CN114891035A - Difunctional tetranuclear metal lithium complex and preparation method and application thereof - Google Patents
Difunctional tetranuclear metal lithium complex and preparation method and application thereof Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 26
- 239000002184 metal Substances 0.000 title claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000010668 complexation reaction Methods 0.000 title description 2
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 24
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- 238000000034 method Methods 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000007857 degradation product Substances 0.000 claims abstract description 6
- 230000015556 catabolic process Effects 0.000 claims abstract description 5
- 238000006731 degradation reaction Methods 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 56
- 230000001588 bifunctional effect Effects 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
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- 239000000178 monomer Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 150000004696 coordination complex Chemical class 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 claims description 6
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 6
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 claims description 6
- 229940057867 methyl lactate Drugs 0.000 claims description 6
- HGHPGHVNTQSTNM-UHFFFAOYSA-N quinolin-2-ylmethanamine Chemical compound C1=CC=CC2=NC(CN)=CC=C21 HGHPGHVNTQSTNM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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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 Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/14—Other (co) polymerisation, e.g. of lactides, epoxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/11—Lithium
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- C08G2230/00—Compositions for preparing biodegradable polymers
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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Abstract
The invention discloses a difunctional tetranuclear metal lithium complex, a preparation method and application thereof, and belongs to the technical field of complex synthesis. The method for applying the difunctional metal lithium complex to catalyzing lactide polymerization and polylactide degradation comprises the following steps: mixing and stirring lactide and a catalyst according to a proportion, and carrying out ring-opening polymerization reaction under the conditions of no water, no oxygen and gas protection to finally obtain polylactide; the degradation product of the polylactide can be obtained in the room temperature environment after the methanol is added into the system. The method has the advantages of simple steps, strong controllability and low cost, can obtain the biodegradable polyester material with better performance, and can degrade the scrapped polyester material into a green solvent. The degradable plastic obtained by the invention meets the requirement of green development and has wide application prospect. The characteristics of high controllability, high activity and multiple functions are realized in the polymerization process, and the polyester material can be chemically recycled into high value-added chemicals so as to achieve the effect of recycling.
Description
Technical Field
The invention belongs to the technical field of complex synthesis, and particularly relates to a bifunctional tetranuclear lithium metal complex, and a preparation method and application thereof.
Background
Since the first commercial production of polyethylene in the 30's of the 20 th century, many high molecular polymers have become an integral part of modern life, widely used for polyester, polyolefin, silicone of fibers and other applications for engineering and rubber. Although these materials are widely used for their excellent mechanical properties and durability, their long degradation time has raised global concern for increasingly severe environmental pollution as a result of the processing of these plastic articles. The european union has decided to ban or restrict the use of certain consumer products containing persistent, non-degradable and toxic substances. The < Chinese 21 st century agenda >' established by the government of China indicates that: "the way of sustainable development is the self-demand and inevitable choice of China in the future and the next century development". Therefore, we are looking for greener alternatives and focus on the study of material degradation.
Furthermore, with the rapid depletion of fossil feedstocks on earth, the development of alternative biodegradable polymers (preferably from sustainable resources) becomes necessary. At present, Polylactide (PLA) has become the leading position in the field due to its excellent biodegradability and biocompatibility, making it an environmentally friendly alternative to traditional petrochemical synthetic polymers. The polymerization of lactide has been studied to date in a variety of catalysts available, including main group metal complexes, transition metals, rare earth metals, alkali/alkaline earth metals, and non-metal organic catalysts. PLA is generally synthesized by metal-catalyzed ring-opening polymerization (ROP), and the current problem is how to modify degradable material catalysts and polyester materials, and expand the application range of cyclic ester materials, such as being applied to the fields of biomedicine, such as sutures and drug carriers, commodity packaging materials, gene delivery carriers, and the like. At the same time, the recycling of plastics is also challenging, and most of the plastics are still dumped in landfills or other dumping ways. For unreasonable recycling, innovation and alternative strategies need to be developed, plastic wastes can be economically converted into valuable products, and effective recycling is achieved to meet the difficult challenges of modern society.
In order to realize circular economy, catalysts are further developed, and multifunctional catalysis is realized, so that the method is an effective method for obtaining the biodegradable material PLA with more excellent performance, and is also a key for solving the problem of chemical degradation of the scrapped degradable plastic PLA.
Disclosure of Invention
Aiming at the problems that part of the existing polyester catalysts have biotoxicity and poor polymerization controllability, and most of the catalysts cannot realize the depolymerization of polylactide, the invention provides a bifunctional tetranuclear metal lithium complex and a preparation method and application thereof.
The invention aims to provide a bifunctional tetranuclear metal lithium complex catalyst which has the advantages of less side reaction, high conversion rate, good selectivity and dual catalytic functions, and a synthesis method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a bifunctional tetranuclear lithium metal complex, the structural formula of which is:
the crystal of the difunctional tetranuclear metal lithium complex belongs to a monoclinic system, a C2/C space group, and the unit cell parameters are as follows:
α＝90(13)°，β＝104.358(5)°，γ＝90°。
a preparation method of a bifunctional tetranuclear metal lithium complex comprises the following synthetic route:
the method comprises the following steps: dissolving silicon-bridged aminoquinaldine in diethyl ether, dropwise adding n-butyllithium with the same molar weight as the silicon-bridged aminoquinaldine while stirring at 0 ℃ under anhydrous and oxygen-free conditions, then recovering to room temperature, continuously stirring for 3-8 h, standing after the reaction is finished, filtering to remove filtrate, washing and purifying with n-hexane for multiple times, concentrating the filtrate, and crystallizing to obtain the bifunctional tetranuclear lithium metal complex.
Further, the specific method of the crystallization is to dissolve the obtained solid product in tetrahydrofuran, concentrate the solid product, and place the solid product at a low temperature of-30 ℃ under the protection of nitrogen to separate out crystals.
Further, the concentration of n-butyllithium was 2.5 mol/L.
An application of a bifunctional tetranuclear metal lithium complex in lactide polymerization and polylactide degradation.
Further, lactide polymerization product is obtained in methylene dichloride solvent under the condition of not needing cocatalyst or under the condition of co-catalysis with cocatalyst benzyl alcohol.
Further, lactide is polymerized in an inert atmosphere at the room temperature of 20-30 ℃.
Further, the molar ratio of the lactide to the bifunctional tetranuclear metal lithium complex is 100: 1-400: 1.
Further, the degradation product of polylactide is obtained in methylene chloride solvent under the condition of co-catalysis with methanol.
Further, the specific method for obtaining the degradation product of the polylactide in the dichloromethane solvent under the co-catalysis condition with the methanol is as follows: preparing an oil bath with the temperature stable at 20-30 ℃; accurately weighing the complex under an inert atmosphere, adding the complex into a bottle A with a stirrer, and adding dichloromethane until the dichloromethane is completely dissolved; preparing a bottle B under the same condition, adding the bottle B according to the molar ratio of lactide to the difunctional tetranuclear metal lithium complex of 100:1, and dissolving the bottle B in dichloromethane; adding the mixed monomer in the bottle B into the bottle A with constant rotating speed, and simultaneously monitoring in real time to ensure complete polymerization; then polylactide and methanol were added at a molar ratio of 10:1 at 600 rpm; sampling every 10min 1 HNMR one-time, real-time monitoring of depolymerization reactionIt should wait for 1h before the polylactide is completely degraded to methyl lactate.
Compared with the prior art, the invention has the following advantages:
the difunctional tetranuclear metal lithium complex as a catalyst has the characteristics of no toxicity, high efficiency, controllability and the like, the monomer conversion rate in the polymerization process is higher than 90%, and the polylactide with controllable molecular weight and narrow molecular weight distribution can be obtained. Meanwhile, the biodegradable plastic is degraded and recycled, and a green solution is obtained through multifunctional catalytic degradation, so that economic green circulation is achieved.
Drawings
FIG. 1 is a single crystal X-ray structural diagram of a bifunctional tetranuclear lithium metal complex of the present invention.
Detailed Description
All reactions were carried out under a blanket of high purity nitrogen or argon dried through a potassium column using standard reaction techniques.
Example 1: synthesis of bifunctional tetranuclear metal lithium complex
A solution of silicon-bridged aminoquinaldine (1.19g, 3.20mmol) in diethyl ether (20mL) was added dropwise at 0 deg.C with stirring under anhydrous and oxygen-free conditions n BuLi (3.00mL, 2.5M in n-hexane, 6.40 mmol). The solution immediately became turbid. After returning to room temperature, the mixture was stirred continuously for 3 hours and purified by washing with n-hexane several times to obtain 1.18g of a yellow solid as a final product in 81% yield.
Example 2: synthesis of bifunctional tetranuclear metal lithium complex
A solution of silicon-bridged aminoquinaldine (1.19g, 3.20mmol) in diethyl ether (30mL) was added dropwise at 0 deg.C with stirring under anhydrous and oxygen-free conditions n BuLi (3.00mL, 2.5M in n-hexane, 6.40 mmol). The solution immediately became turbid. Returning to room temperature, stirring was continued for 8h, and purification was carried out by multiple washes with n-hexane to give the final product as a yellow solid 1.18g, 81% yield.
The test results of the products obtained in the above examples 1 and 2 are the same, and specifically the following are shown:
1 H NMR(600MHz,C 6 D 6 ):δ7.52(d,J＝8.7Hz,5H,ArH),7.41(s,2H,ArH),7.38(t,J＝7.7Hz,2H,ArH),7.07(t,J＝8.1Hz,1H,ArH),6.94(d,J＝8.1Hz,4H,ArH),6.80(s,2H,ArH),6.77(d,J＝8.4Hz,2H,ArH),6.40(m,2H,ArH),3.33(m,8H,THF),2.51(s,3H,CH 3 ),1.89(s,4H,CH 3 ),1.28(m,8H,THF),0.88(s,5H,CH 3 ),0.45(s,6H,SiMe 2 ),0.30(s,6H,SiMe 2 ). 13 C NMR(151MHz,C 6 D 6 )δ158.75,155.41,155.32,146.56,139.10,137.71,136.08,121.66,121.21,117.48,115.58,110.87,109.42,67.36,45.63,25.23,24.68,23.88,4.29,2.07,1.02,-1.87.Anal.calcd for C 52 H 60 Li 4 N 8 O 2 Si 2 :C；68.41；H；6.62；N；12.27.Found:C；68.35；H,6.74；N,12.25。
EXAMPLE 3 Structure determination of bifunctional tetranuclear lithium Metal complexes
Selecting crystals with proper size, collecting crystal data by using Bruker Apex II CCD diffractometer at room temperature, and using a graphite monochromator Mo-Kalpha
As a radiation source. The cell parameters were determined using SMART software and absorption corrected by the SADABS program. The crystal structure is solved by using a SHELXS-2014 program by adopting a direct method and adopting a full matrix least square method based on F 2 Refining is carried out, and theoretical hydrogenation is carried out to determine all H atom positions. The crystal structure is shown in figure 1, and the crystallographic data are shown in table 1.
TABLE 1 crystallographic data for bifunctional tetranuclear lithium metal complexes
Partial bond length
Li(1)-O(1),2.028(7)；Li(1)-N(1),2.118(4)；Li(1)-N(2),2.118(4)；Li(1)-N(5),2.391(2)；Li(1)-N(8),2.391(2)；Li(2)-N(1),2.076(5)；Li(2)-N(4)`,2.097(5)；Li(2)-N(7),2.003(5)；Li(2)-N(8),2.164(5)；Li(3)-O(1),1.932(7)；Li(3)-N(3),2.039(4)；Li(3)-N(4),2.039(4)；Li(4)-N(2),2.076(5)；Li(4)-N(6),2.097(5)；Li(4)-N(4),2.003(5)；Li(4)-N(5),2.164(5)；
Partial bond angle (°) N (1) -Li (1) -O (1) 81.7 (5); n (2) -Li (1) -N (1):114.3 (2); n (1) -Li (1) -N (2):113.98 (12); li (1) -N (1) -Li (2):51.08 (11); li (2) -N (4) -Li (3):89.4 (2); n (3) -Li (3) -N (4):122.8 (3); li (3) -N (3) -Li (4):44.06 (14).
Example 4: application of bifunctional tetranuclear metal lithium complex catalyst
Under nitrogen protection, the compound of example 1 (0.05mmol) above, example 1, was added to a reaction flask, 5mL of dichloromethane solution was added, and then exactly 5mmol of lactide monomer solution was added, maintaining the monomer: catalyst: the cocatalyst was changed to 100:1:0 and the temperature was controlled at 30 ℃ with stirring. After 4 hours of reaction, 0.1mL of the reaction mixture was subjected to 600M nuclear magnetic analysis. At the same time, 3 drops of glacial acetic acid are added to stop the reaction, then 200mL of methanol is added to separate out the product to obtain a white polymer, the supernatant is filtered, and a proper amount of methanol is added to fully clean the precipitate. The conversion was calculated to be 99%, and the molecular weight distribution PDI was 1.60. The PDIs are all detected by GPC.
Example 5: application of bifunctional tetranuclear metal lithium complex catalyst
Under the protection of nitrogen, the compound (0.05mmol) described in example 1 was added into a reaction flask, 5mL of dichloromethane solution was added, 50. mu. mol of cocatalyst benzyl alcohol was added, and pre-reaction was carried out for 30min under stirring. Then exactly 5mmol lactide monomer solution was added, keeping the monomer: catalyst: the cocatalyst was changed to 100:1:1 and the temperature was controlled at 20 ℃ with stirring. After 4 hours of reaction, 0.1mL of the reaction mixture was subjected to 600M nuclear magnetic analysis. At the same time, 3 drops of glacial acetic acid are added to stop the reaction, then 200mL of methanol is added to separate out the product to obtain a white polymer, the supernatant is filtered, and a proper amount of methanol is added to fully clean the precipitate. The conversion was calculated to be 98%, and the molecular weight distribution PDI was 1.18. The PDIs are all detected by GPC.
Example 6: application of bifunctional tetranuclear metal lithium complex catalyst
Under the protection of nitrogen, the compound (0.05mmol) described in example 1 was added into a reaction flask, 5mL of dichloromethane solution was added, 50. mu. mol of cocatalyst benzyl alcohol was added, and pre-reaction was carried out for 30min under stirring. Then exactly 5mmol lactide monomer solution was added, keeping the monomer: catalyst: the cocatalyst was changed to 100:1:1 and the temperature was controlled at 30 ℃ with stirring. After 4 hours of reaction, 0.1mL of the reaction mixture was subjected to 600M nuclear magnetic analysis. At the same time, 3 drops of glacial acetic acid are added to stop the reaction, then 200mL of methanol is added to separate out the product to obtain a white polymer, the supernatant is filtered, and a proper amount of methanol is added to fully clean the precipitate. The conversion was calculated to be 98%, and the molecular weight distribution PDI was 1.19. The PDIs are all detected by GPC.
Example 7: application of bifunctional tetranuclear metal lithium complex catalyst
Under the protection of nitrogen, the compound (0.05mmol) described in example 1 was added into a reaction flask, 5mL of dichloromethane solution was added, 50. mu. mol of cocatalyst benzyl alcohol was added, and pre-reaction was carried out for 30min under stirring. Then exactly 10mmol lactide monomer solution was added, keeping the monomer: catalyst: the cocatalyst was changed to 200:1:1, and the temperature was controlled at 30 ℃ with stirring. After 4 hours of reaction, 0.1mL of the reaction mixture was subjected to 600M nuclear magnetic analysis. At the same time, 3 drops of glacial acetic acid are added to stop the reaction, then 200mL of methanol is added to separate out the product to obtain a white polymer, the supernatant is filtered, and a proper amount of methanol is added to fully clean the precipitate. The conversion was calculated to be 99%, and the molecular weight distribution PDI was 1.21. The PDIs are all detected by GPC.
Example 8: application of bifunctional tetranuclear metal lithium complex catalyst
Under the protection of nitrogen, the compound (0.05mmol) described in example 1 was added into a reaction flask, 5mL of dichloromethane solution was added, 50. mu. mol of cocatalyst benzyl alcohol was added, and pre-reaction was carried out for 30min under stirring. Then exactly 20mmol lactide monomer solution was added, keeping the monomer: catalyst: the cocatalyst was 400:1:1 and the temperature was controlled at 30 ℃ with stirring. After 4 hours of reaction, 0.1mL of the reaction mixture was subjected to 600M nuclear magnetic analysis. At the same time, 3 drops of glacial acetic acid are added to stop the reaction, then 200mL of methanol is added to separate out the product to obtain a white polymer, the supernatant is filtered, and a proper amount of methanol is added to fully clean the precipitate. The conversion was calculated to be 98%, and the molecular weight distribution PDI was 1.30. The PDIs are all detected by GPC.
Example 9: application of bifunctional tetranuclear metal lithium complex catalyst
An oil bath at 20 ℃ stable in temperature was prepared in advance, and the compound (0.05mmol) described in example 1 was charged into a Schlenk flask equipped with a stirrer under nitrogen protection, and 5mL of methylene chloride was added to dissolve completely. Then according to [ LA ]]:[Cat]Lactide monomer was added at a ratio of 100:1 and samples were taken every 1h 1 HNMR is used once, polymerization reaction is monitored in real time, and the conversion rate is over 99 percent after 4 hours. Followed by 2.0mL MeOH (n) PLA :n MeOH 10:1), the depolymerization reaction was monitored in real time, and after 1h the conversion rate exceeded 99% and the polylactide was completely degraded to methyl lactate (Me-La).
Example 10: application of bifunctional tetranuclear metal lithium complex catalyst
An oil bath at 30 ℃ was prepared in advance, which was stable in temperature, and the compound (0.05mmol) described in example 1 was charged into a Schlenk flask equipped with a stirrer under nitrogen protection, and 5mL of methylene chloride was added to completely dissolve it. Then according to [ LA ]]:[Cat]Lactide monomer was added at a ratio of 100:1 and samples were taken every 1h 1 HNMR is used once, polymerization reaction is monitored in real time, and the conversion rate is over 99 percent after 4 hours. Followed by 2.0mL MeOH (n) PLA :n MeOH 10:1), the depolymerization reaction was monitored in real time, and after 1h the conversion rate exceeded 99% and the polylactide was completely degraded to methyl lactate (Me-La).
Those skilled in the art will appreciate that the invention may be practiced without these specific details. Although illustrative embodiments of the present invention have been described above to facilitate the understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, and various changes may be made apparent to those skilled in the art as long as they are within the spirit and scope of the present invention as defined and defined by the appended claims, and all matters of the invention which utilize the inventive concepts are protected.
Claims (10)
1. A bifunctional tetranuclear lithium metal complex characterized by: the structural formula of the bifunctional tetranuclear metal lithium complex is as follows:
the crystal of the difunctional tetranuclear metal lithium complex belongs to a monoclinic system, a C2/C space group, and the unit cell parameters are as follows:
α＝90(13)°，β＝104.358(5)°，γ＝90°。
2. the method of claim 1, wherein the method comprises the steps of: the method comprises the following steps: dissolving silicon-bridged aminoquinaldine in diethyl ether, dropwise adding n-butyllithium with the same molar weight as the silicon-bridged aminoquinaldine while stirring at 0 ℃ under anhydrous and oxygen-free conditions, then recovering to room temperature, continuously stirring for 3-8 h, standing after the reaction is finished, filtering to remove filtrate, washing and purifying with n-hexane for multiple times, concentrating the filtrate, and crystallizing to obtain the bifunctional tetranuclear lithium metal complex.
3. The method for preparing a bifunctional tetranuclear lithium metal complex according to claim 2, characterized in that: the specific method of the crystallization is to dissolve the obtained solid product in tetrahydrofuran, concentrate the solid product and separate out crystals by placing the solid product at a low temperature of-30 ℃ under the protection of nitrogen.
4. The method of claim 2, wherein the method comprises the steps of: the concentration of the n-butyllithium is 2.5 mol/L.
5. The use of a bifunctional tetranuclear lithium metal complex according to claim 2, characterized in that: the method is applied to lactide polymerization and polylactide degradation.
6. Use according to claim 5, characterized in that: under the condition of no need of cocatalyst or under the condition of cocatalyst and benzyl alcohol co-catalysis, the lactide polymerization product is obtained in dichloromethane solvent.
7. Use according to claim 6, characterized in that: and polymerizing the lactide at room temperature under the inert atmosphere at the temperature of 20-30 ℃.
8. Use according to claim 7, characterized in that: the molar ratio of the lactide to the bifunctional tetranuclear metal lithium complex is 100: 1-400: 1.
9. Use according to claim 5, characterized in that: obtaining degradation products of the polylactide in methylene chloride solvent under the condition of co-catalysis with methanol.
10. Use according to claim 9, characterized in that: the specific method for obtaining the degradation product of the polylactide in the dichloromethane solvent under the co-catalysis condition of the degradation product and the methanol is as follows: preparing an oil bath with the temperature stable at 20-30 ℃; accurately weighing the complex under an inert atmosphere, adding the complex into a bottle A with a stirrer, and adding dichloromethane until the dichloromethane is completely dissolved; preparing a bottle B under the same condition, adding the bottle B according to the molar ratio of lactide to the difunctional tetranuclear metal lithium complex of 100:1, and dissolving the bottle B in dichloromethane; adding the mixed monomer in the bottle B into the bottle A with constant rotating speed, and simultaneously monitoring in real time to ensure complete polymerization; then polylactide and methanol were added at a molar ratio of 10:1 at 600 rpm; sampling every 10min 1 Monitoring depolymerization reaction in real time once by HNMR, and waiting for 1h to completely degrade polylactide intoIs methyl lactate.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643417A (en) * | 2012-04-20 | 2012-08-22 | 复旦大学 | Preparation method and application of phenyl-bridged guanyl binuclear rare-earth metal catalyst |
| CN103360431A (en) * | 2013-07-16 | 2013-10-23 | 山西大学 | Metal complex with 8-aminoquinaldine as matrix and synthesis method of metal complex |
| CN107417716A (en) * | 2017-06-09 | 2017-12-01 | 山西大学 | A kind of enol form pyrazine metal complex and synthetic method and application |
| CN109456342A (en) * | 2018-11-23 | 2019-03-12 | 山西大学 | A kind of 1,2- addition quinolyl lithium-complex and its synthetic method and application |
| WO2021179867A1 (en) * | 2020-03-13 | 2021-09-16 | 苏州大学 | Use of n-butyllithium for catalyzing cyanosilanization reaction of aldehyde and silane |
| WO2021253847A1 (en) * | 2020-06-16 | 2021-12-23 | 苏州大学 | Use of deprotonated phenyl bridged β-ketimine lithium compound in hydroboration reaction |
| WO2022040891A1 (en) * | 2020-08-24 | 2022-03-03 | 苏州大学 | USE OF DEPROTONATED PHENYL-BRIDGED β-KETIMINE LITHIUM COORDINATION COMPLEX IN CYANOSILICATE REACTION |
| WO2022041326A1 (en) * | 2020-08-27 | 2022-03-03 | 中国科学院青岛生物能源与过程研究所 | Zinc catalyst for catalyzing ring-opening polymerization of cyclic esters and controlled depolymerization of polyester materials and catalytic method therefor |
-
2022
- 2022-06-07 CN CN202210641896.6A patent/CN114891035B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643417A (en) * | 2012-04-20 | 2012-08-22 | 复旦大学 | Preparation method and application of phenyl-bridged guanyl binuclear rare-earth metal catalyst |
| CN103360431A (en) * | 2013-07-16 | 2013-10-23 | 山西大学 | Metal complex with 8-aminoquinaldine as matrix and synthesis method of metal complex |
| CN107417716A (en) * | 2017-06-09 | 2017-12-01 | 山西大学 | A kind of enol form pyrazine metal complex and synthetic method and application |
| CN109456342A (en) * | 2018-11-23 | 2019-03-12 | 山西大学 | A kind of 1,2- addition quinolyl lithium-complex and its synthetic method and application |
| WO2021179867A1 (en) * | 2020-03-13 | 2021-09-16 | 苏州大学 | Use of n-butyllithium for catalyzing cyanosilanization reaction of aldehyde and silane |
| WO2021253847A1 (en) * | 2020-06-16 | 2021-12-23 | 苏州大学 | Use of deprotonated phenyl bridged β-ketimine lithium compound in hydroboration reaction |
| WO2022040891A1 (en) * | 2020-08-24 | 2022-03-03 | 苏州大学 | USE OF DEPROTONATED PHENYL-BRIDGED β-KETIMINE LITHIUM COORDINATION COMPLEX IN CYANOSILICATE REACTION |
| WO2022041326A1 (en) * | 2020-08-27 | 2022-03-03 | 中国科学院青岛生物能源与过程研究所 | Zinc catalyst for catalyzing ring-opening polymerization of cyclic esters and controlled depolymerization of polyester materials and catalytic method therefor |
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