CN102942579A - Chiral amido and aniline zinc compound and preparation method and application thereof - Google Patents
Chiral amido and aniline zinc compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a chiral amido and aniline zinc compound and a preparation method and an application of the chiral amido and aniline zinc compound. The structural formula is shown as formula I, in which R1 and R2 are alkyls with C1-C4 straight chain or branch chain structures. The preparation method of a catalyst is simple, and the catalytic activity and stereoselectivity of the catalyst are high. The polymerization reaction condition is mild, polymers obtained are high in yield, small in metal residue and good in performance. The molecular weight of the polymers can be well controlled by controlling the polymerization reaction condition.
Description
Technical field
The present invention relates to a kind of cyclic lactone catalyst for ring-opening polymerization, concrete, relate to a class chiral amino anilino zinc catalyst, its preparation method and as the application of cyclic lactone ring-opening polymerization catalyst.
Background technology
Polylactide with and caprolactone copolymer because have good biological degradability, it has 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 united States food and drug administration's approval.Therefore polylactide more and more is subject to people's attention as a kind of novel Biodegradable material.
Alkoxide complexes and the alkyl complexes of main group metal aluminium, magnesium, tin, transition metal, lanthanide series metal etc. can be as the catalyzer of rac-Lactide and caprolactone ring-opening polymerization.The catalyzer of the cyclic lactone ring-opening polymerizations such as current design rac-Lactide and caprolactone is one of study hotspot of Organometallic Chemistry, and purpose is to improve catalytic activity, the molecular weight and molecualr weight distribution of control polymkeric substance.In the ring-opening polymerization of cyclic lactone monomer is anti-, utilize controllable polymerization method to make polymerization process controlled, obtain the polymkeric substance of narrow molecular weight distribution and measurable molecular weight, make it have more excellent mechanical property and good biodegradability is the key of polyreaction research.Because rac-Lactide has left-handed-rac-Lactide, three kinds of steric isomers of dextrorotation-rac-Lactide and Study of Meso-Lactide, so polylactide has multiple sequential structure, comprises that specifically isotaxy, syndiotaxy, atactic, heterotactic and block found structure.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.Because thereby zinc catalyst can be realized the living polymerization predicted molecular weight in the polymerization of rac-Lactide and caprolactone, and molecular weight is narrow, can satisfy the needs of material application facet, so research is many, wherein can be used for the selective opening polymerization of racemization rac-Lactide except beta-diimine and three tooth NNO zinc catalysts, seldom have the zinc catalyst of other bidentate ligand coordinations of document and patent report can be used for the selective opening polymerization of racemization rac-Lactide, so it is very necessary for the selective opening polymerization of racemization rac-Lactide to develop new zinc catalyst.
Summary of the invention
The invention provides a kind of chiral amino anilino zn cpds, this compound is suitable for the cyclic lactone ring-opening polymerization, and catalytic activity is high, and the performance of polymkeric substance is good, and molecular weight is controlled.
The present invention also provides the preparation method of this catalyzer, and is simple to operate, is convenient to implement.
The present invention also provides the application of this catalyzer in lactone polymerization, is particularly suitable for the ring-opening polymerization of catalysis rac-Lactide, caprolactone.
Technical solution of the present invention is as follows:
A kind of chiral amino anilino zn cpds is characterized in that: structural formula is as shown in the formula shown in the I, R in the formula
1, R
2Be the alkyl of C1～C4 straight or branched structure; R
1Be preferably methyl or ethyl, R
2Be preferably methyl or ethyl;
The present invention also provides the preparation method of chiral amino anilino zinc, may further comprise the steps:
(1) preparation part: 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, 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 chiral amino anilino part of formula A structure, Schiff's base and chiral amino anilino ligand structure formula are as follows, R in the formula
1Be the alkyl of C1-C4 straight or branched structure, R
2It also is the alkyl of C1-C4 straight or branched structure; Reaction formula is:
(2) preparation chiral amino anilino zn cpds: chiral amino anilino part and zinc alkyl(s) are reacted in organic solvent, and temperature of reaction is 0～120
oC, the reaction times is 1～36 hour, reaction is by chiral amino anilino zn cpds concentrated, that recrystallization gets formula I 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.
In the preparation process of above-mentioned part, the temperature of condensation reaction is preferably 50～70
oC, the reaction times is preferably 3～12 hours.
In the preparation process of above-mentioned part, the temperature of reduction reaction is preferably 20～70
oC, the reaction times is preferably 2～12 hours.
In the above-mentioned steps (2), the mol ratio of part and zinc alkyl(s) is 1:2～5, preferred 1:2～3.
In the above-mentioned steps (2), temperature of reaction is preferably 20～110
oC, the reaction times is preferably 2～12 hours.
In the above-mentioned steps (2), described zinc alkyl(s) molecular formula is Zn (R
2)
2, R
2Alkyl for C1～C4 straight or branched structure.
In the above-mentioned steps (2), reaction is carried out under protection of inert gas.
In the above-mentioned steps (2), used organic solvent is a kind of in tetrahydrofuran (THF), toluene, hexane, benzene, chloroform and the methylene dichloride or two kinds.
In the above-mentioned steps (2), the recrystallization solvent for use is preferably hexane.
The present invention also provides the application of above-mentioned chiral amino anilino zn cpds, specifically be used as the catalyzer of the ring-opening polymerization of cyclic lactone, described cyclic lactone is one or both in 6-caprolactone (being caprolactone) and the rac-Lactide, wherein, rac-Lactide is one or both in levorotatory lactide and the rac-lactide.Wherein, the structural formula of rac-Lactide is shown in formula IV, and the structural formula of 6-caprolactone is suc as formula shown in (VII).
?
The cyclic lactone ring-opening polymerization specifically may further comprise the steps: chiral amino anilino zn cpds catalyzer, organic solvent, pure promotor and cyclic lactone 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 polylactone.
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 cyclic lactone and amido anilino zinc catalyst is 20～2000:1, and the mol ratio of pure promotor and catalyzer is 2～6:1.
In the above-mentioned ring-opening polymerization, polymeric reaction temperature is 20～115 ℃, 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, stereoselectivity is high, specific selectivity to the monomer polymerization site is strong, and when using rac-lactide as polymerization single polymerization monomer, gained polymerization rac-Lactide regularity is high, can reach 73%, range of application is 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.
Zn cpds method for preparing catalyst of the present invention is simple, and the gained catalyst is active and stereoselectivity is high, thereby can be widely used in the ring-opening polymerization of catalysis rac-Lactide and caprolactone.Because catalyst system is active high, polyreaction can occur at a lower temperature, mild condition, and 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.
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 chiral amino anilino zn cpds catalyzer (formula I)
Chiral amino anilino zn cpds catalyzer is the title complex that is generated by part and zinc alkyl(s) 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 chiral ligand structural 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 room temperature adds three times of molar weight zinc ethyls, be raised to 110 ℃ of reactions 2 hours, and desolventizing, crude product hexane recrystallization gets straight product 1.6g, productive rate 91%.
Embodiment 10
Used chiral ligand structural formula such as following formula (A), wherein R
1Be ethyl, reaction process is: under nitrogen atmosphere, ligand 1 .3g is dissolved in the 20 mL benzene, at four times of molar weight zinc ethyls of 0 ℃ of lower adding, is heated to 60 ℃ of reactions 12 hours, desolventizing, crude product hexane recrystallization.Get straight product 1.4g, productive rate 75%.
Embodiment 11
Used chiral ligand structural formula such as following formula (A), wherein R
1Be sec.-propyl, reaction process is: under nitrogen atmosphere, ligand 1 .0g is dissolved in the 20 mL hexanes, at room temperature adds five times of molar weight zinc ethyls, be raised to after the room temperature, reacted crystallisation by cooling 36 hours.Get straight product 1.1g, productive rate 83%.
Embodiment 12
Used chiral ligand structural formula such as following formula (A), wherein R
1Be methyl, reaction process is: under nitrogen atmosphere, ligand 1 .1g is dissolved in the 20 mL chloroforms, at room temperature adds five times of molar weight zinc methides, be raised to 50 ℃ of reactions 12 hours, and desolventizing, crude product hexane recrystallization gets straight product 1.4g, productive rate 90%.
Embodiment 13
Used chiral ligand structural formula such as following formula (A), wherein R
1Be ethyl, reaction process is: under nitrogen atmosphere, ligand 1 .4g is dissolved in the 15 mL tetrahydrofuran (THF)s, at three times of molar weight zinc methides of 0 ℃ of lower adding, is raised to after the room temperature, be heated to 60 ℃ of reactions 12 hours, desolventizing, crude product hexane recrystallization.Get straight product 1.7g, productive rate 88%.
Embodiment 14
Used chiral ligand structural formula such as following formula (A), wherein R
1Be sec.-propyl, reaction process is: under nitrogen atmosphere, ligand 1 .6g is dissolved in the 25 mL methylene dichloride, at room temperature adds the triplication zinc methide, be raised to after the room temperature, reacted 24 hours, desolventizing, crude product hexane recrystallization.Get straight product 1.6g, productive rate 76%.
The application of catalyzer
Embodiment 15
React under anhydrous and oxygen-free and protection of inert gas, order adds 20 μ mol R in the ampulla after the baking of high-purity argon gas gas washing
1Be methyl, R
2Rac-lactide for zinc catalyst, 40 mL toluene, 40 μ mol benzylalcohols and 20 mmol of ethyl, then room temperature reaction adds a small amount of water termination reaction and dissolve polymer after 1440 minutes, with methanol extraction, washing for several times, vacuum-drying under the room temperature, get 2.6 grams, molecular weight 31.7 ten thousand, molecular weight distribution 1.23, yield 92%.Regularity
PM=68%.
Embodiment 16
React under anhydrous and oxygen-free and protection of inert gas, order adds 300 μ mol R in the ampulla after the baking of high-purity argon gas gas washing
1Be sec.-propyl, R
2Then levorotatory lactide for zinc catalyst, 90 mL toluene, 1200 μ mol benzylalcohols and 60 mmol of methyl places 70
oIn the oil bath of C, react a small amount of water termination reaction of adding and dissolve polymer after 40 minutes, with methanol extraction, washing for several times, vacuum-drying under the room temperature gets 8.0 grams, molecular weight 25.6 ten thousand, molecular weight distribution 1.26, yield 93%.
Embodiment 17
React under anhydrous and oxygen-free and protection of inert gas, order adds 200 μ mol R in the ampulla after the baking of high-purity argon gas gas washing
1Be ethyl, R
2Then caprolactone for zinc catalyst, 40 mL tetrahydrofuran (THF)s, 600 μ mol Virahols and 40 mmol of ethyl places 40
oIn the oil bath of C, react a small amount of water termination reaction of adding and dissolve polymer after 5 minutes, with methanol extraction, washing for several times, vacuum-drying under the room temperature gets 4.4 grams, molecular weight 14.3 ten thousand, molecular weight distribution 1.26, yield 96%.
Embodiment 18
React under anhydrous and oxygen-free and the protection of inert gas, order adds 300 μ mol R in the ampulla after the baking of high-purity argon gas gas washing
1Be propyl group, R
2Be the levorotatory lactide of zinc catalyst, 60 mL toluene, 600 μ mol benzylalcohols and 30 mmol of ethyl, then 70
oThe C reaction adds the caprolactone 70 of 30 mmol after 0.5 hour again
oC reaction 0.5 hour, reaction add a small amount of hydrochloric acid termination reaction when finishing, with methanol extraction, washing for several times, vacuum-drying under the room temperature gets 6.8 grams, molecular weight 27.4 ten thousand, molecular weight distribution 1.37, yield 88%.
Embodiment 19
React under anhydrous and oxygen-free and protection of inert gas, order adds 100 μ mol R in the ampulla after the baking of high-purity argon gas gas washing
1Be sec.-propyl, R
2Levorotatory lactide for zinc catalyst, 30 mL methylene dichloride, 200 μ mol benzylalcohols and 30 mmol of methyl, then reaction adds a small amount of water termination reaction and dissolve polymer under the room temperature condition after 11 hours, with methanol extraction, washing for several times, vacuum-drying under the room temperature, get 3.9 grams, molecular weight 5.6 ten thousand, molecular weight distribution 1.17, yield 90%.
Embodiment 20
React under anhydrous and oxygen-free and protection of inert gas, order adds 200 μ mol R in the ampulla after the baking of high-purity argon gas gas washing
1Be ethyl, R
2Then rac-lactide for zinc catalyst, 40 mL tetrahydrofuran (THF)s, 400 μ mol benzylalcohols and 40 mmol of ethyl places 40
oIn the oil bath of C, react a small amount of water termination reaction of adding and dissolve polymer after 80 minutes, with methanol extraction, washing for several times, vacuum-drying under the room temperature gets 5.1 grams, molecular weight 4.3 ten thousand, molecular weight distribution 1.21, regularity
PM=73%, yield 89%.
Embodiment 21
React under anhydrous and oxygen-free and protection of inert gas, order adds 10 μ mol R in the ampulla after the baking of high-purity argon gas gas washing
1Be propyl group, R
2Rac-lactide for zinc catalyst, 60 mL methylene dichloride, 20 μ mol benzylalcohols and 20 mmol of methyl, then reaction adds a small amount of hydrochloric acid termination reaction under the room temperature condition after 12 hours, with methanol extraction, washing for several times, vacuum-drying under the room temperature, get 2.2 grams, molecular weight 67.6 ten thousand, molecular weight distribution 1.09, regularity
PM=71%, yield 93%.
Embodiment 22
React under anhydrous and oxygen-free and protection of inert gas, order adds 20 μ mol R in the ampulla after the baking of high-purity argon gas gas washing
1Be methyl, R
2Then rac-lactide for zinc catalyst, 60 mL tetrahydrofuran (THF)s, 40 μ mol benzylalcohols and 24 mmol of ethyl places 30
oIn the oil bath of C, react a small amount of water termination reaction of adding and dissolve polymer after 120 minutes, with methanol extraction, washing for several times, vacuum-drying under the room temperature gets 2.5 grams, molecular weight 44.3 ten thousand, molecular weight distribution 1.11, regularity
PM=69%, yield 91%.
Embodiment 23
React under anhydrous and oxygen-free and protection of inert gas, order adds 10 μ mol R in the ampulla after the baking of high-purity argon gas gas washing
1Be propyl group, R
2Then levorotatory lactide for zinc catalyst, 60 mL toluene, 20 μ mol benzylalcohols and 10 mmol of ethyl places 110
oIn the oil bath of C, react the caprolactone that adds 10 mmol after 40 minutes, react a small amount of water termination reaction of adding and dissolve polymer after 40 minutes, with methanol extraction, washing for several times, vacuum-drying under the room temperature gets 2.3 grams, molecular weight 67.2 ten thousand, molecular weight distribution 1.31, yield 89%.
Claims (10)
1. chiral amino anilino zn cpds is characterized in that: structural formula is as shown in the formula shown in the I, R in the formula
1, R
2Be the alkyl of C1-C4 straight or branched structure;
2. chiral amino anilino zn cpds according to claim 1 is characterized in that: R
1Be methyl or ethyl, R
2Be methyl or ethyl.
3. the synthetic method of chiral amino anilino zn cpds according to claim 1 and 2 may further comprise the steps:
(1) preparation part: 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, 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 chiral amino anilino part of formula A structure;
(2) preparation chiral amino anilino zn cpds: chiral amino anilino part and zinc alkyl(s) are reacted in organic solvent, and temperature of reaction is 0～120
oC, the reaction times is 1～36 hour, reaction is by chiral amino anilino zn cpds concentrated, that recrystallization gets formula I structure; Schiff's base and amido anilino ligand structure formula are as follows, R in the formula
1Be the alkyl of C1-C4 straight or branched structure, R
2Also be the alkyl of C1-C4 straight or branched structure:
。
4. preparation method according to claim 3 is characterized in that: N, and the mol ratio of N-dialkylamine benzaldehyde and (1R, 2R)-cyclohexanediamine is 2-3:1; Schiff's base and LiAlH
4Mol ratio be 1:1～1.5; The mol ratio of part and zinc alkyl(s) is 1:2～5.
5. preparation 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; In the reduction reaction, the temperature of reduction reaction is 20～70
oC, the reaction times is 2～12 hours; In the step (2), temperature of reaction is 20～110
oC, the reaction times is 2～12 hours; The mol ratio of part and zinc alkyl(s) is 1:2～3.
6. preparation method according to claim 3, it is characterized in that: described zinc alkyl(s) molecular formula is Zn (R
2)
2, R
2Alkyl for C1～C4 straight or branched structure.
7. preparation method according to claim 3 is characterized in that: the used organic solvent of condensation reaction is a kind of in tetrahydrofuran (THF), methyl alcohol, hexane, ethanol and the chloroform or two kinds in the step (1); The used organic solvent of reduction reaction is that tetrahydrofuran (THF) is or/and ether in the step (1); Used organic solvent is a kind of in tetrahydrofuran (THF), toluene, hexane, benzene, chloroform and the methylene dichloride or two kinds in the step (2); In step (1) and (2), the used solvent of recrystallization is hexane.
8. the application of a claim 1 or 2 described chiral amino anilino zn cpdss, it is characterized in that: as the catalyzer of cyclic lactone ring-opening polymerization, described cyclic lactone is one or both of rac-Lactide and caprolactone, wherein, rac-Lactide is one or both in levorotatory lactide and the rac-lactide.
9. application according to claim 8; it is characterized in that; the cyclic lactone ring-opening polymerization may further comprise the steps: chiral amino anilino zn cpds catalyzer, organic solvent, pure promotor and cyclic lactone 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 polylactone.
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; Cyclic lactone and chiral amino anilino zn cpds catalyst molar ratio are 20～2000:1, and the mol ratio of pure promotor and chiral amino anilino zn cpds catalyzer is 2～6:1; Polymeric reaction temperature is 20～115 ℃, and the time is 5-1440 minute.
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|---|---|---|---|---|
| CN109679082A (en) * | 2018-12-14 | 2019-04-26 | 泰山医学院 | Utilize the method for double-core Chiral Amine imines magnesium complex catalysis glycolide polymerization |
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| CN109679082A (en) * | 2018-12-14 | 2019-04-26 | 泰山医学院 | Utilize the method for double-core Chiral Amine imines magnesium complex catalysis glycolide polymerization |
| CN109679082B (en) * | 2018-12-14 | 2021-04-13 | 泰山医学院 | Method for catalyzing polymerization of glycolide by using binuclear chiral amine imine magnesium complex |
| CN111440281A (en) * | 2020-03-02 | 2020-07-24 | 华南理工大学 | Chiral Schiff base polymers and preparation method and application thereof |
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