CN108003335A - A kind of method of chiral asymmetric aluminum complex catalysis glycolide polymerization using the aldehyde radical containing bigcatkin willow - Google Patents
A kind of method of chiral asymmetric aluminum complex catalysis glycolide polymerization using the aldehyde radical containing bigcatkin willow Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
Abstract
The invention discloses a kind of method of the chiral asymmetric aluminum complex catalysis glycolide polymerization using the aldehyde radical containing bigcatkin willow, comprise the following steps：Catalyst, organic solvent, benzylalcohol co-catalyst and glycolide are mixed, ring-opening polymerization is carried out under anhydrous and oxygen-free and inert gas shielding, carries out reactant after reaction to handle to obtain polyglycolide；The catalyst is the chiral asymmetric aluminum complex of the aldehyde radical containing bigcatkin willow.The chiral asymmetric aluminum complex of containing bigcatkin willow aldehyde radical of the present invention voluntarily to research and develop carries out glycolide ring-opening polymerization as catalyst, the chiral asymmetric aluminum complex method for preparing catalyst of the aldehyde radical containing bigcatkin willow is simple, cost is low, product yield is high, catalyst structure change is various, the divalence N of metal center aluminium and ligand, N, O, O are coordinated, and catalytic activity is high, stereoselectivity is high, reaction rate is fast, obtained polymer is the polymer of benzyloxy end-blocking, narrow molecular weight distribution, molecular weight is controllable, yield is high, meets the market demand.
Description
Technical field
The present invention relates to a kind of method for being catalyzed glycolide polymerization, and in particular to a kind of to utilize the chiral non-of the aldehyde radical containing bigcatkin willow
The method of symmetrical aluminum complex catalysis glycolide polymerization.
Background technology
Under the present situation that oil faces as non-renewable resources exhaustion, rely on petroleum high molecular material it is quick
Development is subject to severely restricts.Macromolecule polymeric material is difficult to degrade, and substantial amounts of macromolecule polymeric material discarded object accumulates in for a long time
Gradually exacerbation is polluted also in actual life caused by environment for human survival.Conventional polymer material faces energy crisis and environment
Pollution two hang-ups, find instead of oil renewable resource, development environment friendly, biodegradation type new material into
For the trend of following macromolecule polymeric material development.
Polyester is the high molecular material of the environmental type of biodegradable, it is more next as the substitute of oil product
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,
Therefore it is 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 method of synthesizing polyester easily is the ring-opening polymerisation method of cyclic lactone, this synthetic method be：Polymerization
Controllability, relatively narrow molecular weight distribution, copolymerized polymer can be formed.Currently used catalyst is mostly that ligand and metal are formed
Complex, the metal in catalyst includes magnesium, calcium, germanium, tin, aluminium, zinc, iron, titanium, zirconium, group of the lanthanides etc..Catalyst gathers for open loop
Closing the speed of reaction, the three-dimensional regularity of resulting polymers and molecular weight has a material impact, and the ligand of catalyst and coordination
The selection of metal is all very crucial for the speed of ring-opening polymerization, the three-dimensional regularity of polymer and molecular weight, therefore grinds
Study carefully the good catalyst ligand of new performance and composition catalyst is very necessary.
The content of the invention
The present invention provides a kind of side of the chiral asymmetric aluminum complex catalysis glycolide polymerization using the aldehyde radical containing bigcatkin willow
Method, this method is easy to operate, and using the chiral asymmetric aluminum complex of the aldehyde radical containing bigcatkin willow voluntarily researched and developed as catalyst, reaction is controllable
Property is good, and obtained polyglycolide molecular weight is controllable, yield is high.
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 a kind of chiral asymmetric aluminum complex catalyst of the special aldehyde radical containing bigcatkin willow of structure, the catalyst
Structural formula such as following formula（Ⅰ）It is shown：
。
The chiral asymmetric aluminum complex of the aldehyde radical containing bigcatkin willow of the invention is complex, by the selection to ligand structure and with
The coordination of metallic aluminium has excellent performance, and ligand structure of the present invention is special, and the selection of substituent is for aluminium cooperation in ligand
Thing has considerable influence as the catalytic performance of cyclic lactone ring-opening polymerization catalyst.Wherein, R is hydrogen, the alkane or halogen of C1-C4
Element, the halogen is fluorine, chlorine, bromine or iodine.Further, catalytic activity is optimal when R is bromine.
The chiral asymmetric aluminum complex of the aldehyde radical of the invention containing bigcatkin willow is to react to obtain by ligand and trimethyl aluminium, it is prepared
Method comprises the following steps：Ligand A is added in organic solvent, -10~0 oTrimethyl aluminium is added under C, makes reaction after adding
Temperature is warmed to room temperature naturally, and temperature then is risen to 30~110oC is reacted, and vacuum drains solvent, washing, mistake after reaction
Filter, obtains the chiral asymmetric aluminum complex of the aldehyde radical containing bigcatkin willow described in formula I.
Ligand A and the equation that trimethyl aluminium reacts are as follows, and the structural formula of wherein ligand A is shown below, and R is hydrogen, C1-
The alkane or halogen of C4, the halogen is fluorine, chlorine, bromine, iodine；R is preferably bromine；
。
In above-mentioned preparation method, the preparation method of ligand A comprises the following steps：P-methyl benzenesulfonic acid is dissolved into dimethylbenzene
In, the chiral cyclohexanediamine of p-methyl benzenesulfonic acid equimolar amounts is first slowly added into, adds the adjacent benzene of p-methyl benzenesulfonic acid equimolar amounts
Dicarboxylic acid anhydride, then heating carry out back flow reaction, are cooled to room temperature after reaction, filter, and obtain p-methyl benzenesulfonic acid and adjacent benzene two
The chiral cyclohexanediamine of formic anhydride protection；The chiral cyclohexanediamine that p-methyl benzenesulfonic acid and phthalic anhydride are protected is dissolved into two
In chloromethanes, saturated sodium bicarbonate aqueous solution is slowly added dropwise and is reacted to slough p-methyl benzenesulfonic acid, liquid separation after reaction will
Gained organic phase is dried with anhydrous magnesium sulfate, is then spin-dried for solvent, obtains the chiral cyclohexanediamine of unilateral phthalic anhydride protection；
Salicylide of chiral cyclohexanediamine and equimolar amounts that unilateral phthalic anhydride is protected or derivatives thereof is dissolved in first
In alcohol, heating carries out back flow reaction, cools down, filters after reaction, and obtained solid is washed with cold methanol, is dry, obtains ligand A；
The structural formula of the salicylaldehyde derivatives is as shown in following formula B, and wherein R is hydrogen, the alkane or halogen of C1-C4, is preferably bromine；
。
In above-mentioned preparation method, addition reaction occurs for ligand A and trimethyl aluminium, and the alkyl of trimethyl aluminium adds to ligand A
In C=O double bonds on, C=O double bonds become C-O singly-bounds.Found by nuclear-magnetism characterizationδ=1.5-2.0 nearby has one group of CH3's
Characteristic peak, this characteristic peak are exactly NC (O) (Ar) CH 3Middle CH3Characteristic peak.
In above-mentioned preparation method, the molar ratio 1 of ligand A and trimethyl aluminium：1~1.3, preferably 1：1~1.05.
In above-mentioned preparation method, the organic solvent is one or both of dry hexane, toluene and hexamethylene, excellent
Elect dry hexane or toluene as.
In above-mentioned preparation method, consumption of organic solvent is reaction raw materials（Ligand A and trimethyl aluminium）The 5~40 of gross mass
Times.
In above-mentioned preparation method, react and carried out under gas shield, the gas is inert gas or nitrogen.
In above-mentioned preparation method, 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, preferably 40~60oC.30~110oC（It is preferred that 40~60oC）
When the time reacted is 1~12 small, when being preferably 3~6 small.After reaction, precipitation is washed with n-hexane.
The chiral asymmetric aluminum complex of the aldehyde radical of the present invention containing bigcatkin willow is in the compound described in formula II
Between product, the chiral asymmetric aluminum complex of the aldehyde radical containing bigcatkin willow is more sensitive to water, anti-after ligand A and trimethyl aluminium react
Answer addition water in liquid to be sufficiently stirred and can hydrolyze aluminum complex, through liquid separation, collect organic phase, the processing of organic phase recycling design, institute
Obtain compound of the residue described in through recrystallization as formula II.Therefore, preparing aluminum complex will be in anhydrous and proton solvent feelings
Carried out under condition.In addition, using the compound described in formula II as raw material, ligand A is replaced with into the compound described in formula II, according to above-mentioned
The preparation method of the chiral asymmetric aluminum complex of the aldehyde radical containing bigcatkin willow can also obtain the chiral asymmetric aluminium of I aldehyde radical containing bigcatkin willow of formula again
Complex.
When preparing the chiral asymmetric aluminum complex of the aldehyde radical containing bigcatkin willow with the compound described in formula II, organic solvent is drying
One or both of hexane, toluene and hexamethylene, be preferably hexane or toluene.Consumption of organic solvent is reaction raw materials（Formula
Compound and trimethyl aluminium described in II）5~40 times of gross mass.Reaction is recrystallized after terminating with dry hexane, is obtained
The chiral asymmetric aluminum complex of formula I containing the bigcatkin willow aldehyde radical high to purity.
The chiral asymmetric aluminum complex of the aldehyde radical of the invention containing bigcatkin willow is complex, and N, N, O, O and aluminium of ligand are matched somebody with somebody
Position, the structure of complex and classical cyclic lactone catalyst（salenAl）Structure it is very similar, excellent catalytic effect, have compared with
High stereoselectivity.The present invention is anti-as cyclic lactone ring-opening polymerisation for the chiral asymmetric aluminum complex of the aldehyde radical containing bigcatkin willow
The application for the catalyst answered also is protected.
During catalyst of the chiral asymmetric aluminum complex of the aldehyde radical containing bigcatkin willow of the invention as cyclic lactone ring-opening polymerization,
The ring-opening polymerisation of glycolide can be catalyzed, obtains a series of polyglycolide.The present invention specifically provides a kind of aqueous using this
The method of the chiral asymmetric aluminum complex catalysis glycolide polymerization of poplar aldehyde radical, comprises the following steps：By the hand of the aldehyde radical containing bigcatkin willow
Property asymmetric aluminum complex catalyst, organic solvent, benzylalcohol co-catalyst and glycolide mixing, in anhydrous and oxygen-free and inert gas
Protection is lower to carry out ring-opening polymerization, carries out reactant after reaction to handle to obtain polyglycolide.
When the chiral asymmetric aluminum complex of the aldehyde radical of the invention containing bigcatkin willow is used as the catalyst of glycolide ring-opening polymerization,
Catalytic activity is optimal when R is bromine.
In above-mentioned ring-opening polymerization, mole of glycolide and the chiral asymmetric aluminum complex catalyst of the aldehyde radical containing bigcatkin willow
Than for 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.
In above-mentioned ring-opening polymerization, organic solvent used in reaction is toluene or tetrahydrofuran, preferably toluene.
In above-mentioned ring-opening polymerization, alcohol co-catalyst is benzylalcohol.Benzylalcohol co-catalyst is chiral non-with the aldehyde radical containing bigcatkin willow
The molar ratio of symmetrical aluminum complex catalyst 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 rise of polymeric reaction temperature, the stereoselectivity of catalyst has reduction
Trend, catalytic activity has elevated trend.
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, 300 minutes, 600 minutes, 900 minutes, 1200 minutes, 1440 minutes etc..
In above-mentioned ring-opening polymerization, cold methanol or ethanol purification polylactone are added after reaction, obtains polylactone after purification.
The molecular weight controllability of gained polyglycolide is high, can be adjusted in the range of 1-14 ten thousand.
The chiral asymmetric aluminum complex of containing bigcatkin willow aldehyde radical of the present invention voluntarily to research and develop carries out glycolide as catalyst
Ring-opening polymerization, the chiral asymmetric aluminum complex method for preparing catalyst of the aldehyde radical containing bigcatkin willow is simple, and cost is low, product yield
Height, catalyst structure change is various, and the divalence N, N, O of metal center aluminium and ligand, O coordinations, catalytic activity is high, stereoselectivity
Height, reaction rate are fast, and obtained polymer is the polymer of benzyloxy end-blocking, and narrow molecular weight distribution, molecular weight is controllable, yield
Height, meets the market demand.
Embodiment
The present invention is further illustrated below by specific embodiment, but the present invention is not limited thereto, and specific protection domain is shown in
Claim.
Prepare the chiral cyclohexanediamine (a) of unilateral protection
0.50 g p-methyl benzenesulfonic acid is dissolved into dimethylbenzene, is first slowly added into the chiral hexamethylene two of p-methyl benzenesulfonic acid equimolar amounts
Amine, adds the phthalic anhydride of p-methyl benzenesulfonic acid equimolar amounts, 8 h of heating reflux reaction, and reaction is cooled to after terminating
Room temperature filters solid, washing, is dried to obtain p-methyl benzenesulfonic acid and the chiral cyclohexanediamine of phthalic anhydride protection.Will be to first
Benzene sulfonic acid and the chiral cyclohexanediamine of phthalic anhydride protection are dissolved into dichloromethane, and excessive carbonic acid is slowly added dropwise in room temperature
Aqueous saturated sodium hydrogen is reacted, and to slough p-methyl benzenesulfonic acid, liquid separation after reaction, is dried with anhydrous magnesium sulfate, be spin-dried for
Solvent, obtains 0.57 g of chiral cyclohexanediamine, 80.1 % of yield of unilateral phthalic anhydride protection.
Prepare the chiral asymmetric nitrogen oxygen ligand of the aldehyde radical containing bigcatkin willow（A）
The chiral asymmetric nitrogen oxygen ligand of the aldehyde radical containing bigcatkin willow（A）Be by the chiral cyclohexanediamine and salicylide of unilateral protection or its spread out
Biology is obtained by condensation reaction, is illustrated 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 chiral cyclohexanediamine of unilateral protection
The salicylide of 0.30 g and equimolar amounts is added in 15 mL methanol, and when heating reflux reaction 12 is small, reaction is cooled after terminating
Filter and washed with cold methanol, filtered, collect and drying is weighed, obtain 0.35 g solids, yield 81.4%.
Products obtained therefrom is characterized, it is as a result as follows：
1H NMR (300 MHz, CDCl3) δ 10.21 (s, 1H, OH), 8.32 (s, 1H, CH=N), 7.72 (d,
J = 7.0 Hz, 1H, Ar–H), 7.60–7.40 (m, 4H, Ar–H), 7.13 (d, J = 7.0 Hz, 1H, Ar–H), 6.82 (d, J = 8.0 Hz, 1H, Ar–H), 6.67 (t, J = 8.0 Hz, 1H, Ar–H), 4.46 (br,
1H, NCH), 3.67 (m, 1H, NCH), 2.43–2.32 (m, 1H, CH2CH2), 2.10–2.03 (m, 1H,
CH2CH2), 1.89-1.80 (m, 3H, CH2CH2), 1.70–1.62 (m, 3H, CH2CH2), 1.51–1.43 (m,
1H, CH2CH2).
HRESI-MS: m/z cacld. C21H20N2O3 [M-H]-; 347.1397, found: 347.1396.
Can be seen that products obtained therefrom from 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 chiral cyclohexanediamine of unilateral protection
3, the 5- dimethyl salicylide of 0.40 g and equimolar amounts is added in 15 mL methanol, and when heating reflux reaction 12 is small, reaction terminates
Later cold filtration is simultaneously washed with cold methanol, is filtered, and collects and drying is weighed, obtain 0.51 g solids, yield 82.3%.
Products obtained therefrom is characterized, it is as a result as follows：
1H NMR (400 MHz, CDCl3) δ12.23 (s, 1H, OH), 8.30 (s, 1H, CH=N), 7.81 (d,
J = 7.0 Hz, 1H, Ar–H), 7.52–7.30 (m, 3H, Ar–H), 6.84 (m, 1H, Ar–H), 6.70 (m,
1H, Ar–H), 4.42 (br, 1H, NCH), 3.67 (m, NCH), 2.40–2.32 (m, 1H, CH2CH2), 2.15
(s, 6H, ArCH3), 1.96–1.90 (m, 1H, CH2CH2), 1.85–1.80 (m, 3H, CH2CH2), 1.68–1.60
(m, 3H, CH2CH2). HRESI-MS: m/z cacld. C23H24N2O3 [M-H]-; 375.1708, found:
375.1710.
Can be seen that products obtained therefrom from 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 chiral cyclohexanediamine of unilateral protection
3, the 5- Dibromosalicylaldehydes of 0.30 g and equimolar amounts add 15 mL methanol in, when heating reflux reaction 12 is small, reaction terminate with
Postcooling is filtered and washed with cold methanol, filtering, collects and drying is weighed, obtain 0.54 g solids, yield 87.1%.
Products obtained therefrom is characterized, it is as a result as follows：
1H NMR (300 MHz, CDCl3) δ 10.20 (s, 1H, OH), 8.10 (s, 1H, CH=N), 7.58–
7.50 (m, 2H, Ar–H), 7.33 (m, 2H, Ar–H), 7.14 (d, J = 6.8 Hz, 1H, Ar–H), 7.10
(d, J = 6.8 Hz, 1H, Ar–H), 4.40 (br, 1H, NCH ), 3.64–3.50 (m, 1H, NCH), 2.29–
2.21 (m, 2H, CH2CH2), 1.90 (br s, 3H, CH2CH2), 1.50-1.43 (m, 2H, CH2CH2)。HRESI-
MS: m/z cacld. C21H18Br2N2O3 [M-H]-; 502.9608, found: 502.9606.
Can be seen that products obtained therefrom from above characterization result is above formula（A）Middle R is the ligand of bromine.
Aluminum complex is prepared using ligand A as raw material（I）
Embodiment 4
Ligand structure formula such as above formula used（A）, wherein R is hydrogen, and reaction process is：In a nitrogen atmosphere, by 0.20 g of ligand A
It is dissolved in 5 mL dry toluenes, the trimethyl aluminium of ligand 1.0 times of moles of A is added at -10 DEG C, question response temperature rises naturally
To after room temperature, be heated to 60 DEG C of reactions 3 it is small when, vacuum drains solvent after reaction terminates, and adds dry n-hexane and filters simultaneously
Washed, filtered with dry n-hexane, collected and drying is weighed, obtain 0.19 g solids, yield 82.6%.
Products therefrom nuclear-magnetism information is as follows, and the compound that R is hydrogen is can be seen that from nuclear-magnetism information（I）Synthesize successfully.
1H NMR (400 MHz, CDCl3) δ 8.15 (s, 1H, ArHC=N), 7.55 (d, J = 7.5 Hz,
1H, Ar–H), 7.51 (d, J = 7.5 Hz, 1H, Ar–H), 7.44 (t, J = 7.4 Hz, 1H, Ar–H),
7.30 (d, J = 5.3 Hz, 1H, Ar–H), 7.10 (d, J = 7.6 Hz, 1H, Ar–H), 6.79–6.65 (m,
3H, Ar–H), 4.45–4.30 (m, 1H, NCH), 3.69 (td, J = 11.5, 3.5 Hz, 1H, NCH), 2.68
(ddd, J = 16.0, 13.4, 3.8 Hz, 1H, CH2CH 2), 2.18–1.85 (m, 5H, CH2CH 2), 1.67 (s,
3H, CCH 3), 1.61–1.35 (m, 2H, CH2CH 2), –0.52(s, 3H, AlCH 3). Anal. Calcd for
C23H25AlN2O3: C 68.30, H 6.23, N 6.93. Found: C 68.33, H 6.30, N 6.95.
Embodiment 5
Ligand structure formula such as above formula used（A）, wherein R is methyl, and reaction process is：Under nitrogen atmosphere, by 0.50 g of ligand A
It is dissolved in 5 mL drying hexamethylenes, the trimethyl aluminium of ligand 1.05 times of moles of A is added at 0 DEG C, question response temperature rises naturally
To after room temperature, heating reaction temperature to 70 DEG C of reactions 1 it is small when, vacuum drains solvent after reaction terminates, add it is dry just oneself
Alkane is filtered and washed with dry n-hexane, is filtered, and collects and drying is weighed, obtain 0.52 g solids, yield 91.2%.
Products therefrom nuclear-magnetism information is as follows, and the compound that R is methyl is can be seen that from nuclear-magnetism information（I）Synthesize successfully.
1H NMR (400 MHz, CDCl3) δ 8.03 (s, 1H, ArHC=N), 7.77 (s, 1H, Ar–H),
7.61 (dd, J = 5.1, 2.7 Hz, 2H, Ar–H), 7.01 (s, 1H, Ar–H), 6.42 (s, 1H, Ar–H),
4.52 (m, 1H, NCH), 3.67 (t, J = 8.9 Hz, 1H, NCH), 2.62–2.52 (m, 1H, CH2CH 2),
2.13 (m, 3H, CH2CH 2), 2.06 (s, 3H, ArCH 3), 2.01 (s, 3H, ArCH 3), 1.98–1.95 (m,
2H, CH2CH 2), 1.70 (s, 3H, CCH 3), 1.61–1.44 (m, 2H, CH2CH 2), –0.48 (s, 3H,
AlCH 3). Anal. Calcd for C25H29AlN2O3: C 69.43, H 6.76, N 6.48. Found: C 69.48,
H 6.70, N 6.53.
Embodiment 6
Ligand structure formula such as above formula used（A）, wherein R is bromine, and reaction process is：Under nitrogen atmosphere, it is 0.20 g of ligand A is molten
In 8 mL dry toluenes, the trimethyl aluminium of ligand 1.1 times of moles of A is added at -5 DEG C, question response temperature is raised to room naturally
Wen Hou, be heated to 40 DEG C reaction 6 it is small when, reaction terminate after vacuum drain solvent, add dry n-hexane filter and use do
Dry n-hexane washing, filtering, is collected and drying is weighed, and obtains 0.21 g products, yield 95.5%.
The nuclear-magnetism information of products obtained therefrom is as follows, it can be seen that R is the compound of bromine（I）Synthesize successfully.
1H NMR (300 MHz, CDCl3) δ 8.13 (s, 1H, ArHC=N), 7.84 (d, J = 7.5 Hz,
1H, Ar–H), 7.74 (s, 2H, Ar–H), 7.61 – 7.49 (m, 2H, Ar–H), 7.44 – 7.35 (m, 1H,
Ar–H), 4.35 (m, 1H, NCH), 3.82 (dd, J = 19.2, 10.6 Hz, 1H, NCH), 2.10–1.97
(m, 5H, CH2CH 2), 1.70 (s, 1H, CCH 3), 1.51–1.47 (m, 3H, CH2CH 2), –0.46 (s, 3H,
AlCH 3). Anal. Calcd for C23H23AlBr2N2O3: C 49.13, H 4.12, N 4.98. Found: C
49.16, H 4.20, N 4.90.
Embodiment 7
Ligand structure formula such as above formula used（A）, wherein R is the tert-butyl group, and reaction process is：Under nitrogen atmosphere, by ligand A 0.10
G is dissolved in 20 mL drying n-hexanes, and the trimethyl aluminium of ligand 1.3 times of moles of A is added at -5 DEG C, and question response temperature is natural
After being raised to room temperature, be heated to 30 DEG C of reactions 12 it is small when, filter simultaneously with dry n-hexane filter wash cake, collect and it is dry weigh, obtain
0.10 g products, yield 90.9%.
The nuclear-magnetism information of products therefrom is as follows, it can be seen that R is the compound of the tert-butyl group（I）Synthesize successfully.
1H NMR (300 MHz, CDCl3) δ 8.13 (s, 1H, ArHC=N), 7.84 (d, J = 7.5 Hz,
1H, Ar–H), 7.74 (s, 2H, Ar–H), 7.61 – 7.49 (m, 2H, Ar–H), 7.44 – 7.35 (m, 1H,
Ar–H), 4.35 (m, 1H, NCH), 3.82 (dd, J = 19.2, 10.6 Hz, 1H, NCH), 2.10–1.97
(m, 5H, CH2CH 2), 1.70 (s, 1H, CCH 3), 1.66 (s, 1H, CCH 3), 1.51–1.47 (m, 3H,
CH2CH 2), 1.33 (s, 9H, CH3), 1.28 (s, 9H, CH3), –0.46 (s, 3H, AlCH 3). Anal.
Calcd for C31H31AlN2O3: C 72.07, H 8.00, N 5.42. Found: C 72.12, H 8.08, N
5.50.
Aluminum complex is prepared for raw material with ligand II（I）
Embodiment 8
R is that the ligand II of hydrogen synthesizes：In a nitrogen atmosphere, by ligand A（R is hydrogen）0.20 g is dissolved in 5 mL dry toluenes,
The trimethyl aluminium of ligand 1.0 times of moles of A is added at -10 DEG C, after question response temperature is raised to room temperature naturally, is heated to 60 DEG C
React 3 it is small when, after reaction terminates, add 31 microlitres of water and stop 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 0.20 g of net product, 95.2 % of yield.
Products obtained therefrom is characterized, it is as a result as follows：
Elemental analysis result： C, 72.55; H, 6.60; N, 7.71 %.
1H NMR (300 MHz, CDCl3) δ 8.29 (s, 1H, CH=N), 7.65 (d, J = 7.3 Hz, 1H,
Ar–H), 7.56 – 7.41 (m, 4H, Ar–H), 7.17 (d, J = 7.1 Hz, 1H, Ar–H), 6.90 (d, J
= 8.2 Hz, 1H, Ar–H), 6.78 (t, J = 7.4 Hz, 1H, Ar–H), 4.47 (td, J = 10.7, 4.3
Hz, 1H, NCH), 3.60 (m, 1H, NCH), 2.41–2.37 (m, 1H, CH2CH2), 2.08–2.00 (m, 1H,
CH2CH2), 1.87-1.83 (m, 3H, CH2CH2), 1.72–1.67 (m, 3H, CH2CH2), 1.57 (s, 3H,
CH3), 1.50–1.47 (m, 1H, CH2CH2).
HRESI-MS: m/z cacld. C22H24N2O3 [M-H]-; 363.1712, found: 363.1710.
Can be seen that products obtained therefrom from above characterization result is above formula（Ⅱ）Middle R is the ligand of hydrogen.
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
0.35 g is dissolved in 12mL drying hexamethylenes, and the trimethyl aluminium of ligand i 1.1 times of moles of I, question response temperature are added at -10 DEG C
Degree nature be raised to room temperature after, be heated to 40 DEG C reaction 6 it is small when, reaction terminate later filtering and with drying n-hexane wash, mistake
Filter, is collected and drying is weighed, and obtains 0.36 g solids, yield 92.3%.For product structure formula as shown in formula I, R is hydrogen.
Embodiment 9
R is that the ligand II of methyl synthesizes：Under nitrogen atmosphere, by ligand A（R is methyl）0.50 g is dissolved in 5 mL drying hexamethylenes
In, the trimethyl aluminium of ligand 1.05 times of moles of A is added at 0 DEG C, after question response temperature is raised to room temperature naturally, heating is reacted
Temperature to 80 DEG C of reactions 1 it is small when, 72 microlitres of water are added after reaction and stop reaction, organic phase is collected in liquid separation, anhydrous sodium sulfate drying,
Solvent is spin-dried for, obtains crude product, by crude product through recrystallizing methanol, obtains 0.47 g of net product, yield 90.4%.
Products obtained therefrom is characterized, it is as a result as follows：
Elemental analysis result： C, 73.46; H, 7.22; N, 7.20 %.
1H NMR (400 MHz, CDCl3) δ13.43 (s, 1H, ArOH), 8.22 (s, 1H, CH=N), 7.60
(d, J = 7.3 Hz, 1H, Ar–H), 7.51–7.34 (m, 3H, Ar–H), 6.91 (m, 1H, Ar–H), 6.78
(m, 1H, Ar–H), 4.37 (td, J = 10.6, 4.1 Hz, 1H, NCH), 3.54 (t, J = 9.3 Hz, 1H,
NCH), 2.43–2.35 (m, 1H, CH2CH2), 2.16 (s, 6H, ArCH3), 1.97–1.92 (m, 1H,
CH2CH2), 1.87–1.84 (m, 3H, CH2CH2), 1.67–1.62 (m, 3H, CH2CH2), 1.55 (s, 3H,
CH3). HRESI-MS: m/z cacld. C24H28N2O3 [M-H]-; 391.2024, found: 391.2020.
Can be seen that products obtained therefrom from above characterization result is above formula（Ⅱ）Middle R is the ligand of methyl.
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 1.0 times of moles of I, question response temperature are added at 0 DEG C
Naturally after being raised to room temperature, heating reaction temperature to 110 DEG C of reactions 1 it is small when, vacuum drains solvent after reaction terminates, and adds and does
Dry n-hexane is filtered and washed with dry n-hexane, is filtered, and collects and drying is weighed, obtain 0.29 g solids, yield
87.9%.For product structure formula as shown in formula I, R is methyl.
Embodiment 10
R is that the ligand II of bromine synthesizes：Under nitrogen atmosphere, by ligand A（R is bromine）0.20 g is dissolved in 8 mL dry toluenes, -5
The trimethyl aluminium of ligand 1.1 times of moles of A is added at DEG C, after question response temperature is raised to room temperature naturally, is heated to 40 DEG C of reactions 6
Hour, reaction adds 21 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 0.19 g of net product, yield 90.5%.
Products obtained therefrom is characterized, it is as a result as follows：
Elemental analysis result： C, 50.60; H, 4.25; N, 5.36%.
1H NMR (300 MHz, CDCl3) δ 8.10 (s, 1H, CH=N), 7.60–7.54 (m, 2H, Ar–H),
7.38 (m, 2H, Ar–H), 7.18 (d, J = 2.2 Hz, 1H, Ar–H), 7.15 (d, J = 2.2 Hz, 1H,
Ar–H), 4.45 (dd, J = 10.7, 6.8 Hz, 1H, NCH ), 3.65–3.47 (m, 1H, NCH), 2.27–
2.20 (m, 2H, CH2CH2), 1.86 (br s, 3H, CH2CH2), 1.66 (s, 3H, CH3), 1.41 (d, J =
12.1 Hz, 2H, CH2CH2)
HRESI-MS: m/z cacld. C22H22Br2N2O3 [M-H]-; 518.9920, found: 518.9924.
Can be seen that products obtained therefrom from above characterization result is above formula（Ⅱ）Middle R is the ligand of bromine.
Ligand structure formula such as above formula used（II）, wherein R is bromine, and reaction process is：Under nitrogen atmosphere, by ligand i I
0.40 g is dissolved in 15 mL drying hexanes, and the trimethyl aluminium of ligand i 1.1 times of moles of I, question response temperature are added at -5 DEG C
Naturally after being raised to room temperature, be heated to 60 DEG C reaction 2 it is small when, reaction terminate later filtering and with drying n-hexane wash, mistake
Filter, is collected and drying is weighed, and obtains 0.40 g products, yield 93.0%.For product structure formula as shown in formula I, R is bromine.
Embodiment 11
R is that the ligand II of the tert-butyl group synthesizes：Under nitrogen atmosphere, by ligand A（R is the tert-butyl group）0.10 g is being dissolved in 5 mL dryings just
In hexane, the trimethyl aluminium of ligand 1.3 times of moles of A is added at -5 DEG C, after question response temperature is raised to room temperature naturally, heating
To 30 DEG C of reactions 12 it is small when, 12 microlitres of water are added after reaction and stop 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 0.09 g of net product, yield 90.0%.
Products obtained therefrom is characterized, it is as a result as follows：
Elemental analysis result： C, 75.63; H, 8.48; N, 5.90%.
1H NMR (300 MHz, CDCl3) δ 9.81 (s, 1H, OH), 8.13 (s, 1H, CH=N), 7.73
(d, J = 7.2 Hz, 1H, Ar–H), 7.61–7.56 (m, 3H, Ar–H), 7.51 (m, 1H, Ar–H), 7.45
(t, J = 7.3 Hz, 1H, Ar–H), 7.21 (d, J = 1.3 Hz, 1H, , Ar–H), 7.10 (m, 1H, Ar–H), 4.50 (m, 1H, NCH), 3.89 (m, 1H, NCH), 2.40–2.36 (m, 1H, CH2CH2), 1.98–1.84
(m, 3H, CH2CH2), 1.67–1.61(m, 2H, CH2CH2), 1.51(s, 3H, CH3), 1.49–1.42 (m, 2H,
CH2CH2), 1.35 (s, 9H, CH3), 1.25 (s, 9H, CH3).
HRESI-MS: m/z cacld. C30H40N2O3 [M-H]-; 475.2960, found: 475.2964.
Can be seen that products obtained therefrom from above characterization result is above formula（Ⅱ）Middle R is the ligand of the tert-butyl group.
Ligand structure formula such as above formula used（II）, wherein R is the tert-butyl group, and reaction process is：Under nitrogen atmosphere, by ligand i I
0.30 g is dissolved in 12 mL dry toluenes, and the trimethyl aluminium of ligand i 1.1 times of moles of I, question response temperature are added at 0 DEG C
Naturally after being raised to room temperature, be heated to 60 DEG C reaction 3 it is small when, reaction terminate later filtering and with drying n-hexane wash, mistake
Filter, is collected and drying is weighed, and obtains 0.30 g products, yield 90.9%.For product structure formula as shown in formula I, R is the tert-butyl group.
Prepare polyglycolide
Embodiment 12
Reacted under anhydrous and oxygen-free and inert gas shielding, the order first in the ampulla after being toasted with high pure nitrogen gas washing
Add 100 μm of ol catalyst（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 adds a small amount of water and terminates reaction after 16 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 2.1 ten thousand.
Embodiment 13
Polyglycolide is prepared according to the method for embodiment 12, unlike：Catalyst used is aluminum complex, R shown in formula I
For methyl.The quality of products obtained therefrom is 1.11 g after reacting 18 minutes, and yield 95.7%, molecular weight is 2.2 ten thousand.
Embodiment 14
Polyglycolide is prepared according to the method for embodiment 12, unlike：Catalyst used is aluminum complex, R shown in formula I
For bromine.The quality of products obtained therefrom is 1.11 g after reacting 9 minutes, and yield 95.7%, molecular weight is 2.2 ten thousand.
Embodiment 15
Polyglycolide is prepared according to the method for embodiment 12, unlike：Catalyst used is aluminum complex, R shown in formula I
For the tert-butyl group.The quality of products obtained therefrom is 1.10 g after reacting 19 minutes, and yield 94.8%, molecular weight is 2.2 ten thousand.
Embodiment 16
Reacted under anhydrous and oxygen-free and inert gas shielding, the order first in the ampulla after being toasted with high pure nitrogen gas washing
Add 100 μm of ol catalyst（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 100oReacted under C, add a small amount of water after reaction and terminate instead
Should, with methanol extraction, washing for several times, it is dried in vacuo at room temperature.
Wherein, when 20 DEG C of reactions 19 are small, 1.09 g products, yield 94.0%, molecular weight 2.0 ten thousand are obtained.
When 40 DEG C of reactions 10 are small, 1.10 g products, yield 94.8%, molecular weight 2.2 ten thousand are obtained.
When 60 DEG C of reactions 5 are small, 1.12 g products, yield 96.6%, molecular weight 2.1 ten thousand are obtained.
Reacted 45 minutes at 80 DEG C, obtain 1.12 g products, yield 96.6%, molecular weight 2.0 ten thousand.
Reacted 18 minutes at 100 DEG C, obtain 1.11 g products, yield 95.7%, molecular weight 2.3 ten thousand.
Embodiment 17
Reacted under anhydrous and oxygen-free and inert gas shielding, the order first in the ampulla after being toasted with high pure nitrogen gas washing
Add 10 μm of ol catalyst（Aluminum complex shown in formula I, R are hydrogen）, 30 μm of ol benzylalcohols, 10 mL tetrahydrofurans and 15
The glycolide of mmol, then 30oA small amount of water, which is added, after when C reactions 18 are small terminates reaction, with methanol extraction, washing for several times, room temperature
Lower vacuum drying, obtains 1.67 g products, yield 96.0%, molecular weight 12.8 ten thousand.
Embodiment 18
Reacted under anhydrous and oxygen-free and inert gas shielding, the order first in the ampulla after being toasted with high pure nitrogen gas washing
Add 10 μm of ol catalyst（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, when reaction 9 is small after add a small amount of water and terminate reaction, with ethanol precipitation, wash
Wash for several times, be dried in vacuo at room temperature, obtain 1.11 g products, yield 95.7%, molecular weight 13.8 ten thousand.
Embodiment 19
Reacted under anhydrous and oxygen-free and inert gas shielding, the order first in the ampulla after being toasted with high pure nitrogen gas washing
Add 200 μm of ol catalyst（Aluminum complex shown in formula I, R are the tert-butyl group）, 200 μm of ol benzylalcohols, 10 mL toluene and 10
The glycolide of mmol, is subsequently placed in 70oIn the oil bath of C, when reaction 5 is small after add a small amount of water and terminate reaction, with methanol extraction, wash
Wash for several times, be dried in vacuo at room temperature, obtain 1.09 g products, yield 94.0%, molecular weight 1.2 ten thousand.
Embodiment 20
Reacted under anhydrous and oxygen-free and inert gas shielding, the order first in the ampulla after being toasted with high pure nitrogen gas washing
Add 10 μm of ol catalyst（Aluminum complex shown in formula I, R are hydrogen）, 20 μm of ol benzylalcohols, 15 mL toluene and 5 mmol second
Lactide, then 90oA small amount of water is added after when C reactions 6 are small and terminates reaction, and with methanol extraction, washing for several times, vacuum is done at room temperature
It is dry, obtain 0.55 g products, yield 94.8%, molecular weight 7.3 ten thousand.
Comparative example 1
The preparation of Raney nickel：Ligand structure formula such as above formula used（II）, R is bromine, and reaction process is：0.20 g of ligand is dissolved in
In 10 mL absolute ethyl alcohols, the nickel acetate of 1.0 times of ligand moles is added at room temperature, when heating reflux reaction 12 is small, reaction terminates
Solvent is concentrated in vacuo later, is added dichloromethane and is separated out solid, filters and simultaneously washed with hexane, dry Raney nickel, its structure
Formula is as follows.
Polyglycolide is prepared according to the method for embodiment 12, unlike：Catalyst used is above-mentioned Raney nickel.Instead
Answer 24 it is small when after add a small amount of water and terminate reaction, with methanol extraction, washing for several times, be dried in vacuo at room temperature, obtain 0.21 g, yield
18.1 %, molecular weight 1.8 ten thousand.The Raney nickel is too low to the polymerization activity of glycolide, 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
It is slow be warmed to room temperature after be heated to 80 DEG C of reactions 12 it is small when, reaction is concentrated in vacuo solvent after terminating, and adds dry hexane and separates out admittedly
Body, filters and is simultaneously washed with hexane, dry Al catalysts, its structural formula LAlMe as follows.
Polyglycolide is prepared according to the method for embodiment 12, unlike：Catalyst used is the Al catalysts.Reaction
1 it is small when after add a small amount of water and terminate reaction, with ethanol precipitation, washing for several times, be dried in vacuo at room temperature, obtain 0.91 gram, yield
78.4%, molecular weight 1.8 ten thousand.
Comparative example 3
Polyglycolide is prepared according to the method for embodiment 12, unlike：Catalyst used is patent 201410609375.8
Catalyst used in middle embodiment 10.A small amount of water is added after reaction 1h and terminates reaction, with ethanol precipitation, washing for several times, at room temperature
Vacuum drying, gained polyglycolide quality are 0.96g, and yield 82.8%, molecular weight is 1.9 ten thousand.
Comparative example 4
Under nitrogen atmosphere, by ligand A（R is methyl）0.50 g is dissolved in 5 mL drying hexamethylenes, and ligand A is added at 0 DEG C
The triisopropylaluminiuand of 1.05 times of moles, after question response temperature is raised to room temperature naturally, heating reaction temperature is small to 80 DEG C of reactions 10
When, 72 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
It is prepared by ligand：Ligand structure formula is, R is methoxyl group.
Synthesized ligand structure formula such as above formula（A）, wherein R is methoxyl group, and reaction process is：By the chiral ring of unilateral protection
3, the 5- dimethoxys salicylide of 0.40 g of hexamethylene diamine and equimolar amounts is added in 20 mL methanol, when heating reflux reaction 12 is small,
Reaction terminates later cold filtration and is washed with cold methanol, filters, and collects and drying is weighed, obtain 0.58 g solids, yield
86.7%。
Aluminum complex is synthesized with ligand A
Ligand structure formula such as above formula used（A）, wherein R is methoxyl group, and reaction process is：In a nitrogen atmosphere, by ligand A
0.30 g is dissolved in 10 mL dry toluenes, the trimethyl aluminium of ligand 1.0 times of moles of A is added at 0 DEG C, question response temperature is certainly
So be raised to room temperature after, be heated to 80 DEG C reaction 4 it is small when, reaction terminate after vacuum drain solvent, add dry n-hexane mistake
Filter and washed with dry n-hexane, filtered, collect and drying is weighed, obtain 0.27 g solids, yield 81.8%.
It is catalyzed glycolide polymerization
Polyglycolide is prepared according to the method for embodiment 12, unlike：Catalyst used is aluminum complex, R shown in formula I
For methoxyl group.The quality of products obtained therefrom is 0.97 g after reacting 30 minutes, and yield 83.6%, molecular weight is 1.9 ten thousand.
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, is washed, dry, obtains p-methyl benzenesulfonic acid and 1, the 3- propane diamine of phthalic anhydride protection.By p-methyl benzenesulfonic acid and neighbour
1, the 3- propane diamine of phthalate anhydride protection is dissolved into dichloromethane, and excessive sodium acid carbonate saturated water is slowly added dropwise at room temperature
Solution is reacted, and to slough p-methyl benzenesulfonic acid, liquid separation after reaction, is dried with anhydrous magnesium sulfate, be spin-dried for solvent, obtain list
1, the 3- propane diamine of side phthalic anhydride protection.The propane diamine of unilateral phthalic anhydride protection and 3, the 5- bis- of equimolar amounts
Bromosalicylaldehyde is heated to reflux in methyl alcohol, and reaction is put into refrigerator after terminating and cools down, and separates out solid, filtering, with cold methanol
Washing, it is dry, obtain compound L D.
The preparation of Al catalysts：Under nitrogen atmosphere, 0.20 g of following formula: compound LD are dissolved in 10 mL dry toluenes,
The trimethyl aluminium of 1.0 times of compound L D moles is added at -10 DEG C, after question response temperature is raised to room temperature naturally, is heated to 110
When DEG C reaction 1 is small, vacuum drains solvent after reaction terminates, and adds dry n-hexane washing, filtering, drying, obtains 0.18
G solids, yield 81.8%, the aluminium compound through hydrolysis after do mass spectral characteristi find such ligand can only unilateral generation addition it is anti-
It should obtain LDAlMe2（HRESI-MS: m/z cacld. C18H14Br2N2O3 [M-H]-; 462.9294, found:
462.9292）.
Polyglycolide is prepared according to the method for embodiment 12, unlike：Catalyst used is the Al catalysts.Reaction
The quality of products obtained therefrom is 0.43 g afterwards, and yield 37.1%, molecular weight is 1.4 ten thousand.
Claims (10)
1. a kind of method of chiral asymmetric aluminum complex catalysis glycolide polymerization using the aldehyde radical containing bigcatkin willow, it is characterized in that including
Following steps：Catalyst, organic solvent, benzylalcohol co-catalyst and glycolide are mixed, in anhydrous and oxygen-free and inert gas shielding
Lower carry out ring-opening polymerization, carries out reactant after reaction to handle to obtain polyglycolide；The catalyst is the aldehyde radical containing bigcatkin willow
Chiral asymmetric aluminum complex, its structural formula as shown in following formula I, wherein, R is hydrogen, the alkane or halogen of C1-C4, is preferably bromine；
。
2. according to the method described in claim 1, it is characterized in that：Method for preparing catalyst is：Ligand A or ligand II, which are added, to be had
In solvent, -10~0 oTrimethyl aluminium is added under C, reaction temperature is warmed to room temperature naturally after adding, then rises to temperature
30~110oC is reacted, and vacuum drains solvent, washing, filtering after reaction, obtains the chiral non-of the aldehyde radical containing bigcatkin willow described in formula I
Symmetrical aluminum complex；Ligand A and II structural formula of ligand are as follows, wherein, R is the alkane or halogen of hydrogen, C1-C4, is preferably all
Bromine；
。
3. according to the method described in claim 2, it is characterized in that：In catalyst preparation process, ligand A or ligand II and trimethyl
The molar ratio 1 of aluminium：1~1.3, preferably 1：1~1.05.
4. according to the method described in claim 2, it is characterized in that：In catalyst preparation process, the organic solvent is dry
One or both of hexane, toluene and hexamethylene；Consumption of organic solvent is 5~40 times of reaction raw materials gross mass.
5. according to the method described in claim 2, it is characterized in that：In catalyst preparation process, it is raised to after room temperature again by temperature
Rise to 30~110oC（It is preferred that 40~60oC）When reaction 1~12 is small, when preferably reaction 3~6 is small.
6. according to the method described in claim 2, it is characterized in that：In catalyst preparation process, react under inert gas shielding
Carry out.
7. according to the method any one of claim 1-6, it is characterized in that：During ring-opening polymerization, glycolide and catalysis
The molar ratio of agent is 50~1500：1.
8. according to the method any one of claim 1-6, it is characterized in that：During ring-opening polymerization, benzylalcohol co-catalyst
Molar ratio with catalyst is 1~3：1.
9. according to the method any one of claim 1-6, it is characterized in that：During ring-opening polymerization, the organic solvent
For toluene or tetrahydrofuran.
10. according to the method any one of claim 1-6, it is characterized in that：During ring-opening polymerization, reaction temperature 20
~110 DEG C, the reaction time is 1-1440 minutes.
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