CN108503576A - Unsymmetric ligand of the base containing o-phenylenediamine and its preparation method and application - Google Patents
Unsymmetric ligand of the base containing o-phenylenediamine and its preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
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- 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
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- 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
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- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
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Abstract
The invention discloses unsymmetric ligands of a kind of base containing o-phenylenediamine and its preparation method and application.Ligand of the present invention can be complexed to form complex with trimethyl aluminium with N, N, O, O quad-tree index.Ligand structure of the present invention is special, preparation method is simple, the aluminum complex of formation can be as the catalyst of cyclic lactone ring-opening polymerization, the catalyst activity is high, and stereoselectivity is high, and reaction rate is quickly, polymerisation is easy to operate, and the product of different molecular weight can be controllably obtained, selectivity is wide, there is good market prospects.
Description
Technical field
The present invention relates to a kind of four tooth nitrogen oxygen ligands of divalent and its preparation method and application, and in particular to one kind is containing adjacent benzene two
The application of the ligand of unsymmetric ligand of amido and preparation method thereof and catalyst as cyclic lactone ring-opening polymerisation.
Background technology
It is the conventional polymer plastics of raw material while offering convenience to the production and life of people using oil, also there is two
A fatal disadvantage：Non-renewable and non-biodegradable.Because oil is non-renewable resources, petroleum is relied on
The fast development of high molecule plastic material is by severely restricts, and high molecule plastic material is difficult to degrade, a large amount of macromolecule
Plastic material waste accumulates in for a long time pollutes also gradually exacerbation caused by environment for human survival in actual life.It finds and replaces
The renewable resource of oil, development environment friendly, biodegradation type new material become the following high molecule plastic material hair
The trend of exhibition.
Polyester is the high molecular material of the environmental type of biodegradable, and the substitute as oil product is more next
More it is concerned by people.In natural living environment, discarded polylactone material can thoroughly be divided by the microorganism in soil
Xie Chengshui and carbon dioxide, it is environmentally friendly and renewable.Because polyester is nontoxic, nonirritant, and has good biocompatibility,
It is therefore widely used in medicine and field of environment protection, such as operation suture thread, packaging, drug controlled release and tissue engineering bracket
Deng.The performance that the excellent biocompatibility of polylactone, biological degradability and sustainable development utilize, makes it have become 21 generation
The most promising high molecular material of discipline.
The advantages of easily method of synthesizing polyester is the ring-opening polymerisation method of cyclic lactone, this synthetic method be：Polymerization
Controllability, relatively narrow molecular weight distribution.Currently used catalyst is mostly the complex that ligand and metal are formed, in catalyst
Metal includes magnesium, calcium, germanium, tin, aluminium, zinc, iron, titanium, zirconium, group of the lanthanides etc..The selection of catalyst for ring-opening polymerization speed,
The three-dimensional regularity of resulting polymers and the performance of molecular weight products obtained therefrom all have a great influence, and the ligand of catalyst and match
The selection of position metal is all very crucial for the speed of ring-opening polymerization, the three-dimensional regularity of polymer and molecular weight, therefore
It studies the good catalyst ligand of new performance and composition catalyst is very necessary.
Invention content
The present invention provides the unsymmetric ligands of two kinds of bases containing o-phenylenediamine, and the ligand structure is special, have nitrogen, four tooth of oxygen
Coordination can form complex with aluminium methyl, which can be as the catalyst of cyclic lactone ring-opening polymerization, catalytic activity
Height, stereoselectivity is high, and performance is good.
The present invention also provides the preparation method of the unsymmetric ligand of the base containing o-phenylenediamine, this method is prepared simply, easily
In realization.
Catalysis the present invention also provides the unsymmetric ligand of the base containing o-phenylenediamine as cyclic lactone ring-opening polymerization
The catalyst of cyclic lactone ring-opening polymerization made of the application of the ligand of agent and the ligand.
The present invention is in the young project of National Nature fund committee（No 21104026）Subsidy under complete, skill of the present invention
Art scheme is as follows：
The present invention provides the unsymmetric ligand of two kinds of bases containing o-phenylenediamine, one of which has following structural formula shown in formula A,
The ligand can also be referred to as compound A or ligand A：
；
There is second of ligand the structural formula as shown in following formula II, the ligand can be referred to as ligand II or compound ii：
。
The present invention has obtained the ligand of above two special construction by research, and o-phenylenediamine base and water are contained in the ligand
Poplar aldehyde radical, the special selection based on the ligand structure can form the property of catalysis cyclic lactone ring-opening polymerization with metallic aluminium
The excellent aluminum complex of energy.Substituent group selects for the aluminum complex as cyclic lactone ring-opening polymerization catalyst in ligand
Catalytic performance have larger impact.Wherein, R is the alkane or halogen of hydrogen, C1-C4, and the halogen is fluorine, chlorine, bromine or iodine.Into one
Step, stereoselectivity is best when R is tertiary butyl, and catalytic activity is best when R is bromine.
The present invention provides the preparation methods of the unsymmetric ligand of above two base containing o-phenylenediamine, wherein matches shown in formula A
The preparation method of body A includes the following steps：P-methyl benzenesulfonic acid is dissolved into dimethylbenzene, p-methyl benzenesulfonic acid etc. is first slowly added into and rubs
The o-phenylenediamine of your amount, adds the phthalic anhydride of p-methyl benzenesulfonic acid equimolar amounts, and then heating carries out back flow reaction, instead
It is cooled to room temperature after answering, filters to take solid, obtained solid is dissolved into dichloromethane, unsaturated carbonate is then slowly added dropwise
Hydrogen sodium water solution is reacted, and to slough p-methyl benzenesulfonic acid, liquid separation after reaction does gained organic phase with anhydrous magnesium sulfate
It is dry, it is then spin-dried for solvent, obtains the o-phenylenediamine of unilateral phthalic anhydride protection；
Salicylide of o-phenylenediamine and equimolar amounts that unilateral phthalic anhydride is protected or derivatives thereof dissolves in methyl alcohol,
Heating carries out back flow reaction, and cooling after reaction, filtering, obtained solid is washed with cold methanol, is dry, ligand shown in formula A；Institute
The structural formula of salicylaldehyde derivatives is stated as shown in following formula B, wherein R be hydrogen, C1-C4 alkane or halogen, preferably tertiary butyl or
Bromine；
。
The preparation method of ligand shown in formula II includes the following steps：Ligand shown in formula A is added in organic solvent, -10
~0 oTrimethyl aluminium is added under C, so that reaction temperature is warmed to room temperature naturally after adding, temperature is then risen to 30~110oC is carried out
Reaction, is added water into reaction solution after reaction, and liquid separation is stood after being sufficiently mixed, and collects organic phase obtained by liquid separation, and recycling has
Solvent obtains crude product, and crude product is recrystallized, and obtains ligand shown in formula II.
II preparation method reaction equation of above-mentioned ligand is as follows, and ligand A first reacts to form aluminum complex with trimethyl aluminium, gained aluminium
Complex is broken water sensitive, in the presence of water Al-O keys, is hydrolyzed into ligand II and Al (OH)3, ligand II enters organic
Xiang Zhong can be obtained by liquid separation, recycling design：
In II preparation method of above-mentioned ligand, the molar ratio 1 of ligand A and trimethyl aluminium：1~1.3, preferably 1：1~1.05.
In II preparation method of above-mentioned ligand, the organic solvent be dry hexane, toluene and one kind in hexamethylene or
Two kinds, preferably dry hexane or toluene.
In II preparation method of above-mentioned ligand, consumption of organic solvent is reaction raw materials（Ligand A and trimethyl aluminium）The 5 of gross mass
~40 times.
In II preparation method of above-mentioned ligand, reaction carries out under gas shield, and the gas is inert gas or nitrogen.
In II preparation method of above-mentioned ligand, reaction nature rises to 30~110 again after being raised to room temperatureoC is reacted, such as
30oC、40oC、50oC、60oC、70oC、80oC、90oC、100oC、110oC is preferably raised to 40~60oC is reacted.30~
110oC（It is preferred that 40~60oC）The time reacted is 1~12 hour, preferably 3~6 hours.
In II preparation method of above-mentioned ligand, after reaction, water is added into reaction solution, liquid separation is stood after being sufficiently mixed.
The dosage of water is the mole of 3 times or so of ligand A.After standing liquid separation, gained organic phase is spin-dried for solvent, remaining crude product first
One or both of alcohol, ethyl alcohol are recrystallized, you can obtain II ligand of formula, II product.
Formula A and the ligand of formula II can react to form aluminium with trimethyl aluminium with N, N, O, O quad-tree index
Complex, gained aluminum complex structural formula is as shown in following formula I, and in formula I, R is the alkane or halogen of hydrogen, C1-C4, and the halogen is
Fluorine, chlorine, bromine or iodine.R is preferably tertiary butyl or bromine；
Aluminum complex shown in the above-mentioned formula I of the present invention, can the ligand II shown in formula II be prepared with trimethyl aluminium, also may be used
To be generated during synthetic ligands II, is reacted and be made with trimethyl aluminium with ligand A, specific preparation method includes following
Step：Ligand A or ligand II are added in organic solvent, -10~0 oTrimethyl aluminium is added under C, makes reaction temperature after adding
Naturally it is warmed to room temperature, temperature is then risen to 30~110oC is reacted, and vacuum drains solvent, washing, filtering after reaction, obtains
Aluminum complex described in formula I.
In above-mentioned aluminum complex preparation method, the molar ratio 1 of ligand A or ligand II and trimethyl aluminium：1~1.3, preferably 1：
1~1.05.
In above-mentioned aluminum complex preparation method, the organic solvent is one kind in the hexane, toluene and hexamethylene of drying
Or two kinds, preferably hexane or toluene.Consumption of organic solvent is reaction raw materials（Ligand A or ligand II and trimethyl aluminium）Gross mass
5~40 times.
In above-mentioned aluminum complex preparation method, reaction nature rises to 30~110 again after being raised to room temperatureoC is reacted, example
Such as 30oC、40oC、50oC、60oC、70oC、80oC、90oC、100oC、110oC is preferably raised to 40~60oC is reacted.30~
110oC（It is preferred that 40~60oC）The time reacted is 1~12 hour, preferably 3~6 hours.
In above-mentioned aluminum complex preparation method, reaction carries out under gas shield, and the gas is inert gas or nitrogen.
After reaction solution is spin-dried for solvent, residue is washed with n-hexane, is then dried, you can obtains the aluminum complex described in formula I.
Aluminum complex shown in the above-mentioned formula I of the present invention can be urged with being used as the catalyst of cyclic lactone ring-opening polymerization
The ring-opening polymerisation of a variety of cyclic lactones such as outside the pale of civilization meso-lactide, Study of Meso-Lactide, levorotatory lactide, caprolactone, glycolide.It should
When catalyst cyclic lactone ring-opening polymerization, with catalytic activity is high, stereoselectivity is good, reaction rate is fast, molecular weight
The advantages that controllability is high can especially obtain the high isotactic poly third of fusing point when being catalyzed rac-lactide polymerization and hand over
Ester, shows higher stereoselectivity, and stereoselectivity reaches as high asP m= 0.80.In catalysis lactide, caprolactone and second
When lactide, obtained polymer is the polymer of benzyloxy sealing end.Therefore, the unsymmetric ligand of present invention base containing o-phenylenediamine is made
For the catalyst of cyclic lactone ring-opening polymerization ligand application also within the scope of the present invention.
When using the aluminum complex described in formula I as catalyst, cyclic lactone ring-opening polymerization specifically includes following steps：It will
Aluminum complex, organic solvent, alcohol co-catalyst described in formula I and cyclic lactone mixing, carry out under anhydrous and oxygen-free and gas shield
Ring-opening polymerization is handled reactant after reaction, obtains polylactone.
In above-mentioned ring-opening polymerization, it is toluene or tetrahydrofuran, preferably toluene to react organic solvent used.Used in reaction
Alcohol co-catalyst is benzylalcohol.
In above-mentioned ring-opening polymerization, the molar ratio of cyclic lactone and catalyst is 50~1500：1, such as 50:1、100：1、
150:1、200:1、300:1、400:1、500:1、600：1、800:1、1000:1、1200:1、1500：1.Alcohol co-catalyst with urge
The molar ratio of agent is 1~3：1.
In above-mentioned ring-opening polymerization, polymeric reaction temperature be 20~110 DEG C, such as 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60
℃、70℃、80℃、90℃、100℃、110℃.With the raising of polymeric reaction temperature, the stereoselectivity of catalyst has reduction
Trend, catalytic activity has raised trend, when reaction temperature is at 80 DEG C, solid when being catalyzed to rac-lactide
Selectivity is reachableP m =0.60, when reaction temperature is at 20 DEG C, stereoselectivity when being catalyzed to rac-lactide can
It reachesP m = 0.80。
In above-mentioned ring-opening polymerization, polymerization reaction time be 1-1440 minutes, such as 1 minute, 10 minutes, 30 minutes,
40 minutes, 60 minutes, 120 minutes, 240 minutes, 600 minutes, 900 minutes, 1200 minutes, 1440 minutes etc..
Cold methanol is added in above-mentioned ring-opening polymerization, after reaction and purifies polylactone, obtains polylactone after purification.
The present invention provides the unsymmetric ligand of two kinds of bases containing o-phenylenediamine, which can be with N, N, O, O quad-tree index, energy
It is complexed to form complex with trimethyl aluminium.Ligand structure of the present invention is special, and preparation method is simple, and the aluminum complex of formation can be made
For the catalyst of cyclic lactone ring-opening polymerization, the catalyst activity is high, and stereoselectivity is high, and reaction rate quickly, is gathered
Conjunction operation is simple, and can controllably obtain the product of different molecular weight, and selectivity is wide, there is good market prospects.
Specific implementation mode
It is further illustrated the present invention below by specific embodiment, but the present invention is not limited thereto, specific protection domain is shown in
Claim.
In following embodiments, the stereoselectivity of isotaxy polylactide is carried out using nuclear magnetic resonance same core decoupling hydrogen spectrum
Test.
Prepare the o-phenylenediamine (a) of unilateral phthalic anhydride protection
0.60 g p-methyl benzenesulfonic acid is dissolved into dimethylbenzene, the o-phenylenediamine of p-methyl benzenesulfonic acid equimolar amounts is first slowly added into,
The phthalic anhydride of p-methyl benzenesulfonic acid equimolar amounts, heating reflux reaction 6h are added, reaction is cooled to room temperature after terminating
Solid is filtered, washs, is dried to obtain solid.Solid is dissolved into dichloromethane, excessive sodium bicarbonate is slowly added dropwise
Saturated aqueous solution, room temperature reaction, after reaction liquid separation are dried with anhydrous magnesium sulfate, are spin-dried for solvent, and unilateral O-phthalic is obtained
0.74 g of o-phenylenediamine of acid anhydrides protection, yield 89.2%.
Prepare the unsymmetric ligand of the base containing o-phenylenediamine（A）
The unsymmetric ligand of the base containing o-phenylenediamine is to pass through condensation by the o-phenylenediamine of unilateral protection and salicylide or derivatives thereof
It is obtained by the reaction, it illustrates below to synthesizing different ligand A.
Embodiment 1
Synthesized ligand structure formula such as above formula（A）, wherein R is hydrogen, and reaction process is：By the o-phenylenediamine of unilateral protection（a）
The salicylide of 0.40 g and equimolar amounts is added in 20 mL methanol, heating reflux reaction 12 hours, and reaction is cooled after terminating
It filters and is washed with cold methanol, filtered, collect and drying is weighed, obtain 0.50 g solids, yield 87.7%.
Products obtained therefrom is characterized, it is as a result as follows：
1H NMR (400 MHz, CDCl3) δ12.86 (s, 1H, OH), 8.42 (s, 1H, ArHC=N), 7.85 (m,
2H, Ar–H), 7.64 (d, J = 7.0 Hz, 1H, Ar–H), 7.56 (m, 1H, Ar–H), 7.44 (m, 3H,
Ar–H), 7.32 (m, 2H, Ar–H), 6.96 (m, 4H, Ar–H).
HRESI-MS: m/z cacld. C21H14N2O3 [M-H]-; 341.0926, found: 341.0924.
Can be seen that products obtained therefrom from the above characterization result is above formula（A）Middle R is the ligand of hydrogen.
Embodiment 2
Synthesized ligand structure formula such as above formula（A）, wherein R is methyl, and reaction process is：By the o-phenylenediamine of unilateral protection（a）
3, the 5- dimethyl salicylides of 0.30 g and equimolar amounts are added in 20 mL methanol, and heating reflux reaction 12 hours, reaction terminates
Later cold filtration is simultaneously washed with cold methanol, is filtered, and collects and drying is weighed, obtain 0.40 g solids, yield 85.1%.
Products obtained therefrom is characterized, it is as a result as follows：
1H NMR (400 MHz, CDCl3) δ12.72 (s, 1H, OH), 8.40 (s, 1H, ArHC=N), 7.80 (m,
2H, Ar–H), 7.66 (m, 2H, Ar–H), 7.15 (m, 3H, Ar–H), 6.92 (s, 1H, Ar–H), 2.15
(s, 3H, ArCH 3), 2.04 (s, 3H, ArCH 3). HRESI-MS: m/z cacld. C23H18N2O3 [M-H]-;
369.1238, found: 369.1238.
Can be seen that products obtained therefrom from the above characterization result is above formula（A）Middle R is the ligand of methyl.
Embodiment 3
Synthesized ligand structure formula such as above formula（A）, wherein R is bromine, and reaction process is：By the o-phenylenediamine of unilateral protection（a）
3, the 5- Dibromosalicylaldehydes of 0.35 g and equimolar amounts be added 20 mL methanol in, heating reflux reaction 12 hours, reaction terminate with
Postcooling is filtered and is washed with cold methanol, filtering, collects and drying is weighed, obtain 0.66 g solids, yield 90.4%.
Products obtained therefrom is characterized, it is as a result as follows：
1H NMR (400 MHz, CDCl3) δ12.64 (s, 1H, OH), 8.344 (s, 1H, ArHC=N), 7.86
(d, J = 7.2 Hz, 1H, Ar–H), 7.68 (m, 3H, Ar–H), 7.42 (m, 2H, Ar–H), 7.36 (m,
1H, Ar–H), 7.10 (m, 3H, Ar–H).
HRESI-MS: m/z cacld. C21H12Br2N2O3 [M-H]-; 496.9134, found: 496.9136.
Can be seen that products obtained therefrom from the above characterization result is above formula（A）Middle R is the ligand of bromine.
Embodiment 4
Synthesized ligand structure formula such as above formula（A）, wherein R is tertiary butyl, and reaction process is：By the o-phenylenediamine of unilateral protection
（a）3, the 5- di-tert-butyl salicylaldehydes of 0.40 g and equimolar amounts are added in 20 mL methanol, heating reflux reaction 12 hours, instead
It should terminate later cold filtration and be washed with cold methanol, be filtered, collect and drying is weighed, obtain 0.66 g solids, yield
86.8%。
Products obtained therefrom is characterized, it is as a result as follows：
1H NMR (400 MHz, CDCl3) δ12.80 (s, 1H, OH), 8.37 (s, 1H, ArHC=N), 7.82 (d,
J = 6.8 Hz, 1H, Ar–H), 7.70 (m, 3H, Ar–H), 7.64 (m, 2H, Ar–H), 7.38 (m, 1H,
Ar–H), 7.12 (m, 3H, Ar–H), 1.31 (s, 9H, CH 3), 1.24 (s, 9H, CH 3).
HRESI-MS: m/z cacld. C29H30N2O3 [M-H]-; 453.2176, found: 453.2177.
Can be seen that products obtained therefrom from the above characterization result is above formula（A）Middle R is the ligand of tertiary butyl.
Prepare the unsymmetric ligand of the base containing o-phenylenediamine（Ⅱ）
The unsymmetric ligand of the base containing o-phenylenediamine（Ⅱ）It being synthesized according to following routes, R is the alkane or halogen of hydrogen, C1-C4, below
Simply enumerate the preparation process of several ligands II.
Embodiment 5
R is that the ligand II of hydrogen synthesizes：In a nitrogen atmosphere, by ligand A（R is hydrogen）0.25 g is dissolved in 10 mL dry toluenes,
The trimethyl aluminium that ligand 1.0 times of moles of A are added at -10 DEG C is heated to 50 DEG C after reaction temperature is raised to room temperature naturally
Reaction 4 hours after reaction terminates, is added 39 microlitres of water and stops reaction, organic phase, anhydrous sodium sulfate drying, rotation are collected in liquid separation
Dry solvent, obtains crude product, by crude product through recrystallizing methanol, obtains 0.21 g of net product, 80.8 % of yield.
Products obtained therefrom is characterized, it is as a result as follows：
1H NMR (400 MHz, CDCl3) δ12.42 (s, 1H, OH), 8.36 (s, 1H, ArHC=N), 7.69 (m,
2H, Ar–H), 7.56 (d, J = 6.2 Hz, 1H, Ar–H), 7.48 (m, 1H, Ar–H), 7.33 (m, 3H,
Ar–H), 7.2 (m, 2H, Ar–H), 6.82 (m, 4H, Ar–H), 1.74 (s, 3H, CH 3).
HRESI-MS: m/z cacld. C22H18N2O3 [M-H]-; 357.1237, found: 357.1239.
Can be seen that products obtained therefrom from the above characterization result is above formula（Ⅱ）Middle R is the ligand of hydrogen.
Embodiment 6
R is that the ligand II of methyl synthesizes：Under nitrogen atmosphere, by ligand A（R is methyl）0.35 g is dissolved in 10 mL drying hexamethylenes
In, the trimethyl aluminium of ligand 1.05 times of moles of A is added at 0 DEG C, after reaction temperature is raised to room temperature naturally, heating reaction
Temperature is reacted 3 hours to 70 DEG C, and 51 microlitres of water are added after reaction and stop reacting, liquid separation collection organic phase, anhydrous sodium sulfate drying,
It is spin-dried for solvent, obtains crude product, by crude product through recrystallizing methanol, obtains 0.30 g of net product, yield 81.1%.
Products obtained therefrom is characterized, it is as a result as follows：
1H NMR (400 MHz, CDCl3) δ12.60 (s, 1H, OH), 8.24 (s, 1H, ArHC=N), 7.60 (m,
2H, Ar–H), 7.46 (m, 2H, Ar–H), 7.12 (m, 3H, Ar–H), 6.80 (s, 1H, Ar–H), 2.10
(s, 3H, ArCH 3), 2.02 (s, 3H, ArCH 3), 1.67 (s, 3H, CCH 3). HRESI-MS: m/z cacld.
C24H22N2O3 [M-H]-; 386.1554, found: 386.1556.
Can be seen that products obtained therefrom from the above characterization result is above formula（Ⅱ）Middle R is the ligand of methyl.
Embodiment 7
R is that the ligand II of bromine synthesizes：Under nitrogen atmosphere, by ligand A（R is bromine）0.35 g is dissolved in 12 mL dry toluenes ,-
The trimethyl aluminium of ligand 1.1 times of moles of A is added at 5 DEG C, after reaction temperature is raised to room temperature naturally, is heated to 50 DEG C of reactions 6
Hour, reaction is added 38 microlitres of water and stops reaction after terminating, organic phase is collected in liquid separation, and anhydrous sodium sulfate drying is spin-dried for molten
Agent obtains crude product, by crude product through ethyl alcohol recrystallization, obtains 0.30 g of net product, yield 83.3%.
Products obtained therefrom is characterized, it is as a result as follows：
1H NMR (400 MHz, CDCl3) δ12.43 (s, 1H, OH), 8.34 (s, 1H, ArHC=N), 7.64 (d,
J = 7.0 Hz, 1H, Ar–H), 7.54 (m, 3H, Ar–H), 7.37 (m, 2H, Ar–H), 7.30 (m, 1H,
Ar–H), 7.08 (m, 3H, Ar–H), 1.67 (s, 1H, CCH 3).
HRESI-MS: m/z cacld. C22H16Br2N2O3 [M-H]-; 512.9449, found: 512.9447.
Can be seen that products obtained therefrom from the above characterization result is above formula（Ⅱ）Middle R is the ligand of bromine.
Embodiment 8
R is that the ligand II of tertiary butyl synthesizes：Under nitrogen atmosphere, by ligand A（R is tertiary butyl）0.25 g is being dissolved in 10 mL dryings just
In hexane, the trimethyl aluminium of ligand 1.3 times of moles of A is added at -5 DEG C, after reaction temperature is raised to room temperature naturally, heating
It is reacted 9 hours to 30 DEG C, 30 microlitres of water is added after reaction and stop reaction, organic phase is collected in liquid separation, and anhydrous sodium sulfate drying is spin-dried for
Solvent obtains crude product, by crude product through recrystallizing methanol, obtains 0.21 g of net product, yield 80.8%.
Products obtained therefrom is characterized, it is as a result as follows：
1H NMR (400 MHz, CDCl3) δ12.67 (s, 1H, OH), 8.30 (s, 1H, ArHC=N), 7.74 (d,
J = 6.6 Hz, 1H, Ar–H), 7.62 (m, 3H, Ar–H), 7.52 (m, 2H, Ar–H), 7.30 (m, 1H,
Ar–H), 7.08 (m, 3H, Ar–H), 1.67 (s, 3H, CCH 3), 1.30 (s, 9H, CH 3), 1.22(s, 9H,
CH 3).
HRESI-MS: m/z cacld. C30H34N2O3 [M-H]-; 469.2491, found: 469.2493.
Can be seen that products obtained therefrom from the above characterization result is above formula（Ⅱ）Middle R is the ligand of tertiary butyl.
Aluminum complex is prepared using ligand A as raw material（I）
Formula（I）Shown aluminum complex is eliminated by alkyl by ligand A and trimethyl aluminium and alkyl addition reaction generates, and reaction equation is such as
Under.
Embodiment 9
Ligand structure formula such as above formula used（A）, wherein R is hydrogen, and reaction process is：In a nitrogen atmosphere, by 0.35 g of ligand A
It is dissolved in 12 mL dry toluenes, the trimethyl aluminium of ligand 1.0 times of moles of A is added at -10 DEG C, waits for that reaction temperature rises naturally
It to after room temperature, is heated to 100 DEG C and reacts 1 hour, vacuum drains solvent after reaction terminates, and dry n-hexane filtering is added simultaneously
It is washed, is filtered with dry n-hexane, collected and drying is weighed, obtain 0.33 g solids, yield 80.5%.
Products therefrom nuclear-magnetism information is as follows, can be seen that the compound that R is hydrogen from nuclear-magnetism information（I）It synthesizes successfully.
1H NMR (400 MHz, CDCl3) δ 8.34 (s, 1H, ArHC=N), 7.63 (m, 2H, Ar–H),
7.51 (d, J = 6.2 Hz, 1H, Ar–H), 7.43 (m, 1H, Ar–H), 7.30 (m, 3H, Ar–H), 7.05
(m, 2H, Ar–H), 6.74 (m, 4H, Ar–H), 1.70 (s, 3H, CH 3), –0.53(s, 3H, AlCH 3).
Anal. Calcd for C23H19AlN2O3: C 69.34, H 4.81, N 7.03. Found: C 69.36, H 4.89,
N 7.00.
Embodiment 10
Ligand structure formula such as above formula used（A）, wherein R is methyl, and reaction process is：Under nitrogen atmosphere, by 0.30 g of ligand A
It is dissolved in 10 mL drying hexamethylenes, the trimethyl aluminium of ligand 1.05 times of moles of A is added at 0 DEG C, wait for reaction temperature nature
After being raised to room temperature, heating reaction temperature to 60 DEG C react 5 hours, reaction terminate after vacuum drain solvent, be added it is dry just
Hexane is filtered and is washed with dry n-hexane, is filtered, and collects and drying is weighed, obtain 0.29g solids, yield 82.9%.
Products therefrom nuclear-magnetism information is as follows, can be seen that the compound that R is methyl from nuclear-magnetism information（I）It synthesizes successfully.
1H NMR (400 MHz, CDCl3) δ 8.35 (s, 1H, ArHC=N), 7.62 (m, 2H, Ar–H),
7.52 (m, 2H, Ar–H), 7.18 (m, 3H, Ar–H), 6.83 (s, 1H, Ar–H), 2.12 (s, 3H,
ArCH 3), 2.06 (s, 3H, ArCH 3), 1.65 (s, 3H, CCH 3), –0.52 (s, 3H, AlCH 3). Anal.
Calcd for C25H23AlN2O3: C 70.41, H 5.44, N 6.57. Found: C 70.44, H 5.49, N
6.64.
Embodiment 11
Ligand structure formula such as above formula used（A）, wherein R is bromine, and reaction process is：Under nitrogen atmosphere, 0.40 g of ligand A is molten
In 12 mL dry toluenes, the trimethyl aluminium of ligand 1.1 times of moles of A is added at -5 DEG C, waits for that reaction temperature is raised to naturally
It after room temperature, is heated to 50 DEG C and reacts 7 hours, vacuum drains solvent after reaction terminates, and dry n-hexane is added filters and be used in combination
Dry n-hexane washing, filtering, is collected and drying is weighed, and obtains 0.37 g solids, yield 84.1%.
The nuclear-magnetism information of products obtained therefrom is as follows, it can be seen that R is the compound of bromine（I）It synthesizes successfully.
1H NMR (400 MHz, CDCl3) δ 8.40 (s, 1H, ArHC=N), 7.89 (d, J = 7.2 Hz,
1H, Ar–H), 7.63 (m, 3H, Ar–H), 7.48 (m, 2H, Ar–H), 7.37 (m, 1H, Ar–H), 7.16
(m, 3H, Ar–H), 1.74 (s, 1H, CCH 3), –0.48 (s, 3H, AlCH 3). Anal. Calcd for
C23H17AlBr2N2O3: C 49.67, H 3.08, N 5.04. Found: C 49.72, H 3.12, N 5.08.
Embodiment 12
Ligand structure formula such as above formula used（A）, wherein R is tertiary butyl, and reaction process is：Under nitrogen atmosphere, by ligand A 0.30
G is dissolved in 12 mL drying n-hexanes, and the trimethyl aluminium of ligand 1.0 times of moles of A is added at -10 DEG C, waits for reaction temperature certainly
It after being so raised to room temperature, is heated to 40 DEG C and reacts 8 hours, filter and weighed with dry n-hexane filter wash cake, collection and drying, obtained
0.27 g solids, yield 79.4%.
The nuclear-magnetism information of products therefrom is as follows, it can be seen that R is the compound of tertiary butyl（I）It synthesizes successfully.
1H NMR (400 MHz, CDCl3) δ 8.34 (s, 1H, ArHC=N), 7.84 (d, J = 7.0 Hz,
1H, Ar–H), 7.64 (m, 3H, Ar–H), 7.55 (m, 2H, Ar–H), 7.34 (m, 1H, Ar–H), 7.13
(m, 3H, Ar–H), 1.65 (s, 3H, CCH 3), 1.34 (s, 9H, CH 3), 1.26(s, 9H, CH 3), –0.48
(s, 3H, AlCH 3). Anal. Calcd for C31H35AlN2O3: C 72.92, H 6.91, N 5.49. Found: C
72.98, H 6.97, N 5.53.
It is that raw material prepares aluminum complex with ligand II（I）
Embodiment 13
Ligand structure formula such as above formula used（II）, wherein R is hydrogen, and reaction process is：In a nitrogen atmosphere, by ligand i I 0.40
G is dissolved in 10 mL drying hexamethylenes, and the trimethyl aluminium of ligand i 1.0 times of moles of I is added at -10 DEG C, waits for reaction temperature certainly
It after being so raised to room temperature, is heated to 40 DEG C and reacts 6 hours, reaction is filtered after terminating and washed with dry n-hexane, is filtered, and is received
Collect and dry and weigh, obtains 0.36 g solids, yield 81.8%.For product structure formula as shown in formula I, R is hydrogen.
Embodiment 14
Ligand structure formula such as above formula used（II）, wherein R is methyl, and reaction process is：Under nitrogen atmosphere, by ligand i I 0.30
G is dissolved in 10 mL dry toluenes, and the trimethyl aluminium of ligand i 1.05 times of moles of I is added at 0 DEG C, waits for reaction temperature nature
After being raised to room temperature, heating reaction temperature is reacted 1 hour to 110 DEG C, and vacuum drains solvent after reaction terminates, and is added dry
N-hexane is filtered and is washed with dry n-hexane, is filtered, and collects and drying is weighed, obtain 0.26 g solids, yield 78.8%.
For product structure formula as shown in formula I, R is methyl.
Embodiment 15
Ligand structure formula such as above formula used（II）, wherein R is bromine, and reaction process is：Under nitrogen atmosphere, by 0.40 g of ligand i I
It is dissolved in 15 mL drying hexanes, the trimethyl aluminium of ligand i 1.0 times of moles of I is added at -5 DEG C, waits for that reaction temperature rises naturally
It to after room temperature, is heated to 60 DEG C and reacts 2 hours, reaction is filtered after terminating and washed with dry n-hexane, is filtered, and is collected
And drying is weighed, and 0.39 g solids, yield 90.7% are obtained.For product structure formula as shown in formula I, R is bromine.
Embodiment 16
Ligand structure formula such as above formula used（II）, wherein R is tertiary butyl, and reaction process is：Under nitrogen atmosphere, by ligand i I
0.30 g is dissolved in 10 mL dry toluenes, and the trimethyl aluminium of ligand i 1.2 times of moles of I is added at 0 DEG C, waits for reaction temperature
Naturally after being raised to room temperature, 50 DEG C is heated to and is reacted 4 hours, reaction is filtered and washed with dry n-hexane, mistake after terminating
Filter, is collected and drying is weighed, and obtains 0.29 g solids, yield 87.9%.For product structure formula as shown in formula I, R is tertiary butyl.
Prepare polyglycolide
Embodiment 17
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
100 μm of ol catalyst are added（Aluminum complex shown in formula I, R are hydrogen）, 100 μm of ol benzylalcohols, 20 mL toluene and 10 mmol
Glycolide, be subsequently placed in 110oIn the oil bath of C, reaction is added a small amount of water and terminates reaction after 14 minutes, with ethanol precipitation, washing
For several times, it is dried in vacuo at room temperature, obtains 1.10 g products, yield 94.8%, molecular weight 2.3 ten thousand.
Embodiment 18
Polyglycolide is prepared according to the method for embodiment 17, unlike：Catalyst used is aluminum complex shown in formula I, R
For methyl.The quality of products obtained therefrom is 1.08 g after reaction 15 minutes, and yield 93.1%, molecular weight is 2.1 ten thousand.
Embodiment 19
Polyglycolide is prepared according to the method for embodiment 17, unlike：Catalyst used is aluminum complex shown in formula I, R
For bromine.The quality of products obtained therefrom is 1.12 g after reaction 8 minutes, and yield 96.6%, molecular weight is 2.1 ten thousand.
Embodiment 20
Polyglycolide is prepared according to the method for embodiment 17, unlike：Catalyst used is aluminum complex shown in formula I, R
For tertiary butyl.The quality of products obtained therefrom is 1.11 g after reaction 18 minutes, and yield 95.7%, molecular weight is 2.2 ten thousand.
Embodiment 21
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
100 μm of ol catalyst are added（Aluminum complex shown in formula I, R are bromine）, 100 μm of ol benzylalcohols, 20 mL toluene and 10 mmol
Glycolide, then respectively 20oC、40oC、60oC、80oC and 100oIt is reacted under C, a small amount of water is added after reaction and terminates instead
It answers, for several times with methanol extraction, washing, is dried in vacuo at room temperature.
Wherein, it is reacted 20 hours at 20 DEG C, obtains 1.10 g products, yield 94.8%, molecular weight 2.2 ten thousand.
It is reacted 11 hours at 40 DEG C, obtains 1.10 g products, yield 94.8%, molecular weight 2.1 ten thousand.
It is reacted 6 hours at 60 DEG C, obtains 1.11 g products, yield 95.7%, molecular weight 2.3 ten thousand.
It is reacted 45 minutes at 80 DEG C, obtains 1.11 g products, yield 95.7%, molecular weight 2.1 ten thousand.
It is reacted 16 minutes at 100 DEG C, obtains 1.12 g products, yield 96.6%, molecular weight 2.2 ten thousand.
Embodiment 22
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
10 μm of ol catalyst are added（Aluminum complex shown in formula I, R are hydrogen）, 30 μm of ol benzylalcohols, 10 mL tetrahydrofurans and 15
The glycolide of mmol, then 30oC is added a small amount of water and terminates reaction after reacting 18 hours, for several times with methanol extraction, washing, room temperature
Lower vacuum drying obtains 1.65 g products, yield 94.8%, molecular weight 14.2 ten thousand.
Embodiment 23
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
10 μm of ol catalyst are added（Aluminum complex shown in formula I, R methyl）, 20 μm of ol benzylalcohols, 20 mL tetrahydrofurans and 10
The glycolide of mmol, is subsequently placed in 50oIn the oil bath of C, reaction is added a small amount of water and terminates reaction after 9 hours, with ethanol precipitation, wash
It washs for several times, is dried in vacuo at room temperature, obtain 1.11 g products, yield 95.7%, molecular weight 14.8 ten thousand.
Embodiment 24
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
200 μm of ol catalyst are added（Aluminum complex shown in formula I, R are tertiary butyl）, 200 μm of ol benzylalcohols, 10 mL toluene and 10
The glycolide of mmol, is subsequently placed in 70oIn the oil bath of C, reaction is added a small amount of water and terminates reaction after 6 hours, with methanol extraction, wash
It washs for several times, is dried in vacuo at room temperature, obtain 1.11 g products, yield 95.7%, molecular weight 1.2 ten thousand.
Embodiment 25
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
10 μm of ol catalyst are added（Aluminum complex shown in formula I, R are hydrogen）, 20 μm of ol benzylalcohols, 15 mL toluene and 5 mmol second
Lactide, then 90oC is added a small amount of water and terminates reaction after reacting 6 hours, for several times with methanol extraction, washing, vacuum is dry at room temperature
It is dry, obtain 0.55 g products, yield 94.8%, molecular weight 7.4 ten thousand.
Prepare poly-epsilon-caprolactone
Embodiment 26
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
100 μm of ol catalyst are added（Aluminum complex shown in formula I, R are hydrogen）, 100 μm of ol benzylalcohols, 10 mL toluene and 10 mmol
Caprolactone, be subsequently placed in 110oIn the oil bath of C, reaction is added a small amount of water and terminates reaction after 6 minutes, with ethanol precipitation, washing
For several times, it is dried in vacuo at room temperature, obtains 1.10 g products, yield 96.5%, molecular weight 2.3 ten thousand.
Embodiment 27
Polycaprolactone is prepared according to the method for embodiment 26, unlike：Catalyst used is aluminum complex shown in formula I, R
For methyl.The quality of products obtained therefrom is 1.11 g after reaction 8 minutes, and yield 97.4%, molecular weight is 2.1 ten thousand.
Embodiment 28
Polycaprolactone is prepared according to the method for embodiment 26, unlike：Catalyst used is aluminum complex shown in formula I, R
For bromine.The quality of products obtained therefrom is 1.12 g after reaction 2 minutes, and yield 98.2%, molecular weight is 2.4 ten thousand.
Embodiment 29
Polycaprolactone is prepared according to the method for embodiment 26, unlike：Catalyst used is aluminum complex shown in formula I, R
For tertiary butyl.The quality of products obtained therefrom is 1.11 g after reaction 9 minutes, and yield 97.4%, molecular weight is 2.2 ten thousand.
Embodiment 30
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
100 μm of ol catalyst are added（Aluminum complex shown in formula I, R are bromine）, 100 μm of ol benzylalcohols, 10 mL toluene and 10 mmol
Caprolactone, then respectively 20oC、40oC、60oC、80oC and 100oIt is reacted under C, a small amount of water is added after reaction and terminates instead
It answers, for several times with methanol extraction, washing, is dried in vacuo at room temperature.
Wherein, it is reacted 40 minutes at 20 DEG C, obtains 1.10 g products, yield 96.5%, molecular weight 2.2 ten thousand.
It is reacted 20 minutes at 40 DEG C, obtains 1.10 g products, yield 96.5%, molecular weight 2.1 ten thousand.
It is reacted 14 minutes at 60 DEG C, obtains 1.11 g products, yield 97.4%, molecular weight 2.2 ten thousand.
It is reacted 11 minutes at 80 DEG C, obtains 1.11 g products, yield 97.4%, molecular weight 2.3 ten thousand.
It is reacted 4 minutes at 100 DEG C, obtains 1.12 g products, yield 98.2%, molecular weight 2.1 ten thousand.
Embodiment 31
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
10 μm of ol catalyst are added（Aluminum complex shown in formula I, R are hydrogen）, 30 μm of ol benzylalcohols, 10 mL tetrahydrofurans and 5 mmol
6-caprolactone, then 30oC reactions are added a small amount of water and terminate reaction after sixty minutes, for several times with ethanol precipitation, washing, at room temperature
Vacuum drying, obtains 0.55 g products, yield 96.5%, molecular weight 6.4 ten thousand.
Embodiment 32
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
10 μm of ol catalyst are added（Aluminum complex shown in formula I, R are methyl）, 30 μm of ol benzylalcohols, 10 mL toluene and 10 mmol
6-caprolactone, then 50oC is added a small amount of water and terminates reaction after reacting 30 minutes, for several times with ethanol precipitation, washing, at room temperature
Vacuum drying, obtains 1.10 g products, yield 96.5%, molecular weight 7.8 ten thousand.
Embodiment 33
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
10 μm of ol catalyst are added（Aluminum complex shown in formula I, R are tertiary butyl）, 20 μm of ol benzylalcohols, 15 mL toluene and 15
The 6-caprolactone of mmol, is subsequently placed in 90oIn the oil bath of C, reaction is added a small amount of water and terminates reaction after 11 minutes, heavy with ethyl alcohol
It forms sediment, wash for several times, be dried in vacuo at room temperature, obtain 1.65 g products, yield 96.5%, molecular weight 16.3 ten thousand.
Embodiment 34
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
100 μm of ol catalyst are added（Aluminum complex shown in formula I, R are hydrogen）, 100 μm of ol benzylalcohols, 10 mL toluene and 5 mmol
6-caprolactone, be subsequently placed in 70oIn the oil bath of C, reaction is added a small amount of water and terminates reaction after 16 minutes, with ethanol precipitation, wash
It washs for several times, is dried in vacuo at room temperature, obtain 0.54 gram of product, yield 94.7%, molecular weight 1.1 ten thousand.
Prepare polylactide
Embodiment 35
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
100 μm of ol catalyst are added（Aluminum complex shown in formula I, R are hydrogen）, 100 μm of ol benzylalcohols, 20 mL toluene and 10 mmol
Rac-lactide, then 20oC is added a small amount of water and terminates reaction after reacting 22 hours, for several times with ethanol precipitation, washing, room
The lower vacuum drying of temperature, obtains 1.35 g products, yield 93.8%.Products therefrom be isotaxy polylactide, molecular weight 2.9 ten thousand,
Isotaxy stereoselectivityP m= 0.75。
Embodiment 36
Polylactide is prepared according to the method for embodiment 35, unlike：Catalyst used is aluminum complex shown in formula I, R
For methyl.The quality of products obtained therefrom is 1.3 3 g after reaction 23 hours, and yield 92.4%, molecular weight is 2.7 ten thousand, Quan Tongli
Structure stereoselectivityP m= 0.78。
Embodiment 37
Polylactide is prepared according to the method for embodiment 35, unlike：Catalyst used is aluminum complex shown in formula I, R
For bromine.The quality of products obtained therefrom is 1.37 g after reaction 21 hours, and yield 95.1%, molecular weight is 2.7 ten thousand, isotaxy
StereoselectivityP m= 0.77。
Embodiment 38
Polylactide is prepared according to the method for embodiment 35, unlike：Catalyst used is aluminum complex shown in formula I, R
For tertiary butyl.The quality of products obtained therefrom is 1.36 g after reaction 24 hours, and yield 94.4%, molecular weight is 2.8 ten thousand, Quan Tong
Vertical structure stereoselectivityP m= 0.80。
Embodiment 39
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
100 μm of ol catalyst are added（Aluminum complex shown in formula I, R are tertiary butyl）, 100 μm of ol benzylalcohols, 10 mL toluene and 10
The rac-lactide of mmol, then respectively 40oC、60oC and 80oIt is reacted under C, a small amount of water is added after reaction and terminates instead
It answers, for several times with methanol extraction, washing, is dried in vacuo at room temperature.
Wherein, it is reacted 22 hours at 40 DEG C, obtains 1.38 g products, yield 95.8%, molecular weight 2.9 ten thousand,P m = 0.76。
It is reacted 19 hours at 60 DEG C, obtains 1.40 g products, yield 97.2%, molecular weight 2.6 ten thousand,P m = 0.68。
It is reacted 16 hours at 80 DEG C, obtains 1.38 g products, yield 95.8%, molecular weight 2.8 ten thousand,P m = 0.60。
Embodiment 40
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
200 μm of ol catalyst are added（Aluminum complex shown in formula I, R are hydrogen）, 200 μm of ol benzylalcohols, 20 mL tetrahydrofurans and 10
The levorotatory lactide of mmol, then 30oC is added a small amount of water and terminates reaction after reacting 21 hours, for several times with ethanol precipitation, washing,
It is dried in vacuo at room temperature, obtains 1.41 g products, yield 97.9%, molecular weight 1.2 ten thousand.
Embodiment 41
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
10 μm of ol catalyst are added（Aluminum complex shown in formula I, R are methyl）, 10 μm of ol benzylalcohols, 10 mL tetrahydrofurans and 5
The Study of Meso-Lactide of mmol, is subsequently placed in 50oIn the oil bath of C, reaction is added a small amount of water and terminates reaction after 18 hours, use ethyl alcohol
Precipitation, washing for several times, are dried in vacuo, obtain 0.68 g products, yield 94.4%, molecular weight 12.1 ten thousand at room temperature.
Embodiment 42
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
10 μm of ol catalyst are added（Aluminum complex shown in formula I, R are bromine）, 30 μm of ol benzylalcohols, 20 mL toluene and 10 mmol
Levorotatory lactide, then 90oC is added a small amount of water and terminates reaction after reacting 3 hours, for several times with ethanol precipitation, washing, at room temperature very
Sky is dry, obtains 1.41 g products, yield 97.9%, molecular weight 7.4 ten thousand.
Embodiment 43
It is reacted under anhydrous and oxygen-free and inert gas shielding, the sequence first in the ampulla after being toasted with high pure nitrogen gas washing
10 μm of ol catalyst are added（Aluminum complex shown in formula I, R are bromine）, 20 μm of ol benzylalcohols, 20 mL toluene and 15 mmol
Levorotatory lactide is subsequently placed in 110oIn the oil bath of C, reaction is added a small amount of water and terminates reaction after 1.5 hours, with ethanol precipitation,
Washing for several times, is dried in vacuo, obtains 2.10 grams of products, yield 97.2%, molecular weight 17.8 ten thousand at room temperature.
Comparative example 1
The preparation of Raney nickel：Ligand structure formula such as above formula used（II）, R is bromine, and reaction process is：0.30 g of ligand is dissolved in
In 20 mL absolute ethyl alcohols, the nickel acetate of 1.0 times of ligand moles is added at room temperature, heating reflux reaction 12 hours, reaction terminates
It is concentrated in vacuo solvent later, dichloromethane is added, solid is precipitated, filter and simultaneously washed with hexane, dry Raney nickel, structure
Formula is as follows.
Polylactide is prepared according to the method for embodiment 43, unlike：Catalyst used is above-mentioned Raney nickel.Instead
A small amount of water is added after answering 24 hours and terminates reaction, for several times with methanol extraction, washing, is dried in vacuo at room temperature, obtains 0.43 g, yield
19.9 %, molecular weight 1.9 ten thousand.The Raney nickel is too low to the polymerization activity of lactide, is not worth.
Comparative example 2
The preparation of Al catalysts：Ligand structure formula such as following formula used（LH2）, reaction process is：In anhydrous and oxygen-free and inert gas
Under protection, 0.20 g of ligand is dissolved in 10 mL toluene, the trimethyl aluminium of 1.0 times of ligand moles is added at -5 DEG C, is delayed
Slowly it is heated to 80 DEG C after being warmed to room temperature to react 12 hours, reaction is concentrated in vacuo solvent after terminating, addition drying hexane is precipitated solid
Body is filtered and is simultaneously washed with hexane, dry Al catalysts, structural formula LAlMe as follows.
Polylactide is prepared according to the method for embodiment 39, unlike：Catalyst used is the Al catalysts.In nothing
It is reacted under water anaerobic and inert gas shielding, is sequentially added 100 in the ampulla after being toasted with high pure nitrogen gas washing first
μm ol catalyst（Aluminum complex shown in formula I, R are tertiary butyl）, 100 μm of ol benzylalcohols, 10 mL toluene and 10 mmol it is outer
Meso-lactide, then respectively 20oC and 80oReacted under C, a small amount of water be added after reaction and terminates reaction, with methanol extraction,
Washing for several times, is dried in vacuo at room temperature.
Wherein, it reacts at 20 DEG C 36 hours and is generated without product, illustrate that the catalyst can not be catalyzed third at a lower temperature
The polymerization of lactide.
1.15 g products, 79.9 % of yield, molecular weight 1.4 ten thousand, the selection of isotaxy solid are reacted 24 hours to obtain at 80 DEG C
PropertyP m = 0.53.It compares with the Al catalysts of embodiment 39, stereoselectivity and activity are all relatively low.
Comparative example 3
Polylactide is prepared according to the method for embodiment 35, unlike：Catalyst used is patent 201410609375.8
Catalyst used in middle embodiment 10.Gained polylactide is heterotactic polylactide, quality 1.33 after reaction
G, yield 92.4%, molecular weight are 1.7 ten thousand, heterotactic stereoselectivityP r It is 0.71.
Comparative example 4
Under nitrogen atmosphere, by ligand A（R is methyl）0.35 g is dissolved in 10 mL drying hexamethylenes, and ligand A is added at 0 DEG C
The triisopropylaluminiuand of 1.05 times of moles, after reaction temperature is raised to room temperature naturally, heating reaction temperature is small to 70 DEG C of reactions 12
When, 51 microlitres of water are added after reaction and stop reaction, organic phase is collected in liquid separation, and anhydrous sodium sulfate drying is spin-dried for solvent, finds to obtain
Compound does not change（Isopropyl does not carry out C=O addition reactions）.Triisopropylaluminiuand can not carry out addition reaction.
Comparative example 5
Polylactide is prepared according to the method for embodiment 35, unlike：Catalyst used is aluminum complex shown in formula I, R
For methoxyl group.The quality of products obtained therefrom is 0.99 g after reaction 36 hours, and yield 68.8%, molecular weight is 1.3 ten thousand, Quan Tong
Vertical structure stereoselectivityP m= 0.67。
Comparative example 6
P-methyl benzenesulfonic acid is dissolved into dimethylbenzene, is first slowly added into 1, the 3- propane diamine of p-methyl benzenesulfonic acid equimolar amounts, then add
Enter the phthalic anhydride of p-methyl benzenesulfonic acid equimolar amounts, heating reflux reaction, reaction is cooled to room temperature by solid after terminating
Filtering, washing, is dried to obtain solid.Solid is dissolved into dichloromethane, the saturated water of excessive sodium bicarbonate is slowly added dropwise
Solution, room temperature reaction, after reaction liquid separation are dried with anhydrous magnesium sulfate, are spin-dried for solvent, obtain unilateral phthalic anhydride and protect
1, the 3- propane diamine of shield.The propane diamine of unilateral phthalic anhydride protection and 3, the 5- Dibromosalicylaldehydes of equimolar amounts are in methyl alcohol
It is heated to reflux, reaction is put into cooling in refrigerator, precipitation solid after terminating, filter, washed with cold methanol, and drying is changed
Close object LD.
The preparation of Al catalysts：Under nitrogen atmosphere, by 0.20 g of compound L D are dissolved in 10 mL dry toluenes, -10
The trimethyl aluminium of 1.0 times of compound L D moles is added at DEG C, after reaction temperature is raised to room temperature naturally, is heated to 110 DEG C instead
It answers 1 hour, vacuum drains solvent after reaction terminates, and dry n-hexane washing, filtering, drying is added, it is solid to obtain 0.18 g
Body, yield 81.8%, the aluminium compound through hydrolysis after do mass spectral characteristi find such ligand can only unilateral generation addition reaction obtain
To LDAlMe2（HRESI-MS: m/z cacld. C18H14Br2N2O3 [M-H]-; 462.9294, found: 462.9292）.
Polylactide is prepared according to the method for embodiment 35, unlike：Catalyst used is the Al catalysts.Reaction
The quality of products obtained therefrom is 0.60 g afterwards, and yield 41.7%, molecular weight is 1.2 ten thousand, no stereoselectivity.
Claims (10)
1. a kind of unsymmetric ligand of base containing o-phenylenediamine, it is characterized in that：Its structural formula is as shown in following formula A or II；Formula A and formula II
In, R is the alkane or halogen of hydrogen, C1-C4, preferably tertiary butyl or bromine；
。
2. a kind of preparation method of the unsymmetric ligand of the base described in claim 1 containing o-phenylenediamine, it is characterized in that including following
Step：
The preparation method of ligand shown in formula A includes the following steps：P-methyl benzenesulfonic acid is dissolved into dimethylbenzene, is first slowly added into pair
The o-phenylenediamine of toluenesulfonic acid equimolar amounts, adds the phthalic anhydride of p-methyl benzenesulfonic acid equimolar amounts, then heat into
Row back flow reaction, is cooled to room temperature after reaction, filters to take solid, and obtained solid is dissolved into dichloromethane, then delays
The slow saturated sodium bicarbonate aqueous solution that is added dropwise is reacted, to slough p-methyl benzenesulfonic acid, liquid separation after reaction, by gained organic phase
It is dried with anhydrous magnesium sulfate, is then spin-dried for solvent, obtain the o-phenylenediamine of unilateral phthalic anhydride protection；
Salicylide of o-phenylenediamine and equimolar amounts that unilateral phthalic anhydride is protected or derivatives thereof dissolves in methyl alcohol,
Heating carries out back flow reaction, and cooling after reaction, filtering, obtained solid is washed with cold methanol, is dry, ligand shown in formula A；Institute
The structural formula for stating salicylide or derivatives thereof is：2-OH-3,5-R2C6H4CHO, wherein R are the alkane or halogen of hydrogen, C1-C4, excellent
It is selected as tertiary butyl or bromine.
3. the preparation method of ligand shown in formula II includes the following steps：Ligand shown in formula A is added in organic solvent, -10~0oTrimethyl aluminium is added under C, so that reaction temperature is warmed to room temperature naturally after adding, temperature is then risen to 30~110oC is reacted,
Water is added into reaction solution after reaction, liquid separation is stood after being sufficiently mixed, collects organic phase obtained by liquid separation, recycling is organic molten
Agent obtains crude product, and crude product is recrystallized, and obtains ligand shown in formula II.
4. preparation method according to claim 2, it is characterized in that：The molar ratio 1 of ligand and trimethyl aluminium shown in formula A：1~
1.3, preferably 1：1~1.05.
5. preparation method according to claim 2, it is characterized in that：The organic solvent is hexane, toluene and the ring of drying
One or both of hexane；Recrystallization solvent is methanol or/and ethyl alcohol.
6. preparation method according to claim 2, it is characterized in that：Consumption of organic solvent be reaction raw materials gross mass 5~
40 times；The dosage of water is the mole of 3 times of ligand shown in formula A.
7. preparation method according to claim 2, it is characterized in that：It is raised to room temperature and temperature is risen to 30~110 again lateroC
（It is preferred that 40~60oC）Reaction 1~12 hour is preferably reacted 3~6 hours.
8. preparation method according to claim 2, it is characterized in that：Reaction carries out under gas shield.
9. the catalyst of the unsymmetric ligand of the base described in claim 1 containing o-phenylenediamine as cyclic lactone ring-opening polymerization
The application of ligand, it is preferred that the cyclic lactone be levorotatory lactide, Study of Meso-Lactide, rac-lactide, glycolide or oneself
Lactone.
10. a kind of catalyst of cyclic lactone ring-opening polymerization, it is characterized in that：It is with the structural formula described in formula I, wherein R is
The alkane or halogen of hydrogen, C1-C4, preferably tertiary butyl or bromine；
。
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