CN109336916A - A kind of synthesis and catalysis 6-caprolactone ring-opening polymerisation of β-pyridine enamine bidentate aluminum complex - Google Patents
A kind of synthesis and catalysis 6-caprolactone ring-opening polymerisation of β-pyridine enamine bidentate aluminum complex Download PDFInfo
- Publication number
- CN109336916A CN109336916A CN201810980422.8A CN201810980422A CN109336916A CN 109336916 A CN109336916 A CN 109336916A CN 201810980422 A CN201810980422 A CN 201810980422A CN 109336916 A CN109336916 A CN 109336916A
- Authority
- CN
- China
- Prior art keywords
- pyridine
- enamine
- bidentate
- catalyst
- aluminum complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to catalyst preparation technical fields, provide the synthesis and catalysis 6-caprolactone ring-opening polymerisation of a kind of β-pyridine enamine bidentate aluminum complex.2- (2- pyridyl group)-acetophenone carries out condensation reaction with the aromatic amine containing different substituents, obtains the ligand containing two nitrogen-atoms, then be coordinated with alkyl aluminum, synthesizes β-pyridine enamine bidentate aluminium metal complex.It can be used for being catalyzed the ring-opening polymerization of 6-caprolactone.The synthetic method of aluminum complex catalyst is simple, be not to air and water it is very sensitive, condition requires lower compared to other similar complexs, and yield is high;The catalyst has good catalytic activity to 6-caprolactone ring-opening polymerization, and the reaction belongs to controllable polymerization reaction.Due to the good biocompatibility of this kind of catalyst, small toxicity, can perform well in catalyzing and synthesizing degradable polyester material.
Description
Technical field
The invention belongs to catalyst preparation technical fields, and in particular to a kind of conjunction of β-pyridine enamine bidentate aluminum complex
At, and its application of the catalyst as 6-caprolactone ring-opening polymerization.
Background technique
Polycaprolactone is a kind of by artificial synthesized polyesters bioabsorbable polymer material.Due to its good biodegrade
Property, biocompatibility, mechanical property, drug permeability and safe and non-toxic, and it is widely used in bio-medical material, organ group
Weaver's journey, packaging material for food etc..In recent years, efficient due to metal complex catalyzed 6-caprolactone ring-opening polymerization
Property and gained polycaprolactone molecular weight controllability, by metal complex cause 6-caprolactone ring-opening polymerization obtain extensively
General concern.Wherein, magnesium, aluminium, zinc, rare earth element class metal complex catalysts can efficiently be catalyzed the ring-opening polymerisation of caprolactone
Reaction.
Aluminium is one kind rich content, environment amenable metallic element in the earth's crust, and preparing its complex, cost is relatively low.With
The structure of the ligand of metal coordination is to influence the key factor of polymerization reaction.Currently, the phenates of aluminium, schiff bases, beta-diimine, alkene
Complexes have been widely used in catalysis 6-caprolactone ring-opening polymerization.The above-mentioned ligand with larger space structure can
For stable metal aluminium center and the generation of aluminium by-product is reduced, thus become the initiator of effective ring-opening polymerization,
So that polymerization reaction has preferable controllability.
Summary of the invention
The purpose of the present invention is to provide a kind of β-pyridine enamine bidentate aluminum complex and its synthesis and the aluminum complexes
The application of catalyst as 6-caprolactone ring-opening polymerization.
The present invention is realized by following technical solution: a kind of β-pyridine enamine bidentate aluminum complex, the β-pyridine alkene
The structural formula of amine bidentate aluminum complex are as follows:
, wherein R1For H, CH3、CH2CH3、CH(CH3)2Or
F;R2For H, F;R3For H, F.
A kind of synthesis β-pyridine enamine bidentate aluminum complex method, with 2- (2- pyridyl group)-acetophenone with contain
The aromatic amine of different substituents carries out condensation reaction, obtains the ligand containing two nitrogen-atoms, then be coordinated with alkyl aluminum, synthesizes
A series of β-pyridine enamine bidentate aluminium metal complex.
Specific step is as follows:
(1) β-pyridine enamine ligand synthesis: at room temperature, by 2- (2- the pyridyl group)-acetophenone and aromatic amine of equimolar amounts
Be dissolved in toluene solvant, be added with aromatic amine molar ratio be 1:50-1:80 trifluoroacetic acid as catalyst, solution is flowed back
24-48 h is reacted, then is removed the water of generation with water segregator, then revolving removes solvent, mixed with petroleum ether and ethyl acetate
Bonding solvent goes out product by pillar layer separation, the β refined-pyridine enamine ligand;
(2) under the conditions of anhydrous and oxygen-free, β-pyridine enamine ligand β-pyridine enamine bidentate aluminum complex synthesis: is dissolved in first
In benzene solvent, the hexane solution of the trimethyl aluminium of 1.2 times of moles is then added dropwise, continues to be stirred to react 3- at room temperature
6 h, then at 100-110 DEG C react 12-24 h, drain toluene solvant after the reaction was completed and obtain sediment, add just oneself
Alkane washing precipitating, stands, is filtered to remove filtrate, obtains β-pyridine enamine bidentate aluminium after residue precipitating is dried under vacuum and cooperates
Object.
The aromatic amine is aniline, 2,6- dimethylaniline, 2,6- diethylaniline, 2,6- diisopropyl aniline, right
Any one in fluoroaniline or 2,3,4,5,6- pentafluoroaniline.The in the mixed solvent petroleum of the petroleum ether and ethyl acetate
Ether: ethyl acetate=7:1-15:1.
A kind of purposes of β-pyridine enamine bidentate aluminum complex, the β-pyridine enamine bidentate aluminum complex is as ε-in oneself
The catalyst of ester ring-opening polymerization is used cooperatively with co-catalyst benzylalcohol, for being catalyzed 6-caprolactone ring-opening polymerization.
Specific steps are as follows:
Under the conditions of anhydrous and oxygen-free, β-pyridine enamine bidentate aluminum complex catalyst solid is dissolved in toluene solvant, according to
Monomer: catalyst: the ratio of co-catalyst is respectively 100:1:1,200:1:1,400:1:1, the ratio of 100:1:0,100:1:2
Example is first added co-catalyst benzylalcohol, is stirred to react 30 min under the conditions of 70-80 DEG C.Monomer 6-caprolactone is added, is controlled
Temperature is stirred to react 20-240 min under the conditions of 70-80 DEG C;During the reaction, when monitoring monomer conversion, between waiting the times
It uniformly extracts reaction solution 5 times every ground, with the conversion ratio of nuclear magnetic resonance spectroscopy analytical calculation extracted reaction solution middle monomer every time, and records
Final conversion ratio;Then 3 drop glacial acetic acids are added and terminate reaction, adds 100 mL methanol and white polymer is precipitated completely,
It is filtered to remove methanol, methanol is added and sufficiently washs white polymer, the polycaprolactone product of purification is finally dried to obtain, goes forward side by side
Row GPC test, obtain the molecular weight of polymer between 2927-35757, and suitable with calculated value, molecular weight distribution compared with
It is narrow, between 1.03-1.19, illustrate to belong to controllable polymerization reaction.
Compared with prior art, the present invention select 2- (2- pyridyl group)-acetophenone containing a N atom with containing different substitutions
Base R1、R2And R3Aromatic amine compounds carry out condensation reaction, obtain three-dimensional effect, electronic effect different β-pyridine enamine
Ligand, then different β-pyridine enamine bidentate aluminum complex catalyst is obtained from alkyl reactive aluminum.The aluminum complex catalyst can
Effectively it is catalyzed 6-caprolactone ring-opening polymerization.Reaction process conditional it is mild (70-80 DEG C of temperature, time 20-240
Min), high conversion rate (up to 99%).The metal complex catalysts of pertinent literature report are catalyzed the anti-of 6-caprolactone ring-opening polymerisation
Answer temperature generally at 100 DEG C or so, the reaction time, final conversion ratio was 90%-92% in 4-6 h.And the aluminium prepared in the present invention
Composition catalyst is 70-80 oC in temperature, when the reaction time is 20-240 min, catalysis caprolactone ring-opening polymerization
Final high conversion rate is up to 99%, it can be seen that for reaction condition than the milder that pertinent literature report, monomer conversion is higher, and category
In controllable polymerization reaction.And such Al catalysts small toxicity, being catalyzed resulting polycaprolactone has preferable biocompatibility,
It is polyester material of good performance.
Synthetic method of the present invention is simple, be not to air and water it is very sensitive, condition require compared to other similar complexs
It is lower, and yield is high;The catalyst has good catalytic activity to 6-caprolactone ring-opening polymerization, and belong to can for the reaction
The polymerization reaction of control.Due to the good biocompatibility of this kind of catalyst, small toxicity, can perform well in catalyzing and synthesizing degradable
Polyester material.
Detailed description of the invention
Fig. 1 β of the present invention-pyridine enamine bidentate aluminium gold metal catalyst 1(R1 = H, R2 = H, R3=H) nuclear magnetic resonance
Hydrogen composes spectrogram.Fig. 2 β of the present invention-pyridine enamine bidentate aluminium gold metal catalyst 1(R1 = H, R2 = H, R3=H) nuclear-magnetism it is total
The carbon that shakes composes spectrogram.Fig. 3 β of the present invention-pyridine enamine bidentate aluminium gold metal catalyst 2(R1 = CH3, R2 = H, R3=H) core
Magnetic resonance hydrogen composes spectrogram.Fig. 4 β of the present invention-pyridine enamine bidentate aluminium gold metal catalyst 2(R1 = CH3, R2 = H, R3=H)
Carbon-13 nmr spectra spectrogram.Fig. 5 β of the present invention-pyridine enamine bidentate aluminium gold metal catalyst 3(R1 = CH2CH3, R2 = H, R3
=H) nuclear magnetic resonance spectroscopy spectrogram.Fig. 6 β of the present invention-pyridine enamine bidentate aluminium gold metal catalyst 3(R1 = CH2CH3, R2 =
H, R3=H) carbon-13 nmr spectra spectrogram.Fig. 7 β of the present invention -4 (R of pyridine enamine bidentate aluminium gold metal catalyst1 = CH
(CH3)2, R2 = H, R3=H) nuclear magnetic resonance spectroscopy spectrogram.Fig. 8 β of the present invention-pyridine enamine bidentate aluminium gold metal catalyst
5(R1 = H, R2 = H, R3=F) nuclear magnetic resonance spectroscopy spectrogram.Fig. 9 β of the present invention-pyridine enamine bidentate aluminum metal catalysis
Agent 5(R1 = H, R2 = H, R3=F) carbon-13 nmr spectra spectrogram.Figure 10 β of the present invention-pyridine enamine bidentate aluminum metal
Catalyst 6(R1 = F, R2 = F, R3=F) nuclear magnetic resonance spectroscopy spectrogram.Figure 11 β of the present invention-pyridine enamine bidentate aluminium
Metallic catalyst 6(R1 = F, R2 = F, R3=F) carbon-13 nmr spectra spectrogram;Figure 12 is synthesis β-pyridine enamine bidentate
The reaction equation of aluminum complex.
Specific embodiment
All reactions are carried out under dried high pure nitrogen protection, are operated using the reaction technology of standard.
Embodiment 1: β-pyridine enamine bidentate aluminium gold metal catalyst 1(R1 = H, R2 = H, R3=H) preparation
Reaction equation as shown in figure 12, by 2- (2- pyridyl group)-acetophenone (2.462 g, 12.48 mmol) and equimolar amounts
Aniline (1.1 mL, 12.48 mmol) is dissolved in 60 mL toluene, and trifluoroacetic acid (0.028 g, 0.248 mmol) conduct is added
Catalyst, then remove the water of generation by 48 h of solution back flow reaction, then with water segregator, then revolving removes solvent, uses petroleum
The mixed solvent that ether and ethyl acetate ratio are 7:1 goes out product by pillar layer separation, and finally revolving removal solvent obtains yellow
Solid β-pyridine enamine ligand HL1, yield 72%.
Under the conditions of anhydrous and oxygen-free, above-mentioned β-pyridine enamine ligand HL1(0.519 g, 1.91 mmol) is dissolved in toluene
In solvent (10 mL), the trimethyl aluminiums of 1.2 times of moles is then added dropwise, and (2.3 mL, 1 mol/L, are dissolved in n-hexane
In solution, 2.3 mmol), continue to be stirred to react 6 h at room temperature, 12 h then reacted at 100 DEG C, are taken out after the reaction was completed
Dry toluene solvant obtains sediment, adds n-hexane washing precipitating, stands, be filtered to remove filtrate, residue is deposited in vacuum
β-pyridine enamine bidentate aluminum complex 1, yield 87% are obtained after lower drying.1H NMR (600 MHz, CDCl3) δ 8.03
(d, J = 5.5 Hz, 1H, ArH), 7.61 (t, J = 7.7 Hz, 1H, ArH), 7.34 – 7.29 (m, 3H,
ArH), 7.21 – 7.18 (m, 4H, ArH), 7.12 (d, J = 8.4 Hz, 1H, ArH), 7.07 (t, J =
7.2 Hz, 2H, ArH), 6.94 (t, J = 6.1 Hz, 1H, ArH), 6.87 (t, J = 7.3 Hz, 1H,
ArH), 6.81 (d, J = 7.6 Hz, 2H, ArH), 5.48 (s, 1H, CH), -0.67 (s, 6H, Al
(CH 3)2). 13C NMR (151 MHz, CDCl3) δ 161.15, 147.86, 142.87, 142.82, 140.81,
138.29, 129.43, 129.25, 128.52, 128.37, 128.35, 128.27, 128.18, 128.07,
128.00, 127.90, 127.84, 127.71, 127.13, 126.03, 125.95, 125.89, 123.66,
122.34, 116.71, 99.03, 1.04, -10.09 .
Embodiment 2: β-pyridine enamine bidentate aluminium gold metal catalyst 2(R1 = CH3, R2 = H, R3=H) preparation
By the 2,6- dimethylaniline (1.1 of 2- (2- pyridyl group)-acetophenone (1.683 g, 8.54 mmol) and equimolar amounts
ML, 8.54 mmol) it is dissolved in 60 mL toluene, trifluoroacetic acid (0.019 g, 0.171 mmol) is added and is used as catalyst, then will
48 h of solution back flow reaction, then removed the water of generation with water segregator, then revolving removes solvent, with petroleum ether and ethyl acetate
Ratio is that the mixed solvent of 7:1 goes out product by pillar layer separation, and finally revolving removal solvent obtains yellow solid β-pyridine alkene
Amine ligand HL2, yield 62%.
Under the conditions of anhydrous and oxygen-free, above-mentioned β-pyridine enamine ligand HL2(0.401 g, 1.34 mmol) is dissolved in toluene
In solvent (10 mL), the trimethyl aluminiums of 1.2 times of moles is then added dropwise, and (1.6 mL, 1 mol/L, are dissolved in n-hexane
In solution, 1.6 mmol), continue to be stirred to react 6 h at room temperature, 12 h then reacted at 100 DEG C, are taken out after the reaction was completed
Dry toluene solvant obtains sediment, adds n-hexane washing precipitating, stands, be filtered to remove filtrate, residue is deposited in vacuum
β-pyridine enamine bidentate aluminum complex 2, yield 86% are obtained after lower drying.1H NMR (600 MHz, CDCl3) δ 7.97
(d, J = 6.0 Hz, 1H, ArH), 7.57 (t, J = 8.0 Hz, 1H, ArH), 7.30 – 7.28 (m, 3H,
ArH), 7.15 (dt, J = 14.2, 6.6 Hz, 3H, ArH), 7.08 (d, J = 8.5 Hz, 1H, ArH),
6.85 (td, J = 17.3, 16.1, 6.8 Hz, 3H, ArH), 5.43 (s, 1H, CH), 2.22 (s, 6H, Ar
(CH 3)2), -0.79 (d, J = 1.9 Hz, 6H, Al(CH 3)2). 13C NMR (151 MHz, CDCl3) δ
142.31, 137.83, 134.59, 128.32, 128.23, 127.97, 127.92, 127.63, 127.26,
124.40, 123.34, 116.37, 116.00, 96.83, 77.05, 76.83, 19.66, 19.58, -10.21.
Embodiment 3: β-pyridine enamine bidentate aluminium gold metal catalyst 3(R1 = CH2CH3, R2 = H, R3=H) preparation
By the 2,6- diethylaniline (1.4 of 2- (2- pyridyl group)-acetophenone (1.64 g, 8.32 mmol) and equimolar amounts
ML, 8.32 mmol) it is dissolved in 60 mL toluene, trifluoroacetic acid (0.019 g, 0.166 mmol) is added and is used as catalyst, then
The water of generation is removed by 48 h of solution back flow reaction, then with water segregator, then revolving removes solvent, with petroleum ether and acetic acid second
Ester ratio is that the mixed solvent of 7:1 goes out product by pillar layer separation, and finally revolving removal solvent obtains yellow solid β-pyridine
Enamine ligand HL3, yield 70%.
Under the conditions of anhydrous and oxygen-free, above-mentioned β-pyridine enamine ligand HL3(0.475 g, 1.45 mmol) is dissolved in toluene
In solvent (10 mL), the trimethyl aluminiums of 1.2 times of moles is then added dropwise, and (1.7 mL, 1 mol/L, are dissolved in n-hexane
In solution, 1.7 mmol), continue to be stirred to react 6 h at room temperature, 12 h then reacted at 100 DEG C, are taken out after the reaction was completed
Dry toluene solvant obtains sediment, adds n-hexane washing precipitating, stands, be filtered to remove filtrate, residue is deposited in vacuum
β-pyridine enamine bidentate aluminum complex 3, yield 82% are obtained after lower drying.1H NMR (600 MHz, C6D6) δ 7.63 (d,J = 6.0 Hz, 1H, ArH), 7.31 (dd, J = 7.2, 1.7 Hz, 2H, ArH), 6.95 (s, 1H, ArH),
6.95 – 6.84 (m, 6H, ArH), 6.74 – 6.67 (m, 1H, ArH), 6.48 (d, J = 8.6 Hz, 1H,
ArH), 6.11 – 6.04 (m, 1H, ArH), 5.44 (d, J = 1.6 Hz, 1H, CH), 2.93 (t, J =
15.1, 7.6, 1.7 Hz, 2H, ArCH 2CH3), 2.61 (t, J = 15.2, 7.5, 1.5 Hz, 2H,
ArCH 2CH3), 1.15 (t, J = 7.5 Hz, 6H, Ar(CH2CH 3)2), -0.31 (s, 6H, Al(CH 3)2). 13C
NMR (151 MHz, C6D6) δ 163.92, 156.22, 143.92, 141.89, 140.69, 139.87, 137.28,
128.22, 128.11, 127.98, 127.78, 127.62, 127.22, 125.55, 125.24, 122.90,
115.80, 97.26, 24.53, 14.04, -10.21 .
Embodiment 4: β-pyridine enamine bidentate aluminium gold metal catalyst 4(R1 = CH(CH3)2, R2 = H, R3=H) preparation
By the 2,6- diisopropyl aniline of 2- (2- pyridyl group)-acetophenone (1.681 g, 8.53 mmol) and equimolar amounts
(1.6 mL, 8.53 mmol) are dissolved in 60 mL toluene, and trifluoroacetic acid (0.020 g, 0.171 mmol) is added as catalysis
Agent, then by 24 h of solution back flow reaction, then removed the water of generation with water segregator, then revolving removes solvent, with petroleum ether with
Ethyl acetate ratio is that the mixed solvent of 7:1 goes out product by pillar layer separation, and finally revolving removal solvent obtains yellow solid
β-pyridine enamine ligand HL4, yield 73%.
Under the conditions of anhydrous and oxygen-free, above-mentioned β-pyridine enamine ligand HL4(0.422 g, 1.18 mmol) is dissolved in toluene
In solvent (10 mL), the trimethyl aluminiums of 1.2 times of moles is then added dropwise, and (1.4 mL, 1 mol/L, are dissolved in n-hexane
In solution, 1.4 mmol), continue to be stirred to react 3 h at room temperature, 12 h then reacted at 100 DEG C, are taken out after the reaction was completed
Dry toluene solvant obtains sediment, adds n-hexane washing precipitating, stands, be filtered to remove filtrate, residue is deposited in vacuum
β-pyridine enamine bidentate aluminum complex 4, yield 92% are obtained after lower drying.1H NMR (600 MHz, C6D6) δ 7.64 (s,
1H, ArH), 7.33 (d, J = 7.2 Hz, 2H, ArH), 6.93 (t, J = 6.2 Hz, 6H, ArH), 6.68
(t, J = 7.6 Hz, 1H, ArH), 6.47 (d, J = 8.4 Hz, 1H, ArH), 6.08 (t, J = 5.8 Hz,
1H, ArH), 5.51 (s, 1H, CH), 3.50 – 3.43 (m, 2H, CH(CH3)2), 1.25 (d, J = 6.2
Hz, 6H, CH(CH 3)2), 1.04 (d, J = 6.3 Hz, 6H, CH(CH 3)2), -0.30 (s, 6H, Al(CH 3)2).13C NMR (151 MHz, C6D6) δ 145.08, 129.17, 128.70, 128.57, 128.37, 128.25,
128.19, 128.07, 128.02, 127.95, 127.61, 127.46, 127.15, 127.15, 125.93,
123.51, 122.82, 116.08, 97.96, 97.96, 28.00, 27.99, 25.42, 25.36, 25.34,
23.14, 23.14, 22.93,-10.42.
Embodiment 5: β-pyridine enamine bidentate aluminium gold metal catalyst 5(R1 = H, R2 = H, R3=F) preparation
By the para-fluoroaniline of 2- (2- pyridyl group)-acetophenone (2.44 g, 12.4 mmol) and equimolar amounts (1.2 mL,
12.4 mmol) it is dissolved in 60 mL toluene, trifluoroacetic acid (0.028 g, 0.248 mmol) is added and is used as catalyst, then by solution
48 h of back flow reaction, then removed the water of generation with water segregator, then revolving removes solvent, with petroleum ether and ethyl acetate ratio
Product is gone out by pillar layer separation for the mixed solvent of 15:1, finally revolving removal solvent obtains yellow solid β-pyridine enamine
Ligand HL5, yield 84%.
Under the conditions of anhydrous and oxygen-free, above-mentioned β-pyridine enamine ligand HL5(0.518 g, 1.79 mmol) is dissolved in toluene
In solvent (10 mL), the trimethyl aluminiums of 1.2 times of moles is then added dropwise, and (2.2 mL, 1 mol/L, are dissolved in n-hexane
In solution, 2.2 mmol), continue to be stirred to react 6 h at room temperature, 24 h then reacted at 110 DEG C, are taken out after the reaction was completed
Dry toluene solvant obtains sediment, adds n-hexane washing precipitating, stands, be filtered to remove filtrate, residue is deposited in vacuum
β-pyridine enamine bidentate aluminum complex 5, yield 75% are obtained after lower drying.1H NMR (600 MHz, CDCl3) δ 8.00 (s,
1H, ArH), 7.60 (q, J = 10.1, 8.8 Hz, 2H, ArH), 7.19 (s, 3H, ArH), 7.10 (d, J
= 7.8 Hz, 1H, ArH), 6.94 (s, 1H, ArH), 6.82 – 6.72 (m, 5H, ArH), 5.44 (s, 1H,
CH), -0.70 (s, 6H, Al(CH 3)2). 13C NMR (151 MHz, CDCl3) δ 161.26, 156.07,
143.88, 142.77, 140.51, 138.36, 135.99, 129.22, 128.37, 128.07, 127.90,
127.78, 127.00, 126.94, 123.68, 122.94, 116.77, 115.18, 114.98, 114.84,
98.71, -10.13.
Embodiment 6: β-pyridine enamine bidentate aluminium gold metal catalyst 6(R1 = F, R2 = F, R3=F) preparation
By the 2,3,4,5,6- pentafluoroaniline of 2- (2- pyridyl group)-acetophenone (2.515 g, 12.8 mmol) and equimolar amounts
(2.34 g, 12.8 mmol) are dissolved in 60 mL toluene, and trifluoroacetic acid (0.029 g, 0.256 mmol) is added as catalysis
Agent, then by 24 h of solution back flow reaction, then removed the water of generation with water segregator, then revolving removes solvent, with petroleum ether with
Ethyl acetate ratio is that the mixed solvent of 10:1 goes out product by pillar layer separation, and it is solid to obtain yellow for finally revolving removal solvent
Body β-pyridine enamine ligand HL6, yield 75%.
Under the conditions of anhydrous and oxygen-free, it is molten that above-mentioned β-pyridine enamine ligand HL6(0.54 g, 1.49 mmol) is dissolved in toluene
In agent, be then added dropwise 1.2 times of moles trimethyl aluminium (1.8 mL, 1 mol/L, are dissolved in hexane solution, 1.8
Mmol), continue to be stirred to react 3 h at room temperature, 24 h are then reacted at 110 DEG C, drain toluene solvant after the reaction was completed and obtain
To sediment, n-hexane washing precipitating is added, stands, is filtered to remove filtrate, is obtained after residue precipitating is dried under vacuum
β-pyridine enamine bidentate aluminum complex 6, yield 90%.1H NMR (600 MHz, CDCl3) δ 8.16 (s, 1H, ArH),
7.78 (t, J = 7.5 Hz, 1H, ArH), 7.37 (d, J = 6.9 Hz, 3H, ArH), 7.28 (s, 3H,
ArH), 7.15 (s, 1H, ArH), 5.75 (s, 1H, CH), -0.71 (s, 6H, Al(CH 3)2). 13C NMR
(151 MHz, CDCl3) δ 160.00, 155.55, 143.21, 139.57, 139.36, 129.11, 128.14,
128.09, 124.37, 118.92, 101.67 , -12.00.
Embodiment 7-12: catalyst 1-6 catalysis 6-caprolactone ring-opening polymerization performance study
Embodiment 7-12 using different β-pyridine enamine bidentate aluminum complex 1-6 in above-described embodiment 1-6 as catalyst,
It is anti-that identical solvent and monomer, catalyst, co-catalyst ratio carry out 6-caprolactone ring-opening polymerisation under conditions of being 100:1:1
It answers.
Under the conditions of anhydrous and oxygen-free, Al catalysts 1-6 solid different prepared by above-described embodiment 1-6 is weighed respectively
About 16-21 mg (50 μm of ol) is dissolved in 4.5 mL toluene solvants, be added at 70 DEG C 0.5 mL benzylalcohol (0.1 mol/L,
It is dissolved in toluene, 50 μm of ol) as co-catalyst, it is stirred to react 30 min.Then, according to monomer: catalyst: co-catalysis
0.5 mL(5 mmol is added in agent=100:1:1 ratio) 6-caprolactone monomer, temperature is controlled respectively to be stirred under the conditions of 70-80 oC
Mix reaction 20-240 min.During the reaction, when monitoring monomer conversion, constant duration 0.1 mL is uniformly extracted reaction solution
5 times, with the conversion ratio of 600 M nuclear magnetic resonance spectroscopy analytical calculations extracted reaction solution middle monomer every time.After complete reaction, it is added
3 drop glacial acetic acids terminate reaction, add 100 mL methanol and white polymer be precipitated completely, be filtered to remove methanol, then plus
Enter methanol and sufficiently wash white polymer, be finally dried to obtain the polycaprolactone product of purification, gained polycaprolactone is subjected to GPC
Test, polymerization results are shown in Table 1 number 1-6.As it can be seen that working as R1For electron-donating group CH3, CH2CH3When (catalyst 2,3), only
Temperature is improved to 80 DEG C, ability catalytic polymerization carries out, but molecular weight differs larger with calculated value, and catalyst 2
Result in occur two different molecular weight values, illustrate there are other side reactions, the poor (embodiment of polymerization reaction controllability
8,9);Work as R1For electron-donating group CH (CH3)2When (catalyst 4), temperature is increased to 80 DEG C, be still unable to catalytic polymerization into
Row (embodiment 10);Work as R3When for electron-withdrawing group (catalyst 5), the activity of catalytic polymerization preferably, molecular weight and theoretical
Calculated value difference is smaller, and molecular weight distribution is relatively narrow, belongs to controllable polymerization reaction (embodiment 11);Work as R1、R2、R3It is H or is
When electron-withdrawing group (catalyst 1,6), quite, molecular weight differs smaller with calculated value to the activity of catalytic polymerization, point
Son amount narrow distribution, belongs to controllable polymerization reaction (embodiment 7,12).
Embodiment 13-16: catalyst 5 is catalyzed ε-in oneself in the case where different monomers, catalyst, co-catalyst ratio
Ester ring-opening polymerisation performance research
Embodiment 13-16 is used as catalyst using β-pyridine enamine bidentate aluminum complex 5 in above-described embodiment 5, in different lists
6-caprolactone ring-opening polymerization is carried out under body, catalyst, co-catalyst ratio.
Under the conditions of anhydrous and oxygen-free, β prepared in above-described embodiment 5-pyridine enamine bidentate aluminum complex aluminium is catalyzed
5 solid of agent weighs 17 mg(50 μm of ol) it is dissolved in 4.5 mL toluene solvants, 0.5 mL benzylalcohol (0.1 is added at 70 DEG C
Mol/L is dissolved in toluene, 50 μm of ol) it is used as co-catalyst, it is stirred to react 30 min(embodiments 15 and benzylalcohol is not added, implement
1 mL benzylalcohol (0.1 mol/L, is dissolved in toluene, 100 μm of ol) is added in example 16).Then, respectively according to different monomers, urge
6-caprolactone monomer (1 mL(10 mmol is added in embodiment 13) monomer is added in agent, co-catalyst ratio, and embodiment 14 is added 2
ML(20 mmol) monomer).Control temperature is stirred to react 20-50 min respectively under the conditions of 70 oC.During the reaction, it monitors
When monomer conversion, uniformly 0.1 mL is extracted reaction solution 5 times to constant duration, it is every with 600 M nuclear magnetic resonance spectroscopy analytical calculations
The conversion ratio of secondary extracted reaction solution middle monomer.Then 3 drop glacial acetic acids are added and terminate reaction, adds 100 mL methanol and makes white
Polymer is precipitated completely, is filtered to remove methanol, is subsequently added into methanol and sufficiently washs white polymer, is finally dried to obtain purification
Gained polycaprolactone is carried out GPC test by polycaprolactone product, and polymerization results are shown in Table 1 number 7-10.As it can be seen that ought be gradually
When increasing monomer concentration, molecular weight is gradually increased, and molecular weight distribution is relatively narrow, belongs to controllable polymerization reaction (embodiment 13,14);When
In system at non-promoted dose, molecular weight differs larger with calculated value, illustrates the poor (embodiment of the controllability of polymerization reaction
15);When the co-catalyst of 2 times of amounts is added in system, catalytic polymerization activity is preferable, molecular weight and calculated value phase
When molecular weight distribution is relatively narrow, belongs to controllable polymerization reaction (embodiment 16).
1 catalyst 1-6 of table is catalyzed 6-caprolactone ring-opening polymerization result
Claims (7)
1. a kind of β-pyridine enamine bidentate aluminum complex, it is characterised in that: the β-pyridine enamine bidentate aluminum complex structure
Formula are as follows:
, wherein R1For H, CH3、CH2CH3、CH(CH3)2Or F;R2For H, F;
R3For H, F.
2. synthesizing a kind of method of β-pyridine enamine bidentate aluminum complex described in claim 1, it is characterised in that: use 2- (2-
Pyridyl group)-acetophenone with the aromatic amine containing different substituents carries out condensation reaction, obtain the ligand containing two nitrogen-atoms, then with
Alkyl aluminum is coordinated, and a series of β-pyridine enamine bidentate aluminium metal complex is synthesized.
3. synthesis β-pyridine enamine bidentate aluminum complex method according to claim 2, it is characterised in that: specific steps
It is as follows:
(1) β-pyridine enamine ligand synthesis: at room temperature, by 2- (2- the pyridyl group)-acetophenone and aromatic amine of equimolar amounts
Be dissolved in toluene solvant, be added with aromatic amine molar ratio be 1:50-1:80 trifluoroacetic acid as catalyst, solution is flowed back
24-48 h is reacted, then is removed the water of generation with water segregator, then revolving removes solvent, mixed with petroleum ether and ethyl acetate
Bonding solvent goes out product by pillar layer separation, the β refined-pyridine enamine ligand;
(2) under the conditions of anhydrous and oxygen-free, β-pyridine enamine ligand β-pyridine enamine bidentate aluminum complex synthesis: is dissolved in first
In benzene solvent, the hexane solution of the trimethyl aluminium of 1.2 times of moles is then added dropwise, continues to be stirred to react 3- at room temperature
6 h, then at 100-110 DEG C react 12-24 h, drain toluene solvant after the reaction was completed and obtain sediment, add just oneself
Alkane washing precipitating, stands, is filtered to remove filtrate, obtains β-pyridine enamine bidentate aluminium after residue precipitating is dried under vacuum and cooperates
Object.
4. synthesis β-pyridine enamine bidentate aluminum complex method according to claim 3, it is characterised in that: the virtue
Fragrant amine be aniline, 2,6- dimethylaniline, 2,6- diethylaniline, 2,6- diisopropyl aniline, para-fluoroaniline or 2,3,4,5,
Any one in 6- pentafluoroaniline.
5. synthesis β-pyridine enamine bidentate aluminum complex method according to claim 3, it is characterised in that: the stone
The in the mixed solvent petroleum ether of oily ether and ethyl acetate: ethyl acetate=7:1-15:1.
6. a kind of β-pyridine enamine bidentate aluminum complex purposes, it is characterised in that: the β-pyridine enamine bidentate aluminum complex
It as the catalyst of 6-caprolactone ring-opening polymerization, is used cooperatively with co-catalyst benzylalcohol, for being catalyzed 6-caprolactone open loop
Polymerization reaction.
7. the application of β according to claim 6-pyridine enamine bidentate aluminum complex, it is characterised in that: specific steps are as follows:
Under the conditions of anhydrous and oxygen-free, β-pyridine enamine bidentate aluminum complex catalyst solid is dissolved in toluene solvant, according to monomer:
Catalyst: the ratio of co-catalyst is respectively 100:1:1,200:1:1,400:1:1, the ratio of 100:1:0,100:1:2,
Under the conditions of 70-80 DEG C, co-catalyst benzylalcohol is first added, is stirred to react 30 min;Monomer 6-caprolactone is added, control temperature exists
20-240 min is stirred to react under the conditions of 70-80 DEG C;During the reaction, monitor monomer conversion when, constant duration it is equal
It is even to extract reaction solution 5 times, with the conversion ratio of nuclear magnetic resonance spectroscopy analytical calculation extracted reaction solution middle monomer every time, and record final turn
Rate;Then 3 drop glacial acetic acids are added and terminate reaction, adds 100 mL methanol and white polymer is precipitated completely, cross and filter out
Methanol is removed, methanol is added and sufficiently washs white polymer, is finally dried to obtain the polycaprolactone product of purification, and carries out GPC
Test.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810980422.8A CN109336916A (en) | 2018-08-27 | 2018-08-27 | A kind of synthesis and catalysis 6-caprolactone ring-opening polymerisation of β-pyridine enamine bidentate aluminum complex |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810980422.8A CN109336916A (en) | 2018-08-27 | 2018-08-27 | A kind of synthesis and catalysis 6-caprolactone ring-opening polymerisation of β-pyridine enamine bidentate aluminum complex |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109336916A true CN109336916A (en) | 2019-02-15 |
Family
ID=65291587
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810980422.8A Pending CN109336916A (en) | 2018-08-27 | 2018-08-27 | A kind of synthesis and catalysis 6-caprolactone ring-opening polymerisation of β-pyridine enamine bidentate aluminum complex |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109336916A (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101928296A (en) * | 2010-07-07 | 2010-12-29 | 中国科学院化学研究所 | 2-(nitrogen heterocycle) benzimidazole complex alkyl aluminum compound, and preparation method and application thereof |
CN106046038A (en) * | 2016-06-02 | 2016-10-26 | 青岛科技大学 | 8-N-arylamine-hydrogenation quinoline complexation aluminum alkyl compound and preparation method and application thereof |
CN106928266A (en) * | 2017-03-03 | 2017-07-07 | 山西大学 | A kind of quinolyl [N, N] bidentate metal chelate catalyst and its synthetic method and application |
CN107001393A (en) * | 2014-11-28 | 2017-08-01 | 优美科股份公司及两合公司 | For thin film fabrication and the new N aminoguanidines metal carbonyl complexes of catalysis |
-
2018
- 2018-08-27 CN CN201810980422.8A patent/CN109336916A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101928296A (en) * | 2010-07-07 | 2010-12-29 | 中国科学院化学研究所 | 2-(nitrogen heterocycle) benzimidazole complex alkyl aluminum compound, and preparation method and application thereof |
CN107001393A (en) * | 2014-11-28 | 2017-08-01 | 优美科股份公司及两合公司 | For thin film fabrication and the new N aminoguanidines metal carbonyl complexes of catalysis |
CN106046038A (en) * | 2016-06-02 | 2016-10-26 | 青岛科技大学 | 8-N-arylamine-hydrogenation quinoline complexation aluminum alkyl compound and preparation method and application thereof |
CN106928266A (en) * | 2017-03-03 | 2017-07-07 | 山西大学 | A kind of quinolyl [N, N] bidentate metal chelate catalyst and its synthetic method and application |
Non-Patent Citations (2)
Title |
---|
MARKUS GRASER ET AL.: "Structurally diverse pyridyl or quinolyl enolato/enamido metal complexes of Li, Zr, Fe, Co, Ni, Cu and Zn", 《INORGANICA CHIMICA ACTA》 * |
PENG WANG ET AL.: "Living ring-opening polymerization of ε-caprolactone catalyzed by β-quinolyl-enamino aluminium complexes: ligand electronic effects", 《DALTON TRANS》 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zheng et al. | Zinc and enolato-magnesium complexes based on bi-, tri-and tetradentate aminophenolate ligands | |
CN101418010B (en) | Novel bridged beta-diimido binuclear aluminum compound and preparation method and use thereof | |
CN102827311A (en) | Binuclear acenaphthene (alpha-diimine) nickel/palladium catalysts for olefins, and preparation method and application thereof | |
CN109879810A (en) | A kind of cyclosubstituted amino phenols oxygroup zinc complex of imidazoles and its preparation method and application | |
Wang et al. | Rare-earth complexes supported by an ansa-bis (amidinate) ligand with a rigid o-phenylene linker: synthesis, structure, and catalytic activity for polymerization of cyclic esters | |
CN104557874B (en) | Quinoline amido indyl zinc, magnesium, calcium compounds and its preparation method and application | |
Yang et al. | The behavior of pyrrolyl ligands within the rare-earth metal alkyl complexes. Insertion of C [double bond, length as m-dash] N and C [double bond, length as m-dash] O double bonds into Ln–σ-C bonds | |
Ji et al. | Synthesis of Ti, Zr, and Hf complexes with a new tetra-azane ligand by one-pot HCl-elimination and their properties as catalysts for production of UHMWPE | |
CN109336916A (en) | A kind of synthesis and catalysis 6-caprolactone ring-opening polymerisation of β-pyridine enamine bidentate aluminum complex | |
Okada et al. | Synthesis of anilinonaphthoquinone-based nickel complexes and their application for olefin polymerization | |
Holton et al. | Regiocontrolled aromatic palladation | |
Gsponer et al. | Ligand‐Dependent Diastereoselectivity in the Palladium‐Catalyzed Copolymerization of Styrene with Carbon Monoxide | |
CN109485840B (en) | Method for catalyzing lactide polymerization by using amine imine magnesium complex | |
CN112142801B (en) | Asymmetric pyridine imine cobalt complex and preparation method and application thereof | |
CN108912010A (en) | A kind of schiff bases manganese compound, preparation method and its application | |
CN106380478B (en) | A kind of preparation method of three metal centers schiff bases aluminium compound, preparation method, application and polylactic acid | |
Ferretti et al. | Unexpected coordination behavior of ruthenium to a polymeric α-diimine containing the poly [bis (arylimino) acenaphthene] fragment | |
Beaufort et al. | Iron (II)–ethylene polymerization catalysts bearing 2, 6-bis (imino) pyrazine ligands: part I. Synthesis and characterization | |
CN111233939B (en) | Asymmetric iminacenaphthene nickel halide complex and preparation method and application thereof | |
Osakada et al. | Reactions of Methoxyallene and of Phenylallene with RhH (CO)(PPh3) 3. Insertion of a C: C Bond into an Rh-H Bond, Giving (. pi.-Allyl) rhodium (I) Complexes | |
Liu et al. | Titanium, aluminum and zinc complexes containing diamine-bis (benzotriazole phenolate) ligands: synthesis, structural characterization and catalytic studies for ring-opening polymerization of ε-caprolactone | |
CN105367590B (en) | Biphenyl backbone chiral amino phenol epoxide double-core zinc, magnesium compound and its preparation method and application | |
CN109456342A (en) | A kind of 1,2- addition quinolyl lithium-complex and its synthetic method and application | |
Wang et al. | Synthesis, Characterization of Zinc Complexes with Neutral α-Diimine Ligands and Application in Ring-opening Polymerization of ε-Caprolactone | |
CN106928266B (en) | A kind of quinolyl [N, N] bidentate metal chelate catalyst and its synthetic method and application |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190215 |
|
RJ01 | Rejection of invention patent application after publication |