CN102924292A - Chiral tetra-amino aniline ligand, aluminum compound thereof, preparation method and application - Google Patents
Chiral tetra-amino aniline ligand, aluminum compound thereof, preparation method and application Download PDFInfo
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- CN102924292A CN102924292A CN2012104378547A CN201210437854A CN102924292A CN 102924292 A CN102924292 A CN 102924292A CN 2012104378547 A CN2012104378547 A CN 2012104378547A CN 201210437854 A CN201210437854 A CN 201210437854A CN 102924292 A CN102924292 A CN 102924292A
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Abstract
The invention discloses a chiral tetra-amino aniline ligand, and a preparation method and application of an aluminum compound thereof. The structural formula of the ligand is represented as the formula (A), wherein R1 is alkyl in a C1-C4 straight chain branched chain structure. The aluminum coordination compound of the chiral tetra-amino aniline ligand can efficiently catalyze ring-opening polymerization reactions of lactide. The ligand and the aluminum compound of the ligand are simple to synthesize, high in product yield coefficient and stable in property, simultaneously catalyst activity is high, selectivity is good, the performance of an obtained polymer is good, and molecular weight and stereoselectivity of the polymer can be regulated by control of polymerization reaction conditions.
Description
Technical field
The present invention relates to a kind of chirality tetradentate ligands and two kinds of rac-Lactide catalyst for ring-opening polymerization, concrete, two kinds of aluminum compound catalyzer that relate to a kind of chirality four tooth amido anilino parts and this part, and their preparation method and the application of this catalyzer in the catalyzing ring-opening polymerization of lactide reaction.
Background technology
Polylactide is having a wide range of applications in fields such as weaving, wrapping material; Because it has outstanding biocompatibility, it is studied widely at aspects such as medicine controlled releasing, surgical sutures, bone fracture internal fixation materials, is that first is used for clinical degradable high score material by food and drug administration's approval.Therefore polylactide more and more is subject to people's attention as a kind of novel Biodegradable material.
Polylactide can be by direct condensation or lactic acid Cyclodimerization body (rac-Lactide) the ring-opening polymerization preparation of lactic acid.The direct polycondensation method production technique is simple, but the molecular weight that is difficult to further improve, and molecular weight distribution is wider, and its performance can not satisfy real requirement.The method of ring-opening polymerization is adopted in the at present preparation of polylactide usually, namely uses first synthesis of lactide from lactic acid, again the polylactide of preparation high molecular under the initiator system effect.Because the existence of methyl on the alpha-position, so that rac-Lactide has L-rac-Lactide (L-LA), D-rac-Lactide (D-LA) and three kinds of steric isomers of Study of Meso-Lactide (meso-LA), therefore, polylactide just has multiple sequential structure, comprises that specifically isotaxy, syndiotaxy, atactic, heterotactic and block found structure.The sequential structure of polylactide has determined the character of polylactide to a great extent: atactic and heterotactic polylactide are amorphous polymers, and they can be obtained by the polymerization of meso-LA or rac-LA; And the polylactide of the vertical structure of isotaxy, syndiotaxy and block all can crystallization; Isotactic polylactide can be polymerized by pure DLA or LLA, the isotaxy PLA(PLLA of high molecular or PDLA) about 180 oC of fusing point; But the fusing point about 230 of the racemic mixture that equivalent PDLA and PLLA form
oC; Between with and the vertical structure polylactide of block be just to be synthesized out recent years, present, can only just can obtain by the stereoselectivity polymerization of rac-Lactide, their crystallinity is very large with the different variation ranges of selectivity of catalyst with fusing point; And with regard to degradation property, the degradation rate of amorphous polylactide will be higher than crystalline polylactide.Because sequential structure has a great impact the character of polylactide, and the sequential structure of polylactide can be controlled by the stereoselectivity polymerization of rac-Lactide, so being developed to for a study hotspot of the stereoselectivity polymerizing catalyst of rac-Lactide.In racemize lactide monomer ring-opening polymerization, how to utilize controllable polymerization method to make polymerization process controlled, obtain the polymkeric substance of narrow molecular weight distribution, measurable molecular weight and different three-dimensional arrangements, make polymkeric substance have the key that more excellent mechanical property and good biodegradability are research, and these solution of problems all rely on the exploitation with the stereoselectivity polymerizing catalyst, and therefore the novel catalyzer that meets the demands of exploitation has crucial meaning.
Summary of the invention
The invention provides a kind of chirality four tooth amido anilino parts, it can obtain well behaved catalyzer with the aluminum alkyls reaction.
The invention provides two kinds of chiral amino anilino aluminum compounds (abbreviation chiral amino anilino aluminium that the reaction of above-mentioned part and aluminum alkyls forms, together lower) and the application of this compound in the rac-Lactide polyreaction, these two kinds of chiral amino anilino aluminum compounds are as the catalyzer of rac-Lactide ring-opening polymerization, catalytic activity is high, stereoselectivity is good, polymeric reaction temperature is low, polymericular weight is controlled, can satisfy different needs.
The present invention also provides the preparation method of above-mentioned part and chiral amino anilino aluminium, and is simple to operate, is convenient to implement.
Technical solution of the present invention is as follows:
A kind of chirality four tooth amido anilino parts, its structural formula are as shown in the formula shown in the A, R in the formula
1Be the alkyl of C1-C4 straight or branched structure, preferred R
1Be methyl or ethyl;
The preparation method of part of the present invention is:
1, with raw material N, condensation reaction occurs in N-dialkylamine benzaldehyde and (1R, 2R)-cyclohexanediamine in organic solvent, and temperature of reaction is 40～70
oC, the reaction times is 2～24 hours, and reaction gets the Schiff's base shown in the formula a by concentrated, recrystallization, and reaction formula is:
2, Schiff's base (the present invention refers to the Schiff's base with formula a structure, and is lower same) is used LiAlH in organic solvent
4Reduce, the temperature of reaction is 0～70
oC, the reaction times is 1～24 hour, must have the chirality four tooth amido anilino parts of formula A structure, reaction formula is:
Among the preparation method of above-mentioned part, N, the mol ratio of N-dialkylamine benzaldehyde and chirality cyclohexanediamine ((1R, 2R)-cyclohexanediamine) is 2～3:1.
Among the preparation method of above-mentioned part, Schiff's base and LiAlH
4Mol ratio be 1:1～1.5.
Among the preparation method of above-mentioned part, the used organic solvent of condensation reaction is a kind of in tetrahydrofuran (THF), methyl alcohol, hexane, ethanol and the chloroform or two kinds, is preferably methyl alcohol, ethanol or hexane.
Among the preparation method of above-mentioned part, the used organic solvent of reduction reaction is that tetrahydrofuran (THF) is or/and ether is preferably tetrahydrofuran (THF) and ether.
Among the preparation method of above-mentioned part, the used organic solvent effect of condensation reaction and reduction reaction is in order to provide reaction required environment, its consumption is little on the reaction impact, those skilled in the art can select the consumption of organic solvent according to actual needs, general, get consumption of organic solvent and be the reactant total mass 5～40 times.
Among the preparation method of above-mentioned part, the used solvent of recrystallization is preferably hexane after the condensation reaction.
Among the preparation method of above-mentioned part, reduction reaction is carried out under the anhydrous and oxygen-free condition.
Among the preparation method of above-mentioned part, the temperature of condensation reaction is preferably 50～70
oC, the reaction times is preferably 3～12 hours.
Among the preparation method of above-mentioned part, the temperature of reduction reaction is preferably 25～70
oC, the reaction times is preferably 2～12 hours.
Above-mentioned part and aluminum alkyls reaction can also obtain the aluminum compound of two kinds of different structures, a kind of is suc as formula the described monokaryon chiral amino of I anilino aluminum compound, another kind is that the compound of these two kinds of structures can be as the catalyzer of rac-Lactide ring-opening polymerization suc as formula the described double-core chiral amino of II anilino aluminum compound;
In above-mentioned formula I and the formula II, R
1Be the alkyl of C1～C4 straight or branched structure, preferable methyl or ethyl, R
2Also be alkyl, preferable methyl or the ethyl of C1～C4 straight or branched structure.R
1With R
2Can be identical, also can be different.
The preparation method of catalyzer is: with chirality four tooth amido anilino parts and the trialkylaluminium (Al (R of formula A
2)
3) in organic medium, react, temperature of reaction is 0～120 ℃, the reaction times is 1～36 hour; Reaction is by the catalyzer that filters, concentrates, recrystallization gets formula I or formula II.
Among the preparation method of above-mentioned catalyzer, mainly decide the structure of gained catalyzer by the control reactant with magnitude relation, when the mol ratio of part and trialkylaluminium is 1:0.8～1, synthetic is the catalyzer of formula I structure, when the mol ratio of part and aluminum alkyls was 1:2～5, synthetic was the catalyzer of formula II structure.
Among the above-mentioned preparation method, trialkylaluminium Al (R
2)
3In R
2Alkyl, preferable methyl or ethyl for C1～C4 straight or branched structure.
Among the above-mentioned preparation method, reaction is carried out under protection of inert gas.
Among the above-mentioned preparation method, during the catalyzer of synthesis type I structure, the mol ratio of part and aluminum alkyls is preferably 1:0.9～1, and during the catalyzer of synthesis type II structure, the mol ratio of part and aluminum alkyls is preferably 1:2～3.
Among the above-mentioned preparation method, temperature of reaction is preferably 20～110
oC, the reaction times is preferably 2～12 hours.
Among the above-mentioned preparation method, the used organic medium of part and trialkylaluminium reaction is a kind of in tetrahydrofuran (THF), toluene, hexane, benzene, chloroform and the methylene dichloride or two kinds.
Among the above-mentioned preparation method, the organic medium effect is the environment that reacts required in order to provide, and its consumption is little on the reaction impact, and those skilled in the art can select the consumption of organic solvent according to actual needs, general, get consumption of organic solvent and be the reactant total mass 5～40 times.
Among the above-mentioned preparation method, the recrystallization solvent for use is preferably hexane.
The catalyzer of formula I of the present invention or formula II can both be as the catalyzer of rac-Lactide ring-opening polymerization, and described rac-Lactide is one or both in levorotatory lactide and the rac-lactide, the structural formula of rac-Lactide as shown in the formula (III):
The rac-Lactide ring-opening polymerization specifically may further comprise the steps: chiral amino anilino Al catalysts, organic solvent, pure promotor and rac-Lactide are mixed; under anhydrous and oxygen-free and protection of inert gas, carry out the polymerization ring-opening reaction, after the reaction reactant processed to get polylactide.
In the above-mentioned ring-opening polymerization, reacting used organic solvent is toluene, methylene dichloride or tetrahydrofuran (THF), preferred toluene.
In the above-mentioned ring-opening polymerization, pure promotor is benzylalcohol or Virahol.
In the above-mentioned ring-opening polymerization, the mol ratio of rac-Lactide and amido anilino Al catalysts is 30～1000:1, and the mol ratio of pure promotor and catalyzer is 1～6:1.
In the above-mentioned ring-opening polymerization, polymeric reaction temperature is 20～110 ℃, and the time is 5-1440 minute.When temperature was high, it is few that monomer polymerization finishes required time, and when temperature was hanged down, it is longer that monomer polymerization finishes required time.
In the catalyzer of the present invention, the catalytic activity of part and the whole catalyzer of metal pair is all influential, (is R in the framework of the present definition
1, R
2Be limited in the scope of alkyl of C1～C4 straight or branched structure), catalyst is active and stereoselectivity is different, but difference is not very large.
Catalyst activity of the present invention is higher, and consumption is relatively less in use, so the metal residual in polymeric articles is relatively less.In addition, in the prior art, the polymkeric substance ring-opening reaction that molecular weight is higher is carried out under vacuum condition, the operation difficulty is larger, and the catalyzer of general usefulness is stannous octoate now, the molecular weight distribution of this catalyzer resulting polymers when the catalysis ring-opening polymerization is wider, poor controllability; And the present invention need not to carry out under vacuum condition, as long as guarantee anhydrous, anaerobic and inert conditions, should be more simple, amount ratio by control polymerization single polymerization monomer and catalyzer can obtain the narrower polymkeric substance of molecular weight distribution in addition, molecular weight is all better in the molecular weight controllability of the polymkeric substance below 700,000, and therefore catalyzer of the present invention is strong to the controllability of molecular weight comparatively speaking.In addition, catalyzer of the present invention is chiral catalyst, and stereoselectivity is high, and is strong to the specific selectivity in monomer polymerization site, the polymerization of catalysis rac-lactide
PmReach as high as 78%, make the resulting polymers range of application wider, and general achirality catalyst rac-lactide when carrying out ring-opening polymerization the polymkeric substance of gained be unregulated polymer, use range is narrow.
Part of the present invention and aluminum compound preparation method are simple, and product yield is high, stable in properties, and that the gained catalyst structure changes is various, catalytic activity and stereoselectivity is high, safety non-toxic, thereby can be used for the ring-opening polymerization of catalysis rac-Lactide.Because catalyst system is active high, polyreaction can occur at a lower temperature, mild condition; Catalyzer is chirality, and stereoselectivity is good, and the molecular weight of product that obtains is high, productive rate is high, metal residual is few.In addition, polymerization technology is simple, can adopt common solution polymerization process, by the control of polymeric reaction condition, can regulate and control the molecular weight of polymkeric substance, and the products obtained therefrom performance is better, and applicability is stronger.
Embodiment
Further specify the present invention below by specific embodiment, but the present invention is not limited to this, concrete protection domain see claim.
Embodiment
Further specify the present invention below by specific embodiment, but the present invention is not limited to this, concrete protection domain see claim.
Preparation chiral amino anilino part
Embodiment 1
Get N, N-dimethylbenzaldehyde (10.6 g, 71 mmol) is dissolved in 25 ml hexanes, slowly drips (1R, 2R)-cyclohexanediamine (4.0 g, 35.5 mmol), drips the afterreaction reflux and stirs 10 hours.Crystallisation by cooling filters and obtains the buff powder Schiff's base
a10.3 g, productive rate 77%.
Embodiment 2
At N
2Under the atmosphere, the Schiff's base (7.2 g, 19.1 mmol) of getting embodiment 1 is dissolved in the ether of 50 ml dryings, slowly repeatedly adds on a small quantity lithium aluminum hydride (0.74 g, 19.1 mmol) under 0 ℃, adds afterreaction and slowly rises to stirring at room 8 hours.Reaction finishes slowly to add 1.3 mL frozen water stopped reaction in the backward reaction system, adds 1.3 mL NaOH(3M again) aqueous solution, 3.9 mL water filter, and filter cake washs with 30 ml ethyl acetate, collects filtrate, and solvent removed in vacuo obtains weak yellow liquid
A6.6 g, productive rate 91%.
Embodiment 3
Get N, N-diethylbenzaldehyde (7.0 g, 39.5 mmol) is dissolved in 25 ml tetrahydrofuran (THF)s, slowly drips (1R, 2R)-cyclohexanediamine (1.5 g, 13.2 mmol), drips afterreaction and is heated to 40 ℃, stirs 24 hours.Concentrated solution after reaction finishes adds 13 mL hexane crystallisation by cooling, filters to obtain the buff powder Schiff's base
a3.5 g, productive rate 61%.
Embodiment 4
At N
2Under the atmosphere, the Schiff's base (4.0 g, 9.2 mmol) of getting embodiment 3 is dissolved in the tetrahydrofuran (THF) of 40 ml dryings, under 0 ℃, slowly repeatedly add on a small quantity lithium aluminum hydride (0.5 g, 13.8 mmol), add afterreaction and slowly rise to room temperature, be heated to 70 ℃, stirred 2 hours.Reaction finishes slowly to add 0.9 mL frozen water stopped reaction in the backward reaction system, adds 0.9 mL NaOH(3M again) aqueous solution, 2.7 mL water filter, and filter cake washs with 40 ml ethyl acetate, collects filtrate, and solvent removed in vacuo obtains weak yellow liquid
A3.7 g, productive rate 93%.
Embodiment 5
Get N, N-dipropyl phenyl aldehyde (6.0 g, 29.2 mmol) is dissolved in 30 ml ethanol, slowly drips (1R, 2R)-cyclohexanediamine (1.7 g, 14.6 mmol), drips afterreaction and is heated to 50 ℃, stirs 12 hours.Concentrated solution after reaction finishes adds 10 mL hexane crystallisation by cooling, filters to obtain the buff powder Schiff's base
a4.8 g, productive rate 67%.
Embodiment 6
At N
2Under the atmosphere, the Schiff's base (5.0 g, 10.2 mmol) of getting embodiment 5 is dissolved in the ether of 40 ml dryings, slowly repeatedly adds on a small quantity lithium aluminum hydride (0.39 g, 10.2 mmol) under 0 ℃, adds afterreaction and slowly rises to room temperature, stirs 12 hours.Reaction finishes slowly to add 0.6 mL frozen water stopped reaction in the backward reaction system, adds 0.6 mL NaOH(3M again) aqueous solution, 1.8 mL water filter, and filter cake washs with 40 ml ethyl acetate, collects filtrate, and solvent removed in vacuo obtains weak yellow liquid
A4.8 g, productive rate 95%.
Embodiment 7
Get N, N-di-isopropyl phenyl aldehyde (7.2 g, 35 mmol) is dissolved in 40 ml chloroforms, slowly drips (1R, 2R)-cyclohexanediamine (0.5 g, 14 mmol), drips afterreaction and is heated to 60 ℃, stirs 8 hours.Concentrated solution after reaction finishes adds 10 mL hexane crystallisation by cooling, filters to obtain the buff powder Schiff's base
a4.3 g, productive rate 63%.
Embodiment 8
At N
2Under the atmosphere, the Schiff's base (4.2 g, 8.6 mmol) of getting embodiment 7 is dissolved in the ether of 40 ml dryings, slowly repeatedly adds on a small quantity lithium aluminum hydride (0.4 g, 10.3 mmol) under 0 ℃, adds afterreaction and slowly rises to room temperature, stirs 24 hours.Reaction finishes slowly to add 0.6 mL frozen water stopped reaction in the backward reaction system, adds 0.6 mL NaOH(3M again) aqueous solution, 1.8 mL water filter, and filter cake washs with 40 ml ethyl acetate, collects filtrate, and solvent removed in vacuo obtains weak yellow liquid
A4.0 g, productive rate 95%.
Preparation monokaryon chiral amino aniline Al catalysts (I)
Monokaryon chiral amino aniline Al catalysts is the title complex that is generated by part and trialkylaluminium reaction, and the structural formula of its part is as shown in the formula (A), and the below gives an example to the resulting catalyzer of different ligands, and preferred part is R
1Be methyl, ethyl, the part of propyl group; R
2Preferable methyl, ethyl.
Embodiment 9
Used ligand structure formula such as following formula (A), wherein R
1Be methyl, reaction process is: under nitrogen atmosphere, ligand 1 .2 g is dissolved in the 20 mL toluene, at one times of molar weight trimethyl aluminium of 0 ℃ of lower adding, be raised to 115 ℃ of reactions 2 hours, desolventizing, crude product hexane recrystallization gets straight product 1.2 g, productive rate 93%.
Embodiment 10
Used ligand structure formula such as following formula (A), wherein R
1Be ethyl, reaction process is: under nitrogen atmosphere, ligand 1 .1 g is dissolved in the 25 mL benzene, at 0.8 times of molar weight trimethyl aluminium of 0 ℃ of lower adding, is raised to after the room temperature, be heated to 60 ℃ of reactions 12 hours, and desolventizing, crude product is heavy with the hexane crystallization.Get straight product 0.9 g, productive rate 78 %.
Embodiment 11
Used ligand structure formula such as following formula (A), wherein R
1Be propyl group, reaction process is: under nitrogen atmosphere, ligand 1 .5g is dissolved in the 10 mL hexanes, at 0.9 times of molar weight trimethyl aluminium of 0 ℃ of lower adding, is raised to after the room temperature, be heated to 60 ℃ of reactions 12 hours, crystallisation by cooling.Get straight product 1.0 g, productive rate 76%.
Embodiment 12
Used ligand structure formula such as following formula (A), wherein R
1Be methyl, reaction process is: under nitrogen atmosphere, ligand 1 .2g is dissolved in the 20 mL methylene dichloride, at one times of molar weight triethyl aluminum of 0 ℃ of lower adding, be raised to room temperature reaction 12 hours, desolventizing, crude product hexane recrystallization gets straight product 0.9 g, productive rate 66%.
Embodiment 13
Used ligand structure formula such as following formula (A), wherein R
1Be ethyl, reaction process is: under nitrogen atmosphere, ligand 1 .3g is dissolved in the 35 mL benzene, at 0.9 times of molar weight triethyl aluminum of 0 ℃ of lower adding, is raised to after the room temperature, be heated to 40 ℃ of reactions 18 hours, desolventizing, crude product hexane recrystallization.Get straight product 1.0g, productive rate 71%.
Embodiment 14
Used ligand structure formula such as following formula (A), wherein R
1Be propyl group, reaction process is: under nitrogen atmosphere, part 0.9 g is dissolved in the 25 mL toluene, at 0.9 times of molar weight triethyl aluminum of 0 ℃ of lower adding, is raised to after the room temperature, be heated to 70 ℃ of reactions 10 hours, desolventizing, crude product hexane recrystallization.Get straight product 0.7g, productive rate 69%.
Embodiment 15
Used ligand structure formula such as following formula (A), wherein R
1Be sec.-propyl, reaction process is: under nitrogen atmosphere, ligand 1 .0 g is dissolved in the 20 mL hexanes, at one times of molar weight triethyl aluminum of 0 ℃ of lower adding, is raised to after the room temperature, be heated to 60 ℃ of reactions 24 hours, the cooling recrystallization.Get straight product 1.0 g, productive rate 91%.
Embodiment 16
Used ligand structure formula such as following formula (A), wherein R
1Be sec.-propyl, reaction process is: under nitrogen atmosphere, part 0.93 g is dissolved in the 10 mL methylene dichloride, at 0.9 times of molar weight trimethyl aluminium of 0 ℃ of lower adding, is raised to after the room temperature, reacted desolventizing, crude product hexane recrystallization 36 hours.Get straight product 0.75 g, productive rate 83%.
Preparation double-core chiral amino aniline Al catalysts (II)
Double-core amido aniline Al catalysts is the title complex that is generated by part and trialkylaluminium reaction, and the structural formula of its part is as shown in the formula (A), and the below gives an example to the resulting catalyzer of different ligands, and preferred part is R
1Be methyl, ethyl, the part of propyl group; R
2Preferable methyl, ethyl.
Embodiment 17
Used ligand structure formula such as following formula (A), wherein R
1Be methyl, reaction process is: under nitrogen atmosphere, ligand 1 .2 g is dissolved in the 15 mL toluene, at 0 ℃ of lower twice molar weight trimethyl aluminium that adds, is raised to 110 ℃ of reactions 3 hours, and desolventizing, crude product hexane recrystallization gets straight product 1.4 g, productive rate 88%.
Embodiment 18
Used ligand structure formula such as following formula (A), wherein R
1Be ethyl, reaction process is: under nitrogen atmosphere, ligand 1 .5 g is dissolved in the 35 mL benzene, at room temperature adds three times of molar weight trimethyl aluminiums, be heated to 70 ℃ of reactions 12 hours, desolventizing, crude product hexane recrystallization.Get straight product 1.7 g, productive rate 91%.
Embodiment 19
Used ligand structure formula such as following formula (A), wherein R
1Be sec.-propyl, reaction process is: under nitrogen atmosphere, ligand 1 .9 g is dissolved in the 15 mL hexanes, at five times of molar weight trimethyl aluminiums of 0 ℃ of lower adding, is raised to after the room temperature, reacted crystallisation by cooling 24 hours.Get straight product 2.0 g, productive rate 87%.
Embodiment 20
Used ligand structure formula such as following formula (A), wherein R
1Be methyl, reaction process is: under nitrogen atmosphere, ligand 1 .4g is dissolved in the 20 mL toluene, at five times of molar weight triethyl aluminums of 0 ℃ of lower adding, is raised to 60 ℃ of reactions 8 hours, and desolventizing, crude product hexane recrystallization gets straight product 1.2g, productive rate 83%.
Embodiment 21
Used ligand structure formula such as following formula (A), wherein R
1Be ethyl, reaction process is: under nitrogen atmosphere, ligand 1 .0g is dissolved in the 25 mL benzene, at three times of molar weight trimethyl aluminiums of 0 ℃ of lower adding, is raised to after the room temperature, be heated to 70 ℃ of reactions 24 hours, desolventizing, crude product hexane recrystallization.Get straight product 1.1g, productive rate 76%.
Embodiment 22
Used ligand structure formula such as following formula (A), wherein R
1Be propyl group, reaction process is: under nitrogen atmosphere, ligand 1 .9g is dissolved in the 15 mL hexanes, at 0 ℃ of lower triplication triethyl aluminum that adds, is raised to after the room temperature, reacted the cooling recrystallization 36 hours.Get straight product 0.9g, productive rate 72%.
The application of catalyzer
Embodiment 23
React under anhydrous and oxygen-free and protection of inert gas, order adds 90 μ mol R in the ampulla after the baking of high-purity argon gas gas washing
1Be methyl, R
2Then rac-lactide for monokaryon chiral aluminum catalysts, 60 mL toluene, 90 μ mol benzylalcohols and 30 mmol of methyl places 40
oIn the oil bath of C, react a small amount of water termination reaction of adding after 3 hours, with methanol extraction, washing for several times, vacuum-drying under the room temperature gets 3.9 grams, molecular weight 11.2 ten thousand, molecular weight distribution 1.17, yield 90%, regularity
PM=65%.
Embodiment 24
React under anhydrous and oxygen-free and protection of inert gas, order adds 40 μ mol R in the ampulla after the baking of high-purity argon gas gas washing
1Be methyl, R
2Then rac-lactide for double-core Al catalysts, 60 mL toluene, 120 μ mol benzylalcohols and 8 mmol of ethyl places 110
oIn the oil bath of C, react a small amount of water termination reaction of adding after 10 minutes, with methanol extraction, washing for several times, vacuum-drying under the room temperature gets 1.0 grams, molecular weight 8.3 ten thousand, molecular weight distribution 1.23, yield 89%, regularity
PM=56%.
Embodiment 25
React under anhydrous and oxygen-free and protection of inert gas, order adds 60 μ mol R in the ampulla after the baking of high-purity argon gas gas washing
1Be sec.-propyl, R
2Rac-lactide for monokaryon chiral aluminum catalysts, 90 mL methylene dichloride, 150 μ mol Virahols and 60 mmol of ethyl, room temperature reaction adds a small amount of water termination reaction after 10 hours, with methanol extraction, washing for several times, vacuum-drying under the room temperature, get 7.9 grams, molecular weight 17.8 ten thousand, molecular weight distribution 1.13, yield 91%, regularity
PM=73%.
Embodiment 26
React under anhydrous and oxygen-free and protection of inert gas, order adds 70 μ mol R in the ampulla after the baking of high-purity argon gas gas washing
1Be ethyl, R
2Then levorotatory lactide for double-core chiral aluminum catalysts, 30 mL tetrahydrofuran (THF)s, 280 μ mol Virahols and 70 mmol of ethyl is heated to 110
oThe C reaction adds a small amount of hydrochloric acid termination reaction after 0.5 hour, with methanol extraction, washing for several times, vacuum-drying under the room temperature gets 9.0 grams, molecular weight 25.8 ten thousand, molecular weight distribution 1.37, yield 89%.
Embodiment 27
React under anhydrous and oxygen-free and the protection of inert gas, order adds 40 μ mol R in the ampulla after the baking of high-purity argon gas gas washing
1Be propyl group, R
2Then levorotatory lactide for double-core chiral aluminum catalysts, 30 mL toluene, 240 μ mol benzylalcohols and 40 mmol of methyl places 70
oIn the oil bath of C, react a small amount of water termination reaction of adding after 3 hours, with ethanol precipitation, washing for several times, vacuum-drying under the room temperature gets 5.0 grams, molecular weight 18.5 ten thousand, molecular weight distribution 1.28, yield 87%.
Embodiment 28
React under anhydrous and oxygen-free and the protection of inert gas, order adds 30 μ mol R in the ampulla after the baking of high-purity argon gas gas washing
1Be methyl, R
2Rac-lactide for monokaryon chiral aluminum catalysts, 60 mL methylene dichloride, 30 μ mol benzylalcohols and 30 mmol of methyl, then place room temperature reaction 24 hours, add a small amount of water termination reaction after the reaction, with methanol extraction, washing for several times, vacuum-drying under the room temperature gets 3.9 grams, molecular weight 57.8 ten thousand, molecular weight distribution 1.18, yield 91%, regularity
PM=78%.
Embodiment 29
React under anhydrous and oxygen-free and the protection of inert gas, order adds 20 μ mol R in the ampulla after the baking of high-purity argon gas gas washing
1Be ethyl, R
2Be the levorotatory lactide of monokaryon chiral aluminum catalysts, 60 mL toluene, 80 μ mol benzylalcohols and 20 mmol of sec.-propyl, 70
oThe C reaction added a small amount of hydrochloric acid termination reaction after 7 hours, and with ethanol precipitation, washing for several times, vacuum-drying under the room temperature gets 2.6 grams, molecular weight 27.5 ten thousand, molecular weight distribution 1.29, yield 90%.
Embodiment 30
React under anhydrous and oxygen-free and the protection of inert gas, order adds 40 μ mol R in the ampulla after the baking of high-purity argon gas gas washing
1Be ethyl, R
2Be the levorotatory lactide of monokaryon chiral aluminum catalysts, 60 mL toluene, 40 μ mol benzylalcohols and 40 mmol of methyl, 80
oThe C reaction added a small amount of hydrochloric acid termination reaction after 8 hours, and with ethanol precipitation, washing for several times, vacuum-drying under the room temperature gets 4.2 grams, molecular weight 700,000, molecular weight distribution 1.38, yield 91%.
Embodiment 31
React under anhydrous and oxygen-free and the protection of inert gas, order adds 30 μ mol R in the ampulla after the baking of high-purity argon gas gas washing
1Be methyl, R
2Be the levorotatory lactide of double-core chiral aluminum catalysts, 10 mL toluene, 60 μ mol benzylalcohols and 3 mmol of ethyl, 80
oThe C reaction added a small amount of hydrochloric acid termination reaction after 1 hour, and with ethanol precipitation, washing for several times, vacuum-drying under the room temperature gets 0.3 gram, molecular weight 19.2 ten thousand, molecular weight distribution 1.13, yield 93%.
Claims (10)
1. chirality four tooth amido anilino parts is characterized in that: structural formula is as shown in the formula shown in the A, R in the formula
1Alkyl for the straight or branched structure of C1-C4;
2. chirality four tooth amido anilino parts according to claim 1 is characterized in that: R
1Be methyl or ethyl.
3. the synthetic method of a claim 1 or 2 described chirality four tooth amido anilino parts, it is characterized in that may further comprise the steps: with raw material N, condensation reaction occurs in N-dialkylamine benzaldehyde and (1R, 2R)-cyclohexanediamine in organic solvent, temperature of reaction is 40～70
oC, the reaction times is 2～24 hours, reaction gets the Schiff's base shown in the formula a by concentrated, recrystallization; Schiff's base is used LiAlH in organic solvent
4Reduce, the temperature of reaction is 0～70
oC, the reaction times is 1～24 hour, must have the chirality four tooth amido anilino parts of formula A structure;
4. synthetic method according to claim 3, it is characterized in that: in the condensation reaction, the temperature of condensation reaction is 50～70
oC, the reaction times is 3～12 hours; The used organic solvent of condensation reaction is a kind of in tetrahydrofuran (THF), methyl alcohol, hexane, ethanol and the chloroform or two kinds; N, the mol ratio of N-dialkylamine benzaldehyde and (1R, 2R)-cyclohexanediamine is 2～3:1;
In the reduction reaction, the temperature of reduction reaction is 25～70
oC, the reaction times is 2～12 hours; The used organic solvent of reduction reaction is that tetrahydrofuran (THF) is or/and ether; Schiff's base and LiAlH
4Mol ratio be 1:1～1.5.
5. chiral amino anilino aluminum compound is characterized in that: its structural formula is as shown in the formula shown in I or the II, in the formula, and R
1, R
2Be the alkyl of C1-C4 straight or branched structure;
6. chiral amino anilino aluminum compound according to claim 5 is characterized in that: R
1Be methyl or ethyl, R
2Be methyl or ethyl.
7. the synthetic method of a claim 5 or 6 described chiral amino anilino aluminum compounds, it is characterized in that may further comprise the steps: chirality four tooth amido anilino parts and the trialkylaluminium of claim 1 are reacted in organic medium, and temperature of reaction is 0～120
oC, the reaction times is 1～36 hour; Reaction is by the catalyzer that filters, concentrates, recrystallization gets formula I or formula II; During the catalyzer of synthesis type I structure, the mol ratio of part and aluminum alkyls is 1:0.8～1, and during the catalyzer of synthesis type II structure, the mol ratio of part and aluminum alkyls is 1:2～5.
8. synthetic method according to claim 7, it is characterized in that: described trialkylaluminium molecular formula is Al (R
2)
3, R
2Alkyl for C1～C4 straight or branched structure;
During the catalyzer of synthesis type I structure, the mol ratio of part and aluminum alkyls is 1:0.9～1, and during the catalyzer of synthesis type II structure, the mol ratio of part and aluminum alkyls is 1:2～3;
Organic medium is a kind of in tetrahydrofuran (THF), toluene, hexane, benzene, chloroform and the methylene dichloride or two kinds;
The temperature of reaction of part and trialkylaluminium is 20～110
oC, the reaction times is 2～12 hours.
9. the application of a claim 5 or 6 described chiral amino anilino aluminum compounds; it is characterized in that: as the catalyzer of rac-Lactide ring-opening polymerization; described rac-Lactide is one or both in levorotatory lactide, the rac-lactide; reaction may further comprise the steps: chiral amino anilino aluminum compound catalyzer, organic solvent, pure promotor and rac-Lactide are mixed; under anhydrous and oxygen-free and protection of inert gas, carry out the polymerization ring-opening reaction, after the reaction reactant processed to get polylactide.
10. application according to claim 9 is characterized in that: the used organic solvent of polyreaction is toluene, methylene dichloride or tetrahydrofuran (THF), and pure promotor is benzylalcohol or Virahol; Rac-Lactide and chiral amino anilino aluminum compound catalyst molar ratio are 30～1000:1, and the mol ratio of pure promotor and chiral amino anilino aluminum compound catalyzer is 1～6:1; Polymeric reaction temperature is 20～110 ℃, and the time is 5-1440 minute.
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