CN116212960A - Aryloxy cyclic ether skeleton metal complex catalyst and preparation method and application thereof - Google Patents

Aryloxy cyclic ether skeleton metal complex catalyst and preparation method and application thereof Download PDF

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CN116212960A
CN116212960A CN202310008974.3A CN202310008974A CN116212960A CN 116212960 A CN116212960 A CN 116212960A CN 202310008974 A CN202310008974 A CN 202310008974A CN 116212960 A CN116212960 A CN 116212960A
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compound
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catalyst
lactide
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范天熙
任一臻
吕英东
朱小瑞
刘万弼
李彬
韩丙浩
刘建峰
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Wanhua Chemical Group Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
    • C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/22—Tin compounds
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/20—Constitutive chemical elements of heterogeneous catalysts of Group II (IIA or IIB) of the Periodic Table
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/40—Constitutive chemical elements of heterogeneous catalysts of Group IV (IVA or IVB) of the Periodic Table
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Abstract

The invention provides an aryloxy cyclic ether skeleton metal complex catalyst, a preparation method and application thereof. The catalyst takes a formula I as a ligand, and has the following structural formula:

Description

Aryloxy cyclic ether skeleton metal complex catalyst and preparation method and application thereof
Technical Field
The invention relates to an aryloxy cyclic ether skeleton metal complex catalyst, a preparation method thereof and application of the catalyst in preparation of lactide from L-lactic acid.
Background
Lactide is an important raw material for the synthesis of polylactic acid. The polylactic acid material has good biodegradability, biocompatibility and good mechanical strength, is an ideal biodegradable material, and has wide application prospect in the aspects of human tissue repair, wound suturing, and controlled release of medicines and pesticides; in other application fields, polylactic acid replaces the traditional polymer material, so that the pollution and harm to the environment can be reduced. The main method of polylactic acid synthesis in industry is lactide ring-opening polymerization, and this technology has been described in many patent documents, for example: US5053522A, US5247058A, US5357035A, US6005067a, US6277951B1, US6326458B1, US5274127a, US20050222379A1, US20120302724A1, US20110155557A1, CN1951933a, CN1594313a, CN1488628A, WO2010105143A2, etc. At present, the industrial production mainly adopts a method that a tin-based chemical substance is used as a catalyst (such as stannous 2-ethylhexanoate (1I), stannic chloride and the like) under a vacuum environment by heating at high temperature, and polylactic acid is generated through four steps of dehydration, prepolymerization, depolymerization and ring-opening polymerization. In order to avoid oxidation of the reactants under high temperature conditions (. Gtoreq.180 ℃), the chemical reaction is usually carried out in an inert gas atmosphere (e.g.nitrogen).
In the process of prepolymerization and depolymerization, the high-temperature low-pressure reaction conditions (the temperature is 200-240 ℃ and the pressure is 5-15 hpa) can depolymerize part of the oligomers, and meanwhile, the other part of the oligomers are further polymerized into polymers with higher molecular weight, a large amount of tan kettle residue high polymers are often generated in the process, the tin-based catalyst has obvious catalytic effect on the depolymerization process though homogeneous catalysis, a large amount of kettle residues are generated, the optical purity of crude lactide is low, and the cost of the subsequent separation and purification process is increased. The yield of lactide synthesized by conventional methods is generally only 50% -70%. For example, U.S. patent application US5053522a mentions a process for the synthesis of lactide using a tin-based catalyst, requiring a high temperature of 200-260 ℃ to separate the lactide product in 69% yield. In the single batch production of US patent application US5274127a, the yield of lactide was 56.8%. While the low catalytic efficiency of other metal compounds for the prepolymerization and the depolymerization reactions leads to a decrease (< 70%) in the yield of lactide production. For example, zinc oxide particles are used in US patent 201203027A1, and lactide products are obtained by distillation separation at high temperatures of 230-240 ℃ with yields below 72%. Meanwhile, according to experiments and literature experience, a large amount of byproducts can be generated in the process of lactide ring-opening polymerization of polylactic acid by using low-purity lactide raw materials, and polylactic acid products which can be applied on a large scale can not be prepared, so that the high-yield and high-purity lactide process generated in the steps of pre-polymerization and depolymerization is a decisive core step of a process for synthesizing the polylactic acid products which can be applied on a large scale in an industrial scale, and in the main flow process for synthesizing lactide by using the existing lactic acid, the lactide synthesis method has low yield, and the reaction condition needs high temperature and high vacuum degree, has severe condition and needs further optimization and improvement, so that the energy consumption in the production process and the production cost are reduced.
Disclosure of Invention
The invention aims to provide an aryloxy cyclic ether skeleton metal complex catalyst and a preparation method thereof. On one hand, the ligand structure of the invention has larger molecular space, obtains larger steric hindrance, and obviously enhances the stereoselectivity of the catalyst on crude lactide; catalytic stability under this system; on the other hand, the active metal is taken as a central atom, so that the reaction activity of the catalyst is enhanced, the optical purity of crude lactide in the lactide synthesis reaction process is obviously improved, and the regularity of the space structure of a polymerization product is further obviously improved.
The invention also provides the application of the catalyst in preparing lactide from L-lactic acid, so that the lactide yield and the optical purity are higher (the lactide yield can reach 80.0-95.0% and the optical purity is more than 99.9%) in the lactide synthesis and depolymerization process.
In order to achieve the above object, the present invention provides the following technical solutions:
an aryloxy cyclic ether skeleton metal complex catalyst, which takes II-IVA, IIB and transition metal as active components M, preferably one or more of Sn, zn, ga and Ti, zn, al, zr, wherein the ligand has the structural formula as follows:
Figure BDA0004037107150000031
wherein R is 1 ～R 12 Selected from hydrogen, halogen or any one of the following groups: c (C) 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkyl oxy, C 6-14 Aryl, C 6-14 An aryloxy group; t (T) 1 And T 2 Each independently selected from divalent hydrocarbon or silane groups having 1 to 20 atoms other than hydrogen, or inert substituted derivatives of the above; x is a monovalent substituent having 1 to 20 atoms other than hydrogen, or two X groups together are a divalent substituent having 1 to 40 atoms other than hydrogen.
Preferably, R 1～ R 12 Any one selected from substituted methyl, substituted phenyl, dibenzo ring, alkyl, fluorenyl and anthryl; more preferably, t-butyl, 3, 5-di-t-butylphenyl, benzyl, fluorenyl, benzhydryl.
Preferably T 1 、T 2 Each independently selected from divalent hydrocarbon groups having 3 to 10 atoms; preferably, T1 and T2 are each 1, 3-propanediyl, 1, 4-butanediyl, 2, 4-pentanediyl, 1, 5-pentanediyl, 1, 3-di (propylene) phenyl, and methylene trans-1, 2-cyclohexanediyl.
Preferably, each X is independently selected from monovalent substituent groups having 1 to 10 atoms, or two X groups together are divalent substituent groups having 1 to 20 atoms without hydrogen; further preferably, X is halogen, methyl, benzyl or dimethylamino; more preferably, X is chloro, methyl or benzyl.
Further, the bimetallic complex of the aryloxy ether skeleton in the invention can be prepared by the following method: the reaction process is shown in the following formula,
Figure BDA0004037107150000051
comprises the following steps:
(1) Reacting a substituted brominated phenol, triphenylphosphine, aldehyde No. 1 in the presence of n-butyllithium to produce product No. 3, preferably a substituted brominated phenol: aldehyde No. 1: triphenylphosphine: n-butyllithium molar ratio = 1: (1.1-1.5): (1.1-2): (1.1 to 1.5), reaction temperature: the reaction time is 8 to 12 hours at the temperature of 80 to 100 ℃;
Figure BDA0004037107150000061
(2) Reacting compound 3 with dihydropyran in the presence of p-toluenesulfonic acid and pyridine to prepare compound 4; preferably, compound 3: dihydropyran: p-toluene sulfonic acid: molar ratio of pyridine = 1: (1.1-1.7): (0.1-0.4): (0.2-0.4), the reaction temperature is-10-0 ℃ and the reaction time is 1-3 h;
Figure BDA0004037107150000062
(3) Reacting compound 4 with trimethylborate in the presence of butyllithium gives compound 5, preferably compound 4: trimethyl borate: butyllithium molar ratio = 1: (0.4-1.5): (0.9-1.5) the reaction temperature is-20-0 ℃, and the reaction time of each step is 0.5-2 h;
Figure BDA0004037107150000071
(4) Reacting the compound 5 with the compound 6 under alkaline conditions and in a solvent to obtain a compound 7, wherein the catalyst is (bis-diphenylphosphino ferrocene) palladium dichloride; preferably Na 2 CO 3 Providing alkaline conditions, wherein the proportion is compound 5: compound 6: na (Na) 2 CO 3 : catalyst = 1: (1.1-1.9): (2-4.8): (0.0005-0.001), the reaction temperature is 60-80 ℃, the reaction time is 2-4 h, the compound 7 and pyridine p-toluenesulfonate react in the presence of methanol to obtain the compound 8, the reaction is 60-70 ℃, the reaction time is 2-4 h, and the preferential chemical reaction is carried outCompound 7: pyridine p-toluene sulfonate: methanol molar ratio = 1: (0.1-0.25): (2-4.3).
Figure BDA0004037107150000072
(5) Reacting compound 8 with dibromo substituent in alkaline solution to obtain compound 9 at 40-80 ℃ for 5-8 h, preferably reactant No. 8: dibromo substituents: the alkali is preferably Cs 2 CO 3 ＝1：(1.3～2)：(3～6)；
Figure BDA0004037107150000081
(6) Compound 9 is subjected to hydrogenation reaction under the catalysis of pd/C to prepare compound 10,
reaction temperature is 50-70 ℃, reaction time is 1-3H, reaction H 2 The pressure is 0.5-0.9 Mpa, preferably compound 9: pd/C molar ratio = 1: (0.1 to 0.2);
(7) Reacting the compound 10 with active metal source at 50-90 ℃ for 3-5 h to obtain target catalyst; preferably, compound 10: active metal source molar ratio = 1: (1.2-2.5)
Figure BDA0004037107150000082
As a preferred embodiment, the method for preparing the catalyst comprises the steps of:
(1) The substituted brominated phenol was added to a three-necked flask equipped with a reflux condenser equipped with a solvent (the solvent may be selected from toluene, tetrahydrofuran, ethylene glycol dimethyl ether, preferably toluene) (200 ml), triphenylphosphine was added to the stirred solution and the reaction was heated to 80 to 100℃for 1 to 2 hours, and the reaction mixture was cooled to room temperature. The salt was collected by vacuum filtration and the excess triphenylphosphine was rinsed off with hexane; drying the phosphine salt under vacuum for >24 hours to ensure complete removal of residual solvent and water; the phosphine salt was added to a flame-dried 3-neck round bottom flask equipped with a stir bar and equipped with a reflux condenser, the phosphine salt was suspended in toluene solvent, and nBuLi was added. After 30 minutes, aldehyde No. 1 was added under nitrogen flow, and the reaction was heated under reflux for 8 to 12 hours. And preparing the No. 3 products with different R structures.
(2) Dihydropyran was added to a dichloromethane solution (80 ml) of compound 3 at-10 to 0℃with the addition of p-toluenesulfonic acid and pyridine. After the reaction was completed, it was neutralized with 1M sodium hydroxide, extracted with dichloromethane and water, the organic phase was washed with saturated sodium chloride solution, concentrated and passed through a column (petroleum ether: dichloromethane=8:1). Product No. 4 of different R structures was obtained.
(3) Under nitrogen atmosphere, dissolving the product No. 4 in dry THF, stirring for 3-10 minutes at the temperature of minus 20-0 ℃, slowly dripping butyl lithium, reacting for 0.5-2 hours, slowly dripping trimethyl borate, taking out a reaction bottle, stirring for 0.5-2 hours at room temperature, then adding 1M hydrochloric acid solution to adjust the pH of the solution to 6, extracting with diethyl ether, drying the spin-dried solvent, and recrystallizing n-hexane to obtain a white solid compound 5.
(4) Product No. 5 and reactant No. 6 were reacted in ethylene glycol dimethyl ether (DME, 150 ml), and 2M Na was added to the reaction solution 2 CO 3 15-35 ml, nitrogen atmosphere; the reaction temperature is 60-80 ℃, the reaction time is 2-4 h, and the conventional catalyst (diphenylphosphino ferrocene) palladium dichloride (Pd (dppf) is used for catalytic reaction 2 Cl 2 ) Ethyl acetate was used after the reaction: quench the reaction with water 2:1,300 ml. Yield is good>90% by column (petroleum ether: ethyl acetate=10:1) gives product 7. Adding pyridine p-toluenesulfonate (PPTS) and methanol, reacting at 60-70 ℃ for 2-4 h, adding water into the reaction solution, fully stirring, layering, discharging the water phase, extracting for three times, and concentrating the organic phase. Concentrating the organic phase, adding 0.4L of methanol, stirring for 1h, filtering, adding methanol, crystallizing again, and purifying to obtain No. 8 THP-removed powder.
(5) Adding reactant No. 8 into 50ml of acetone, adding dibromo substituent into the mixture, adding 0.17 to 0.34mol/LCs 2 CO 3 200-350 ml of solution; the reaction temperature is 40-80 ℃ and the reaction time is 5-8 h. Cooled to room temperature, and after most of the acetone is distilled off, 200ml of CH is added 2 Cl 2 And water (1:1), the organic layer was separated and the aqueous phase was treated with CH 2 Cl 2 Extraction 3 times, removal of solvent under reduced pressure, column chromatography purification of crude product using petroleum ether: dichloro=10:1, giving product 9.
(6) Taking No. 9 product, pd/C, etOH (100 ml, ligand weight fraction 5% -9%) in a hydrogenation reactor, nitrogen substitution 3 times, reacting H 2 The pressure is 0.5-0.9 Mpa, the reaction temperature is 50-70 ℃, the reaction time is 1-3 h, after the filtration of the sintering filter head, the colorless solution is cooled to room temperature and filtered to obtain the debenzylation ligand 10.
(7) Dissolving the No. 10 ligand in 50-100 mL toluene, adding the toluene into dichloromethane (100-200 mL) containing active metal source at the reaction temperature of-15-0 ℃, stirring and dispersing, reacting for 3-5 h at 50-90 ℃, carrying out suction filtration, washing once with 200mL anhydrous n-hexane, and carrying out suction filtration to obtain the target catalyst.
The invention also provides application of the metal organic catalyst in catalyzing lactic acid monomer polycondensation and lactide synthesis. The lactide reaction steps are two steps: firstly, polycondensation reaction and secondly lactide synthesis reaction, wherein the polycondensation reaction temperature is 140-170 ℃, preferably 150-160 ℃, the reaction pressure is 30-50 hpa, and the reaction time is 0.5-3 h according to the application; and/or, in the lactide synthesis stage, the reaction temperature is 160-280 ℃, preferably 160-240 ℃, the reaction pressure is 10-25 hpa, and the reaction time is 0.5-1 h. The catalyst addition amount in the polycondensation and lactide synthesis stage is 0.01% -1% based on the mass of lactic acid. Further, the optical purity of the crude lactide obtained in the lactide reaction process under the optimal condition is 97.8-99.9%.
The invention improves the problems of reaction activity and controllability by changing the steric hindrance and activity of the central metal by using amine donors; in particular to a method for synthesizing lactide from lactic acid oligomer, which can obtain high-light pure lactide.
The invention has the following positive effects: the catalyst adopted by the invention is green and environment-friendly, can realize the polycondensation of monomers and the synthesis of cyclic esters under the conventional condition, has high-efficiency and high-controllable active polymerization, can obviously improve the optical purity index of lactide, and has the following advantages:
(1) The metal catalyst adopted by the invention catalyzes the polyester reaction, especially polylactic acid to synthesize and polymerize, and the metals zinc, calcium, magnesium and tin are cheap and easy to obtain, and zinc, calcium and magnesium are preferable as one of microelements of human body, so that the polymerization process is more environment-friendly and environment-friendly, and the synthesized polyester material has less biotoxicity, so that the synthetic polyester material has wider application prospect in the fields of biological medicine and the like;
(2) The catalyst provided by the invention has stronger stability in a high-temperature acidic environment, the molecular weight of the lactic acid prepolymer can be controlled by using the catalyst, the catalyst can reach 1000-3500 stably, the kettle residue rate in the polymerization process is reduced, the selectivity of L-lactide in crude lactide is obviously improved, and the catalyst has stronger industrial application prospect.
(3) The principle of the catalyst system capable of greatly improving the lactide synthesis process conditions in the prepolymerization and depolymerization process is as follows: the closed cyclic ether skeleton structure ensures that the cyclic ether skeleton structure is stable in high-temperature polymerization and certain acid environment, and can achieve the remarkable effects of efficiently opening pi bonds between carbon and oxygen bonds in esterification reaction, promoting the efficient formation of tetrahedron intermediate products, reducing reaction activation energy and accelerating reaction; meanwhile, the catalyst can obviously improve the selectivity of L-lactide in crude lactide through the unique space structure.
(4) The metal catalyst reaction system adopted by the invention has weak dependence on raw material L-lactic acid, high L-lactide selectivity, L-lactide content (optical purity) of more than 99 percent, and good thermal stability and acid resistance, accords with the principle of green development, and has a certain industrial application prospect.
Detailed Description
The following examples are not intended to limit the scope of the invention, and modifications and equivalent substitutions are intended to be included within the scope of the claims without departing from the spirit and scope of the invention.
Analytical methods instrument and conditions:
1. the instrument model of nuclear magnetic resonance spectrum nuclear magnetic resonance is: bruker DMX-500 (H: 500MHz,13C:125 MHz). Hydrogen spectrum sample configuration: 5-10 mg, carbon spectrum sample configuration: about 20mg, and 0.5-0.6mL of deuterated reagent are added to test the temperature at room temperature.
GPC test
GPC measurements were performed on a set of LC-20AD solvent delivery pumps, wyatt OPTILAB rEX refractive index detectors and Styragel P8512-10E3A10, P8512-10E4A10 and P8512-10E5A10 in effective molar mass ranges of 100-40000, 400-500000 and 10000 ～ 2000000, respectively. THF was used as eluent (flow rate 1ml min1, t=40c).
GC test
Agilent6820 gas chromatograph, column: OV-1 capillary column (50 m.times.0.25 mm); column temperature: (programmed heating) the initial temperature is 129 ℃, the temperature is kept for 4min, the heating rate is 0.5 ℃/min, the termination temperature is 132 ℃, and the temperature is kept for 35min; vaporization temperature: 280 ℃; detector temperature: 250 ℃; split ratio: 80:1, a step of; carrier gas: high-purity hydrogen with the pressure of 0.1MPa; tail blowing: 29ml/min; sample injection mode: split-flow sample injection; sample injection amount: 0.2uL.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The concentrations in the examples below are molar concentrations unless otherwise specified. Materials, reagents, etc. used in the following examples are all commercially available, and the main information is as follows:
2-bromomethyl-4, 6-di-tert-butylphenol: (Xinnuke catalyst Co., ltd.)
6-benzyl-1- (benzyloxy) -7-bromo-8- (tert-butyl) -4- (9H-fluoren-9-yl) -2-naphthaldehyde: (Xinnuke catalyst Co., ltd.)
4-methylenediphenyl-2- (bromomethyl) -6- (tert-butyl) phenol: (Xinnuke catalyst Co., ltd.)
1- (benzyloxy) -7-bromo-3, 5-bis (3, 5-di-tert-butylphenyl) -2-naphthaldehyde (Xinnuke catalyst Co., ltd.)
Dichloromethane: AR, ala-dine
Dihydropyran: AR, ala-dine
Pyridine: AR, ala-dine
Trimethyl borate: AR, ala-dine
Sodium chloride: AR, alemtuyether: AR, ala-dine
P-toluene sulfonic acid: AR, ala-dine
Hydrochloric acid: AR, ala-dine
Dichloro [1,1' -bis (diphenylphosphine) ferrocene]Palladium (Pd (dppf) 2 Cl 2 ): AR, aledine 1, 3-dibromopropane: AR, innochem1, 3-bis (3-bromopropyl) benzene: AR, innochem
Sncl 4 (thf) 2 ：AR,Innochem
Methyl calcium bromide: AR, innochem
Toluene: AR, innochem
Triphenylphosphine: AR, innochem
nBuLi：AR,Innochem
Palladium carbon: AR, innochem
Silica gel: AR, alfa ethylene glycol dimethyl ether of 200-300 meshes: AR, innochem ethyl acetate: AR, innochem
Petroleum ether: AR, innochem
Methanol: AR, innochem
N-hexane: AR, innochem
The synthetic route 1 is shown in the following formula:
Figure BDA0004037107150000151
[ example 2 ]
Preparation of Compound 3
2-bromomethyl-4, 6-di-t-butylphenol (0.024 mol) was charged into a three-necked flask equipped with a reflux condenser equipped with toluene (200 ml), triphenylphosphine (0.026 mol) was added to the stirred solution and the reaction was heated to 80℃for 8 hours, and the reaction mixture was cooled to room temperature. The salt was collected by vacuum filtration and the excess triphenylphosphine was rinsed off with hexane; drying the phosphine salt under vacuum for >24 hours to ensure complete removal of residual solvent and water; the phosphine salt was added to a flame-dried 3-neck round bottom flask equipped with a stir bar and equipped with a reflux condenser. The salt was suspended in a solvent and nBuLi (0.026 mol) was added, after 30 minutes, the reactant 6-benzyl-1- (benzyloxy) -7-bromo-8- (tert-butyl) -4- (9H-fluoren-9-yl) -2-naphthaldehyde (compound No. 1, 0.022 mol) was added under a stream of nitrogen and the reaction was heated to reflux for 8 hours. Product No. 3 was prepared in 75% yield.
δ H (400MHz,Chloroform-d)7.90(2H,d,J 8.5),7.73(1H,s),7.55(2H,d,J8.5),7.48(2H,d,J 7.5),7.40(2H,t,J 7.5),7.38(3H,d,J 8.5),7.32(1H,m)7.28(4H,m),7.23(2H,d,J 7.5),7.20(1H,t,J 7.5),7.16(1H,s),7.06(1H,s),7.05(2H,d,J 15.1),5.84(1H,s),5.16(3H,s),4.10(2H,s),1.48(9H,s),1.40(9H,s),1.35(9H,s).
Preparation of Compound 5
To a dichloromethane solution (80 ml) of the product 3 (0.018 mol) at-10℃was added dihydropyran (0.0194 mol) while p-toluenesulfonic acid (0.0034 mol) and pyridine (0.0034 mol) were added. After completion of the reaction for 1h, it was neutralized with 1M sodium hydroxide and extracted with dichloromethane and water, the organic phase was washed with saturated sodium chloride solution, concentrated and passed through a column (petroleum ether: dichloromethane=8:1). Product No. 4 (0.017 mol) was obtained in 97% yield.
Under nitrogen atmosphere, product No. 4 (0.017 mol) was dissolved in 60ml of dry THF, stirred at-20 ℃ for 3 minutes, butyllithium 2.2M (7.7 ml) was slowly added dropwise, trimethyl borate (0.87 ml) was slowly added dropwise after 2h of reaction, the reaction flask was taken out and stirred at room temperature for 0.5h, then 1M hydrochloric acid solution was added to adjust the pH of the solution to 6, extracted with diethyl ether, dried spin-dried solvent, and n-hexane recrystallized to give a white solid with a yield of 85% (0.0145 mol).
δ H (400MHz,Chloroform-d)7.90(2H,d,J 8.5),7.68(1H,s),7.55(2H,d,J8.5),7.48(2H,d,J 7.5),7.40(2H,t,J 7.5),7.38(2H,d,J 8.5),7.32(2H,m)7.28(4H,m),7.23(3H,d,J 7.5),7.20(1H,t,J 7.5),7.05(2H,d,J 15.1),5.80(1H,m),5.16(3H,s),4.10(2H,s),4.02(2H,s),3.74(1H,dd,J 12.4,7.1),3.64(1H,m),1.91(2H,m),1.78(2H,m),1.57(2H,m),1.48(9H,s),1.40(9H,s),1.35(9H,s).
Preparation of Compound 8
To a solution of product No. 5 (0.015 mol) and reactant No. 6' (0.016 mol) in ethylene glycol dimethyl ether (DME, 150 ml) was added in sequence the catalyst Pd (dppf) 2 Cl 2 (0.0000075mol)，2M Na 2 CO 3 15 ml, nitrogen atmosphere; reaction temperature 60 ℃, reverse reactionThe reaction time is 2h, the catalytic reaction is conventional, and ethyl acetate is used after the reaction is finished: the reaction was quenched with water 2:1,300 ml. Yield is good>90% was passed through a column (petroleum ether: ethyl acetate=10:1) to give product 7 (0.0123 mol). Pyridine p-toluenesulfonate (PPTS) (0.00123 mol) and methanol (0.0246 mol) were then added thereto, followed by reaction at 60℃for 2 hours. The reaction solution was added with 300ml of water, stirred sufficiently, layered, the aqueous phase was drained, extracted three times with 200ml of ethyl acetate, the organic phase was concentrated, stirred with 0.4L of methanol for 2 hours, filtered, and recrystallized and purified with methanol to give product No. 8 (0.011 mol), yield 73.3%.
δ H (400MHz,Chloroform-d)9.58(1H,s),7.93(1H,s),7.90(2H,d,J 8.5),7.55(2H,d,J 8.5),7.50(1H,s),7.48(2H,d,J 7.5),7.43(1H,s),7.40(2H,t,J 7.5),7.38(2H,d,J 8.5),7.32(1H,m),7.28(6H,m),7.23(4H,d,J 7.5),7.20(2H,t,J7.5),7.17(1H,s),7.16(1H,s),7.06(1H,s),7.05(2H,d,J 15.1),5.84(1H,s),5.16(3H,s),4.10(2H,s),4.07(2H,s),1.48(9H,s),1.40(18H,s),1.35(9H,s).
Preparation of Compound 9
Taking reactant No. 8 (0.011 mol) into 50ml of acetone, taking dibromo substituent (T) 1 =1, 3-dibromopropane, 0.015mol, t 2 =1, 3-bis (3-bromopropyl) benzene, 0.015 mol), 0.17mol/L Cs was added 2 CO 3 200ml of solution; the reaction temperature was 40℃for 5 hours. Cooled to room temperature, and after most of the acetone is distilled off, 200ml of CH is added 2 Cl 2 And water (1:1), the organic layer was separated and the aqueous phase was treated with CH 2 Cl 2 Extraction 3 times, removal of solvent under reduced pressure, column chromatography purification of crude product using petroleum ether: dichloro=10:1, giving product 9 (0.0085 mol), 78% yield.
δ H (400MHz,Chloroform-d)7.93(2H,s),7.90(4H,d,J 8.5),7.55(4H,d,J8.5),7.50(2H,s),7.48(4H,d,J 7.5),7.43(2H,s),7.40(4H,t,J 7.5),7.38(4H,d,J8.5),7.32(2H,m),7.28(12H,m),7.23(8H,d,J 7.5),7.20(5H,t,J 7.5),7.17(2H,s),7.16(2H,s),7.06(2H,s),7.05(4H,d,J 15.1),7.02(2H,d,J 7.5),6.96(1H,s),5.16(6H,s),4.12(4H,d,J 7.1),4.10(4H,s),4.09(4H,m),4.07(4H,s),2.70(4H,d,J 7.1),2.20(2H,m),1.98(4H,m),1.48(18H,s),1.40(36H,s),1.35(18H,s).
9： 13 C NMR(100MHz,chloroform-d)δ154.72,154.49,152.68,144.73,143.92,143.30,142.70,141.73,140.36,139.28,139.08,137.75,136.91,136.10,136.03,135.14,134.90,134.85,131.53,130.93,130.71,129.71,129.59,129.20,128.99,128.91,128.89,128.82,128.60,128.37,128.35,128.34,128.24,128.01,127.93,127.89,127.75,127.48,127.20,127.12,126.91,126.33,125.02,124.77,121.99,119.75,74.95,72.25,69.62,51.26,42.49,41.05,36.57,35.25,34.91,32.75,31.84,31.36,30.41,30.29,29.42.
Preparation of catalyst 10
Taking No. 9 ligand (0.0085 mol), pd/C (0.0009 mol), etOH (100 ml) in a hydrogenation reactor, nitrogen substitution 3 times, reacting H 2 The pressure is 0.5Mpa, the reaction temperature is 50 ℃ and the reaction time is 3 hours, after the filtration by a sintering filter head, the colorless solution is cooled to room temperature and filtered to obtain debenzylated ligand (0.0076 mol) which is further dissolved in 50ml toluene, and the active metal source Sncl is added at the reaction temperature of minus 15 DEG C 4 (thf) 2 (0.0091 mol) in dichloromethane (100 mL), stirring and dispersing, reacting at 50 ℃ for 3h, suction filtering, washing with 200mL anhydrous n-hexane once, suction filtering to obtain the target catalyst 10 (0.006 mol)
δ H (400MHz,Chloroform-d)7.93(2H,s),7.90(4H,d,J 8.5),7.55(4H,d,J8.5),7.50(2H,s),7.43(2H,s),7.38(4H,d,J 8.5),7.28(12H,m),7.23(8H,d,J7.5),7.20(5H,t,J 7.5),7.17(2H,s),7.16(2H,s),7.06(2H,s),7.05(4H,d,J 15.1),7.02(2H,d,J 7.5),6.96(1H,s),5.16(2H,s),4.12(4H,d,J 7.1),4.10(4H,s),4.09(4H,m),4.07(4H,s),2.70(4H,d,J 7.1),2.20(2H,m),1.98(4H,m),1.48(18H,s),1.40(36H,s),1.35(18H,s).
10： 13 C NMR(100MHz,chloroform-d)δ154.72,154.49,151.51,144.73,143.83,143.30,142.70,141.73,140.36,139.32,139.08,137.75,136.91,135.26,135.24,135.14,134.93,132.04,131.65,130.71,129.72,129.20,129.18,128.99,128.89,128.82,128.34,128.24,128.01,127.89,127.82,127.75,127.48,127.20,127.12,126.91,126.48,126.33,125.02,123.74,123.62,119.75,72.25,69.62,51.30,42.49,41.05,36.54,35.25,34.91,32.75,31.87,31.36,30.41,30.29,29.42.
The synthetic route 2 is shown in the following formula:
Figure BDA0004037107150000201
[ example 2 ]
Preparation of Compound 3'
4-methylenediphenyl-2- (bromomethyl) -6- (t-butyl) phenol (0.044 mol) was charged into a three-necked flask equipped with a reflux condenser equipped with toluene (200 ml), triphenylphosphine (0.088 mol) was added to the stirred solution and the reaction was heated to 100℃for 2 hours, and the reaction mixture was cooled to room temperature. The salt was collected by vacuum filtration and the excess triphenylphosphine was rinsed off with hexane; drying the phosphine salt under vacuum for >24 hours to ensure complete removal of residual solvent and water; the phosphine salt was added to a neck round bottom flask equipped with a stir bar and equipped with a reflux condenser. The salt was suspended in a solvent and nBuLi (0.066 mol) was added, after 2h, the reactant 1- (benzyloxy) -7-bromo-3, 5-bis (3, 5-di-tert-butylphenyl) -2-naphthaldehyde (1' substance, 0.066 mol) was added under nitrogen flow and the reaction was heated to reflux for 2 h. Product number 3' (0.033) was prepared in 75% yield.
δ H (400MHz,Chloroform-d)8.54(1H,s),7.73(4H,s),7.55(2H,s),7.48(3H,d,J 7.5),7.45(1H,s),7.40(2H,t,J 7.5),7.31(5H,m),7.21(2H,m),7.14(4H,d,J 7.5),7.05(2H,d,J 15.1),6.93(2H,s),5.84(1H,s),5.41(1H,s),5.16(2H,s),1.40(9H,s),1.32(36H,s).
Preparation of Compound 5'
Dihydropyran (0.0561 mol) was added to a dichloromethane solution (80 ml) of the product 3' (0.033 mol) at 0℃while p-toluenesulfonic acid (0.0132 mol) and pyridine (0.0132 mol) were added. After the reaction was completed, it was neutralized with 1M sodium hydroxide, extracted with dichloromethane and water, the organic phase was washed with saturated sodium chloride solution, concentrated and passed through a column (petroleum ether: dichloromethane=8:1). Product No. 4 (0.032 mol) was obtained in 97% yield.
Under nitrogen atmosphere, the product No. 4 (0.032 mol) was dissolved in 60ml of dry THF, stirred at 0deg.C for 10 min, butyllithium 2.2M (21.81 ml) was slowly added dropwise, after 2h of reaction, trimethylborate (18.3 mol/L,2.63 ml) was slowly added dropwise, the reaction flask was taken out and stirred at room temperature for 2h, then 1M hydrochloric acid solution was added to adjust the pH of the solution to 6, extracted with diethyl ether, dried spin-dry solvent, and recrystallized from n-hexane to give a white solid with 5' yield of 85% (0.027 mol).
δ H (400MHz,Chloroform-d)8.54(1H,s),7.73(4H,s),7.55(2H,s),7.48(3H,d,J 7.5),7.45(1H,s),7.40(2H,t,J 7.5),7.31(5H,m),7.21(2H,m),7.14(4H,d,J7.5),7.05(2H,d,J 15.1),6.93(2H,s),5.80(1H,m),5.41(1H,s),5.16(2H,s),4.02(2H,s),3.74(1H,dd,J 12.4,7.1),3.64(1H,m),1.91(2H,m),1.78(2H,m),1.69(2H,m),1.57(2H,m),1.40(9H,s),1.32(36H,s).
Preparation of Compound 8'
To a solution of product No. 5 (0.027 mol) and reactant No. 6 (2- (4- (anthracene-9-yl) -2-bromophenoxy) tetrahydro-2H-pyran, 0.0275 mol) in ethylene glycol dimethyl ether (DME, 150 ml) was added in sequence the catalyst Pd (dppf) 2 Cl 2 (0.0000027mol)，2M Na 2 CO 3 15 ml, nitrogen atmosphere; the reaction temperature is 80 ℃, the reaction time is 4 hours, the catalytic reaction is conventional, and ethyl acetate is used after the reaction is finished: quench the reaction with water 2:1,300 ml. Yield is good>90% was passed through a column (petroleum ether: ethyl acetate=10:1) to give product 7' (0.0243 mol). Pyridine p-toluenesulfonate (PPTS) (0.00625 mol) and methanol (0.1044 mol) were then added and reacted at 70℃for 4 hours. The reaction mixture was stirred with 300ml of water, separated into layers, the aqueous phase was drained, extracted three times with 200ml of ethyl acetate, the organic phase was concentrated, stirred with 0.4L of methanol for 1h, filtered, and recrystallized and purified with methanol to give product No. 8 (0.0198 mol) in 73.3% yield.
δ H (400MHz,Chloroform-d)8.39(1H,s),8.33(1H,s),8.18(2H,d,J 8.7),8.03(2H,d,J 8.7),7.94(1H,s),7.73(4H,s),7.67(1H,s),7.58(1H,s),7.55(2H,d,J 7.5),7.48(3H,m),7.43(4H,m),7.40(2H,t,J 7.5),7.31(5H,m),7.21(3H,m),7.14(4H,d,J 7.5),7.05(2H,d,J 15.1),6.93(2H,s),5.84(1H,s),5.41(1H,s),5.16(2H,s),4.58(1H,s),3.63(2H,t,J 7.1),2.87(2H,t,J 7.1),1.40(9H,s),1.32(36H,s).
Preparation of Compound 9'
The reaction product No. 8 (0.0198 mol) was taken up in 50ml of acetone and dibromo (T) 1 = (1, 11-dibromododecane-4)7-diyl) diphenyl, 0.026mol, T 2 =1, 3-bis (4-bromobutyl) cyclohexane, 0.027 mol), 0.34mol/L Cs was added 2 CO 3 350ml of solution; the reaction temperature was 80℃for 8 hours. Cooled to room temperature, and after most of the acetone is distilled off, 200ml of CH is added 2 Cl 2 And water (1:1), the organic layer was separated and the aqueous phase was treated with CH 2 Cl 2 Extraction 3 times, removal of solvent under reduced pressure, column chromatography purification of crude product using petroleum ether: dichloro=10:1, giving product 9' (0.015 mol), 78% yield.
δ H (400MHz,Chloroform-d)8.39(2H,s),8.33(2H,s),8.18(4H,d,J 8.7),8.03(4H,d,J 8.7),7.94(2H,s),7.73(8H,s),7.67(2H,s),7.58(2H,s),7.55(4H,d,J 7.5),7.48(6H,m),7.43(8H,m),7.40(4H,t,J 7.5),7.31(10H,m),7.28(4H,m),7.25(4H,m),7.21(8H,m),7.14(8H,d,J 7.5),7.05(4H,d,J 15.1),6.93(4H,s),5.41(2H,s),5.16(4H,s),4.02(4H,m),3.63(4H,t,J 7.1),3.53(4H,m),2.87(4H,t,J 7.1),2.57(2H,m),1.92(4H,m),1.85(2H,m),1.82(4H,m),1.71(6H,m),1.56(4H,m),1.45(4H,m),1.42(6H,m),1.40(18H,s),1.36(6H,m),1.32(72H,s).
13 C NMR(100MHz,chloroform-d)δ155.11,152.79,152.03,151.86,146.87,146.79,143.52,139.00,138.73,137.60,137.34,137.05,136.69,136.62,136.49,136.03,135.99,135.91,135.52,133.42,132.92,131.87,130.93,130.30,129.79,129.62,128.90,128.85,128.82,128.81,128.60,128.40,128.37,127.87,127.53,127.34,127.31,127.18,127.16,127.14,127.07,126.88,126.79,126.26,125.73,125.58,125.44,124.47,123.56,123.21,121.71,121.34,74.95,72.53,72.46,71.02,68.08,56.68,46.36,46.04,38.31,35.32,34.93,34.90,34.67,33.77,33.60,33.53,32.83,32.66,31.27,30.41,29.46,29.21,27.24,25.17,24.64,22.65.
Preparation of catalyst 10'
Taking No. 9 ligand (0.015 mol), pd/C (0.0003 mol), etOH (100 ml) in a hydrogenation reactor, nitrogen substitution 3 times, reaction H 2 The pressure is 0.9mpa, the reaction temperature is 70 ℃ and the reaction time is 3h, after the filtration by a sintering filter head, the colorless solution is cooled to room temperature and filtered to obtain debenzylated ligand (0.0133 mol), the debenzylated ligand is further dissolved in 50ml toluene, the reaction temperature is 0 ℃ and the active metal source is addedMethyl calcium bromide (0.0333 mol) in methylene chloride (200 mL), stirring and dispersing, reacting for 5h under the protection of nitrogen at 90 ℃, then carrying out suction filtration, washing once with 200mL of anhydrous n-hexane, and carrying out suction filtration to obtain the target catalyst 10' (0.013 mol)
δ H (400MHz,Chloroform-d)8.39(1H,s),8.33(1H,s),8.18(2H,d,J 8.7),8.03(2H,d,J 8.7),7.94(1H,s),7.73(4H,s),7.67(1H,s),7.58(1H,s),7.55(2H,d,J 7.5),7.48(1H,s),7.43(4H,m),7.31(4H,m),7.28(2H,m),7.25(2H,m),7.21(4H,m),7.14(4H,d,J 7.5),7.05(2H,d,J 15.1),6.93(2H,s),5.41(1H,s),4.02(2H,m),3.63(2H,t,J 7.1),3.53(2H,m),2.87(2H,t,J 7.1),2.57(1H,m),2.12(3H,s),1.92(2H,m),1.85(1H,m),1.82(2H,m),1.71(2H,m),1.56(2H,m),1.45(2H,m),1.42(3H,m),1.40(9H,s),1.36(3H,m),1.32(36H,s).
13 C NMR(100MHz,chloroform-d)δ155.11,152.23,152.03,151.86,146.87,146.79,143.52,139.28,138.73,137.75,137.34,136.99,136.80,136.70,136.69,135.91,135.52,134.39,132.92,131.87,131.36,130.02,129.79,129.62,129.52,128.94,128.85,128.82,128.81,128.60,128.40,127.83,127.53,127.29,127.18,127.16,127.14,127.07,126.88,126.79,126.42,126.26,125.73,124.47,123.56,123.37,123.21,121.60,120.29,72.53,72.46,71.02,68.08,56.68,46.36,46.04,38.31,35.32,34.93,34.90,34.67,33.77,33.60,33.53,32.83,32.66,31.27,30.41,29.46,29.21,27.24,25.17,24.64,22.65,20.72.
[ example 3 ]
Ti series Metal catalyst Synthesis procedure similar to example 1, ligand No. 9 (0.0085 mol), pd/C (0.0009 mol), etOH (100 ml) was taken and placed in a hydrogenation reactor, nitrogen was replaced 3 times, reaction H 2 The pressure is 0.9Mpa, the reaction temperature is 50 ℃ and the reaction time is 3 hours, after the filtration by a sintering filter head, the colorless solution is cooled to room temperature and filtered to obtain debenzylated ligand (0.0076 mol) which is further dissolved in 50ml toluene, the reaction temperature is 15 ℃ below zero, and Ticl containing active metal source is added 4 (thf) 2 (0.0094 mol) in methylene chloride (100 mL), stirring and dispersing, reacting at 60 ℃ for 1h, then suction filtering, washing with 200mL of anhydrous n-hexane once, suction filtering to obtain the target catalyst 10 (0.006 mol)
[ example 4 ]
The synthesis method of the zirconium-based metal catalyst is similar to that of example 2, and the final active metal complexation is to take 9' ligand (0.015 mol), pd/C (0.00018 mol), etOH (100 ml) in a hydrogenation reactor, and nitrogen replacement is carried out for 3 times, reaction H 2 The reaction temperature is 90 ℃ under the pressure of 0.5mpa and the reaction time is 3h, after the filtration of a sintering filter head, the colorless solution is cooled to room temperature and filtered to obtain debenzylated ligand (0.0133 mol), the debenzylated ligand is further dissolved in 50mL toluene, methylene dichloride (200 mL) containing active metal source methyl calcium bromide (0.0019 mol) is added at the reaction temperature of 0 ℃ for stirring and dispersing, the reaction is carried out for 5h under the protection of nitrogen at the temperature of 40 ℃, and then the suction filtration is carried out, the washing is carried out once by 200mL anhydrous n-hexane, and the suction filtration is carried out to obtain the target catalyst 10' (0.013 mol)
Example 5 the condensation reaction and lactide synthesis reaction are as follows: 300g of an aqueous D, L-lactic acid solution (87 wt%) was fed into a 1L prepolymerization reactor and dehydrated to a water content at a temperature of 50hpa at 160℃<0.1 percent of SnL which is a prepared catalyst is added with 0.286g under the protection of nitrogen 2 (example 1), the system pressure is 30hpa, the reaction is carried out for 60min, the molecular weight of the lactic acid oligomer obtained by the prepolymerization reaction is distributed at about 1500, and the distribution coefficient is 1.21-1.27; finally, taking out the pre-polymerization reaction liquid, placing the pre-polymerization reaction liquid in a depolymerization reaction kettle, heating to 240 ℃, reacting for 30min under the system pressure of 25hpa, and obtaining crude lactide with the optical purity of 99.7%.
Example 6 the condensation reaction and lactide synthesis reaction are as follows: 300g of an aqueous D, L-lactic acid solution (87% by weight) was fed into a 1L prepolymerization reactor and dehydrated to a water content at 50hpa at a temperature of 150℃<0.1% under nitrogen, 0.292g of the prepared catalyst CaL was added 2 (example 2), the system pressure is 25hpa, the reaction is carried out for 60min, the molecular weight of the lactic acid oligomer obtained by the prepolymerization reaction is distributed at about 1500, and the distribution coefficient is 1.23-1.29; finally, taking out the pre-polymerization reaction liquid, placing the pre-polymerization reaction liquid in a depolymerization reaction kettle, heating to 200 ℃, reacting for 1h under the system pressure of 25hpa, and obtaining crude lactide with the optical purity of 99.6%.
Example 7 the condensation reaction and lactide synthesis reaction are as follows: 300g of an aqueous D, L-lactic acid solution (87 wt%) was fed into a 1L prepolymerization reactor and dehydrated to a water content at 100hpa at a temperature of 150℃<0.1％Under the protection of nitrogen, 0.295g of prepared catalyst TiL is added 2 (example 3), the system pressure is 25hpa, the reaction is carried out for 3 hours, the molecular weight of the lactic acid oligomer obtained by the prepolymerization reaction is distributed at about 1500, and the distribution coefficient is 1.29; finally, taking out the pre-polymerization reaction liquid, placing the pre-polymerization reaction liquid in a depolymerization reaction kettle, heating to 280 ℃, reacting for 2 hours under the system pressure of 25hpa, and obtaining crude lactide with the optical purity of 99.3%.
Example 8 the condensation reaction and lactide synthesis reaction are as follows: 300g of an aqueous D, L-lactic acid solution (87% by weight) was fed into a 1L prepolymerization reactor and dehydrated to a water content at 50hpa at a temperature of 150℃<0.1 percent of ZrL, 0.304g of the prepared catalyst is added under the protection of nitrogen 2 (example 4), the system pressure is 25hpa, the reaction is carried out for 60min, the molecular weight of the lactic acid oligomer obtained by the prepolymerization reaction is distributed at about 1500, and the distribution coefficient is 1.24; finally, taking out the pre-polymerization reaction liquid, placing the pre-polymerization reaction liquid in a depolymerization reaction kettle, heating to 260 ℃, reacting for 1h under the system pressure of 25hpa, and obtaining crude lactide with the optical purity of 99.4%.
The condensation reaction and lactide synthesis reaction are as follows: 300g of D, L-lactic acid aqueous solution (87 wt%) is added into a 1L pre-polymerization reactor, the system temperature is raised to 150 ℃ and 50hpa, the water content is dehydrated to be less than 0.1%, 0.294g of stannous octoate which is a prepared catalyst is added under the protection of nitrogen, the molecular weight distribution of lactic acid oligomer obtained by the pre-polymerization reaction is about 1500, and the distribution coefficient is 1.39-1.51; finally, taking out the pre-polymerization reaction liquid, placing the pre-polymerization reaction liquid in a depolymerization reaction kettle, heating to 260 ℃, reacting for 30min under the system pressure of 25hpa, and obtaining crude lactide with the optical purity of 49.6%.
It should be understood that the above-described specific embodiments are only for explaining the present invention and are not intended to limit the present invention. Obvious variations or modifications which are extended by the spirit of the present invention are still within the scope of the present invention.

Claims (9)

1. The aryloxy cyclic ether skeleton metal complex catalyst is characterized by taking a formula I as a ligand, wherein the structural formula of the catalyst is as follows:
Figure FDA0004037107140000011
the catalyst takes II-IVA, IIB and transition metal as active components M, preferably one or more of Sn, zn, ca, ti, zr, more preferably Sn, ca, ti, zr; r is R 1 ～R 12 Selected from hydrogen, halogen or any one of the following groups: c (C) 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkyl oxy, C 6-14 Aryl, C 6-14 An aryloxy group; t (T) 1 And T 2 Each independently selected from divalent hydrocarbon groups having 1 to 20 atoms other than hydrogen, or inert substituted derivatives of the above; x is a monovalent substituent having 1 to 20 atoms other than hydrogen, or two X groups together are a divalent substituent having 1 to 40 atoms other than hydrogen.
2. The catalyst of claim 1 wherein R 1～ R 12 Any one selected from substituted methyl, substituted phenyl, dibenzo ring, alkyl, fluorenyl and anthryl; preferably t-butyl, 3, 5-di-t-butylphenyl, benzyl, fluorenyl, benzhydryl.
3. The catalyst according to claim 1 or 2, characterized in that T 1 、T 2 Each independently selected from divalent hydrocarbon groups having 3 to 10 atoms; preferably, T1 and T2 are each 1, 3-propanediyl, 1, 4-butanediyl, 2, 4-pentanediyl, 1, 5-pentanediyl, 1, 3-di (propylene) phenyl, and methylene trans-1, 2-cyclohexanediyl.
4. A catalyst according to any one of claims 1 to 3, wherein each X is independently selected from a monovalent substituent group having 1 to 10 atoms, or two X groups together are a divalent substituent group having 1 to 20 atoms, not counting hydrogen; preferably, X is halogen, methyl, benzyl; more preferably, X is chloro, methyl or benzyl.
5. The method for producing a catalyst according to any one of claims 1 to 4, comprising the steps of:
(1) Reacting a substituted brominated phenol, triphenylphosphine, aldehyde No. 1 in the presence of n-butyllithium to produce product No. 3, preferably a substituted brominated phenol: aldehyde No. 1: triphenylphosphine: n-butyllithium molar ratio = 1: (1.1-1.5): (1.1-2): (1.1 to 1.5), reaction temperature: the reaction time is 8 to 12 hours at the temperature of 80 to 100 ℃;
Figure FDA0004037107140000021
(2) Reacting compound 3 with dihydropyran in the presence of p-toluenesulfonic acid and pyridine to prepare compound 4; preferably, compound 3: dihydropyran: p-toluene sulfonic acid: molar ratio of pyridine = 1: (1.1-1.7): (0.1-0.4): (0.2-0.4), the reaction temperature is-10-0 ℃ and the reaction time is 1-3 h;
Figure FDA0004037107140000031
(3) Reacting compound 4 with trimethylborate in the presence of butyllithium gives compound 5, preferably compound 4: trimethyl borate: butyllithium molar ratio = 1: (0.4-1.5): (0.9-1.5) the reaction temperature is-20-0 ℃, and the reaction time of each step is 0.5-2 h;
Figure FDA0004037107140000032
(4) Reacting the compound 5 with the compound 6 under alkaline conditions and in a solvent to obtain a compound 7, wherein the catalyst is (bis-diphenylphosphino ferrocene) palladium dichloride; the compound 7 is reacted with pyridine p-toluenesulfonate in the presence of methanol to obtain compound 8, preferably at 60-70 ℃ for 2-4 h, compound 7: pyridine p-toluene sulfonate: methanol molar ratio = 1: (0.1-0.25): (2-4.3);
Figure FDA0004037107140000041
(5) Reacting compound 8 with dibromo-substituent in alkaline solution to obtain compound 9, preferably at 40-80 ℃ for 5-8 h, reactant No. 8: dibromo substituents: the alkali is preferably Cs 2 CO 3 ＝1：(1.3～2)：(3～6)；
Figure FDA0004037107140000042
(6) Compound 9 is subjected to hydrogenation reaction under the catalysis of pd/C to prepare compound 10,
preferably, the reaction temperature is 50-70 ℃, the reaction time is 1-3H, and the reaction H 2 The pressure is 0.5-0.9 Mpa, compound 9: pd/C molar ratio = 1: (0.1 to 0.2);
(7) Reacting the compound 10 with active metal source at 50-90 ℃ for 3-5 h to obtain target catalyst; preferably, compound 10: active metal source molar ratio = 1: (1.2-2.5)
Figure FDA0004037107140000051
6. The method according to claim 5, wherein in the step (4), na 2 CO 3 Providing alkaline conditions, wherein the proportion is compound 5: compound 6: na (Na) 2 CO 3 : catalyst = 1: (1.1-1.9):
(2-4.8): (0.0005-0.001), the reaction temperature is 60-80 ℃ and the reaction time is 2-4 h.
7. Use of the catalyst according to any one of claims 1-4 or the catalyst prepared by the preparation method of claim 5 or 6 for catalyzing polycondensation of lactic acid monomers, lactide synthesis.
8. Use according to claim 7, characterized in that the polycondensation reaction temperature is 140-170 ℃, preferably 150-160 ℃, the reaction pressure is 30-50 hpa, the reaction time is 0.5-3 h; and/or, in the lactide synthesis stage, the reaction temperature is 160-280 ℃, preferably 160-240 ℃, the reaction pressure is 10-25 hpa, and the reaction time is 0.5-1 h.
9. Use according to claim 7 or 8, characterized in that the catalyst addition in the polycondensation and lactide synthesis stage is 0.01% to 1% by mass of lactic acid.
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