CN109705159B - Preparation method and application of phosphorus-nitrogen-containing ligand alkyl aluminum compound - Google Patents
Preparation method and application of phosphorus-nitrogen-containing ligand alkyl aluminum compound Download PDFInfo
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Abstract
The invention discloses a preparation method of a 2-diphenylphosphine benzaldehyde-aniline alkyl aluminum compound and application thereof in ring-opening polymerization of lactone and lactide. The preparation method of the 2-diphenylphosphine benzaldehyde-aniline alkyl aluminum compound comprises the following steps: dissolving a 2-diphenylphosphinobenzaldehyde-aniline ligand in 30-100 mL of an anhydrous solvent, adding 1.0-1.5 molar equivalent of alkyl aluminum, and stirring and reacting for 12-24 hours under the protection of nitrogen at the reaction temperature of 20-100 ℃; the solvent was removed under reduced pressure and washed three times with a poor solvent to give the corresponding alkyl aluminum compound. The 2-diphenylphosphine benzaldehyde-aniline alkyl aluminum compound is a high-efficiency lactone and lactide ring-opening polymerization catalyst and can be used for the polymerization reaction of different lactones. The 2-diphenylphosphine benzaldehyde-aniline alkyl aluminum compound has the following obvious advantages: the raw materials are cheap and easy to obtain, the synthesis route is simple, the product yield is high, and the properties are stable; the activity of catalyzing the ring-opening polymerization of caprolactone is high, and the controllability is good; the prepared polycaprolactone polymer material has controllable molecular weight and low molecular weight distribution.
Description
Technical Field
The invention relates to a preparation method and application of an organic aluminum compound, in particular to a preparation method of a 2-diphenylphosphine benzaldehyde-aniline alkyl aluminum compound and application thereof in ring-opening polymerization of lactone and lactide.
Background
Compared with the traditional polymer material, the degradable polyester polymer material has obvious advantages in the aspects of environmental friendliness, biocompatibility and the like, is a new generation of material with wide development prospect, and meets the requirements of ecological and sustainable development. Among them, aliphatic polyesters are a very important class of degradable polymeric materials, and have been rapidly developed in recent years.
Biodegradable polyesters such as PCL, PLA and the like have good biocompatibility and biodegradability, can be completely biodegraded under natural environmental conditions, and do not cause any pollution to the environment, so the biodegradable polyesters can be widely used in the field of medicine, can be used as drug carriers, can regulate the drug release rate by controlling the degradation rate, can also be used as surgical sutures, can be naturally degraded in organisms, are non-toxic and harmless to the organisms, and do not need to be disconnected. In addition, biodegradable polyesters are also being developed in the industrial and agricultural fields, and are excellent environmentally friendly materials that are used as substitutes for difficult-to-degrade materials such as plastics using petroleum as a raw material.
Aliphatic polyesters widely studied and applied at present comprise polylactic acid (PLA), Polycaprolactone (PCL), polyglycolic acid (PGA), Polyhydroxybutyrate (PHB) and copolymers thereof, and are mainly prepared by a method of catalyzing ring-opening polymerization of monomers, and commonly used catalysts comprise zinc isopropoxide, stannous octoate and the like. Among them, stannous octoate, which has a fast reaction rate and can obtain a polyester material with high yield and high molecular weight, is most widely used, but has disadvantages in that the reactivity is not very high, and a long reaction time and a high reaction temperature are required. In recent years, organometallic aluminum compounds have attracted great attention as ring-opening polymerization catalysts due to their excellent characteristics in catalyzing ring-opening polymerization of lactones, and are used for preparing biodegradable aliphatic polyester polymer materials with controllable molecular weight, narrow molecular weight distribution and regular blocks or stereo structure. Representative catalyst models for comparison among these organometallic aluminum catalysts include Salen (Salen) aluminum catalyst (j.am. chem. so., 2002,124,1316; proc.natl.acad.sci.u.s.a.2006,103,15343), salicylaldiminium aluminum catalyst (Macromolecules,2005,38, 5363; Dalton trans.2012,41,11587; Organometallics 2009,28,2179), bridged bisphenol-aluminum catalyst (macromoles 2001,34,6196), tetraphenylporphyrin aluminum catalyst (j.am. chem. so.2004, 126,11030), bimetallic aluminum catalyst (Organometallics 2014,33, 6474; chem. commu.2008, 4717).
The applicant previously reported a series of aluminium metal catalysts for aliphatic polyester synthesis, such as Chinese j.polym.sci.2018,36,149; J.Polym.Sci., Part A: Polym.Chem.2018,56,611; new j. chem.2017,41,2358; organometallics 2017,36, 1736; the related inventions ZL201610369322.2, ZL201610370061.6 and ZL201610383016.4 are applied. The catalysts referred to in the above reports or patents are all nitrogen and oxygen containing aluminum metal catalysts, while the present invention reports a phosphorus and nitrogen containing aluminum metal catalyst, in particular to a preparation method of 2-diphenylphosphine benzaldehyde-aniline alkyl aluminum compound and an application thereof in ring-opening polymerization. The aluminum catalyst has the characteristics of simple preparation, low cost, high activity and good controllability, and the prepared aliphatic polyester has the characteristics of controllable microstructure, degradability and good biocompatibility.
Disclosure of Invention
The invention aims to provide a preparation method of a 2-diphenylphosphinobenzaldehyde-aniline alkyl aluminum compound and application thereof in ring-opening polymerization.
The invention provides a 2-diphenylphosphorylbenzaldehyde-phenylamine alkyl aluminum compound shown as a formula (I):
wherein R is selected from methyl, ethyl and isopropyl; r1Selected from hydrogen, methyl, isopropyl, benzhydryl; r2Selected from hydrogen and isopropyl.
Preferably, the aluminium metal complex of the present invention is selected from any one of the following complexes:
Al1:L1AlMe2L1＝2-Ph2P-C6H4-CH2-NH-C6H5；
Al2:L2AlMe2L2＝2-Ph2P-C6H4-CH2-NH-2,6-Me-C6H3；
Al3:L3AlMe2L3＝2-Ph2P-C6H4-CH2-NH-2,6-iPr-C6H3；
Al4:L1AlMe2L4＝2-Ph2P-C6H4-CH2-NH-2,6-Ph2CH-4-iPr-C6H2；
the invention provides a preparation method of the 2-diphenylphosphine benzaldehyde-aniline alkyl aluminum compound, which comprises the following steps:
(1) under the nitrogen atmosphere, reacting 2-diphenylphosphine benzaldehyde and substituted aniline according to the weight ratio of 0.8-1.2: mixing the components in a molar ratio of 0.8-1.5, adding 5-20 mg of p-toluenesulfonic acid in a catalytic amount, and stirring and reacting in a mixed solvent of methanol and dichloromethane (the volume ratio of the methanol to the dichloromethane is 1: 1-5) for 6-48 hours; and removing the mixed solvent under reduced pressure, adding methanol into the obtained product, performing ultrasonic treatment, filtering and draining the product, adding 2-5 molar equivalent of lithium aluminum hydride into the obtained imine, and reacting for two days to obtain the 2-diphenylphosphine benzaldehyde-aniline ligand.
(2) Dissolving a 2-diphenylphosphinobenzaldehyde-aniline ligand in 30-100 mL of an anhydrous solvent, adding 1.0-1.5 molar equivalent of alkyl aluminum, and stirring and reacting for 12-24 hours under the protection of nitrogen at the reaction temperature of 20-100 ℃; the solvent was removed under reduced pressure and washed three times with a poor solvent to give the corresponding alkyl aluminum compound.
In the above preparation method, the anhydrous solvent is selected from benzene, toluene, xylene, tetrahydrofuran, preferably toluene; the poor solvent is selected from n-hexane, n-pentane, n-heptane, cyclohexane, preferably n-hexane.
The invention also provides application of the 2-diphenylphosphinobenzaldehyde-aniline alkyl aluminum compound shown in the formula (I) in catalyzing ring-opening polymerization reaction of lactone and lactide.
In the above applications, the lactones and lactides include caprolactone, lactide, glycolide, butyrolactone, valerolactone, heptalactone, octalactone, preferably caprolactone.
In the above application, the molar ratio of the diphenylphosphinobenzaldehyde-aniline alkyl aluminum compound to the lactide and lactone is 1: 10-10000, preferably 1: 100.
in the above application, the solvent for the polymerization reaction may be benzene, toluene, n-hexane, tetrahydrofuran and dichloromethane, and toluene is preferred.
In the above application, the temperature of the polymerization reaction is 0 ℃ to 110 ℃.
In the application, the time of the polymerization reaction is 0.1-12 h.
In the above application, alcohol can be added as a cocatalyst in the polymerization reaction, wherein the alcohol is methanol, ethanol, isopropanol, n-butanol, ethylene glycol, glycerol, or benzyl alcohol; the molar ratio of the alcohol to the 2-diphenylphosphine benzaldehyde-aniline alkyl aluminum compound is 0-30: 1, preferably 1: 1.
the 2-diphenylphosphorylbenzaldehyde-aniline alkyl aluminum compound provided by the invention is convenient to prepare, low in cost, stable in property and high in catalytic activity, and is particularly suitable for catalyzing the ring-opening polymerization of caprolactone. The molecular weight of the polymer can be regulated and controlled by controlling the polymerization reaction conditions, and the molecular weight can be from thousands to hundreds of thousands.
Drawings
FIG. 1 is a crystal structure diagram of compound Al 2.
FIG. 2 is a crystal structure diagram of compound Al 3.
FIG. 3 is a crystal structure diagram of compound Al 4.
FIG. 4 is a GPC chart of the polymer obtained in example 6.
FIG. 5 is a GPC chart of the polymer obtained in example 7.
FIG. 6 is a GPC chart of the polymer obtained in example 8.
FIG. 7 is a GPC chart of the polymer obtained in example 9.
FIG. 8 is a MALDI TOF chart of the polymer obtained in example 9.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited thereto. Embodiments of the present invention will allow those skilled in the art to more fully understand the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
L1 (2-Ph) in the present invention2P-C6H4-CH2-NH-C6H5)、L2(2-Ph2P-C6H4-CH2-NH-2,6-Me-C6H3) And L3 (2-Ph)2P-C6H4-CH2-NH-2,6-iPr-C6H3) Synthesized according to the methods reported in the New Journal of Chemistry, 2003,27,414 and Chemistry-A European Journal,2007,13,834, respectively.
Example 1 ligand L4 (2-Ph)2P-C6H4-CH2-NH-2,6-Ph2CH-4-iPr-C6H2) Preparation of
Reacting 2, 6-bis (diphenylmethyl) -4-isopropyl-aniline (2, 6-Ph)2CH-4-iPr-C6H2-NH24.67g,10.0mmol), 2-diphenylphosphinobenzaldehyde (2.90g,10.0mmol) and 10mg of p-toluenesulfonic acid were mixed in 100mL of toluene, refluxed for 12 hours under a nitrogen atmosphere and washed with methanol to obtain imine (2-Ph) as a product2P-C6H4-CH＝N-2,6-Ph2CH-4-iPr-C6H22.22g,3mmol) with LiAlH4(0.57g,15mmol) was dissolved in 60mL of anhydrous tetrahydrofuran and reacted at room temperature under nitrogen for 2 days, quenched with 0.57mL of water followed by 0.57mL of 15% aqueous sodium hydroxide to give 1.93g,2.6mmol, 87% yield of the L4 compound as a white solid.1H NMR(CDCl3):δ7.34–7.11(m,25H),7.04(d,J＝7.0Hz,8H),6.83(dd,J＝7.4and 4.5Hz,1H),6.64(s,2H),6.17(s,2H),4.09–4.01(br,2H),3.28–3.20(br,1H),2.61(hept,J＝6.7Hz,1H),0.97(d,J＝6.9Hz,6H).13C NMR(CDCl3):144.62,144.36,143.43,143.09,138.80,136.78(d,JPC＝10.2Hz),135.50(d,JPC＝13.7Hz),133.99,133.80,129.81,129.53(d,JPC＝5.7Hz),129.38,128.76,128.66(d,JPC＝6.9Hz),128.26,127.73,127.39,126.20,53.79,53.57,51.29,33.55,24.02.31P NMR(CDCl3):-16.28.Anal.Calcd for C54H48NP:C,87.42；H,6.52；N,1.89.Found:C,87.23；H,6.36；N,1.57.
Example 2, Compound Al1(L1 AlMe)2) Preparation of
Ligand L1 (2-Ph) under nitrogen atmosphere2P-C6H4-CH2-NH-2,6-Ph2CH-4-iPr-C6H20.367g, 1mmol) was dissolved in 20mL of toluene and 1.1 molar equivalent was slowly addedAlMe3(1.2mmol, 0.6mL, 2M in toluene), and stirred at 80 ℃ for 16 hours. The toluene solvent was removed under reduced pressure, and n-hexane (3X 10mL) was added thereto for washing to obtain 0.354g, 0.82mmol, 82% of a white solid Al1 compound.1H NMR(CDCl3):δ7.66(t,J＝6.3Hz,1H),7.47(t,J＝7.5Hz,1H),7.45–7.41(m,2H),7.39–7.32(m,4H),7.30–7.20(m,5H),7.10(t,J＝8.3Hz,1H),7.02(dd,J＝8.5and 7.3Hz,2H),6.79(d,J＝8.1Hz,2H),6.49(t,J＝7.2Hz,1H),4.52(s,2H),-0.50(d,JPH＝4.3Hz,6H).13C NMR(CDCl3):154.29,149.89(d,JPC＝14.1Hz),135.81,133.60(d,JPC＝12.9Hz),131.30,130.74,130.38(d,JPC＝9.5Hz),129.13,129.03,128.85,128.51,128.19,127.51(d,JPC＝5.6Hz),127.11,126.80,115.05,52.05,-7.92(d,JPC＝21.1Hz).31P NMR(CDCl3):-26.27.Anal.Calcd for C27H27AlNP:C,76.58；H,6.43；N,3.31.Found:C,76.50；H,6.22；N,3.18.
Example 3 Compound Al2(L2 AlMe)2) Preparation of
The procedure is as in example 2, complex Al2(L2 AlMe)2) Yield: 0.361g, 0.80mmol, 80%.1H NMR(CDCl3):δ7.56–7.49(m,2H),7.49–7.43(m,4H),7.43–7.36(m,4H),7.31(t,J＝7.4Hz,1H),7.22(t,J＝7.4Hz,1H),7.09–7.01(m,2H),6.99(d,J＝7.4Hz,2H),6.84(t,J＝7.4Hz,1H),4.15(s,2H),1.98(s,6H),-0.67(d,JPH＝3.7Hz,6H).13C NMR(CDCl3):152.46,150.98(d,JPC＝13.4Hz),137.80,134.92,134.03(d,JPC＝12.7Hz),130.95,130.80,129.15(d,JPC＝9.1Hz),128.89,128.82,128.59,128.08,127.40,127.11,127.01(d,JPC＝5.7Hz),122.61,57.49,19.59,-9.18(d,JPC＝21.3Hz).31P NMR(CDCl3):-25.01.Anal.Calcd for C29H31AlNP:C,77.14；H,6.92；N,3.10.Found:C,77.05；H,6.71；N,2.99.
Example 4, Compound Al3(L3 AlMe)2) Preparation of
The procedure is as in example 2, complex Al3(L3 AlMe)2) Yield: 0.385g, 0.76mmol，76％。1H NMR(CDCl3):δ7.53–7.49(m,2H),7.48–7.44(m,4H),7.39(t,J＝8.4Hz,4H),7.30(t,J＝7.4Hz,1H),7.22(t,J＝7.4Hz,1H),7.13(d,J＝6.7Hz,1H),7.10(d,J＝6.5Hz,1H),7.06–7.01(m,3H),4.22(s,2H,CH2-N),3.33(hept,J＝6.9Hz,2H,CHMeMe),1.07(d,J＝6.9Hz,6H,CHMeMe),0.80(d,J＝6.9Hz,6H,CHMeMe),-0.72(d,JPH＝3.9Hz,6H,Al-Me).13C NMR(CDCl3):150.70,150.56,149.53(d,JPC＝4.1Hz),148.22(d,JPC＝1.2Hz),135.26,133.68(d,JPC＝12.8Hz),130.76,130.57,129.44(d,JPC＝9.5Hz),129.10,128.98(d,JPC＝9.0Hz),128.80,127.11,127.01(d,JPC＝5.6Hz),126.83,123.51,123.22,59.71(d,JPC＝3.7Hz),28.06,25.09,24.36,-9.88(d,JPC＝21.5Hz).31P NMR(CDCl3):-25.94.Anal.Calcd for C33H39AlNP:C,78.08；H,7.74；N,2.76.Found:C,77.98；H,7.49；N,2.65.
Example 5, Compound Al4(L4 AlMe)2) Preparation of
The procedure is as in example 2, compound Al4(L4 AlMe)2) Yield: 0.686g, 0.86mmol, 86%.1H NMR(CDCl3):δ7.45–7.37(m,2H),7.36–7.29(m,8H),7.20–7.00(m,14H),6.94–6.87(m,1H),6.85(d,J＝7.2Hz,4H),6.81–6.76(m,4H),6.70(s,2H),6.20–6.21(m,1H),6.09(s,2H),3.84(s,2H),2.62(hept,J＝6.9Hz,1H),0.99(d,J＝6.9Hz,6H),-0.76(d,JPH＝4.2Hz,6H).13C NMR(CDCl3):151.12,150.97,150.73(d,JPC＝4.5Hz),146.60,145.64,144.51,142.44,142.26,135.35,133.72(d,JPC＝12.6Hz),130.74,130.55,129.78(d,JPC＝13.2Hz),129.59,129.23,129.06,128.93(d,JPC＝9.2Hz),128.63,128.57,128.50,128.25,128.13,127.67(d,JPC＝8.0Hz),126.40,126.34,126.08,125.34(d,JPC＝6.4Hz),124.93,124.64,59.61,51.15,33.29,23.88,-8.71(d,JPC＝21.9Hz).31P NMR(CDCl3):-26.81.Anal.Calcd for C56H53AlNP:C,84.29；H,6.69；N,1.76.Found:C,84.02；H,6.51.49；N,1.88.
Example 6, Compound Al1 and benzyl alcohol catalyzed polymerization of ε -caprolactone
In a Schlenk flask, 0.228g of ε -caprolactone was added under anhydrous and anaerobic conditions, 1mL of TOL was added, 20. mu. mol of complex Al1(8.5mg), and 2.1. mu.L of benzyl alcohol (20. mu. mol) was dissolved in 1mL of TOL, and the resulting solution was added to the Schlenk flask with a syringe to initiate polymerization. Controlling the reaction temperature to react for 20min at 25 ℃, adding 1mL of 5% acetic acid methanol solution, pouring into methanol to precipitate out a polymer, filtering, and drying in vacuum for 24 hours to obtain polycaprolactone. Conversion rate: 93 percent. The number average molecular weight M of the polycaprolactonen:1.24×104g/mol, molecular weight distribution PDI 1.14. The number average molecular weight is determined by gel permeation chromatography with Agilent 1260 Infinity and THF as solvent at a flow rate of 1mL min-1The test temperature was 40 ℃.
Example 7, Compound Al2 and benzyl alcohol catalyzed polymerization of ε -caprolactone
In a Schlenk flask, 0.228g of ε -caprolactone was added under anhydrous and anaerobic conditions, 1mL of TOL was added, 20. mu. mol of complex Al2(9.0mg), and 2.1. mu.L of benzyl alcohol (20. mu. mol) was dissolved in 1mL of TOL, and the resulting solution was added to the Schlenk flask with a syringe to initiate polymerization. Controlling the reaction temperature to react for 20min at 25 ℃, adding 1mL of 5% acetic acid methanol solution, pouring into methanol to precipitate out a polymer, filtering, and drying in vacuum for 24 hours to obtain polycaprolactone. Conversion rate: 79 percent. The number average molecular weight M of the polycaprolactonen:1.14×104g/mol, molecular weight distribution PDI 1.20. The number average molecular weight is determined by gel permeation chromatography with Agilent 1260 Infinity and THF as solvent at a flow rate of 1mL min-1The test temperature was 40 ℃.
Example 8, Compound Al3 and benzyl alcohol catalyzed polymerization of ε -caprolactone
In a Schlenk flask, 0.228g of ε -caprolactone was added under anhydrous and anaerobic conditions, 1mL of TOL was added, 20. mu. mol of complex Al3(10.2mg), and 2.1. mu.L of benzyl alcohol (20. mu. mol) was dissolved in 1mL of TOL, and the resulting solution was added to the Schlenk flask with a syringe to initiate polymerization. Controlling the reaction temperature to react for 20min at 25 ℃, adding 1mL of 5% acetic acid methanol solution, pouring into methanol to precipitate out a polymer, filtering, and drying in vacuum for 24 hours to obtain polycaprolactone. Conversion rate: 75 percent. The number average molecular weight M of the polycaprolactonen:1.01×104g/mol, molecular weight distribution PDI 1.19. The number average molecular weight is determined by gel permeation chromatography with Agilent 1260 Infinity and THF as solvent at a flow rate of 1mL min-1The test temperature was 40 ℃.
Example 9, Compound Al4 and benzyl alcohol catalyzed polymerization of ε -caprolactone
In a Schlenk flask, 0.228g of ε -caprolactone was added under anhydrous and anaerobic conditions, 1mL of TOL was added, 20. mu. mol of complex Al4(16.0mg), and 2.1. mu.L of benzyl alcohol (20. mu. mol) was dissolved in 1mL of TOL, and the resulting solution was added to the Schlenk flask with a syringe to initiate polymerization. Controlling the reaction temperature to react for 20min at 25 ℃, adding 1mL of 5% acetic acid methanol solution, pouring into methanol to precipitate out a polymer, filtering, and drying in vacuum for 24 hours to obtain polycaprolactone. Conversion rate: 95 percent. The number average molecular weight M of the polycaprolactonen:1.33×104g/mol, molecular weight distribution PDI 1.14. The number average molecular weight is determined by gel permeation chromatography with Agilent 1260 Infinity and THF as solvent at a flow rate of 1mL min-1The test temperature was 40 ℃.
Example 10, Compound Al1 and benzyl alcohol catalyzed polymerization of ε -caprolactone
In a Schlenk flask, 0.228g of ε -caprolactone was added under anhydrous and anaerobic conditions, 1mL of TOL was added, 20. mu. mol of complex Al1(8.5mg), and 2.1. mu.L of benzyl alcohol (20. mu. mol) was dissolved in 1mL of TOL, and the resulting solution was added to the Schlenk flask with a syringe to initiate polymerization. Controlling the reaction temperature at 70 ℃ for reaction for 10min, adding 1mL of 5% acetic acid methanol solution, pouring into methanol to precipitate out a polymer, filtering, and carrying out vacuum drying for 24 hours to obtain polycaprolactone. Conversion rate: is more than 99 percent. The number average molecular weight M of the polycaprolactonen:1.31×104g/mol, molecular weight distribution PDI 1.33. The number average molecular weight is determined by gel permeation chromatography with Agilent 1260 Infinity and THF as solvent at a flow rate of 1mL min-1The test temperature was 40 ℃.
Example 11, Compound Al2 and benzyl alcohol catalyzed polymerization of ε -caprolactone
In a Schlenk flask, 0.228g of ε -caprolactone was added under anhydrous and anaerobic conditions, 1mL of TOL was added, 20. mu. mol of complex Al2(9.0mg), and 2.1. mu.L of benzyl alcohol (20. mu. mol) was dissolved in 1mL of TOL, and the resulting solution was added to the Schlenk flask with a syringe to initiate polymerization. Control is reversedReacting at 70 ℃ for 10min, adding 1mL of 5% acetic acid methanol solution, pouring into methanol to precipitate out a polymer, filtering, and vacuum drying for 24 hours to obtain polycaprolactone. Conversion rate: 56 percent. The number average molecular weight M of the polycaprolactonen:8.3×103g/mol, molecular weight distribution PDI 1.41. The number average molecular weight is determined by gel permeation chromatography with Agilent 1260 Infinity and THF as solvent at a flow rate of 1mL min-1The test temperature was 40 ℃.
Example 12 polymerization of epsilon-caprolactone catalyzed by Compound Al3 and benzyl alcohol
In a Schlenk flask, 0.228g of ε -caprolactone was added under anhydrous and anaerobic conditions, 1mL of TOL was added, 20. mu. mol of complex Al3(10.2mg), and 2.1. mu.L of benzyl alcohol (20. mu. mol) was dissolved in 1mL of TOL, and the resulting solution was added to the Schlenk flask with a syringe to initiate polymerization. Controlling the reaction temperature at 70 ℃ for reaction for 10min, adding 1mL of 5% acetic acid methanol solution, pouring into methanol to precipitate out a polymer, filtering, and carrying out vacuum drying for 24 hours to obtain polycaprolactone. Conversion rate: and 63 percent. The number average molecular weight M of the polycaprolactonen:8.7×103g/mol, molecular weight distribution PDI 1.41. The number average molecular weight is determined by gel permeation chromatography with Agilent 1260 Infinity and THF as solvent at a flow rate of 1mL min-1The test temperature was 40 ℃.
Example 13, Compound Al4 and benzyl alcohol catalyzed polymerization of ε -caprolactone
In a Schlenk flask, 0.228g of ε -caprolactone was added under anhydrous and anaerobic conditions, 1mL of TOL was added, 20. mu. mol of complex Al4(16.0mg), and 2.1. mu.L of benzyl alcohol (20. mu. mol) was dissolved in 1mL of TOL, and the resulting solution was added to the Schlenk flask with a syringe to initiate polymerization. Controlling the reaction temperature at 70 ℃ for reaction for 10min, adding 1mL of 5% acetic acid methanol solution, pouring into methanol to precipitate out a polymer, filtering, and carrying out vacuum drying for 24 hours to obtain polycaprolactone. Conversion rate: is more than 99 percent. The number average molecular weight M of the polycaprolactonen:1.44×104g/mol, molecular weight distribution PDI 1.21. The number average molecular weight is determined by gel permeation chromatography with Agilent 1260 Infinity and THF as solvent at a flow rate of 1mL min-1The test temperature was 40 ℃.
Example 14, Compound Al4 and benzyl alcohol catalyzed polymerization of ε -caprolactone
In a Schlenk flask, 0.228g of ε -caprolactone was added under anhydrous and anaerobic conditions, 1mL of TOL, 10. mu. mol of complex Al4(8.0mg), and 1.1. mu.L of benzyl alcohol (10. mu. mol) was dissolved in 1mL of TOL, and the resulting solution was added to the Schlenk flask with a syringe to initiate polymerization. Controlling the reaction temperature at 70 ℃ for reaction for 15min, adding 1mL of 5% acetic acid methanol solution, pouring into methanol to precipitate out a polymer, filtering, and carrying out vacuum drying for 24 hours to obtain polycaprolactone. Conversion rate: 96 percent. The number average molecular weight M of the polycaprolactonen:2.61×104g/mol, molecular weight distribution PDI 1.41. The number average molecular weight is determined by gel permeation chromatography with Agilent 1260 Infinity and THF as solvent at a flow rate of 1mL min-1The test temperature was 40 ℃.
Example 15, Compound Al4 and benzyl alcohol catalyzed polymerization of ε -caprolactone
In a Schlenk flask, 0.228g of ε -caprolactone was added under anhydrous and anaerobic conditions, 1mL of TOL, 4. mu. mol of complex Al4(3.2mg), and 0.4. mu.L of benzyl alcohol (4. mu. mol) was dissolved in 1mL of TOL, and the resulting solution was added to the Schlenk flask via a syringe to initiate polymerization. Controlling the reaction temperature at 70 ℃ for 30min, adding 1mL of 5% acetic acid methanol solution, pouring into methanol to precipitate out a polymer, filtering, and vacuum-drying for 24 hours to obtain polycaprolactone. Conversion rate: is more than 99 percent. The number average molecular weight M of the polycaprolactonen:5.12×104g/mol, molecular weight distribution PDI 1.32. The number average molecular weight is determined by gel permeation chromatography with Agilent 1260 Infinity and THF as solvent at a flow rate of 1mL min-1The test temperature was 40 ℃.
Example 16, Compound Al4 and benzyl alcohol catalyzed polymerization of ε -caprolactone
In a Schlenk flask, 0.228g of ε -caprolactone was added under anhydrous and anaerobic conditions, 1mL of TOL, 2. mu. mol of complex Al4(1.6mg), and 0.2. mu.L of benzyl alcohol (2. mu. mol) was dissolved in 1mL of TOL, and the resulting solution was added to the Schlenk flask via a syringe to initiate polymerization. Controlling the reaction temperature at 70 ℃ for reaction for 60min, adding 1mL of 5% acetic acid methanol solution, pouring into methanol to precipitate out a polymer, filtering, and carrying out vacuum drying for 24 hours to obtain polycaprolactone. Conversion rate: is more than 99 percent. The number average molecular weight M of the polycaprolactonen:7.32×104g/mol, molecular weight distribution PDI 1.29. Method for measuring number average molecular weightThe method is gel permeation chromatography, Agilent 1260 Infinity, THF as solvent, flow rate of 1mL min-1The test temperature was 40 ℃.
Example 17, Compound Al4 and benzyl alcohol catalyzed polymerization of ε -caprolactone
In a Schlenk flask, 0.456g of ε -caprolactone was added under anhydrous and anaerobic conditions, 1mL of TOL, 2. mu. mol of complex Al4(1.6mg), and 0.2. mu.L of benzyl alcohol (2. mu. mol) was dissolved in 1mL of TOL, and the resulting solution was added to the Schlenk flask via a syringe to initiate polymerization. Controlling the reaction temperature to react for 15min at 110 ℃, adding 1mL of 5% acetic acid methanol solution, pouring into methanol to precipitate out a polymer, filtering, and drying in vacuum for 24 hours to obtain polycaprolactone. Conversion rate: 91 percent. The number average molecular weight M of the polycaprolactonen:1.19×105g/mol, molecular weight distribution PDI 1.53. The number average molecular weight is determined by gel permeation chromatography with Agilent 1260 Infinity and THF as solvent at a flow rate of 1mL min-1The test temperature was 40 ℃.
Example 18, Compound Al4 and benzyl alcohol catalyzed polymerization of ε -caprolactone
In a Schlenk flask, 0.228g of ε -caprolactone was added under anhydrous and anaerobic conditions, 1mL of TOL was added, 10. mu. mol of complex Al4(8.0mg), and 2.1. mu.L of benzyl alcohol (20. mu. mol) was dissolved in 1mL of TOL, and the resulting solution was added to the Schlenk flask with a syringe to initiate polymerization. Controlling the reaction temperature at 70 ℃ for reaction for 15min, adding 1mL of 5% acetic acid methanol solution, pouring into methanol to precipitate out a polymer, filtering, and carrying out vacuum drying for 24 hours to obtain polycaprolactone. Conversion rate: 93 percent. The number average molecular weight M of the polycaprolactonen:1.29×104g/mol, molecular weight distribution PDI 1.18. The number average molecular weight is determined by gel permeation chromatography with Agilent 1260 Infinity and THF as solvent at a flow rate of 1mL min-1The test temperature was 40 ℃.
Example 19 polymerization of ε -caprolactone catalyzed by Compound Al4 and benzyl alcohol
In a Schlenk flask, 0.228g of ε -caprolactone was added under anhydrous and anaerobic conditions, 1mL of TOL was added, 4. mu. mol of complex Al4(3.2mg), and 2.1. mu.L of benzyl alcohol (20. mu. mol) was dissolved in 1mL of TOL, and the resulting solution was added to the Schlenk flask with a syringe to initiate polymerization. Controlling the reaction temperature at 70 ℃ for 30min, adding 1mL of 5% acetic acid methanol solution, and pouring into methanolPrecipitating the polymer, filtering, and vacuum drying for 24 hr to obtain polycaprolactone. Conversion rate: 97 percent. The number average molecular weight M of the polycaprolactonen:1.38×104g/mol, molecular weight distribution PDI 1.13. The number average molecular weight is determined by gel permeation chromatography with Agilent 1260 Infinity and THF as solvent at a flow rate of 1mL min-1The test temperature was 40 ℃.
Example 20, Compound Al4 and benzyl alcohol catalyzed polymerization of ε -caprolactone
In a Schlenk flask, 0.228g of ε -caprolactone was added under anhydrous and anaerobic conditions, 1mL of TOL, 2. mu. mol of complex Al4(1.6mg), and 2.1. mu.L of benzyl alcohol (20. mu. mol) was dissolved in 1mL of TOL, and the resulting solution was added to the Schlenk flask with a syringe to initiate polymerization. Controlling the reaction temperature at 70 ℃ for 2h, adding 1mL of 5% acetic acid methanol solution, pouring into methanol to precipitate out a polymer, filtering, and vacuum-drying for 24 h to obtain polycaprolactone. Conversion rate: 90 percent. The number average molecular weight M of the polycaprolactonen:1.18×104g/mol, molecular weight distribution PDI 1.13. The number average molecular weight is determined by gel permeation chromatography with Agilent 1260 Infinity and THF as solvent at a flow rate of 1mL min-1The test temperature was 40 ℃.
Example 21 polymerization of ε -caprolactone catalyzed by Compound Al4 and benzyl alcohol
In a Schlenk flask, 0.228g of ε -caprolactone was added under anhydrous and anaerobic conditions, 1mL of TOL, 1. mu. mol of complex Al4(0.8mg), and 2.1. mu.L of benzyl alcohol (20. mu. mol) was dissolved in 1mL of TOL, and the resulting solution was added to the Schlenk flask with a syringe to initiate polymerization. Controlling the reaction temperature at 70 ℃ for reaction for 3h, adding 1mL of 5% acetic acid methanol solution, pouring into methanol to precipitate out a polymer, filtering, and carrying out vacuum drying for 24 h to obtain polycaprolactone. Conversion rate: 90 percent. The number average molecular weight M of the polycaprolactonen:1.15×104g/mol, molecular weight distribution PDI 1.10. The number average molecular weight is determined by gel permeation chromatography with Agilent 1260 Infinity and THF as solvent at a flow rate of 1mL min-1The test temperature was 40 ℃.
Example 22, Compound Al4 and benzyl alcohol catalysis of polymerization of L-lactide
In a Schlenk flask, 0.288g L-lactide was added under anhydrous and oxygen-free conditions, and1mL of TOL, 20. mu. mol of complex Al4(16.0mg), and 2.1. mu.L of benzyl alcohol (20. mu. mol) were dissolved in 1mL of TOL, and the resulting solution was injected into a Schlenk flask with a syringe to initiate polymerization. Controlling the reaction temperature at 70 ℃ for 4.5h, adding 1mL of 5% acetic acid methanol solution, pouring into methanol to precipitate out a polymer, filtering, and vacuum-drying for 24 h to obtain polycaprolactone. Conversion rate: 91 percent. The number average molecular weight M of the polycaprolactonen:1.17×104g/mol, molecular weight distribution PDI 1.16. The number average molecular weight is determined by gel permeation chromatography with Agilent 1260 Infinity and THF as solvent at a flow rate of 1mL min-1The test temperature was 40 ℃.
Claims (9)
1. A2-diphenylphosphine benzaldehyde-aniline alkyl aluminum compound has a structure shown in a formula (I):
wherein R is selected from methyl, ethyl and isopropyl; r1Selected from hydrogen, methyl, isopropyl, benzhydryl; r2Selected from hydrogen and isopropyl.
2. The 2-diphenylphosphine benzaldehyde-aniline alkyl-aluminum compound as claimed in claim 1, which contains one 2-diphenylphosphine benzaldehyde-aniline ligand, wherein R is1Selected from hydrogen, methyl, isopropyl, benzhydryl; r2Selected from hydrogen and isopropyl.
3. The process for preparing a 2-diphenylphosphinobenzaldehyde-aniline ligand according to claim 2, comprising the following steps: under the nitrogen atmosphere, reacting 2-diphenylphosphine benzaldehyde and substituted aniline according to the weight ratio of 0.8-1.2: after mixing according to the molar ratio of 0.8-1.5, adding 5-20 mg of p-toluenesulfonic acid in a catalytic amount, wherein the volume ratio is 1: stirring and reacting 1-5 parts of a mixed solvent of methanol and dichloromethane for 6-48 hours; and removing the mixed solvent under reduced pressure, adding methanol into the obtained product, performing ultrasonic treatment, filtering and draining the product, adding 2-5 molar equivalent of lithium aluminum hydride into the obtained imine, and reacting for two days to obtain the 2-diphenylphosphine benzaldehyde-aniline ligand.
4. The process for the preparation of 2-diphenylphosphinobenzaldehyde-aniline alkyl-aluminum compounds according to any one of claims 1-2, comprising the following steps: dissolving a 2-diphenylphosphine benzaldehyde-aniline ligand in 30-100 mL of an anhydrous solvent, adding 1.0-1.5 molar equivalent of alkyl aluminum, stirring and reacting for 12-24 hours under the protection of nitrogen, wherein the reaction temperature is 20-100 ℃; the solvent was removed under reduced pressure and washed three times with a poor solvent to give the corresponding alkyl aluminum compound.
5. The method of claim 4, wherein: the alkyl aluminium being AlR3R is selected from methyl, ethyl and isopropyl; the molar ratio of the 2-diphenylphosphinobenzaldehyde-aniline ligand to the aluminum alkyl is 1: 1.0 to 1.5.
6. The method of claim 4, wherein the anhydrous solvent used in the reaction is selected from benzene, toluene, xylene, tetrahydrofuran; the poor solvent is selected from n-hexane, n-pentane, n-heptane and cyclohexane; the reaction temperature range is 20-100 ℃; the reaction time is 12-24 hours.
7. Use of the 2-diphenylphosphine benzaldehyde-aniline alkyl-aluminum compound as claimed in claim 1, for the catalysis of the polymerization of caprolactone, lactide, glycolide, butyrolactone, valerolactone, heptalactone, octalactone.
8. The application of claim 7, wherein 2-diphenylphosphine benzaldehyde-aniline alkyl aluminum compound is used as a catalyst to catalyze caprolactone to polymerize at 0-110 ℃, and the molar ratio of the catalyst to caprolactone during polymerization is 1: 10-10000; the polymerization time is 0.1-12 h; the polymerization solvent is selected from the group consisting of benzene, toluene, n-hexane, tetrahydrofuran and dichloromethane.
9. The application of the compound as claimed in claim 7, wherein methanol, ethanol, isopropanol, n-butanol, ethylene glycol, glycerol and benzyl alcohol are added as initiators during initiation of polymerization, and the molar ratio of the initiators to the catalyst 2-diphenylphosphine benzaldehyde-aniline alkyl aluminum compound is 0-30: 1.
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