CN116102726A - Chiral organoboron catalyst, preparation method thereof and application thereof in preparation of optically active polycarbonate or polyester - Google Patents

Chiral organoboron catalyst, preparation method thereof and application thereof in preparation of optically active polycarbonate or polyester Download PDF

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CN116102726A
CN116102726A CN202310283775.3A CN202310283775A CN116102726A CN 116102726 A CN116102726 A CN 116102726A CN 202310283775 A CN202310283775 A CN 202310283775A CN 116102726 A CN116102726 A CN 116102726A
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catalyst
chiral
organoboron
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product
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李窈
杜鹏
吕小兵
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Dalian University of Technology
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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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
    • 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
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The invention belongs to the field of high polymer materials, and particularly relates to a chiral organoboron catalyst, a preparation method thereof and application thereof in preparation of optically active polycarbonate or polyester. The chiral organoboron catalyst comprises an organoboron-onium salt double-function catalyst and an organoboron and onium salt double-component catalyst, wherein the organoboron-onium salt double-function catalyst is formed by assembling an organoboron Lewis acid center and a Lewis base onium salt into a chiral binaphthyl skeleton with an axis; the double-component catalyst of organic boron and onium salt is a double-component catalyst formed by introducing organic boron Lewis acid center into chiral skeleton and matching with cocatalyst salt. The invention has the advantages of low catalyst dosage, high activity, controllable molecular weight, narrow distribution, wide application temperature range and adjustable polymer structure. In addition, as no metal residues exist in the polymer, the application of the polycarbonate and the polyester in the fields of food packaging, medical materials and the like can be greatly expanded.

Description

Chiral organoboron catalyst, preparation method thereof and application thereof in preparation of optically active polycarbonate or polyester
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a chiral organoboron catalyst, a preparation method thereof and application thereof in preparation of optically active polycarbonate or polyester.
Background
Polycarbonates and polyesters are widely used in the automotive industry, biomedical, food packaging, electrochemical and other fields. Compared with other methods for synthesizing polycarbonate and polyester, the method for synthesizing the copolymer with different structures by utilizing the copolymerization of alkylene oxide and carbon dioxide or cyclic anhydride not only has atom economy, but also has various alkylene oxide types. Accordingly, the preparation of polycarbonates and polyesters by the copolymerization of alkylene oxides has gained attention in recent years.
Currently, chiral metal catalysts have been realized to catalyze the desymmetrical copolymerization of alkylene oxides with carbon dioxide or cyclic anhydrides with high enantioselectivity, such as bimetallic Salen Co (III) complexes based on biphenyl bridges (CN 103102480B), bimetallic Salen Al complexes based on biphenyl or binaphthyl bridges (CN 106117532B), bimetallic bifunctional Salen Al complexes based on binaphthyl or hydrogenated binaphthyl bridges (CN 114163627A), for catalyzing the desymmetrical copolymerization of alkylene oxides, successfully producing polycarbonates or polyesters with perfect isotactic structure. However, the general synthesis procedure of the metal complex is complicated, the tolerance to water/oxygen is poor, and the metal residues usually color and toxicity the polycarbonate and the polyester, and the complete removal of toxic metal residues is still a difficult challenge, thus preventing the application of the metal complex in the fields of electronic products, biomedicine and the like.
In the past twenty years, the organic catalyst has been widely used in the field of organic synthesis because of the advantages of low cost, easy obtainment, no toxic metal residue and the like. In 2016, feng et al reported for the first time that triethylboron/PPNCl catalytic system achieved alternating copolymerization of alkylene oxide with carbon dioxide (j.am.chem.soc.2016, 138, 11117-11120). Subsequently, the subject group (CN 109679077B) in Meng Yue utilizes commercial (thio) urea/organic base catalyzed ring opening copolymerization of alkylene oxide with cyclic anhydride to produce polyesters. The polymerization not only has very high catalytic activity (TOF is up to 456h -1 ) And product selectivity>99% selectivity of polyester), and reduces the production cost of the polyester, and expands the application prospect of the polyester in degradable materials. Tao Youhua A (CN 114605621A) designs a hydrogen bond donor-boron organic catalyst which is simple in synthesis and can be adjusted in a modularized way, and the catalyst is also used for catalyzing ring-opening copolymerization of alkylene oxide and cyclic anhydrideExhibits high catalytic activity (TOF value up to 408 h) -1 ) And product selectivity>Polyester selectivity of 99%). Notably, the Wu Anpeng group reports a series of organoboron-based electrophilic-nucleophilic bifunctional catalysts with extremely high activity in catalyzing alkylene oxide copolymerization, achieving a conversion efficiency of 5.0kg polycarbonate/g catalyst and 7.4kg polyester/g catalyst (CN 110938087 B,CN 113087882 A,CN 112387307B).
Although the organic catalyst shows very excellent catalytic activity in the copolymerization reaction of alkylene oxide in the patent report, the obtained polycarbonate and polyester are random structures, and the random polycarbonate and polyester materials show relatively poor thermodynamic performance and mechanical performance, which limits the practical application in various fields.
Disclosure of Invention
In order to solve the technical problems, the invention provides a chiral organoboron catalyst and application thereof in high-efficiency catalytic asymmetric copolymerization of alkylene oxide and carbon dioxide or cyclic anhydride, which can prepare polycarbonate and polyester with controllable molecular weight and narrow molecular weight distribution in a wider temperature range, and meanwhile, the prepared copolymer has medium enantioselectivity and is an optically active polycarbonate and polyester material.
The technical scheme of the invention is as follows:
the chiral organoboron catalyst comprises an organoboron-onium salt bifunctional catalyst and a double-component catalyst consisting of organoboron and onium salt; wherein the organoboron-onium salt bifunctional catalyst is formed by assembling organoboron Lewis acid center and Lewis base onium salt into a binaphthyl skeleton with axial chirality; the double-component catalyst composed of the organic boron and the onium salt is a main catalyst formed by introducing the organic boron Lewis acid center into a chiral framework and is matched with a cocatalyst
Figure BDA0004138954400000021
A double-component catalyst composed of salt. The organoboron-onium salt bifunctional catalyst and organoboron and onium salt bifunctional catalystThe structural general formula of the component catalyst is as follows:
Figure BDA0004138954400000031
wherein, the specific structure of the organoboron-onium salt bifunctional catalyst is as follows:
Figure BDA0004138954400000032
the main catalyst of the organoboron and onium salt double-component catalyst has the specific structure that:
Figure BDA0004138954400000033
cocatalyst for organic boron-onium salt double-component catalyst
Figure BDA0004138954400000036
The salt is bis (triphenylphosphine) -imine chloride (PPNCl), and the specific structure is as follows:
Figure BDA0004138954400000034
in the chiral organoboron catalysts, the synthesis reaction equation of the bifunctional catalyst 1 is as follows:
Figure BDA0004138954400000035
the specific preparation steps of the bifunctional catalyst 1 are as follows:
under the protection of inert gas, the (R) -2,2 '-bis (bromomethyl) -1,1' -binaphthyl and K are mixed in a molar ratio of 1:2:1 2 CO 3 Mixing with diallylamine, dissolving in acetonitrile, refluxing at 90-150 deg.c for 6-10 hr, adding water to quench, separating organic phase, extracting water phase with organic solvent, decompressing to eliminate solvent to obtain coarse product, and passing the coarse product through columnAfter chromatographic purification, the binaphthyl chiral ammonium salt is obtained; under the protection of inert gas, 9-boron bicyclo [3.3.1]Mixing tetrahydrofuran solutions of nonane and binaphthyl chiral ammonium salts, wherein 9-borobicyclo [3.3.1]The molar ratio of nonane to binaphthyl chiral ammonium salt is 2:1, then the reaction is carried out for 2 to 12 hours at the temperature of 40 to 60 ℃, the filtration is carried out, the filter cake is washed by n-hexane for multiple times, and the bifunctional catalyst 1 is obtained after vacuum drying.
In the chiral organoboron catalysts, the synthesis reaction equation of the bifunctional catalyst 2 is as follows:
Figure BDA0004138954400000041
the specific preparation steps of the bifunctional catalyst 2 are as follows:
under the protection of inert gas, the (R) -2,2 '-bis (bromomethyl) -1,1' -binaphthyl and K are mixed in a molar ratio of 1:2:1 2 CO 3 Mixing with N-methylallylamine, dissolving with acetonitrile, refluxing at 90-150 ℃ for 6-10 hours, adding water for quenching reaction, separating an organic phase, extracting a water phase with an organic solvent, removing the solvent under reduced pressure to obtain a crude product, and purifying the crude product by column chromatography to obtain binaphthyl chiral ammonium salt; under the protection of inert gas, 9-boron bicyclo [3.3.1]Mixing tetrahydrofuran solutions of nonane and binaphthyl chiral ammonium salts, wherein 9-borobicyclo [3.3.1]The molar ratio of nonane to binaphthyl chiral ammonium salt is 1:1, then the reaction is carried out for 2 to 12 hours at the temperature of 40 to 60 ℃, the filtration is carried out, the filter cake is washed by n-hexane for multiple times, and the bifunctional catalyst 2 is obtained after vacuum drying.
In the chiral organoboron catalysts, the synthetic reaction equation of the main catalyst 1 of the two-component catalyst is as follows:
Figure BDA0004138954400000042
the preparation method of the main catalyst 1 of the two-component catalyst comprises the following steps:
under the protection of inert gas, (R) -spiro diphenol and trifluoro methane sulfonic anhydride with the mol ratio of 1:2:3 are added at the temperature of 0 DEG CAnd pyridine, dissolved in methylene chloride, and then stirred at room temperature for 8-12 h. After the reaction is finished, adding water to quench the reaction, separating an organic phase, extracting an aqueous phase with ethyl acetate, decompressing and removing a solvent to obtain a crude product, and purifying the crude product through column chromatography to obtain a trifluoro methane sulfonate product. Under the protection of inert gas, mixing tetra (triphenylphosphine) palladium, trifluoro methane sulfonic acid esterification product and zinc cyanide with the molar ratio of 1:10:20, dissolving with N, N-dimethylformamide, and then reacting for 12-24 hours at 110-150 ℃. Diluting the reacted mixture with ethyl acetate, washing with saturated sodium chloride solution and saturated sodium carbonate solution in turn, and spin-evaporating to remove solvent to obtain crude product, and purifying the crude product by column chromatography to obtain cyanation product. Mixing the cyanation product with an excessive amount of acid, and stirring for 32-48 hours at 130-160 ℃, wherein the acid is HOAc and H in a volume ratio of 1:2:3 2 O and H 2 SO 4 Mixing. Diluting with a small amount of water, extracting with ethyl acetate, concentrating under reduced pressure, and purifying the crude product by column chromatography to obtain the corresponding carboxylic acid product. Under the protection of inert gas, mixing the carboxylic acid product and the lithium aluminum hydride tetrahydrofuran solution, wherein the molar ratio of the carboxylic acid product to the lithium aluminum hydride is 1:10, and refluxing for 12-24 hours at 80-100 ℃. After the water quenching reaction, dilute hydrochloric acid is added until no obvious precipitate exists in the solution, an organic phase is separated, and the corresponding hydroxyl product is obtained after decompression and concentration. The hydroxyl product and pyridinium chlorochromate (PCC) with the molar ratio of 1:3 are dissolved in methylene dichloride under the protection of inert gas, and then stirred for 5 to 10 hours at room temperature. Concentrating under reduced pressure, and purifying the reaction product by column chromatography to obtain the corresponding aldehyde group product. Under the protection of inert gas, aldehyde group products and methyl triphenyl phosphorus iodide (PPh) with the molar ratio of 1:10:10 are treated 3 MeI) and potassium tert-butoxide are mixed, dissolved in tetrahydrofuran and reacted at room temperature for 5-12 hr. And (3) adding water to quench the reaction, separating out an organic phase, concentrating under reduced pressure to obtain a crude product, and purifying the crude product by column chromatography to obtain the (R) -spirodiene. Under the protection of inert gas, 9-boron bicyclo [3.3.1]Mixing a solution of nonane and (R) -spirodiene in tetrahydrofuran, wherein 9-borobicyclo [3.3.1]The molar ratio of nonane to (R) -spirodiene is 2:1, and the temperature is 40-60 DEG CAfter reacting for 2-12 h, filtering, washing filter cake with normal hexane for many times, and vacuum drying to obtain the main catalyst 1 of the double-component catalyst.
In the chiral organoboron catalysts, the synthetic reaction equation of the main catalyst 2 of the two-component catalyst is as follows:
Figure BDA0004138954400000061
the preparation method of the main catalyst 2 of the two-component catalyst comprises the following steps:
under the protection of inert gas, mixing 9-borabicyclo [3.3.1] nonane and (1S) - (-) -beta-pinene tetrahydrofuran solution, wherein the mol ratio of the 9-borabicyclo [3.3.1] nonane to the (1S) - (-) -beta-pinene is 1:1, reacting for 2-12 hours at 40-60 ℃, carrying out suction filtration, washing a filter cake with n-hexane for multiple times, and carrying out vacuum drying to obtain the main catalyst 2 of the double-component catalyst.
A method for preparing optically active polycarbonate or polyester by using chiral organoboron catalyst, the reaction equation is:
Figure BDA0004138954400000062
the specific reaction process is as follows: adding chiral organoboron catalyst, meso-alkylene oxide and cyclic anhydride or carbon dioxide into a high-pressure reaction kettle, adding an organic solvent, and stopping the reaction when no obvious anhydride solid exists in the reaction liquid or the expected consumption of alkylene oxide is reached; dissolving the crude product in dichloromethane, adding methanol, stirring vigorously to precipitate polymer, and repeating the precipitation process repeatedly to obtain optically active polycarbonate or polyester.
The inert gas is nitrogen or argon.
The organic solvent is one or more of tetrahydrofuran, toluene, methylene dichloride, n-hexane and acetonitrile.
The cyclic anhydride:
Figure BDA0004138954400000071
is->
Figure BDA0004138954400000072
One or more of them are mixed;
the meso-alkylene oxide:
Figure BDA0004138954400000073
one or more of them are mixed;
the molar ratio of the meso-alkylene oxide to the chiral organoboron catalyst is 500:1-200000:1.
The molar ratio of the meso-alkylene oxide to the cyclic anhydride is 1:1-5:1.
When adding carbon dioxide, the pressure of the carbon dioxide is 0.1-5.0 MPa.
The reaction temperature is-20-150 ℃.
The reaction time is 0.1-80 h.
The molecular weight of the optically active polyester or polycarbonate is 1000-1000000 g/mol, and the molecular weight distribution is 1.05-2.50.
The content of carbonate units in the optically active polycarbonate is higher than 95%; the content of the ester unit in the optical active polyester is higher than 90%, and the enantioselectivity of the carbonate unit and the ester unit in the optical active polycarbonate or the polyester is 10-80%.
The beneficial effects of the invention are that
(1) At low catalyst concentrations, higher catalytic activity is still achieved.
(2) The catalyst can efficiently catalyze the reaction in a wider temperature range.
(3) The catalyst activity is high, and the selectivity of the polymerization product is high; the molecular weight is controllable, the distribution is narrow, the application temperature range is wide, and the polymer structure can be regulated and controlled.
(4) The polycarbonate and the polyester have complete alternate structures, the selectivity and the structural selectivity of the polymerization product are higher than 90 percent, and the enantiomer excess value of the glycol obtained after degradation is between 10 and 80 percent.
(5) Unlike metal catalyst catalyzed polymerization which would result in coloration of the polymer, chiral organic catalysts catalyze both the resulting polycarbonate and polyester to be colorless.
(6) Because no metal residue exists in the polymer, the application of the polycarbonate and the polyester in the fields of food packaging, medical materials and the like can be greatly expanded.
Detailed Description
The technical solutions of the present invention are further stated below by examples.
Examples 1-2 are examples of the preparation method of the bifunctional catalyst 1-2; examples 3 to 4 are examples of the preparation method of the main catalyst 1 to 2 of the two-component catalyst.
Examples 5-8 are examples of optically active polycarbonate preparation using the chiral organoboron catalysts of the present invention; examples 9-12 are examples of optically active polyester preparation using the chiral organoboron catalysts of the present invention.
The names and numbers of the bifunctional catalyst 1-2, the main catalyst 1-2 of the two-component catalyst, the cocatalyst, the meso-alkylene oxide and the cyclic anhydride are shown in the following formulas.
Figure BDA0004138954400000081
Example 1:
the synthesis reaction equation of the bifunctional catalyst 1 is:
Figure BDA0004138954400000082
the specific preparation steps of the bifunctional catalyst 1 are as follows:
(R) -2,2 '-bis (bromomethyl) -1,1' -binaphthyl (250 mg,0.58 mmol) and K in a molar ratio of 1:2:1 are reacted under nitrogen 2 CO 3 (160 mg,1.16 mmol) and diallylamine (56 mg,0.58 mmol) were mixed and completely dissolved with acetonitrile, and thenRefluxing at 90deg.C for 10 hr, adding water to quench the reaction, separating the organic phase, extracting the aqueous phase with dichloromethane (10 mL×3), mixing the organic phases, drying with anhydrous sodium sulfate, rotary evaporating to remove solvent, and purifying the crude product by column chromatography to obtain binaphthyl chiral ammonium salt; the binaphthyl chiral ammonium salt (0.3 g,0.7 mmol) was dissolved in tetrahydrofuran under nitrogen protection, followed by a slow dropwise addition of 9-borabicyclo [3.3.1]]Nonane (2.8 mL of 0.5M tetrahydrofuran solution, 1.4 mmol) was reacted at 60℃for 10h. After concentrating under reduced pressure, n-hexane was added, a white solid was precipitated at the bottom of the flask, filtered, and the cake was washed (10 mL. Times.3) with n-hexane and dried in vacuo to give bifunctional catalyst 1. 1 H NMR(600MHz,CDCl 3 ):δ8.04–8.01(m,2H),7.98–7.97(m,2H),7.95–7.93(m,2H),7.57–7.46(m,2H),7.36–7.35(m,3H),7.22–7.18(m,1H),5.09–4.98(m,2H),3.93–3.77(m,2H),3.62–3.60(m,2H),3.25–3.20(m,2H),1.88–1.65(m,12H),1.58–1.50(m,12H),1.38–1.35(m,4H),1.26–1.19(m,5H),1.11–1.03(m,3H)。
Example 2:
the synthesis reaction equation of the bifunctional catalyst 2 is:
Figure BDA0004138954400000091
the specific preparation steps of the bifunctional catalyst 1 are as follows:
(R) -2,2 '-bis (bromomethyl) -1,1' -binaphthyl (250 mg,0.58 mmol) and K in a molar ratio of 1:2:1 are reacted under nitrogen 2 CO 3 (160 mg,1.16 mmol) and N-methylallylamine (41 mg,0.58 mmol) were mixed, completely dissolved with acetonitrile, refluxed at 90℃for 10 hours, then quenched with water, the organic phase was separated, the aqueous phase was extracted with dichloromethane (10 mL. Times.3), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation, and finally the crude product was purified by column chromatography to give a binaphthyl chiral ammonium salt; the binaphthyl chiral ammonium salt (0.3 g,0.7 mmol) was dissolved in tetrahydrofuran under nitrogen protection, followed by a slow dropwise addition of 9-borabicyclo [3.3.1]]Nonane (1.4 mL of 0.5M tetrahydrofuran solution, 0.7 mmol) was reacted at 60℃for 10h. Concentrating under reduced pressure, adding n-jiThe alkane precipitated from the bottom of the flask as a white solid, which was filtered and the filter cake was washed (10 mL. Times.3) with n-hexane and dried in vacuo to give bifunctional catalyst 2. 1 H NMR(600MHz,CDCl 3 ):δ8.01–7.93(m,6H),7.49–7.25(m,6H),5.21–5.02(m,2H),3.89–3.53(m,3H),3.51–3.29(m,4H),1.68–1.51(m,13H),1.35–1.00(m,5H)。
Example 3:
the synthesis reaction equation of the main catalyst 1 of the two-component catalyst is as follows:
Figure BDA0004138954400000101
the preparation method of the main catalyst 1 of the two-component catalyst comprises the following steps:
after dissolving (R) -spirodiphenol (2.0 g,2.1 mmol) in dichloromethane under nitrogen protection, pyridine (2.8 mL) and trifluoromethanesulfonic anhydride (3.3 mL) were added at 0deg.C. Followed by stirring at room temperature for 12h. After the reaction, adding water to quench the reaction, using dilute hydrochloric acid (1M) and saturated sodium bicarbonate solution to enable the pH value of the mixture to be 6-7, separating an organic phase, extracting an aqueous phase with ethyl acetate (30 mL multiplied by 3), decompressing and removing a solvent to obtain a crude product, and purifying the crude product through column chromatography to obtain a trifluoromethanesulfonic acid esterification product. The triflate (5.0 g,9.7 mmol), zinc cyanide (2.7 g,22.5 mmol), tetrakis (triphenylphosphine) palladium (1.2 g,1.0 mmol) were dissolved in N, N-dimethylformamide under nitrogen and subsequently reacted at 140℃for 24h. Diluting the mixture with proper amount of ethyl acetate, washing with saturated sodium chloride solution and saturated sodium carbonate solution in sequence, removing the solvent by rotary evaporation to obtain a crude product, and purifying the crude product by column chromatography to obtain a cyanation product. Cyanation product (3.5 g,13.0 mmol), H 2 O (60 mL), HOAc (30 mL) and H 2 SO 4 (90 mL) and stirred at 145℃for 48h. Dilute with small amounts of water, extract with ethyl acetate (100 mL x 3), combine the organic phases and concentrate under reduced pressure, and purify the crude product by column chromatography to give the corresponding carboxylic acid product. After lithium aluminum hydride (2.5 g,64.9 mmol) was dissolved in tetrahydrofuran under nitrogen, a solution of the carboxylic acid product (2.0 g,6.49 mmol) in tetrahydrofuran was added to the reaction system at 0 ℃And stirring was continued for 30min at 0℃followed by gradual heating to 80℃and refluxing for 24h. Adding water to quench the reaction, adding dilute hydrochloric acid (1M) until no obvious precipitate exists in the solution, separating out an organic phase, and concentrating under reduced pressure to obtain a corresponding hydroxyl product. The hydroxy product (1.6 g,5.59 mmol) was dissolved with pyridinium chlorochromate (3.6 g,16.8 mmol) in dichloromethane under nitrogen and stirred at room temperature for 5h. Concentrating under reduced pressure, and purifying the crude product by column chromatography to obtain the corresponding aldehyde product. Methyl triphenyl phosphine iodide (7.5 g,18.5 mmol) and potassium tert-butoxide (2.1 g,18.5 mmol) are dissolved in tetrahydrofuran under nitrogen protection at 0deg.C and the system is kept stirring for a further 30min at 0deg.C. After addition of a solution of the aldehyde product (0.5 g,1.85 mmol) in tetrahydrofuran, the system was gradually returned to room temperature and reacted at room temperature for 12h. And (3) adding water to quench the reaction, separating out an organic phase, concentrating under reduced pressure to obtain a crude product, and purifying the crude product by column chromatography to obtain the (R) -spirodiene. (R) -spirodiene (0.3 g,1.1 mmol) was dissolved in tetrahydrofuran under nitrogen, followed by slow dropwise addition of 9-borobicyclo [3.3.1]Nonane (4.4 mL of 0.5M tetrahydrofuran solution, 2.2 mmol) was reacted at 60℃for 10h. After concentrating under reduced pressure, adding n-hexane, precipitating white solid at the bottom of the bottle, filtering, washing (10 mL×3) the filter cake with n-hexane, and vacuum drying to obtain the main catalyst 1 of the two-component catalyst. 1 H NMR(400MHz,CDCl 3 ):δ7.14–7.11(m,2H),7.05(d,J＝8.0Hz,2H),7.00(d,J＝8.0Hz,2H),3.09–2.93(m,4H),2.42–2.15(m,8H),1.80–1.69(m,12H),1.57–1.40(m,16H),1.13–1.06(m,4H)。
Example 4:
the synthesis reaction equation of the main catalyst 2 of the two-component catalyst is as follows:
Figure BDA0004138954400000111
the preparation method of the main catalyst 1 of the two-component catalyst comprises the following steps:
(1S) - (-) -beta-pinene (0.5 g,2.1 mmol) was dissolved in tetrahydrofuran under nitrogen protection, followed by slow dropwise addition of 9-borobicyclo [3.3.1]Nonane (4.2 mL of 0.5M tetrahydrofuran solution, 2.1mmol) at 60℃for 10h. After concentrating under reduced pressure, adding n-hexane, precipitating white solid at the bottom of the bottle, filtering, washing (10 mL×3) the filter cake with n-hexane, and vacuum drying to obtain main catalyst 2 of the two-component catalyst. 1 HNMR(600MHz,CDCl 3 ):δ2.41–2.39(m,1H),2.05–2.01(m,1H),1.86–1.85(m,9H),1.76–1.68(m,9H),1.48–1.40(m,2H),1.26–1.22(m,3H),1.20(s,3H),0.87(s,3H)。
Example 5: the 20mL autoclave with the magnetons is dried for more than 12 hours at 120 ℃, vacuumized, cooled to room temperature and filled with argon for preparation. Under argon atmosphere, injecting a homogeneous solution formed by a bifunctional catalyst 1 (R=H) and CHO with a molar ratio of 1:500 into an autoclave, sealing the autoclave, introducing 2.0MPa carbon dioxide, reacting at 25 ℃ for 24 hours, stopping stirring, and slowly releasing unreacted carbon dioxide. Removing a very small amount of the reaction mixture for 1 By H NMR analysis, the conversion frequency was found to be 14H -1 The carbonate unit content is greater than 99%. The remaining polymerization product was dissolved in dichloromethane/precipitated with methanol, the above procedure was repeated three times and washed, and dried under vacuum to constant weight. The molecular weight of the polycarbonate was determined to be 6.0Kg/mol and the molecular weight distribution was determined to be 1.20 by gel permeation chromatography. The polymer was hydrolyzed to diol with dilute NaOH and its enantioselectivity was 20% as determined by chiral gas chromatography.
Example 6: the 20mL autoclave with the magnetons is dried for more than 12 hours at 120 ℃, vacuumized, cooled to room temperature and filled with argon for preparation. Under argon atmosphere, injecting a homogeneous solution formed by a bifunctional catalyst 1 (R=Ar) and CHO with a molar ratio of 1:500 into an autoclave, sealing the autoclave, introducing 2.0MPa carbon dioxide, reacting at 25 ℃ for 72 hours, stopping stirring, and slowly releasing unreacted carbon dioxide. Removing a very small amount of the reaction mixture for 1 By H NMR analysis, the conversion frequency was calculated to be 3H -1 The carbonate unit content is greater than 99%. The remaining polymerization product was dissolved in dichloromethane/precipitated with methanol, the above procedure was repeated three times and washed, and dried under vacuum to constant weight. The molecular weight of the polycarbonate was determined to be 6.8Kg/mol and the molecular weight distribution was determined to be 1.20 by gel permeation chromatography. Hydrolysis of the Polymer into Di with dilute NaOH solutionAlcohol, with a enantioselectivity of 68% as determined by chiral gas chromatography.
Example 7: the 20mL autoclave with the magnetons is dried for more than 12 hours at 120 ℃, vacuumized, cooled to room temperature and filled with argon for preparation. Under argon atmosphere, injecting a homogeneous solution formed by a main catalyst 1, a cocatalyst PPNCl and CHO of a two-component catalyst with a molar ratio of 1:1:500 into an autoclave, sealing the autoclave, introducing 2.0MPa of carbon dioxide, reacting at 25 ℃ for 3 hours, stopping stirring, and slowly releasing unreacted carbon dioxide. Removing a very small amount of the reaction mixture for 1 By H NMR analysis, the conversion frequency was calculated to be 30H -1 The carbonate unit content is greater than 99%. The remaining polymerization product was dissolved in dichloromethane/precipitated with methanol, the above procedure was repeated three times and washed, and dried under vacuum to constant weight. The molecular weight of the polycarbonate was determined to be 4.5Kg/mol and the molecular weight distribution was determined to be 1.20 by gel permeation chromatography. The polymer was hydrolyzed to diol with dilute NaOH and its enantioselectivity was 24% as determined by chiral gas chromatography.
Comparative example 7-1: the 20mL autoclave with the magnetons is dried for more than 12 hours at 120 ℃, vacuumized, cooled to room temperature and filled with argon for preparation. Under argon atmosphere, injecting a homogeneous solution formed by a main catalyst 1, a cocatalyst PPNCl and CHO of a two-component catalyst with a molar ratio of 1:1:1000 into an autoclave, sealing the autoclave, introducing 2.0MPa of carbon dioxide, placing the autoclave at 150 ℃ for reaction, enabling the pressure of the carbon dioxide of a reaction system to be constant through a regulating valve, stopping stirring after reacting for 20min, and slowly releasing unreacted carbon dioxide. Removing a very small amount of the reaction mixture for 1 By H NMR analysis, the conversion frequency was found to be 1033H -1 The carbonate unit content is greater than 99%. The remaining polymerization product was dissolved in dichloromethane/precipitated with methanol, the above procedure was repeated three times and washed, and dried under vacuum to constant weight. The molecular weight of the polycarbonate was determined to be 6.7Kg/mol and the molecular weight distribution was determined to be 1.17 by gel permeation chromatography. The polymer was hydrolyzed to diol with dilute NaOH and its enantioselectivity was 16% as determined by chiral gas chromatography.
Comparative example 7-2: drying at 120deg.C for 12 hr or more in 20mL autoclave equipped with magneton, and vacuumizingAnd after the mixture is cooled to room temperature, filling argon gas for preparation. Under argon atmosphere, injecting a homogeneous solution formed by a main catalyst 1, a cocatalyst PPNCl and CHO of a two-component catalyst with a molar ratio of 1:1:500 into an autoclave, sealing the autoclave, introducing 2.0MPa of carbon dioxide, placing the autoclave at a temperature of minus 20 ℃ for reaction, stopping stirring after reacting for 42 hours, and slowly releasing unreacted carbon dioxide. Removing a very small amount of the reaction mixture for 1 By H NMR analysis, the conversion frequency was calculated to be 3H -1 The carbonate unit content is greater than 99%. The remaining polymerization product was dissolved in dichloromethane/precipitated with methanol, the above procedure was repeated three times and washed, and dried under vacuum to constant weight. The molecular weight of the polycarbonate was determined to be 6.1Kg/mol and the molecular weight distribution was determined to be 1.19 by gel permeation chromatography. The polymer was hydrolyzed to diol with dilute NaOH and its enantioselectivity was 26% as determined by chiral gas chromatography.
Comparative example 7-3: the 100mL autoclave with the magnetons is dried for more than 12 hours at 120 ℃, vacuumized, cooled to room temperature and filled with argon for preparation. Under argon atmosphere, the main catalyst 1 of the double-component catalyst with the molar ratio of 1:1:100000, a cocatalyst PPNCl and CHO are put into a homogeneous solution autoclave, 2.0MPa carbon dioxide is introduced after the autoclave is closed, the reaction system is placed at 100 ℃ for reaction, the carbon dioxide pressure of the reaction system can be kept constant through a regulating valve, and after the reaction is carried out for 10 hours, the stirring is stopped, and unreacted carbon dioxide is slowly released. Removing a very small amount of the reaction mixture for 1 By H NMR analysis, the conversion frequency was 833H -1 The carbonate unit content is greater than 99%. The remaining polymerization product was dissolved in dichloromethane/precipitated with methanol, the above procedure was repeated three times and washed, and dried under vacuum to constant weight. The molecular weight of the polycarbonate was 56.2Kg/mol as measured by gel permeation chromatography, and the molecular weight distribution was 1.22. The polymer was hydrolyzed to diol with dilute NaOH and its enantioselectivity was 10% as determined by chiral gas chromatography.
Comparative examples 7 to 4: the 100mL autoclave with the magnetons is dried for more than 12 hours at 120 ℃, vacuumized, cooled to room temperature and filled with argon for preparation. Under argon atmosphere, the main catalyst 1 of the double-component catalyst, the cocatalyst PPNCl and CHO with the mol ratio of 1:1:200000 are formedInjecting the homogeneous solution into an autoclave, sealing the autoclave, introducing 5.0MPa of carbon dioxide, placing the autoclave at 100 ℃ for reaction, enabling a regulating valve to be used for keeping constant the pressure of the carbon dioxide in the reaction system, stopping stirring after the reaction is carried out for 24 hours, and slowly releasing unreacted carbon dioxide. Removing a very small amount of the reaction mixture for 1 H NMR analysis can calculate the conversion frequency to 770H -1 The carbonate unit content is greater than 99%. The remaining polymerization product was dissolved in dichloromethane/precipitated with methanol, the above procedure was repeated three times and washed, and dried under vacuum to constant weight. The molecular weight of the polycarbonate was 89.1Kg/mol as measured by gel permeation chromatography, and the molecular weight distribution was 1.30. The polymer was hydrolyzed to diol with dilute NaOH and its enantioselectivity was 10% as determined by chiral gas chromatography.
Comparative examples 7 to 5: the 20mL autoclave with the magnetons is dried for more than 12 hours at 120 ℃, vacuumized, cooled to room temperature and filled with argon for preparation. Under argon atmosphere, injecting a homogeneous solution formed by a main catalyst 1, a cocatalyst PPNCl and CPO of a two-component catalyst with the molar ratio of 1:1:500 into an autoclave, sealing the autoclave, introducing 2.0MPa of carbon dioxide, reacting at 25 ℃ for 72 hours, stopping stirring, and slowly releasing unreacted carbon dioxide. Removing a very small amount of the reaction mixture for 1 By H NMR analysis, the conversion frequency was calculated to be 3H -1 The carbonate unit content is greater than 99%. The remaining polymerization product was dissolved in dichloromethane/precipitated with methanol, the above procedure was repeated three times and washed, and dried under vacuum to constant weight. The molecular weight of the polycarbonate was 17.4Kg/mol and the molecular weight distribution was 1.18 as determined by gel permeation chromatography. The polymer was hydrolyzed to diol with dilute NaOH and its enantioselectivity was 12% as determined by chiral gas chromatography.
Comparative examples 7 to 6: the 20mL autoclave with the magnetons is dried for more than 12 hours at 120 ℃, vacuumized, cooled to room temperature and filled with argon for preparation. Under argon atmosphere, injecting a homogeneous solution formed by a main catalyst 1, a cocatalyst PPNCl and CDO of a two-component catalyst with the molar ratio of 1:1:500 into an autoclave, sealing the autoclave, introducing 2.0MPa of carbon dioxide, reacting at 25 ℃ for 12 hours, stopping stirring, and slowly releasing unreacted carbon dioxide. Take out very littleAmount of reaction mixture for 1 By H NMR analysis, the conversion frequency was calculated to be 3H -1 The carbonate unit content is greater than 99%. The remaining polymerization product was dissolved in dichloromethane/precipitated with methanol, the above procedure was repeated three times and washed, and dried under vacuum to constant weight. The molecular weight of the polycarbonate was 3.4Kg/mol and the molecular weight distribution was 1.18 as determined by gel permeation chromatography. The polymer was hydrolyzed to diol with dilute NaOH and its enantioselectivity was 16% as determined by chiral gas chromatography.
Comparative examples 7 to 7: the 20mL autoclave with the magnetons is dried for more than 12 hours at 120 ℃, vacuumized, cooled to room temperature and filled with argon for preparation. Under argon atmosphere, injecting a homogeneous solution formed by a main catalyst 1, a cocatalyst PPNCl and CBO of a two-component catalyst with the molar ratio of 1:1:500 into an autoclave, sealing the autoclave, introducing 2.0MPa of carbon dioxide, reacting at 25 ℃ for 32 hours, stopping stirring, and slowly releasing unreacted carbon dioxide. Removing a very small amount of the reaction mixture for 1 By H NMR analysis, the conversion frequency was calculated to be 12H -1 The carbonate unit content is greater than 99%. The remaining polymerization product was dissolved in dichloromethane/precipitated with methanol, the above procedure was repeated three times and washed, and dried under vacuum to constant weight. The molecular weight of the polycarbonate was determined to be 13.0Kg/mol and the molecular weight distribution was determined to be 1.16 by gel permeation chromatography. The polymer was hydrolyzed to diol with dilute NaOH and its enantioselectivity was 22% as determined by chiral gas chromatography.
Comparative examples 7 to 8: the 20mL autoclave with the magnetons is dried for more than 12 hours at 120 ℃, vacuumized, cooled to room temperature and filled with argon for preparation. Under argon atmosphere, injecting a homogeneous solution formed by a main catalyst 1, a cocatalyst PPNCl and a CEO of a two-component catalyst with a molar ratio of 1:1:500 into an autoclave, sealing the autoclave, introducing 2.0MPa of carbon dioxide, reacting at 25 ℃ for 18 hours, stopping stirring, and slowly releasing unreacted carbon dioxide. Removing a very small amount of the reaction mixture for 1 By H NMR analysis, the conversion frequency was calculated to be 4H -1 The carbonate unit content is greater than 99%. The remaining polymerization product was dissolved in methylene chloride/precipitated with methanol, and the above procedure was repeated three times and washed, and dried under vacuum untilConstant weight. The molecular weight of the polycarbonate was 3.4Kg/mol as measured by gel permeation chromatography, and the molecular weight distribution was 1.27. The polymer was hydrolyzed to diol with dilute NaOH and its enantioselectivity was 14% as determined by chiral gas chromatography.
Example 8: the 20mL autoclave with the magnetons is dried for more than 12 hours at 120 ℃, vacuumized, cooled to room temperature and filled with argon for preparation. Under argon atmosphere, injecting a homogeneous solution formed by a main catalyst 2, a cocatalyst PPNCl and CHO of a two-component catalyst with a molar ratio of 1:1:500 into an autoclave, sealing the autoclave, introducing 0.1MPa carbon dioxide, reacting at 25 ℃ for 72 hours, stopping stirring, and slowly releasing unreacted carbon dioxide. Removing a very small amount of the reaction mixture for 1 By H NMR analysis, the conversion frequency was calculated to be 3H -1 The carbonate unit content is greater than 99%. The remaining polymerization product was dissolved in dichloromethane/precipitated with methanol, the above procedure was repeated three times and washed, and dried under vacuum to constant weight. The molecular weight of the polycarbonate was 7.5Kg/mol as measured by gel permeation chromatography, and the molecular weight distribution was 1.17. The polymer was hydrolyzed to diol with dilute NaOH and its enantioselectivity was 11% as determined by chiral gas chromatography.
Example 9: 10mL Xu Linke bottle with magneton is dried for more than 12 hours at 120 ℃, vacuumized, cooled to room temperature and filled with argon for preparation. Under argon atmosphere, a mixed solution of a bifunctional catalyst 1 (r=h), PA and CHO in a molar ratio of 1:250:1000 was injected into a Xu Linke bottle, 0.2mL of tetrahydrofuran was added as a solvent, and the reaction system was closed and stirred at 50 ℃. After 40 hours of clarification in the reaction solution, the reaction was stopped after no obvious solid cyclic anhydride was present. Removing a very small amount of the reaction mixture for 1 By H NMR analysis, the conversion frequency was calculated to be 4H -1 The ester unit content was 90%. The remaining polymerization product was dissolved in dichloromethane/precipitated with methanol, the above procedure was repeated three times and washed, and dried under vacuum to constant weight. The molecular weight of the polyester was 7.1Kg/mol and the molecular weight distribution was 1.23 as determined by gel permeation chromatography. The polymer was hydrolyzed to diol with dilute NaOH and its enantioselectivity was 16% as determined by chiral gas chromatography.
Example 10: matching withThe 10mL Xu Linke bottle with the magnetons is dried for more than 12 hours at 120 ℃, vacuumized, cooled to room temperature and filled with argon for preparation. Under argon atmosphere, mixed solution of bifunctional catalyst 2 (r=h), PA and CHO in a molar ratio of 1:250:1000 was injected into Xu Linke bottle, 0.2mL tetrahydrofuran was added as solvent, and the reaction system was closed and stirred at 50 ℃. After the reaction solution is clarified for 24 hours, the reaction is stopped after no obvious solid cyclic anhydride exists. Removing a very small amount of the reaction mixture for 1 HNMR analysis can calculate the conversion frequency to be 4h -1 The ester unit content is greater than 99%. The remaining polymerization product was dissolved in dichloromethane/precipitated with methanol, the above procedure was repeated three times and washed, and dried under vacuum to constant weight. The molecular weight of the polyester was determined to be 4.0Kg/mol and the molecular weight distribution was determined to be 1.21 by gel permeation chromatography. The polymer was hydrolyzed to diol with dilute NaOH and its enantioselectivity was 22% as determined by chiral gas chromatography.
Example 11: 10mL Xu Linke bottle with magneton is dried for more than 12 hours at 120 ℃, vacuumized, cooled to room temperature and filled with argon for preparation. Under argon atmosphere, mixed solution of bifunctional catalyst 2 (r=ar), PA and CHO in a molar ratio of 1:250:1000 was injected into Xu Linke bottle, 0.2mL tetrahydrofuran was added as solvent, and the reaction system was closed and stirred at 50 ℃. After the reaction solution is clarified for 24 hours, the reaction is stopped after no obvious solid cyclic anhydride exists. Removing a very small amount of the reaction mixture for 1 By H NMR analysis, the conversion frequency was calculated to be 3.6H -1 The ester unit content is greater than 99%. The remaining polymerization product was dissolved in dichloromethane/precipitated with methanol, the above procedure was repeated three times and washed, and dried under vacuum to constant weight. The molecular weight of the polyester was 3.8Kg/mol and the molecular weight distribution was 1.15 as determined by gel permeation chromatography. The polymer was hydrolyzed to diol with dilute NaOH and its enantioselectivity was 78% as determined by chiral gas chromatography.
Example 12: 10mL Xu Linke bottle with magneton is dried for more than 12 hours at 120 ℃, vacuumized, cooled to room temperature and filled with argon for preparation. Under argon atmosphere, the main catalyst 2 of the double-component catalyst with the mol ratio of 1:1:1000:1000, the cocatalyst PPNCl, PA and CHO are formedThe mixed solution was poured into Xu Linke bottles, and 0.5mL of tetrahydrofuran was added as a solvent, and the reaction system was closed and stirred at 50 ℃. After the reaction solution is clarified for 72 hours, the reaction is stopped after no obvious solid cyclic anhydride exists. Removing a very small amount of the reaction mixture for 1 By H NMR analysis, the conversion frequency was calculated to be 2H -1 The ester unit content is greater than 99%. The remaining polymerization product was dissolved in dichloromethane/precipitated with methanol, the above procedure was repeated three times and washed, and dried under vacuum to constant weight. The molecular weight of the polyester was 8.5Kg/mol and the molecular weight distribution was 1.22 as determined by gel permeation chromatography. The polymer was hydrolyzed to diol with dilute NaOH and its enantioselectivity was 14% as determined by chiral gas chromatography.

Claims (10)

1. The chiral organoboron catalyst is characterized by comprising an organoboron-onium salt bifunctional catalyst and a double-component catalyst consisting of organoboron and onium salt; wherein the organoboron-onium salt bifunctional catalyst is formed by assembling organoboron Lewis acid center and Lewis base onium salt into a binaphthyl skeleton with axial chirality; the double-component catalyst composed of the organic boron and the onium salt is a main catalyst formed by introducing the organic boron Lewis acid center into a chiral framework and is matched with a cocatalyst
Figure FDA0004138954390000014
A two-component catalyst comprising a salt; the organic boron-onium salt double-function catalyst and the organic boron-onium salt double-component catalyst have the following structural general formula:
Figure FDA0004138954390000011
wherein, the specific structure of the organoboron-onium salt bifunctional catalyst is as follows:
Figure FDA0004138954390000012
the main catalyst of the organoboron and onium salt double-component catalyst has the specific structure that:
Figure FDA0004138954390000013
cocatalyst for organic boron-onium salt double-component catalyst
Figure FDA0004138954390000015
The salt is bis (triphenylphosphine) -imine chloride (PPNCl), and the specific structure is as follows:
Figure FDA0004138954390000021
2. a chiral organoboron catalyst of the type described in claim 1, characterized in that,
the synthesis reaction equation of the bifunctional catalyst 1 is as follows:
Figure FDA0004138954390000022
the specific preparation steps of the bifunctional catalyst 1 are as follows:
under the protection of inert gas, the (R) -2,2 '-bis (bromomethyl) -1,1' -binaphthyl and K are mixed in a molar ratio of 1:2:1 2 CO 3 Mixing with diallylamine, dissolving with acetonitrile, refluxing at 90-150 deg.c for 6-10 hr, adding water to quench to react, separating organic phase, extracting water phase with organic solvent, decompressing to eliminate solvent to obtain coarse product, purifying the coarse product with column chromatography to obtain chiral binaphthyl ammonium salt; under the protection of inert gas, 9-boron bicyclo [3.3.1]Mixing tetrahydrofuran solutions of nonane and binaphthyl chiral ammonium salts, wherein 9-borobicyclo [3.3.1]The molar ratio of nonane to binaphthyl chiral ammonium salt is 2:1, and then the reaction is carried out for 2 to 12 hours at the temperature of 40 to 60 ℃, the filtration is carried out, the filter cake is washed by n-hexane for multiple times, and the vacuum drying is carried outObtaining the bifunctional catalyst 1;
the synthesis reaction equation of the bifunctional catalyst 2 is as follows:
Figure FDA0004138954390000023
the specific preparation steps of the bifunctional catalyst 2 are as follows:
under the protection of inert gas, the (R) -2,2 '-bis (bromomethyl) -1,1' -binaphthyl and K are mixed in a molar ratio of 1:2:1 2 CO 3 Mixing with N-methylallylamine, dissolving with acetonitrile, refluxing at 90-150 ℃ for 6-10 hours, adding water for quenching reaction, separating an organic phase, extracting a water phase with an organic solvent, removing the solvent under reduced pressure to obtain a crude product, and purifying the crude product by column chromatography to obtain binaphthyl chiral ammonium salt; under the protection of inert gas, 9-boron bicyclo [3.3.1]Mixing tetrahydrofuran solutions of nonane and binaphthyl chiral ammonium salts, wherein 9-borobicyclo [3.3.1]The molar ratio of nonane to binaphthyl chiral ammonium salt is 1:1, then the reaction is carried out for 2 to 12 hours at the temperature of 40 to 60 ℃, suction filtration is carried out, the filter cake is washed by n-hexane for multiple times, and the bifunctional catalyst 2 is obtained after vacuum drying;
the synthesis reaction equation of the main catalyst 1 of the two-component catalyst is as follows:
Figure FDA0004138954390000031
the preparation method of the main catalyst 1 of the two-component catalyst comprises the following steps:
mixing (R) -spirodiphenol, trifluoro methanesulfonic anhydride and pyridine in a molar ratio of 1:2:3 at 0 ℃ under the protection of inert gas, dissolving with dichloromethane, and then stirring for 8-12 h at room temperature; after the reaction is finished, adding water to quench the reaction, separating an organic phase, extracting a water phase with ethyl acetate, decompressing and removing a solvent to obtain a crude product, and purifying the crude product through column chromatography to obtain a trifluoro methane sulfonate product; mixing tetra (triphenylphosphine) palladium, trifluoromethane sulfonic acid esterification product and zinc cyanide in a molar ratio of 1:10:20 under the protection of inert gasDissolving with N, N-dimethylformamide, and then placing the mixture at 110-150 ℃ to react for 12-24 hours; diluting the reacted mixture with ethyl acetate, washing with saturated sodium chloride solution and saturated sodium carbonate solution in sequence, removing solvent by rotary evaporation to obtain a crude product, and purifying the crude product by column chromatography to obtain a cyanation product; mixing the cyanation product with an excessive amount of acid, and stirring for 32-48 hours at 130-160 ℃, wherein the acid is HOAc and H in a volume ratio of 1:2:3 2 O and H 2 SO 4 Mixing; diluting with water, extracting with ethyl acetate, concentrating under reduced pressure, and purifying the crude product by column chromatography to obtain corresponding carboxylic acid product; under the protection of inert gas, mixing a carboxylic acid product and a tetrahydrofuran solution of lithium aluminum hydride, wherein the molar ratio of the carboxylic acid product to the lithium aluminum hydride is 1:10, and refluxing for 12-24 hours at 80-100 ℃; adding water to quench reaction, adding dilute hydrochloric acid until no obvious precipitate exists in the solution, separating out an organic phase, and concentrating under reduced pressure to obtain a corresponding hydroxyl product; under the protection of inert gas, dissolving a hydroxyl product and pyridinium chlorochromate in a molar ratio of 1:3 in methylene dichloride, and stirring for 5-10 hours at room temperature; concentrating under reduced pressure, purifying the reaction product by column chromatography to obtain a corresponding aldehyde group product; under the protection of inert gas, mixing aldehyde product, methyl triphenyl phosphorus iodide and potassium tert-butoxide in a molar ratio of 1:10:10, dissolving the mixture with tetrahydrofuran, and reacting for 5 to 12 hours at room temperature; adding water to quench reaction, separating out an organic phase, concentrating under reduced pressure to obtain a crude product, and purifying the crude product by column chromatography to obtain (R) -spirodiene; under the protection of inert gas, 9-boron bicyclo [3.3.1]Mixing a solution of nonane and (R) -spirodiene in tetrahydrofuran, wherein 9-borobicyclo [3.3.1]The mol ratio of nonane to (R) -spirodiene is 2:1, after reacting for 2-12 hours at 40-60 ℃, suction filtering is carried out, filter cakes are washed by n-hexane for multiple times, and a main catalyst 1 of the double-component catalyst is obtained after vacuum drying;
the synthesis reaction equation of the main catalyst 2 of the two-component catalyst is as follows:
Figure FDA0004138954390000041
the preparation method of the main catalyst 2 of the two-component catalyst comprises the following steps:
under the protection of inert gas, mixing 9-borabicyclo [3.3.1] nonane and (1S) - (-) -beta-pinene tetrahydrofuran solution, wherein the mol ratio of the 9-borabicyclo [3.3.1] nonane to the (1S) - (-) -beta-pinene is 1:1, reacting for 2-12 hours at 40-60 ℃, carrying out suction filtration, washing a filter cake with n-hexane for multiple times, and carrying out vacuum drying to obtain the main catalyst 2 of the double-component catalyst.
3. A method for preparing optically active polycarbonate or polyester using a chiral organoboron catalyst of claim 1, wherein the reaction equation is:
Figure FDA0004138954390000042
the specific reaction process is as follows: adding a chiral organoboron catalyst, meso-alkylene oxide and cyclic anhydride or carbon dioxide into a reaction kettle, adding an organic solvent, and stopping the reaction when no obvious anhydride solid exists in the reaction liquid or the expected consumption of alkylene oxide is reached; dissolving the crude product in dichloromethane, adding methanol, stirring vigorously to precipitate polymer, and repeating the precipitation process repeatedly to obtain optically active polycarbonate or polyester.
4. A process for preparing optically active polycarbonates or polyesters using a chiral organoboron catalyst according to claim 3,
the inert gas is nitrogen or argon;
the organic solvent is one or more than two of tetrahydrofuran, toluene, methylene dichloride, n-hexane and acetonitrile;
the cyclic anhydride:
Figure FDA0004138954390000051
is->
Figure FDA0004138954390000052
One or more of them are mixed;
the meso-alkylene oxide:
Figure FDA0004138954390000053
is->
Figure FDA0004138954390000054
One or two or more of them are mixed.
5. A process for preparing optically active polycarbonates or polyesters using a chiral organoboron catalyst of the type according to claim 3 or 4,
the molar ratio of the meso-alkylene oxide to the chiral organoboron catalyst is 500:1-200000:1;
the molar ratio of the meso-alkylene oxide to the cyclic anhydride is 1:1-5:1;
when adding carbon dioxide, the pressure of the carbon dioxide is 0.1-5.0 MPa.
6. A process for preparing optically active polycarbonates or polyesters using a chiral organoboron catalyst of the type according to claim 3 or 4,
the reaction temperature is-20-150 ℃;
the reaction time is 0.1-80 h.
7. The method for preparing optically active polycarbonate or polyester by using chiral organoboron catalyst according to claim 5,
the reaction temperature is-20-150 ℃;
the reaction time is 0.1-80 h.
8. The method for preparing optically active polycarbonate or polyester by using chiral organoboron catalyst as described in claim 3, 4 or 7, wherein the molecular weight of the optically active polyester or polycarbonate is 1000-1000000 g/mol and the molecular weight distribution is 1.05-2.50.
9. The method for preparing optically active polycarbonate or polyester by using chiral organoboron catalyst according to claim 5, wherein the molecular weight of the optically active polyester or polycarbonate is 1000-1000000 g/mol and the molecular weight distribution is 1.05-2.50.
10. The method for preparing optically active polycarbonate or polyester by using the chiral organoboron catalyst as described in claim 3, 4, 7 or 9, wherein the content of carbonate units in the optically active polycarbonate is higher than 95%; the content of the ester unit in the optical active polyester is higher than 90%, and the enantioselectivity of the carbonate unit and the ester unit in the optical active polycarbonate or the polyester is 10-80%.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117887059A (en) * 2024-03-15 2024-04-16 中国科学院过程工程研究所 Method for selectively synthesizing polycarbonate or cyclic carbonate

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117887059A (en) * 2024-03-15 2024-04-16 中国科学院过程工程研究所 Method for selectively synthesizing polycarbonate or cyclic carbonate

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