogen or nitrogen phosphine), the oxidant and the solvent is 0.01 to 0.025 millimoles: 0.01 to 0.025 mmol: 0.02 to 0.05 millimoles: 0.5 to 3 milliliters (corresponding to the condition of 1mL of propylene oxide).
Preferably, in the step 3, the catalytic copolymerization reaction contains 50-70 bar of carbon monoxide, the reaction temperature is 70-90 ℃ and the time is 7-18 hours.
Preferably, the catalytic copolymerization reaction contains 60-70 bar of carbon monoxide, the reaction temperature is 80-90 ℃ and the time is 7-9 hours.
Under the reaction conditions, the conversion of the reactant was 100%, the yield was 82%, and the product selectivity was 94%.
Preferably, the epoxy compound has the general formula:
wherein R 1、R2、R3、R4 is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, fluoroalkyl, etheralkyl, aminoalkyl, aryl, aralkyl, ester, aminoacyl, ketone, aldehyde,
Preferably, the epoxy compound is selected from EO, PO, BO, HO, OO, PGE, BGE, IPGE or BGA.
In summary, the application provides a cobalt-based catalyst composition and a method for preparing polyester by catalyzing copolymerization of epoxy and carbon monoxide, wherein the cobalt-based catalyst composition comprises a cobalt catalyst and a ligand, the ligand is selected from oxidation, vulcanization or selenide of biphosphine, dinitrogen or nitrogen phosphine, after complexing with the cobalt catalyst, the ligand is disproportionated to obtain ionic cobalt salt, the ionic cobalt salt comprises bivalent cobalt salt which is stably coordinated with the ligand and a free cobalt anion which only contains carbonyl coordination, the bivalent cobalt salt which is stably coordinated with the ligand is used as Lewis acid to be more electron-deficient due to oxygen coordination of epoxy so as to activate epoxy, and is used as counter ion to stabilize the cobalt anion, the cobalt anion is used as nucleophilic reagent to nucleophilic attack epoxy so as to open a carbon-cobalt bond, then alkyl migration is carried out to insert carbonyl, and an acyl cobalt intermediate is constructed, so that polyhydroxycarboxylate is obtained. And after the construction of one-step polymerization and unit construction is completed, cobalt ions in the acyl cobalt intermediate can attack epoxy activated by another molecule, and the polymerization reaction is circulated all the time, so that the improvement of the yield and the molecular weight of polyhydroxyalkanoate is facilitated, and the technical problem of complex polyhydroxyalkanoate catalytic system in the prior art is solved.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present application, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a diagram showing a catalytic process for preparing polyester by copolymerizing epoxy and carbon monoxide by using a cobalt-based catalyst composition provided by the application, and FIG. 2 is a schematic diagram showing a reaction of an epoxy compound described in example 2; FIG. 3 is a diagram showing the reaction scheme for preparing polyhydroxyalkanoates described in example 3; FIG. 4 is a diagram showing the reaction scheme for preparing polyhydroxyalkanoates as described in example 4; FIG. 5 is a diagram showing the reaction scheme for preparing polyhydroxyalkanoates as described in example 5; FIG. 6 is a diagram showing the reaction scheme for preparing polyhydroxyalkanoates as described in example 6; FIG. 7 is a diagram showing the reaction scheme for preparing polyhydroxyalkanoates as described in example 7; FIG. 8 is a diagram showing the reaction scheme for preparing polyhydroxyalkanoates as described in example 8; FIG. 9 is a diagram showing the reaction scheme for preparing polyhydroxyalkanoates as described in example 9; FIG. 10 is a diagram showing the reaction scheme for preparing polyhydroxyalkanoates as described in example 10;
FIG. 11 is a diagram showing the reaction scheme for preparing polyhydroxyalkanoates as described in example 11; FIG. 12 is a diagram showing the reaction scheme for preparing polyhydroxyalkanoates as described in example 12; FIG. 13 is a diagram showing the reaction scheme for preparing polyhydroxyalkanoates as described in example 13;
FIG. 14 is a diagram showing the reaction scheme for preparing polyhydroxyalkanoates as described in example 14; FIG. 15 is a diagram showing the reaction scheme for preparing polyhydroxyalkanoates as described in example 15; FIG. 16 is a diagram showing the reaction scheme for preparing polyhydroxyalkanoates as described in example 16;
FIG. 17 is a diagram showing the reaction scheme for preparing polyhydroxyalkanoates as described in example 17; FIG. 18 is a diagram showing the reaction scheme for preparing polyhydroxyalkanoates as described in example 18; FIG. 19 is a diagram showing the reaction scheme for preparing polyhydroxyalkanoates as described in example 19;
FIG. 20 is a diagram showing the reaction scheme for preparing polyhydroxyalkanoates as described in example 20; FIG. 21 is a diagram showing the reaction scheme for preparing a first polyhydroxyalkanoate as described in example 21; FIG. 22 is a diagram showing the reaction scheme for preparing a second polyhydroxyalkanoate according to example 21, and FIG. 23 is a schematic structural view of a ligand according to the present application;
In FIG. 23, R 5、R6、R7、R8 is independently selected from hydrogen, alkyl, cycloalkyl, etheralkyl, aminoalkyl, alkoxy, alkylamino, aryl, substituted aryl, aryloxy, arylamino, aralkyl, acyl, etheralkyl, or hydroxy.
Detailed Description
A cobalt-based catalyst composition and a method for preparing polyester by catalyzing copolymerization of epoxy and carbon monoxide are used for solving the technical problem of complex polyhydroxycarboxylate catalytic system in the prior art.
The following description of the embodiments of the present application will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the application are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
The embodiment of the application provides a cobalt-based catalyst composition, which comprises the following components: cobalt catalyst and ligand, ligand is selected from the oxidation, sulfuration or selenide of diphosphine, dinitrogen or nitrogen phosphine, wherein, the oxidation, sulfuration or selenide of diphosphine, dinitrogen or nitrogen phosphine is concretely a compound containing oxygen, sulfur or selenium on at least one atom; meanwhile, it should be noted that, since the ligand of the biphosphine, the dinitrogen and the nitrogen phosphine can react in situ in the presence of the oxidizing agent to obtain the oxidation, the sulfuration or the selenide of the biphosphine, the ligand in the composition of the cobalt-based catalyst composition may be selected from the group consisting of the biphosphine, the dinitrogen and the combination of the nitrogen phosphine and the oxidizing agent.
It should be noted that, since lewis acid can coordinate with oxygen of epoxy to cause more electron deficiency and activate epoxy, nucleophilic attack of nucleophilic reagent makes epoxy open loop and build carbon-cobalt bond, then alkyl migration and insertion carbonyl, build acyl cobalt intermediate, complete one step of polymerization and unit construction, cobalt ion in acyl cobalt intermediate attacks another molecule of activated epoxy and circulates polymerization reaction all the time, thus obtaining epoxy compound with higher molecular weight, thus, lewis acid and nucleophilic reagent can be generated in polymerization reaction, and oxidation, vulcanization or selenide of biphosphine, dinitrogen or nitrogen phosphine can be realized, and cobalt salt such as CO 2(CO)8 can be disproportionated into cobalt salt and cobalt anion due to stronger lewis base, and divalent cobalt salt can be well stabilized and catalytic activity can be kept for a long time due to stronger lewis base.
Example 2
The embodiment of the application provides a preparation method of a ligand WenPhos and a ligand WenPhos-oxide in a cobalt-based catalyst composition, which comprises the following steps:
step 1, preparation of diphenylsulfone derivative
Step 1.1, injecting 20.5mL of 2, 6-tetramethylpiperidine into a 500mL Schlenk bottle, adding 100mL tetrahydrofuran as a solvent, putting the reaction bottle into a low-temperature reactor at the temperature of minus 78 ℃, slowly dropwise adding 75mL of 1.6M n-butyllithium n-hexane solution into the system, and stirring at the temperature for 2 hours after the dropwise addition is finished;
Step 1.2, after stirring, dissolving 10.9g of diphenyl sulfone into 50mL of tetrahydrofuran solution, slowly dripping the solution into a Schlenk bottle, after dripping, raising the reaction temperature to 0 ℃, and stirring for 3 hours at 0 ℃;
Step 1.3, after stirring was completed, 6.3mL of dimethyldichlorosilane was dissolved in 5mL of tetrahydrofuran solution, slowly added dropwise to a reaction flask, stirred at 0 degrees celsius for 1 hour, then cooled to room temperature and stirred overnight, after completion of the reaction, the reaction was quenched with dilute hydrochloric acid, then extracted with dichloromethane, concentrated and passed through a column (PE: ea=5:1) to give 3.61g (26%) of diphenyl sulfone derivative as a white solid.
Step2, preparation of ligand WenPhos
Step 2.1, 18mL of 1.6M n-hexane solution of n-butyllithium is added dropwise to a reaction vessel containing 4.8mL of tetrahydrofuran solution of 2, 6-tetramethylpiperidine, and the mixture is stirred and mixed for the first time;
step 2.2, dropwise adding 3.3g of tetrahydrofuran solution of diphenyl sulfone derivative into the reaction container, and carrying out second stirring and mixing;
Step 2.3, dropwise adding 4.8mL of tetrahydrofuran solution of diphenyl phosphine chloride into the reaction container, sequentially stirring and mixing the solution, stirring the solution for reaction overnight, quenching the reaction, and cooling the reaction solution at the temperature of minus 20 ℃ to separate out 3.5g (45%) of white powder, namely the ligand WenPhos.
Step 3, preparation of ligand WenPhos-oxide
Step 3.1, adding 3.1mmol of 5.5M t-butanol decane solution into 1g of ligand Wenphos, dissolving in 60mL of anhydrous toluene solution, and stirring overnight at room temperature to obtain ligand WenPhos-oxide solution;
Step 3.2, spin-drying the ligand WenPhos-oxide solution;
Step 3.3, adding 10mL of n-hexane and performing ultrasonic treatment for 10 minutes. Filtration in a glove box gives a solid crude product. The crude product was then pumped under a strong vacuum oil pump to dry the system remaining solvent to give the pure product as a white powder (760 mg, 72%) WenPhos-oxide.
Wherein, ligand WenPhos nuclear magnetic resonance hydrogen spectrum, phosphorus spectrum, carbon spectrum, infrared spectrum and mass spectrum data are:
1H NMR(400MHz,CDCl3):δ7.63(d,J＝5.8Hz,2H),7.32–7.24(m,14H),7.21–7.16(m,8H),6.89–6.86(m,2H),0.69(s,6H).
31P NMR(192MHz,CDCl3):δ-6.35.
13C NMR(101MHz,CDCl3):δ151.91(d,J＝18.0Hz),141.29,139.00(d,J＝40.0Hz),138.51(d,J＝16.2Hz),136.34,134.49,134.36(d,J＝22.0Hz),130.67,128.57,128.52(d,J＝3.6Hz),-0.75.
IR(KBr):3451,3057,1435,1311,1153,747,697,610cm-1.
MS(ESI):m/z(％)(M+H)+:643(100).
HRMS(APCI):m/z calc'd for C38H33O2P2SSi(M+H)+:643.1440,found 643.1439.
The ligand WenPhos-oxide nuclear magnetic resonance hydrogen spectrum, phosphorus spectrum, carbon spectrum, infrared spectrum and mass spectrum data are as follows: m.p. =291.4-293.4 ℃ TLC: R f =0.50 in 1:10meoh/DCM.
1H NMR(600MHz,CDCl3):δ8.00–7.97(m,2H),7.82(d,J＝7.2Hz,2H),7.56–7.41(m,14H),7.35–7.33(m,8H),0.64(s,6H).
31P NMR(192MHz,CDCl3):δ33.16.
13C NMR(101MHz,CDCl3):δ152.39(d,J＝3.7Hz),139.34(d,J＝4.6Hz),138.38(d,J＝9.7Hz),136.98(d,J＝2.4Hz),133.95(d,J＝111.4Hz),132.79,131.97(d,J＝9.9Hz),131.16(d,J＝2.9Hz),130.50(d,J＝10.3Hz),128.17(d,J＝12.8Hz),-1.68.
IR(KBr):3423,1635,1439,1319,1197,1115,852,821,753,721,696,617,580,540cm-1.
MS(ESI):m/z(％)(M+H)+:675(100).
HRMS(APCI):m/z calc'd for C38H33O4P2SSi(M+H)+:675.1339,found 675.1336.
The structures of ligand WenPhos and ligand WenPhos-oxide are:
From the structure of ligand WenPhos-oxide, it can be seen that it contains two s=o bonds, one of which can coordinate with cobalt to form in situ a complex, the complex catalyst contains two parts, a divalent cobalt cation coordinated by phosphorus oxygen and sulfur oxygen and a Co (Co) 4 – ion with strong nucleophilicity, the divalent cobalt cation coordinated by phosphorus oxygen and sulfur oxygen as lewis acid can coordinate with oxygen of epoxy to cause more electron deficiency and activate epoxy, while nucleophile nucleophilic attacks epoxy to open ring and build carbon-cobalt bond, then alkyl migration and insertion carbonyl occur to build acyl cobalt intermediate, completing the construction of one step of polymerization and unit, cobalt ion in acyl cobalt intermediate attacks another molecule activated epoxy, and the polymerization reaction is circulated all the time, thus obtaining epoxy compound with higher molecular weight, the reaction principle is shown in fig. 2.
The structure of ligand WenPhos also contains two s=o bonds, which also catalyzes the copolymerization of epoxy and carbon monoxide to produce polyesters, and it is expected that the oxygen atoms in the diphenyl ether in Xantphos (O 2) cannot coordinate due to the spatial distance.
To further illustrate the reliability of the above principle, the present specification specifically demonstrates the effect of ligand WenPhos and ligand WenPhos-oxide to catalyze the copolymerization of epoxy and carbon monoxide to produce polyesters by examples 3-12.
Example 3
To verify the specific effect of ligand WenPhos in catalyzing the copolymerization of epoxy and carbon monoxide to prepare polyester, the embodiment of the application provides an embodiment of preparing polyhydroxyalkanoate by catalyzing the copolymerization of epoxy compound and carbon monoxide by using a cobalt-based catalyst composition, wherein the cobalt-based catalyst composition is cobalt catalyst and ligand, the cobalt catalyst is Co 2(CO)8, and the ligand is WenPhos, and the method comprises the following steps:
Step 1, adding 0.05 mmole of WenPhos,0.05 mmole of cobalt catalyst Co 2(CO)8 and 2mL of solvent toluene and 0.1 mmole of 5.5M t-butylperoxy decane solution into a 5mL glass bottle in a glove box, stirring for 2 hours, transferring to an autoclave after stirring, adding 5mL of toluene and 100.1 mmole of propylene oxide, stirring for 15 minutes, and transferring the autoclave out of the glove box;
step 2, replacing the cobalt-based catalyst composition, the epoxy compound and the solvent with 20bar carbon monoxide for 3 times after the transfer of the epoxy compound and the solvent is completed, and replacing air in the autoclave;
And step 3, filling 60bar of carbon monoxide into the autoclave, and heating to 90 ℃ for reaction for 120 hours. After the reaction is completed, the autoclave is cooled to room temperature, and then carbon monoxide of the system is slowly released;
Step 4, the reactant is diluted with 50mL of dichloromethane and transferred into a 200mL flask, 25mL of 30% hydrogen peroxide solution is added, and the system is stirred until colorless. The resulting mixture was extracted with methylene chloride and concentrated to give a nearly colorless viscous product (6.44 g, 73%) which was subjected to nuclear magnetic resonance spectroscopy, carbon spectroscopy and GPC analysis, as shown below, to give a polyhydroxyalkanoate as a colorless viscous product.
1H NMR(400MHz,CDCl3):δ5.28–5.22(m,1H),2.64–2.58(m,1H),2.53–2.43(m,1H),1.28(t,J＝5.5Hz,3H).13C NMR(101MHz,CDCl3):δ169.30,169.19,67.72,67.66,40.89,40.83,40.76,40.70,19.85,19.80.Mn:8.0kg/mol.1.90.
The reaction formula of cobalt catalyst Co 2(CO)8 and ligand WenPhos for catalyzing carbon monoxide and propylene oxide to prepare polyhydroxyalkanoate is shown in figure 3.
Example 4
To verify the specific effect of another ligand WenPhos-oxide to catalyze the copolymerization of epoxy and carbon monoxide to prepare polyester, the embodiment of the application provides an embodiment of preparing polyhydroxyalkanoate by catalyzing the copolymerization of epoxy compound and carbon monoxide by a cobalt-based catalyst composition, wherein the cobalt-based catalyst composition is cobalt catalyst and ligand, the cobalt catalyst is Co 2(CO)8, and the ligand is WenPhos-oxide, and the method comprises the following steps:
Step 1, stirring 0.01mmol WenPhos-oxide and 0.01mmol cobalt catalyst Co 2(CO)8 and 1mL solvent toluene and 14.3mmol propylene oxide in a glove box for 15 min;
step 2, replacing the cobalt-based catalyst composition, the epoxy compound and the solvent with 20bar carbon monoxide for 3 times after the transfer of the epoxy compound and the solvent is completed, and replacing air in the autoclave;
and step 3, filling 60bar of carbon monoxide into the autoclave, and heating to 80 ℃ for reaction for 30 hours. After the reaction is completed, the autoclave is cooled to room temperature, and then carbon monoxide of the system is slowly released;
Step 4, the reaction is diluted with 10mL of dichloromethane and transferred to a 50mL flask, 5mL of 30% hydrogen peroxide solution is added, and the system is stirred until colorless. The resulting product was then extracted with methylene chloride and concentrated to give a nearly colorless viscous product (970 mg, 79%) which was subjected to nuclear magnetic resonance spectroscopy, carbon spectroscopy and GPC analysis, as shown below, to give a polyhydroxyalkanoate as the prepared product.
1H NMR(400MHz,CDCl3):δ5.28–5.22(m,1H),2.64–2.58(m,1H),2.53–2.43(m,1H),1.28(t,J＝5.5Hz,3H).13C NMR(101MHz,CDCl3):δ169.30,169.19,67.72,67.66,40.89,40.83,40.76,40.70,19.85,19.80.Mn:12.2kg/mol.1.44.
The reaction scheme for preparing polyhydroxyalkanoate in this example is shown in FIG. 4.
Example 5
The present examples provide examples of the preparation of polyhydroxyalkanoates by copolymerizing an epoxy compound with carbon monoxide using a cobalt-based catalyst composition, differing from example 4 in that:
The cobalt-based catalyst composition was a combination of 0.01mmol WenPhos-oxide and 0.01mmol Co 2(CO)8; the solvent was 1mL toluene, the epoxide was 14.3mmol (S) -PO, and the carbon monoxide was 60bar CO, and reacted at 80℃for 32h to give 940mg (77%) of a white powder.
Nuclear magnetic hydrogen spectrum, carbon spectrum and GPC analysis were performed on the white powder, and the results are shown below, indicating that the white powder obtained was polyhydroxyalkanoate.
1H NMR(400MHz,CDCl3):δ5.38–5.18(m,1H),2.66–2.58(m,1H),2.50–2.45(m,1H),1.29(d,J＝6.3Hz,3H).13C NMR(101MHz,CDCl3):δ169.30,67.77,40.94,19.91.Mn:22.5kg/mol.1.83.
The reaction scheme for preparing polyhydroxyalkanoate in this example is shown in FIG. 5.
Example 6
The present examples provide examples of the preparation of polyhydroxyalkanoates by copolymerizing an epoxy compound with carbon monoxide using a cobalt-based catalyst composition, differing from example 4 in that:
The cobalt-based catalyst composition was a combination of 0.01mmol WenPhos-oxide and 0.01mmol Co 2(CO)8; the solvent was 1mL toluene, the epoxide was 14.3mmol BO, the carbon monoxide was 60bar CO, and the reaction was carried out at 80℃for 39h to give 1.06g (74%) of a nearly colorless viscous product.
Nuclear magnetic hydrogen, carbon and GPC analysis were performed on the colorless viscous product, and the results are shown below, indicating that the product was prepared as polyhydroxyalkanoate.
1H NMR(400MHz,CDCl3):δ5.18–5.12(m,1H),2.65–2.44(m,2H),1.64–1.59(m,2H),0.92–0.88(m,3H).13C NMR(101MHz,CDCl3):δ169.77,169.73,169.64,169.59,72.10,72.04,72.00,38.83,38.79,38.66,38.60,38.56,26.90,26.85,9.47,9.42.Mn:6.4kg/mol.1.42.
The reaction scheme for preparing polyhydroxyalkanoate in this example is shown in FIG. 6.
Example 7
The present examples provide examples of the preparation of polyhydroxyalkanoates by copolymerizing an epoxy compound with carbon monoxide using a cobalt-based catalyst composition, differing from example 4 in that:
the cobalt-based catalyst composition was a combination of 0.01mmol WenPhos-oxide and 0.01mmol Co 2(CO)8; the solvent was 1mL toluene, the epoxide was 14.3mmol HO, the carbon monoxide was 60bar CO, and the reaction was carried out at 80℃for 34h to give 1.42g (78%) of a nearly colorless viscous product.
Nuclear magnetic hydrogen, carbon and GPC analysis were performed on the colorless viscous product, and the results are shown below, indicating that the prepared product was polyhydroxycarboxylate.
1H NMR(400MHz,CDCl3):δ5.21–5.18(m,1H),2.66–2.41(m,2H),1.62–1.56(m,2H),1.33–1.22(m,4H),0.89(t,J＝6.7Hz,3H).13C NMR(101MHz,CDCl3):δ169.64,169.53,70.98,70.94,70.90,39.24,39.09,33.66,33.62,27.33,27.31,27.28,27.25,22.53,14.01.Mn:8.2kg/mol.1.22.
The reaction scheme for preparing polyhydroxycarboxylate in this example is shown in FIG. 7.
Example 8
The present examples provide examples of the preparation of polyhydroxyalkanoates by copolymerizing an epoxy compound with carbon monoxide using a cobalt-based catalyst composition, differing from example 4 in that:
The cobalt-based catalyst composition was a combination of 0.01mmol WenPhos-oxide and 0.01mmol Co 2(CO)8; the solvent was 1mL toluene, the epoxide was 14.3mmol OO, the carbon monoxide was 60bar CO, and the reaction was carried out at 80℃for 26h to give 1.57g (70%) of the product as a nearly colorless viscous product.
Nuclear magnetic hydrogen, carbon and GPC analysis were performed on the colorless viscous product, and the results are shown below, indicating that the prepared product was polyhydroxycarboxylate.
1H NMR(400MHz,CDCl3):δ5.22–5.17(m,1H),2.59–2.47(m,2H),1.67–1.52(m,2H),1.37–1.19(m,8H),0.88(t,J＝6.7Hz,3H).13C NMR(101MHz,CDCl3):δ169.60,169.49,70.94,70.92,70.89,39.20,39.07,33.96,33.92,31.78,29.14,25.19,25.14,25.10,22.64,14.11.Mn:8.5kg/mol.1.33.
The reaction scheme for preparing polyhydroxycarboxylate in this example is shown in FIG. 8.
Example 9
The present examples provide examples of the preparation of polyhydroxyalkanoates by copolymerizing an epoxy compound with carbon monoxide using a cobalt-based catalyst composition, differing from example 4 in that:
The cobalt-based catalyst composition was a combination of 0.05mmol WenPhos-oxide and 0.05mmol Co 2(CO)8; the solvent was 2mL toluene, the epoxide 14.3mmol PGE, and carbon monoxide 60bar CO, and reacted at 80℃for 15h to give 2.07g (81%) of the product as a dark red solid.
Nuclear magnetic hydrogen, carbon and GPC analysis were performed on the dark red solid product, and the results are shown below, indicating that the product was prepared as polyhydroxycarboxylate.
1H NMR(400MHz,CDCl3):δ7.26–7.19(m,2H),6.91–6.79(m,3H),5.47–5.45(m,1H),3.99–3.96(m,2H),2.74–2.71(m,2H).13C NMR(101MHz,CDCl3):δ169.30,169.19,158.36,129.66,121.44,114.75,69.18,69.06,67.90,35.75.Mn:6.8kg/mol.：1.63.
The reaction scheme for preparing polyhydroxycarboxylate in this example is shown in FIG. 9.
Example 10
The present examples provide examples of the preparation of polyhydroxyalkanoates by copolymerizing an epoxy compound with carbon monoxide using a cobalt-based catalyst composition, differing from example 4 in that:
The cobalt-based catalyst composition was a combination of 0.05mmol WenPhos-oxide and 0.05mmol Co 2(CO)8; the solvent was 2mL toluene, the epoxide was 14.3mmol (R) -BGE, and the carbon monoxide was 60bar CO, and the reaction was carried out at 80℃for 20h to give 1.12g (40%) of a nearly colorless viscous product.
Nuclear magnetic hydrogen, carbon and GPC analysis were performed on the colorless viscous product, and the results are shown below, indicating that the prepared product was polyhydroxycarboxylate.
1H NMR(400MHz,CDCl3):δ7.30–7.23(m,5H),5.49–5.29(m,1H),4.55–4.33(m,2H),3.56–3.43(m,2H),2.66–2.59(m,2H).13C NMR(101MHz,CDCl3):δ169.29,137.96,128.52,127.80,127.76,73.20,70.27,69.39,35.95.Mn:3.0kg/mol.:1.36.
The reaction scheme for preparing polyhydroxycarboxylate in this example is shown in FIG. 10.
Example 11
The present examples provide examples of the preparation of polyhydroxyalkanoates by copolymerizing an epoxy compound with carbon monoxide using a cobalt-based catalyst composition, differing from example 4 in that:
The cobalt-based catalyst composition was a combination of 0.05mmol WenPhos-oxide and 0.05mmol Co 2(CO)8; the solvent was 2mL toluene, the epoxide was 14.3mmol IPGE, the carbon monoxide was 60bar CO, and the reaction was carried out at 80℃for 36h to give 1.70g (83%) of a nearly colorless viscous product.
Nuclear magnetic hydrogen, carbon and GPC analysis were performed on the colorless viscous product, and the results are shown below, indicating that the prepared product was polyhydroxycarboxylate.
1H NMR(400MHz,CDCl3):δ5.31–5.28(m,1H),3.57–3.52(m,3H),2.70–2.65(m,2H),1.13–1.12(m,6H).13C NMR(101MHz,CDCl3):δ169.60,169.51,72.27,72.25,69.88,69.81,68.19,68.11,36.01,35.89,22.11,22.06.Mn:3.6kg/mol.：1.53.
The reaction formula for preparing polyhydroxycarboxylate in this example is shown in figure 11.
Example 12
The present examples provide examples of the preparation of polyhydroxyalkanoates by copolymerizing an epoxy compound with carbon monoxide using a cobalt-based catalyst composition, differing from example 4 in that:
The cobalt-based catalyst composition was a combination of 0.05mmol WenPhos-oxide and 0.05mmol Co 2(CO)8; the solvent was 2mL toluene, the epoxy compound was 14.3mmol (R) -BGA, and the carbon monoxide was 60bar CO, and the reaction was carried out at 80℃for 16h to give 2.06g (84%) of a nearly colorless viscous product.
Nuclear magnetic hydrogen, carbon and GPC analysis were performed on the colorless viscous product, and the results are shown below, indicating that the prepared product was polyhydroxycarboxylate.
1H NMR(400MHz,CDCl3):δ5.60–5.25(m,1H),4.36–4.33(m,1H),4.14–4.09(m,1H),2.69–2.65(m,2H),2.33–2.28(m,2H),1.69–1.60(m,2H),0.95(t,J＝7.4Hz,3H).13C NMR(101MHz,CDCl3):δ173.09,168.59,68.62,63.71,35.88,35.52,18.36,13.68.Mn:3.3kg/mol.1.36./>
The reaction scheme for preparing polyhydroxycarboxylate in this example is shown in FIG. 12.
Example 13
The present examples provide examples of the preparation of polyhydroxycarboxylic esters by copolymerizing an epoxide with carbon monoxide using a cobalt-based catalyst composition comprising a different cobalt catalyst and a ligand Xantphos,
The reaction scheme for preparing polyhydroxycarboxylate in this example is shown in FIG. 13.
The catalytic conditions of the different cobalt catalysts are shown in the following table, and the performance of the Co 2(CO)8 cobalt catalyst is better than that of the Co 4(CO)12 cobalt catalyst, but the Co 4(CO)12 cobalt catalyst can catalyze the copolymerization of the epoxy compound and carbon monoxide to prepare polyhydroxyalkanoate by combining the ligand.
Example 14
The embodiment of the application provides an embodiment of preparing polyhydroxyalkanoate by catalyzing the copolymerization of an epoxy compound and carbon monoxide by a cobalt-based catalyst composition consisting of a Co 2(CO)8 cobalt catalyst and a ligand Xantphos, wherein an oxidant is additionally added.
The reaction formula and the reaction result for preparing polyhydroxyalkanoate in this example are shown in FIG. 14.
Example 15
The present application provides an example of the preparation of polyhydroxycarboxylate by copolymerization of an epoxide compound with carbon monoxide catalyzed by a cobalt-based catalyst composition consisting of a Co 2(CO)8 cobalt catalyst and a ligand Xantphos, wherein different solvents are selected.
The reaction formula and the reaction result of the preparation of polyhydroxyalkanoate in this example are shown in FIG. 15.
As can be seen from the table, toluene is selected as the solvent to catalyze the copolymerization of the epoxy compound and carbon monoxide to prepare the polyhydroxyalkanoate with optimal performance.
Example 16
The embodiment of the application provides an embodiment of preparing polyhydroxyalkanoate by catalyzing copolymerization of an epoxy compound and carbon monoxide by a cobalt-based catalyst composition consisting of a Co 2(CO)8 cobalt catalyst and a ligand Xantphos, wherein air is added in a reaction system.
The reaction formula and the reaction result for preparing polyhydroxyalkanoate in this example are shown in FIG. 16.
The influence of air in the reaction system on the catalytic performance is shown in the following table, and the conversion rate is improved to a certain extent by adding a small amount of air which is not higher than 2 milliliters of air.
Example 17
The embodiment of the application provides an embodiment of preparing polyhydroxyalkanoate by catalyzing copolymerization of an epoxy compound and carbon monoxide by a cobalt-based catalyst composition consisting of a Co 2(CO)8 cobalt catalyst and a ligand Xantphos, wherein water is added in a reaction system.
The reaction formula and the reaction result of the polyhydroxyalkanoate prepared in this example are shown in FIG. 17.
The influence of water on the catalytic performance in the reaction system is shown in the following table, and the catalyst is found to have certain tolerance to water.
Wherein, the reaction process is as follows: in a glove box, 0.05mmol of ligand and 0.05mmol of Co 2(CO)8 were added to the autoclave, 2mL of toluene were added, and a quantity of water and 1mL of propylene oxide were stirred for fifteen minutes. After stirring, the autoclave was transferred out of the glove box and replaced three times with 25bar CO and re-aerated to 60bar. The autoclave was then placed in an oil bath and heated. a is conventional toluene which has not been treated with sodium. b is carried out using 0.025mmol L12,0.025mmol of cobalt octacarbonyl with 1ml toluene at 80 ℃.
Example 18
The present application provides an example of the preparation of polyhydroxyalkanoates by copolymerizing an epoxy compound with carbon monoxide by a cobalt-based catalyst composition comprising a Co 2(CO)8 cobalt catalyst and different ligands.
The reaction formula and the reaction result for preparing polyhydroxyalkanoate in this example are shown in FIG. 18.
Wherein, the reaction process is as follows: in a glove box, 0.05mmol of ligand, 0.05mmol of Co 2(CO)8, and 0.05mmol of additive were added separately using a 5mL glass bottle, and 2mL toluene and 1mL propylene oxide were added and stirred for 15 minutes. After stirring, the glass bottle was transferred out of the glove box, transferred into the autoclave under air, then replaced three times with 25bar carbon monoxide, and then charged with carbon monoxide to 60bar, and the autoclave was put into an oil bath and heated for 20h. After the reaction is finished, the product is dissolved in 10mL of dichloromethane, 5mL of 30% hydrogen peroxide is added, the mixture is stirred to be colorless, and then the dichloromethane is used for extraction and spin drying to obtain the product. Nuclear magnetic yield, b 28.6mmol of propylene oxide, 0.1mmol of ligand, 0.1mmol of cobalt octacarbonyl and 10ml of toluene are introduced into a 100ml autoclave.
Phosphine oxide ligands prepared in situ with other phosphine ligands such as L17, L18, etc., except for the attachment of a large steric hindrance group to the phosphine, are capable of catalyzing copolymerization of epoxy with carbon monoxide to produce polyesters.
Example 19
The present application provides examples of the preparation of polyhydroxyalkanoates by copolymerizing an epoxide with carbon monoxide using a cobalt-based catalyst composition comprising a Co 2(CO)8 cobalt catalyst and different phosphine oxide ligands.
The reaction formula and the reaction result of the polyhydroxyalkanoate prepared in this example are shown in FIG. 19.
Wherein, the reaction process is as follows: in a glove box, 0.05mmol of ligand and 0.05mmol of Co 2(CO)8 were added to the autoclave, 2mL of toluene and 1mL of propylene oxide were added, and stirring was continued for fifteen minutes. After stirring, the autoclave was transferred out of the glove box and replaced three times with 25bar CO and re-aerated to 60bar. The autoclave was then placed in an oil bath and heated. a nuclear magnetic yield. b 0.01mmol ligand reacted with 0.01mmol Co 2(CO)8 at 80℃with the addition of 0.05mmol additive add2.c 0.01mmol ligand was reacted with 0.01mmol cobalt octacarbonyl and 1ml toluene at 80 degrees celsius. d 0.01mmol ligand, 0.01mmol cobalt octacarbonyl, 1mL toluene and 28.6mmol propylene oxide (2 mL) were reacted at 90 ℃. e 0.1mmol ligand.
Example 20
The present application provides an example of the preparation of polyhydroxyalkanoates by copolymerizing an epoxide with carbon monoxide by a cobalt-based catalyst composition consisting of a Co 2(CO)8 cobalt catalyst and an in situ oxidized phosphine oxide ligand.
The reaction formula and the reaction result of the polyhydroxyalkanoate prepared in this example are shown in FIG. 20.
Wherein, the reaction process is as follows: in a glove box, 0.025mmol ligand and 0.05mmol t-butyl peroxide were added to a 5mL glass bottle and 2mL toluene was added and stirred for 1-3 hours. After the completion of the stirring, the mixture was transferred to an autoclave, and 0.025mmol of Co 2(CO)8 and 1mL of propylene oxide were added thereto, and the autoclave was transferred out of the glove box and stirred for another 15 minutes. After stirring was completed, three recharges were replaced with 25bar CO to 60bar. The autoclave was then placed in an oil bath and heated. a nuclear magnetic yield.
Example 21
The embodiment of the application provides an embodiment of preparing polyhydroxyalkanoate by catalyzing copolymerization of an epoxy compound and carbon monoxide by a cobalt-based catalyst composition consisting of a Co 2(CO)8 cobalt catalyst and a ligand shown as L2/L12, wherein the ratio of metal, ligand, additive and solvent in a reaction system is different, and the reaction formula and the reaction result of the preparation of polyhydroxyalkanoate are shown in the accompanying figures 21-22.
Wherein, the reaction process is as follows: the metal, ligand L2, additives were added to the autoclave in the glove box, followed by toluene and propylene oxide. Stirring at normal temperature for 15 min, charging carbon monoxide and heating to 90 ℃. The reaction temperature of a is 100 ℃.
Wherein, the reaction process is as follows: ligand L12 and t-butyl peroxide were added to a 5mL glass bottle in a glove box, and toluene was added and stirred for 1-3 hours. After the completion of the stirring, the mixture was transferred to an autoclave, co 2(CO)8 and 1mL of propylene oxide were added, and the autoclave was transferred out of the glove box and stirred for another 15 minutes. After stirring was completed, three recharges were replaced with 25bar CO to 60bar. The autoclave was then placed in an oil bath and heated. a 80 degrees celsius. b 0.008mmol Co (OTf) 2 was added. The amount of propylene oxide was 2mL.
The above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.

Claims (5)

1. An active ligand, wherein the active ligand has a structure represented by formula WenPhos or formula WenPhos oxide:
formula WenPhos;
formula WenPhos oxide.
2. The method for preparing an active ligand according to claim 1, wherein the active ligand of formula WenPhos comprises the steps of:
step 1, dropwise adding n-hexane solution of n-butyllithium into a reaction container containing tetrahydrofuran solution of 2, 6-tetramethylpiperidine, and mixing by first stirring;
step 2, dropwise adding a tetrahydrofuran solution of the diphenyl sulfone derivative into the reaction container, and stirring and mixing the mixture for the second time;
step 3, dropwise adding tetrahydrofuran solution of diphenyl phosphine chloride into the reaction container, stirring and mixing in sequence for the third time, stirring and reacting overnight, and quenching the reaction to obtain a ligand WenPhos;
In the step 1, the temperature of the n-hexane solution dripping process of the n-butyllithium is-78 ℃, and the temperature of the first stirring process is-78 ℃;
In the step2, the temperature of the tetrahydrofuran solution dripping process of diphenyl sulfone is-78 ℃, and the temperature of the second stirring process is zero ℃;
In the step 3, the temperature of the tetrahydrofuran solution dropwise adding process of the dimethyl dichlorosilane is zero ℃, the temperature of the third stirring process is zero ℃, and the temperature of the stirring reaction is room temperature;
In step 2, the structure of the diphenyl sulfone derivative is as follows:
。
3. The method for preparing an active ligand according to claim 1, wherein the active ligand of formula WenPhos oxide comprises the steps of:
step 1, adding tert-butyl peroxide or hydrogen peroxide into a toluene solution of a ligand WenPhos, and stirring overnight at room temperature to obtain a ligand WenPhos oxide solution;
step 2, spin-drying the ligand WenPhos oxide solution, and adding n-hexane for ultrasonic treatment to obtain ligand WenPhos oxide suspension;
step 3, filtering the ligand WenPhos oxide suspension to obtain the ligand WenPhos oxide.
4. The method for preparing polyester by catalyzing copolymerization of epoxy and carbon monoxide is characterized by comprising the following steps:
Step 1, adding a cobalt-based catalyst composition, an epoxy compound and a solvent into a reaction container, and stirring and mixing;
Step 2, replacing air or nitrogen in the reaction vessel with carbon monoxide, and transferring the carbon monoxide to a reaction kettle;
Step 3, adding a carbon monoxide reactant into the reaction kettle to perform catalytic copolymerization reaction;
the reaction vessel comprises a glove box and an autoclave;
the temperature of the catalytic copolymerization reaction is 60-150 ℃ and the time is 5-60 hours;
The cobalt-based catalyst composition comprises a cobalt catalyst and a ligand;
The ligand is as follows: the active ligand of formula WenPhos oxide of claim 1 or the combination of the active ligand of formula WenPhos of claim 1 and an oxidizing agent.
5. The method of catalyzing the copolymerization of epoxy and carbon monoxide to produce a polyester according to claim 4, wherein the epoxy is selected from EO, PO, (S) -PO, (R) -PO, BO, HO, OO, PGE, (R) -BGE, IPGE, or (R) -BGA.
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