CN104387283B - A kind of four tooth nitrogen oxygen part and application thereof - Google Patents
A kind of four tooth nitrogen oxygen part and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of four tooth nitrogen oxygen part and application thereof, shown in the following formula II of ligand structure formula, in formula, R is hydrogen or halogen. This part performance is good, it is possible to reacting generation aluminum complex with alkyl aluminum, preparation method is simple, and product yield is high, stable in properties. The ring-opening polymerization of the efficient catalysis lactide of described aluminium methyl coordination compound energy, and catalyst activity is high, polymerization technology is simple, by the control to polymeric reaction condition, stereochemical structure and the molecular weight of polymer can be regulated and controled, meet different demands, have good market prospect.
Description
Technical field
The present invention relates to a kind of four tooth nitrogen oxygen parts and preparation method thereof, further relate to the application as the part of the catalyst preparing lactide ring-opening polymerization of this four teeth nitrogen oxygen part.
Background technology
The biodegradated polymer materals such as polylactide had both had the feature of conventional polymer material, do not pollute the environment after a procedure again, and medically also have been widely used, studied widely in medicine controlled releasing, surgical sutures, bone fracture internal fixation material etc.
Its purposes is had a great impact by the structure of polylactide material and molecular weight, for instance as backing material, it is desirable to high molecular and high mechanical properties, and as medicinal film material, then reply medicine has permeability. Molecular weight distribution can be controlled by controllable polymerization method, obtain narrow molecular weight distribution and the polymer of measurable molecular weight. Now, the catalyst major part for polylactide synthesis is metal complex, by the adjustment of part can regulate and control the stereo selectivity of catalyst, obtains the polymer that three-dimensional regularity is high, in order to can better play its machinery, physics and degradation property. Therefore, better in order to obtain three-dimensional regularity polymer, it is necessary to the catalyst of exploitation different performance improves three-dimensional regularity and the molecular weight of polymer, and catalyst develop, the part studying performance good is most important.
Summary of the invention
The invention provides a kind of four tooth nitrogen oxygen parts, this part can nitrogen, nitrogen, oxygen, oxygen quad-tree index, this part can form complex with various metals, wherein with aluminium methyl formed coordination compound can as the catalyst of lactide ring-opening polymerization, catalysis activity is high, and performance is good.
Technical solution of the present invention is as follows:
A kind of four tooth nitrogen oxygen parts, have the structural formula shown in following formula II, and in formula, R is hydrogen or halogen;
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In above-mentioned four tooth nitrogen oxygen parts, halogen is preferably fluorine or bromine.
The preparation method of above-mentioned four tooth nitrogen oxygen parts, comprise the following steps: by raw material A (N, N '-dimethyl-N, N '-diphenyl ethylene diamine) it is dissolved in absolute ether, n-BuLi is slowly dripped at 0 DEG C, it is slowly raised to room temperature reaction 12 hours, cooling to 0 DEG C after reaction, slowly the benzaldehyde of dropping benzaldehyde or replacement, is raised to room temperature, react 12 hours, being subsequently adding water stopped reaction, separatory collects organic facies, obtains thick product, thick product, through recrystallizing methanol, obtains four teeth nitrogen oxygen part (formula II).
Reaction equation is as follows:
In above-mentioned preparation method, the consumption of the benzaldehyde of n-BuLi, benzaldehyde or replacement is 2 times of moles of raw material A.
Above-mentioned part reacts with aluminium methyl, can form the aluminium methyl coordination compound of four tooth nitrogen oxygen parts, and it has the structural formula shown in following formula I, and in formula, R is hydrogen or halogen;
In the aluminium methyl coordination compound of above-mentioned four tooth nitrogen oxygen parts, halogen is preferably fluorine or bromine.
The preparation method of the aluminium methyl coordination compound of above-mentioned four tooth nitrogen oxygen parts, comprise the following steps: with four tooth nitrogen oxygen parts shown in formula II for part, part is joined in organic solvent, at-20��0 DEG C, add the trimethyl aluminium of equimolar amounts, after adding, reactant liquor is risen to naturally room temperature, then heat to 80 DEG C of reaction 12h, solvent is pumped after having reacted, obtain thick product, thick product recrystallization, obtain the aluminium methyl coordination compound (formula I) of four tooth nitrogen oxygen parts. Reaction equation is as follows:
In above-mentioned preparation method, reaction carries out under inert gas shielding.
In above-mentioned preparation method, described organic solvent is the saturated alkane of C5��C10 or aromatic hydrocarbon or alkyl halide organic solvent, it is preferred to toluene, oxolane or chloroform.
In above-mentioned preparation method, consumption of organic solvent should be 5��20 times of reaction raw materials gross mass.
In above-mentioned preparation method, recrystallization solvent for use is normal hexane.
The aluminium methyl coordination compound of the present invention four tooth nitrogen oxygen part can be used as the catalyst of lactide ring-opening polymerization, and described lactide is levorotatory lactide or rac-lactide. When substituent R in coordination compound is hydrogen, coordination compound is high as catalyst activity, the time used when catalyzing and synthesizing the polyester of same molecular amount is short, substituent R is that fluorine takes second place, substituent R is that the time used by bromine is the longest, this shows sterically hindered catalyst activity has certain impact, and along with sterically hindered increase, the activity of catalyst decreases. Catalyst of the present invention also has good stereo selectivity, experiments show that, when R is fluorine, stereo selectivity is best, and bromine takes second place, and hydrogen is minimum, and the stereo selectivity of the electron attraction more powerful catalyst of this explanation substituent group is more high.
When the aluminium methyl coordination compound of the present invention four tooth nitrogen oxygen part is used as the catalyst of lactide ring-opening polymerization, reaction rate quickly, and can obtain the lactone of molecular weight within the scope of 2000-170000 according to demand, and molecular weight controllability is high.
Lactide ring-opening polymerization specifically includes following steps: the aluminium methyl composition catalyst of four tooth nitrogen oxygen parts, organic solvent, alcohol promoter and lactide are mixed; polymerization ring-opening reaction is carried out under anhydrous and oxygen-free and inert gas shielding; after reaction, reactant is processed, obtain polylactide.
In above-mentioned ring-opening polymerization, add cold methanol purification polylactide after reaction, obtain the polylactide after purification.
In above-mentioned ring-opening polymerization, the mol ratio of lactide and catalyst is 30��2000:1, it is preferable that 500-1000:1; The mol ratio of alcohol promoter and catalyst is 1��4:1.
In above-mentioned ring-opening polymerization, polymeric reaction temperature is 20��120 DEG C, it is preferred to 20-70 DEG C; Time is 3-24 hour, it is preferred to 6 hours to 15 hours.
In above-mentioned ring-opening polymerization, alcohol promoter is benzylalcohol or isopropanol.
In above-mentioned ring-opening polymerization, reaction organic solvent used is toluene, chloroform or oxolane, it is preferable that toluene.
In above-mentioned ring-opening polymerization, cause the polymerization of lactide using the aluminium methyl coordination compound of the present invention four tooth nitrogen oxygen part as catalyst, thus obtaining a series of polylactide. The molecular weight Mn of the final gained polylactide of the present invention is between 2000��170000, by regulating reaction condition (amount ratio etc. of lactide monomer and catalyst also cocatalyst), the polymer of different molecular weight ranges can be obtained, and molecular weight distribution is narrow.
The invention provides a kind of four tooth nitrogen oxygen parts, this part can N, N, O, O quad-tree index, with various metals complexation formed coordination compound. Ligand structure of the present invention is special, preparation method is simple, the aluminum complex formed can as the catalyst of lactide ring-opening polymerization, catalysis activity is high, and quickly, polyreaction is simple to operate for reaction rate, and the product obtaining different molecular weight that can be controlled, the molecular weight of the polymer prepared can from 2 thousand to ten seven ten thousand, and selectivity is wide, has good market prospect.
Accompanying drawing explanation
Fig. 1 is the crystal schematic diagram of the present invention four tooth nitrogen oxygen part, and wherein R is hydrogen.
Detailed description of the invention
Further illustrating the present invention below by specific embodiment, but the present invention is not limited to this, concrete protection domain is shown in claim.
Raw material A used by the present invention can prepare voluntarily by the method disclosed in prior art, and the raw material A used by following embodiment adopts document " EmilFr hlich; DarstellungvonN, N '-Dialkyl-methylendiaryl-diaminenundHomologen, ChemischeBerichte; Vol.40; (1907); P.764 " method disclosed in obtains; step is: by 1; the methylphenylamine of 2-Bromofume and its 2 moles of times amount reacts 12 hours under 100 DEG C of conditions; obtain purple mixture; mixture obtains white solid through pillar layer separation (petrol ether/ethyl acetate=10/1); be raw material A, productivity 81wt%.
Prepare four tooth nitrogen oxygen parts
According to following route synthesizing new four tooth nitrogen oxygen part, the following formula II of structural formula of gained part, simply enumerate the preparation process of several part below. Preferred part R is hydrogen, fluorine, bromine.
Embodiment 1
Ligand structure formula as above formula II used, wherein R is hydrogen, and course of reaction is: be dissolved in 30mL absolute ether by raw material A (N, N '-dimethyl-N, N '-diphenyl ethylene diamine) (8.30g, 34.6mmol), 0oC slowly drips the n-BuLi of raw material A twice mole, after being slowly raised to room temperature reaction 12 hours, cools to 0oC, slowly drips the benzaldehyde (7.34g, 69.2mmol) of raw material A twice mole, reacts 12 hours after being raised to room temperature, adds water stopped reaction after reaction, and separatory collects organic facies, obtains thick product, obtains net product 10.52g, productivity 67% through recrystallizing methanol.
Products obtained therefrom is characterized, and result is as follows:
Elementary analysis result: C, 79.69; H, 7.18; N, 6.24%.
1HNMR(400MHz,CDCl3)��7.36�C7.29(m,8H,Ar�CH),7.27�C7.22(m,4H,Ar�CH),7.20�C7.16(m,2H,Ar�CH),7.15�C7.09(m,2H,Ar�CH),7.06(dd,J=7.7,1.5Hz,2H,Ar�CH),6.02(s,2H,ArCHOH),5.98(s,2H,ArCHOH),2.98(s,4H,NCH2),2.48(s,6H,CH3).
13CNMR(100MHz,CDCl3)��150.49,144.08,139.35,129.54,128.43,128.14,126.98,126.77,125.62,122.40,74.00,54.98,44.64.
From above characterization result it can be seen that products obtained therefrom is upper formula II, R is the part of hydrogen.
The crystal schematic diagram of products obtained therefrom is as shown in Figure 1.
Embodiment 2
Ligand structure formula as above formula II used, wherein R is fluorine, and course of reaction is: be dissolved in 30mL absolute ether by raw material A (7.60g, 31.6mmol), 0oC slowly drips the n-BuLi of raw material A twice mole, after being slowly raised to room temperature reaction 12 hours, cools to 0oC, slowly drips the o fluorobenzaldehyde (7.82g, 63.2mmol) of 2 times of moles of raw material A, reacts 12 hours after being raised to room temperature, adds water stopped reaction after reaction, and separatory collects organic facies, obtains thick product, obtains net product 12.03g, productivity 78% through recrystallizing methanol.
Products obtained therefrom is characterized, and result is as follows:
Elementary analysis result: C, 73.79; H, 6.25; N, 5.81%.
1HNMR(400MHz,CDCl3)��7.59(t,J=7.6Hz,2H,Ar�CH),7.30�C7.24(m,4H,Ar�CH),7.17(t,J=8.0Hz,3H,Ar�CH),7.08(dd,J=9.2,4.0Hz,2H,Ar�CH),7.04�C6.98(m,3H,Ar�CH),6.91(d,J=7.7Hz,2H,Ar�CH),6.49(s,2H,ArCHOH),6.23(s,2H,ArCHOH)3.18(s,4H,NCH2),2.72(s,6H,CH3).
13CNMR(100MHz,CDCl3)��161.24,158.79,138.78,130.57,128.80,128.66,128.40,125.90,124.17,122.24,115.17,114.95,67.33,55.12,44.91.
From above characterization result it can be seen that products obtained therefrom is upper formula II, R is the part of fluorine.
Embodiment 3
Ligand structure formula as above formula II used, wherein R is bromine, and course of reaction is: be dissolved in 30mL absolute ether by raw material A (6.50g, 27.0mmol), 0oC slowly drips the n-BuLi of raw material A twice mole, after being slowly raised to room temperature reaction 12 hours, cools to 0oC, slowly drips the o-bromobenzaldehye (9.91g, 54.0mmol) of 2 times of moles of raw material A, reacts 12 hours after being raised to room temperature, adds water stopped reaction after reaction, and separatory collects organic facies, obtains thick product, obtains net product 6.92g, productivity 42% through recrystallizing methanol.
Products obtained therefrom is characterized, and result is as follows:
Elementary analysis result: C, 59.12; H, 4.87; N, 4.65%.
1HNMR(400MHz,CDCl3)��7.66(dd,J=7.7,1.3Hz,2H,Ar�CH),7.53(d,J=1.1Hz,2H,Ar�CH),7.36(t,J=7.7Hz,2H,Ar�CH),7.28(d,J=3.3Hz,2H,Ar�CH),7.22�C7.13(m,2H,Ar�CH),7.01(d,J=4.5Hz,2H,Ar�CH),6.67(d,J=7.6Hz,2H,Ar�CH),6.45(br,2H,ArCHOH)6.33(s,2H,ArCH),3.22(s,4H,NCH2),2.82(s,6H,CH3).
13CNMR(100MHz,CDCl3) �� 150.85,141.74,138.73,132.46,129.38,128.82,128.79,128.16,127.57,125.76,123.26,122.00,71.56,54.99,44.60.
From above characterization result it can be seen that products obtained therefrom is upper formula II, R is the part of bromine.
Prepare the aluminium methyl coordination compound of four tooth nitrogen oxygen parts
The aluminium methyl coordination compound of nitrogen oxygen coordination is to be reacted, by part (formula II) and trimethyl aluminium, the coordination compound generated, the following formula II of structural formula of its part, the following formula I of complex structure formula, illustrates to the catalyst that different ligands is obtained below, it is preferred that part R is hydrogen, fluorine, bromine.
Embodiment 4
Part used is the part of embodiment 1 preparation, R is hydrogen, and course of reaction is: under nitrogen atmosphere, by part (0.52g, 1.1mmol) it is dissolved in 10mL toluene, at 0 DEG C, add the trimethyl aluminium of equimolar amounts, be slowly raised to room temperature, be heated to 80 DEG C and react 12 hours, remove solvent, crude product hexane recrystallization, obtains net product 0.49g, productivity 91%.
Products obtained therefrom is characterized, and result is as follows:
Elementary analysis result: C, 75.63; H, 6.79; N, 5.74%.
1HNMR(400MHz,CDCl3)��7.42(d,J=7.9Hz,4H,Ph�CH),7.35(d,J=5.7Hz,8H,Ph�CH),7.28(s,2H,Ph�CH),7.19(m,2H,Ph�CH),7.18(m,2H,Ph�CH),5.00(s,2H,PhCHO),4.07(t,J=6.5Hz,4H,NCH2),2.35(s,6H,CH3),�C1.22(s,3H,Al�CCH3).13CNMR(101MHz,CDCl3)��151.06,132.89,131.30,130.06,129.62,129.10,128.37,125.36,120.05,118.20,53.33,40.71,21.54,�C9.11.
From above characterization result it can be seen that products obtained therefrom is upper formula I, R is the coordination compound of hydrogen.
Embodiment 5
Part used is the part of embodiment 2 preparation, R is fluorine, and course of reaction is: under nitrogen atmosphere, by part (0.71g, 1.40mmoL) it is dissolved in 15mL oxolane, at-20 DEG C, add equimolar amounts trimethyl aluminium, be slowly raised to room temperature, be heated to 80 DEG C and react 12 hours, remove solvent, crude product hexane recrystallization, obtains net product 0.65g, productivity 87%.
Products obtained therefrom is characterized, and result is as follows:
Elementary analysis result: C, 70.51; H, 5.97; N, 5.41%.
1HNMR(400MHz,CDCl3,293K):��7.89(d,J=2.9Hz,2H,Ar�CH),7.82(d,J=2.8Hz,2H,Ph�CH),7.64�C7.56(m,4H,Ph�CH),7.43�C7.38(m,8H,Ph�CH),7.24(m,2H,PhCHO),3.15(s,2H,NCH2),3.03(s,2H,NCH2),2.45(s,6H,CH3),�C1.19(s,6H,AlCH3).13CNMR(101MHz,CDCl3,293K):��198.97,154.91,142.45,141.26140.54,138.52,137.08,135.17,127.01,122.41,121.71,118.33,53.50,45.22,12.35,�C9.10.
From above characterization result it can be seen that products obtained therefrom is upper formula I, R is the coordination compound of fluorine.
Embodiment 6
Part used is the part of embodiment 3 preparation, R is bromine, and course of reaction is: under nitrogen atmosphere, by part (0.93g, 1.50mmoL) it is dissolved in 15mL oxolane, at 0 DEG C, add equimolar amounts trimethyl aluminium, be slowly raised to room temperature, be heated to 50 DEG C and react 12 hours, remove solvent, crude product hexane recrystallization, obtains net product 0.80g, productivity 81%.
Products obtained therefrom is characterized, and result is as follows:
Elementary analysis result: C, 57.32; H, 4.84; N, 4.39%.
1HNMR(400MHz,CDCl3)��7.77(d,J=7.6Hz,2H,Ph�CH),7.54(d,J=7.0Hz,2H,Ph�CH),7.48�C7.38(m,5H,Ph�CH),7.27(d,J=7.8Hz,7H,Ph�CH),6.99�C6.92(m,2H,PhCHO),2.90(s,2H,NCH2),2.51(s,2H,NCH2),2.38(s,6H,CH3),�C1.21(s,3H,Al�CCH3).
13CNMR(101MHz,CDCl3)��198.19,151.06,137.91,132.89,131.30,129.91,129.10,128.37,125.36,122.68,120.05,118.20,53.33,40.71,21.54,�C9.11.
From above characterization result it can be seen that products obtained therefrom is upper formula I, R is the coordination compound of bromine.
The application of aluminum complex
Embodiment 7
React under anhydrous and oxygen-free and inert gas shielding; first in the ampulla after toasting with high pure nitrogen gas washing, 25 ��m of olR of order addition are the rac-lactide of the catalyst of hydrogen, 40mL oxolane, 50 ��m of ol benzylalcohols and 50mmol, are subsequently placed in 20oIn the environment of C, stopped reaction after reacting 12 hours, precipitate with cold methanol, wash for several times, ambient temperature in vacuum dries, and obtains 7.06 grams, molecular weight 6.6 ten thousand, and molecular weight distribution is 1.13, stereo selectivity (Pr=0.70), yield 98%.
Embodiment 8
React under anhydrous and oxygen-free and inert gas shielding; first in the ampulla after toasting with high pure nitrogen gas washing, 25 ��m of olR of order addition are the rac-lactide of the catalyst of fluorine, 40mL oxolane, 50 ��m of ol benzylalcohols and 50mmol, are subsequently placed in 20oIn the environment of C, stopped reaction after reacting 13 hours, precipitate with cold methanol, wash for several times, ambient temperature in vacuum dries, and obtains product, molecular weight 6.7 ten thousand, and molecular weight distribution is 1.11, stereo selectivity (Pr=0.76), yield 98%.
Embodiment 9
React under anhydrous and oxygen-free and inert gas shielding; first in the ampulla after toasting with high pure nitrogen gas washing, 25 ��m of olR of order addition are the rac-lactide of the catalyst of bromine, 40mL oxolane, 50 ��m of ol benzylalcohols and 50mmol, are subsequently placed in 20oIn the environment of C, stopped reaction after reacting 16 hours, precipitate with cold methanol, wash for several times, ambient temperature in vacuum dries, and obtains product, molecular weight 6.6 ten thousand, and molecular weight distribution is 1.12, stereo selectivity (Pr=0.72), yield 97%.
Embodiment 10
All operations all carries out under anhydrous and oxygen-free and inert gas shielding. First, in the ampulla after toasting with high pure nitrogen gas washing, 25 ��m of olR of order addition are the rac-lactide of the catalyst of hydrogen, 30mL oxolane, 50 ��m of ol isopropanols and 42mmol, are subsequently placed in 50oReacting 14 hours stopped reaction in the oil bath of C, precipitate with cold methanol, wash for several times, ambient temperature in vacuum dries, and obtains 5.81 grams, molecular weight 8.5 ten thousand, and molecular weight distribution is 1.11, stereo selectivity (Pr=0.64), yield 96%.
Embodiment 11
All operations all carries out under anhydrous and oxygen-free and inert gas shielding. First, in the ampulla after toasting with high pure nitrogen gas washing, 25 ��m of olR of order addition are the levorotatory lactide of the catalyst of hydrogen, 15mL toluene, 75 ��m of ol benzylalcohols and 10mmol, are subsequently placed in 120oReacting 13 hours stopped reaction in the oil bath of C, precipitate with cold methanol, wash for several times, ambient temperature in vacuum dries, and obtains 1.40 grams, molecular weight 6.8 ten thousand, and molecular weight distribution is 1.09, yield 97%.
Embodiment 12
All operations all carries out under anhydrous and oxygen-free and inert gas shielding. First, in the ampulla after toasting with high pure nitrogen gas washing, 35 ��m of olR of order addition are the rac-lactide of the catalyst of fluorine, 10mL toluene, 35 ��m of ol benzylalcohols and 4mmol, are subsequently placed in 20oIn the environment of C, reacting 18 hours stopped reaction, precipitate with cold methanol, wash for several times, ambient temperature in vacuum dries, and obtains 0.56 gram, molecular weight 8.9 ten thousand, and molecular weight distribution is 1.10, stereo selectivity (Pr=0.74) yield 97%.
Embodiment 13
All operations all carries out under anhydrous and oxygen-free and inert gas shielding. First, in the ampulla after toasting with high pure nitrogen gas washing, 100 ��m of olR of order addition are the rac-lactide of the catalyst of bromine, 10mL toluene, 200 ��m of ol benzylalcohols and 3mmol, are subsequently placed in 20oIn the environment of C, reacting 24 hours stopped reaction, precipitate with cold methanol, wash for several times, ambient temperature in vacuum dries, and obtains 0.42 gram, molecular weight 0.7 ten thousand, and molecular weight distribution is 1.13, stereo selectivity (Pr=0.72), yield 96%.
Embodiment 14
All operations all carries out under anhydrous and oxygen-free and inert gas shielding. First, in the ampulla after toasting with high pure nitrogen gas washing, 25 ��m of olR of order addition are the levorotatory lactide of the catalyst of hydrogen, 30mL oxolane, 100 ��m of ol benzylalcohols and 25mmol, are subsequently placed in 50oReacting 16 hours stopped reaction in the oil bath of C, precipitate with cold methanol, wash for several times, ambient temperature in vacuum dries, and obtains 3.53 grams, molecular weight 10.9 ten thousand, and molecular weight distribution is 1.08, yield 98%.
Embodiment 15
All operations all carries out under anhydrous and oxygen-free and inert gas shielding. First, in the ampulla after toasting with high pure nitrogen gas washing, 15 ��m of olR of order addition are the levorotatory lactide of the catalyst of hydrogen group, 20mL toluene, 15 ��m of ol benzylalcohols and 8mmol, are subsequently placed in 70oReacting 19 hours stopped reaction in the oil bath of C, precipitate with cold methanol, wash for several times, ambient temperature in vacuum dries, and obtains 1.11 grams, molecular weight 16.5 ten thousand, and molecular weight distribution is 1.12, yield 96%.
Comparative example 1
Raw material A (8.30g, 34.6mmol) is dissolved in 30mL absolute ether, 0oC slowly drips the n-BuLi of raw material A twice mole, after being slowly raised to room temperature reaction 12 hours, cools to 0oC, slowly drip the benzophenone (69.2mmol) of raw material A twice mole, react 12 hours after being raised to room temperature, water stopped reaction is added after reaction, obtain being insoluble in the compound of usual vehicle, DMF and DMSO is difficult to dissolve, and the unknown compound obtained is only dissolve in acid, it is impossible to it is carried out the sign of necessity.
Comparative example 2
Raw material A (8.30g, 34.6mmol) is dissolved in 30mL absolute ether, 0oC slowly drips the n-BuLi of raw material A twice mole, after being slowly raised to room temperature reaction 12 hours, cools to 0oC, slowly drips the dry acetone (69.2mmol) of raw material A twice mole, reacts 12 hours after being raised to room temperature, adds water stopped reaction after reaction, and the compound productivity obtained is very low (lower than 5%), it does not have using value.
Claims (3)
1. four tooth nitrogen oxygen parts, is characterized in that: have the structural formula shown in following formula II, and in formula, R is hydrogen or halogen;
��
2. four tooth nitrogen oxygen parts according to claim 1, is characterized in that: described halogen is fluorine or bromine.
3. four tooth nitrogen oxygen parts described in claim 1 or 2 are as the application of the part of the catalyst preparing lactide ring-opening polymerization.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899061A (en) * | 2009-06-01 | 2010-12-01 | 北京化工大学 | Synthesis for zinc complex containing ligands of N and O and application of zinc complex in catalysis of ring opening polymerization of caprolactone |
| CN102531929A (en) * | 2011-12-15 | 2012-07-04 | 中国石油天然气股份有限公司 | Compound containing N and O heteroatom, preparation and application thereof |
| CN102924293A (en) * | 2012-11-06 | 2013-02-13 | 济南大学 | Four-chain amido anilino group ligand, aluminium compound of ligand, preparation method of ligand and application of ligand |
-
2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899061A (en) * | 2009-06-01 | 2010-12-01 | 北京化工大学 | Synthesis for zinc complex containing ligands of N and O and application of zinc complex in catalysis of ring opening polymerization of caprolactone |
| CN102531929A (en) * | 2011-12-15 | 2012-07-04 | 中国石油天然气股份有限公司 | Compound containing N and O heteroatom, preparation and application thereof |
| CN102924293A (en) * | 2012-11-06 | 2013-02-13 | 济南大学 | Four-chain amido anilino group ligand, aluminium compound of ligand, preparation method of ligand and application of ligand |
Non-Patent Citations (2)
| Title |
|---|
| Remarkable Stereocontrol in the Polymerization of Racemic Lactide Using Aluminum Initiators Supported by Tetradentate Aminophenoxide Ligands;Pimpa Hormnirun et al.;《J. AM. CHEM. SOC.》;20040212;第126卷;2688-2689 * |
| ε-己内酯开环聚合金属配合物催化剂研究进展;申淼;《高分子通报》;20110228;55-63 * |
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