CN102942579B - 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 the application as cyclic lactone ring-opening polymerization catalyst.
Background technology
Polylactide and its caprolactone copolymer owing to having 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 in medicine controlled releasing, surgical sutures, bone fracture internal fixation material etc., is that first is ratified for clinical degradable high score material by united States food and drug administration.Therefore polylactide is more and more subject to people's attention as a kind of novel Biodegradable material.
The alkoxide complexes of main group metal aluminium, magnesium, tin, transition metal, lanthanide series metal etc. and alkyl complexes can 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 object is to improve catalytic activity, controls the molecular weight and molecualr weight distribution of polymkeric substance.In the ring-opening polymerization of cyclic lactone monomer is anti-, controllable polymerization method is utilized to make polymerization process controlled, obtain the polymkeric substance of narrow molecular weight distribution and measurable molecular weight, make it have the key that more excellent mechanical property and good biodegradability are polyreaction research.Because rac-Lactide has left-handed-rac-Lactide, dextrorotation-rac-Lactide and Study of Meso-Lactide three kinds of steric isomers, therefore polylactide has multiple sequential structure, specifically comprises isotaxy, syndiotaxy, atactic, heterotactic and block and founds structure.The character of sequential structure to polylactide has a great impact, and the sequential structure of polylactide can be controlled by the stereoselectivity polymerization of rac-Lactide.Because zinc catalyst can realize living polymerization thus predicted molecular weight in the polymerization of rac-Lactide and caprolactone, and molecular weight is narrow, the needs of materials application aspect can be met, so research is many, wherein except beta-diimine and three tooth NNO zinc catalysts can be used for the selective opening polymerization of meso-lactide, seldom there is the zinc catalyst of document and other bidentate ligand coordinations of patent report can be used for the selective opening polymerization of meso-lactide, therefore develop new zinc catalyst very necessary for the selective opening polymerization of meso-lactide.
Summary of the invention
The invention provides a kind of chiral amino anilino zn cpds, this compound is suitable for cyclic lactone ring-opening polymerization, and catalytic activity is high, and the performance of polymkeric substance is good, and molecular weight is controlled.
Present invention also offers the preparation method of this catalyzer, simple to operate, be convenient to implement.
Present invention also offers the application of this catalyzer in lactone polymerization, be 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 as shown in the formula shown in I, R in 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;
。
Present invention also offers the preparation method of chiral amino anilino zinc, comprise the following steps:
(1) part is prepared: raw material N, N-dialkylamine benzaldehyde and (1R, 2R)-cyclohexanediamine in organic solvent condensation reaction are occurred, and temperature of reaction is 40 ~ 70
oc, the reaction times is 2 ~ 24 hours, obtains the Schiff's base shown in formula a after reaction through 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 as follows, R in formula
1for the alkyl of C1-C4 straight or branched structure, R
2also be the alkyl of C1-C4 straight or branched structure; Reaction formula is:
(2) prepare chiral amino anilino zn cpds: chiral amino anilino part and zinc alkyl(s) are reacted in organic solvent, temperature of reaction is 0 ~ 120
oc, the reaction times is 1 ~ 36 hour, through concentrated, that recrystallization obtains formula I structure chiral amino anilino zn cpds after reaction; Reaction formula is:
In the preparation method of above-mentioned part, the mol ratio of N, N-dialkylamine benzaldehyde and chirality cyclohexanediamine ((1R, 2R)-cyclohexanediamine) is 2 ~ 3:1.
In the preparation method of above-mentioned part, Schiff's base and LiAlH
4mol ratio be 1:1 ~ 1.5.
In the preparation method of above-mentioned part, condensation reaction organic solvent used is one in tetrahydrofuran (THF), methyl alcohol, hexane, ethanol and chloroform or two kinds, is preferably methyl alcohol, ethanol or hexane.
In the preparation method of above-mentioned part, reduction reaction organic solvent used be tetrahydrofuran (THF) or/and ether, be preferably tetrahydrofuran (THF) and ether.
In the preparation method of above-mentioned part, condensation reaction and reduction reaction organic solvent effect used are the environment in order to provide needed for reaction, its consumption is little on reaction impact, those skilled in the art can select the consumption of organic solvent according to actual needs, general, get 5 ~ 40 times that consumption of organic solvent is reactant total mass.
In the preparation method of above-mentioned part, the solvent that after condensation reaction, recrystallization is used is preferably hexane.
In the preparation method of above-mentioned part, reduction reaction is carried out under 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 above-mentioned steps (2), the mol ratio of part and zinc alkyl(s) is 1:2 ~ 5, preferred 1:2 ~ 3.
In above-mentioned steps (2), temperature of reaction is preferably 20 ~ 110
oc, the reaction times is preferably 2 ~ 12 hours.
In above-mentioned steps (2), described zinc alkyl(s) molecular formula is Zn (R
2)
2, R
2for the alkyl of C1 ~ C4 straight or branched structure.
In above-mentioned steps (2), react and carry out under protection of inert gas.
In above-mentioned steps (2), organic solvent used is one in tetrahydrofuran (THF), toluene, hexane, benzene, chloroform and methylene dichloride or two kinds.
In above-mentioned steps (2), recrystallization solvent for use is preferably hexane.
Present invention also offers 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 (i.e. caprolactone) and rac-Lactide, wherein, rac-Lactide is one or both in levorotatory lactide and rac-lactide.Wherein, the structural formula of rac-Lactide is as shown in formula IV, and the structural formula of 6-caprolactone is such as formula shown in (VII).
Cyclic lactone ring-opening polymerization specifically comprises the following steps: chiral amino anilino zn cpds catalyzer, organic solvent, alcohol promotor and cyclic lactone are mixed; under anhydrous and oxygen-free and protection of inert gas, carry out polymerization ring-opening reaction, after reaction, reactant is carried out processing to obtain polylactone.
In above-mentioned ring-opening polymerization, reacting organic solvent used is toluene, methylene dichloride or tetrahydrofuran (THF), preferred toluene.
In above-mentioned ring-opening polymerization, alcohol promotor is benzylalcohol or Virahol.
In 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 alcohol promotor and catalyzer is 2 ~ 6:1.
In above-mentioned ring-opening polymerization, polymeric reaction temperature is 20 ~ 115 DEG C, and the time is 5-1440 minute.During temperature height, it is few that monomer polymerization terminates required time, and when temperature is low, it is longer that monomer polymerization terminates required time.
In catalyzer of the present invention, the catalytic activity of part and the whole catalyzer of metal pair all has impact, (i.e. R in the framework of the present definition
1, R
2in the scope being limited to the alkyl of C1 ~ C4 straight or branched structure), catalyst activity and stereoselectivity 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, operation difficulty is larger, and catalyzer general is now stannous octoate, the molecular weight distribution of this catalyzer resulting polymers when catalyzed ring opening polymerization reacts is wider, poor controllability; And the present invention is without the need to carrying out under vacuum, as long as ensure anhydrous, anaerobic and inert conditions, should be more simple, in addition the amount ratio by controlling polymerization single polymerization monomer and catalyzer can obtain the narrower polymkeric substance of molecular weight distribution, the molecular weight controllability of the polymkeric substance of molecular weight below 700,000 is all better, 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, strong to the specific selectivity in monomer polymerization site, when using rac-lactide as polymerization single polymerization monomer, gained polymerized lactide regularity is high, can 73% be reached, range of application is wider, and when general achiral catalyst catalysis rac-lactide carries out ring-opening polymerization, the polymkeric substance of gained is unregulated polymer, and use range is narrow.
Zn cpds method for preparing catalyst of the present invention is simple, gained catalyst activity and stereoselectivity high, thus can be widely used in the ring-opening polymerization of catalysis rac-Lactide and caprolactone.Because the activity of catalyst system is 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 products obtained therefrom performance is better, and applicability is stronger.
Embodiment
Further illustrate the present invention below by specific embodiment, but the present invention is not limited to this, concrete protection domain see claim.
prepare 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 rear reaction reflux and stir 10 hours.Crystallisation by cooling, filters and obtains buff powder Schiff's base
a10.3 g, productive rate 77%.
embodiment 2
At N
2under atmosphere, the Schiff's base (7.2 g, 19.1 mmol) of Example 1 is dissolved in the ether of 50 ml dryings, at 0 DEG C, slowly repeatedly add lithium aluminum hydride (0.74 g on a small quantity, 19.1 mmol), add rear sluggish and rise to stirring at room temperature 8 hours.Reaction terminates slowly to add 1.3 mL frozen water stopped reaction in backward reaction system, then adds 1.3 mL NaOH(3M) aqueous solution, 3.9 mL water, filter, filter cake 30 ml ethyl acetate are washed, and collect filtrate, 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 drip (1R, 2R)-cyclohexanediamine (1.5 g, 13.2 mmol), drip rear reaction heating and be heated to 40 DEG C, stir 24 hours.Reaction terminates rear concentrated solution, adds 13 mL hexane crystallisation by cooling, filters and obtains buff powder Schiff's base
a3.5 g, productive rate 61%.
embodiment 4
At N
2under atmosphere, the Schiff's base (4.0 g, 9.2 mmol) of Example 3 is dissolved in the tetrahydrofuran (THF) of 40 ml dryings, at 0 DEG C, slowly repeatedly add lithium aluminum hydride (0.5 g, 13.8 mmol) on a small quantity, add rear sluggish and rise to room temperature, be heated to 70 DEG C, stir 2 hours.Reaction terminates slowly to add 0.9 mL frozen water stopped reaction in backward reaction system, then adds 0.9 mL NaOH(3M) aqueous solution, 2.7 mL water, filter, filter cake 40 ml ethyl acetate are washed, and collect filtrate, solvent removed in vacuo obtains weak yellow liquid
a3.7 g, productive rate 93%.
embodiment 5
Get N, N-dipropylbenzaldehyde (6.0 g, 29.2 mmol) is dissolved in 30 ml ethanol, slowly drips (1R, 2R)-cyclohexanediamine (1.7 g, 14.6 mmol), drips rear reaction heating and be heated to 50 DEG C, stir 12 hours.Reaction terminates rear concentrated solution, adds 10 mL hexane crystallisation by cooling, filters and obtains buff powder Schiff's base
a4.8 g, productive rate 67%.
embodiment 6
At N
2under atmosphere, the Schiff's base (5.0 g, 10.2 mmol) of Example 5 is dissolved in the ether of 40 ml dryings, slowly lithium aluminum hydride (0.39 g is repeatedly added on a small quantity at 0 DEG C, 10.2 mmol), add rear sluggish and rise to room temperature, stir 12 hours.Reaction terminates slowly to add 0.6 mL frozen water stopped reaction in backward reaction system, then adds 0.6 mL NaOH(3M) aqueous solution, 1.8 mL water, filter, filter cake 40 ml ethyl acetate are washed, and collect filtrate, 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 rear reaction heating and be heated to 60 DEG C, stir 8 hours.Reaction terminates rear concentrated solution, adds 10 mL hexane crystallisation by cooling, filters and obtains buff powder Schiff's base
a4.3 g, productive rate 63%.
embodiment 8
At N
2under atmosphere, the Schiff's base (4.2 g, 8.6 mmol) of Example 7 is dissolved in the ether of 40 ml dryings, slowly lithium aluminum hydride (0.4 g is repeatedly added on a small quantity at 0 DEG C, 10.3 mmol), add rear sluggish and rise to room temperature, stir 24 hours.Reaction terminates slowly to add 0.6 mL frozen water stopped reaction in backward reaction system, then adds 0.6 mL NaOH(3M) aqueous solution, 1.8 mL water, filter, filter cake 40 ml ethyl acetate are washed, and collect filtrate, solvent removed in vacuo obtains weak yellow liquid
a4.0 g, productive rate 95%.
prepare chiral amino anilino zn cpds catalyzer (formula I)
Chiral amino anilino zn cpds catalyzer reacts by part and zinc alkyl(s) the title complex generated, and the structural formula of its part, as shown in the formula (A), is illustrated to the catalyzer that different ligands obtains below, and preferred part is R
1for methyl, ethyl, the part of propyl group; R
2preferable methyl, ethyl.
embodiment 9
Chiral ligand structural formula used as above formula (A), wherein R
1for methyl, reaction process is: under nitrogen atmosphere, is dissolved in 15 mL toluene by ligand 1 .2 g, at room temperature adds three times of molar weight zinc ethyls, and be raised to 110 DEG C of reactions 2 hours, except desolventizing, crude product hexane recrystallization, obtains straight product 1.6g, productive rate 91%.
embodiment 10
Chiral ligand structural formula used as above formula (A), wherein R
1for ethyl, reaction process is: under nitrogen atmosphere, is dissolved in by ligand 1 .3g in 20 mL benzene, adds four times of molar weight zinc ethyls at 0 DEG C, is heated to 60 DEG C of reactions 12 hours, except desolventizing, and crude product hexane recrystallization.Obtain straight product 1.4g, productive rate 75%.
embodiment 11
Chiral ligand structural formula used as above formula (A), wherein R
1for sec.-propyl, reaction process is: under nitrogen atmosphere, is dissolved in by ligand 1 .0g in 20 mL hexanes, at room temperature adds five times of molar weight zinc ethyls, after being raised to room temperature, reacts 36 hours, crystallisation by cooling.Obtain straight product 1.1g, productive rate 83%.
embodiment 12
Chiral ligand structural formula used as above formula (A), wherein R
1for methyl, reaction process is: under nitrogen atmosphere, is dissolved in by ligand 1 .1g in 20 mL chloroforms, at room temperature adds five times of molar weight zinc methides, and be raised to 50 DEG C of reactions 12 hours, except desolventizing, crude product hexane recrystallization, obtains straight product 1.4g, productive rate 90%.
embodiment 13
Chiral ligand structural formula used as above formula (A), wherein R
1for ethyl, reaction process is: under nitrogen atmosphere, is dissolved in by ligand 1 .4g in 15 mL tetrahydrofuran (THF)s, adds three times of molar weight zinc methides at 0 DEG C, after being raised to room temperature, is heated to 60 DEG C of reactions 12 hours, except desolventizing, and crude product hexane recrystallization.Obtain straight product 1.7g, productive rate 88%.
embodiment 14
Chiral ligand structural formula used as above formula (A), wherein R
1for sec.-propyl, reaction process is: under nitrogen atmosphere, is dissolved in by ligand 1 .6g in 25 mL methylene dichloride, at room temperature adds triplication zinc methide, after being raised to room temperature, reacts 24 hours, except desolventizing, and crude product hexane recrystallization.Obtain straight product 1.6g, productive rate 76%.
the application of catalyzer
embodiment 15
React under anhydrous and oxygen-free and protection of inert gas, adding 20 μm of ol R by order in the ampulla after the baking of high-purity argon gas gas washing
1for methyl, R
2for the rac-lactide of the zinc catalyst of ethyl, 40 mL toluene, 40 μm of ol benzylalcohols and 20 mmol, then room temperature reaction adds a small amount of water termination reaction and dissolve polymer after 1440 minutes, with methanol extraction, washing several, ambient temperature in vacuum is dry, obtain 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, adding 300 μm of ol R by order in the ampulla after the baking of high-purity argon gas gas washing
1for sec.-propyl, R
2for the levorotatory lactide of the zinc catalyst of methyl, 90 mL toluene, 1200 μm of ol benzylalcohols and 60 mmol, be then placed in 70
oin the oil bath of C, react and add a small amount of water termination reaction and dissolve polymer after 40 minutes, with methanol extraction, washing several, ambient temperature in vacuum is dry, obtains 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, adding 200 μm of ol R by order in the ampulla after the baking of high-purity argon gas gas washing
1for ethyl, R
2for the caprolactone of the zinc catalyst of ethyl, 40 mL tetrahydrofuran (THF)s, 600 μm of ol Virahols and 40 mmol, be then placed in 40
oin the oil bath of C, react and add a small amount of water termination reaction and dissolve polymer after 5 minutes, with methanol extraction, washing several, ambient temperature in vacuum is dry, obtains 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 protection of inert gas, adding 300 μm of ol R by order in the ampulla after the baking of high-purity argon gas gas washing
1for propyl group, R
2for the levorotatory lactide of the zinc catalyst of ethyl, 60 mL toluene, 600 μm of ol benzylalcohols and 30 mmol, then 70
oafter C reacts 0.5 hour, then add the caprolactone 70 of 30 mmol
oc reacts 0.5 hour, adds a small amount of hydrochloric acid termination reaction at the end of reaction, and with methanol extraction, washing several, ambient temperature in vacuum is dry, obtains 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, adding 100 μm of ol R by order in the ampulla after the baking of high-purity argon gas gas washing
1for sec.-propyl, R
2for the levorotatory lactide of the zinc catalyst of methyl, 30 mL methylene dichloride, 200 μm of ol benzylalcohols and 30 mmol, then react under room temperature condition after 11 hours and add a small amount of water termination reaction and dissolve polymer, with methanol extraction, washing several, ambient temperature in vacuum is dry, obtain 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, adding 200 μm of ol R by order in the ampulla after the baking of high-purity argon gas gas washing
1for ethyl, R
2for the rac-lactide of the zinc catalyst of ethyl, 40 mL tetrahydrofuran (THF)s, 400 μm of ol benzylalcohols and 40 mmol, be then placed in 40
oin the oil bath of C, react and add a small amount of water termination reaction and dissolve polymer after 80 minutes, with methanol extraction, washing several, ambient temperature in vacuum is dry, obtains 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, adding 10 μm of ol R by order in the ampulla after the baking of high-purity argon gas gas washing
1for propyl group, R
2for the rac-lactide of the zinc catalyst of methyl, 60 mL methylene dichloride, 20 μm of ol benzylalcohols and 20 mmol, then react under room temperature condition after 12 hours and add a small amount of hydrochloric acid termination reaction, with methanol extraction, washing several, ambient temperature in vacuum is dry, obtain 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, adding 20 μm of ol R by order in the ampulla after the baking of high-purity argon gas gas washing
1for methyl, R
2for the rac-lactide of the zinc catalyst of ethyl, 60 mL tetrahydrofuran (THF)s, 40 μm of ol benzylalcohols and 24 mmol, be then placed in 30
oin the oil bath of C, react and add a small amount of water termination reaction and dissolve polymer after 120 minutes, with methanol extraction, washing several, ambient temperature in vacuum is dry, obtains 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, adding 10 μm of ol R by order in the ampulla after the baking of high-purity argon gas gas washing
1for propyl group, R
2for the levorotatory lactide of the zinc catalyst of ethyl, 60 mL toluene, 20 μm of ol benzylalcohols and 10 mmol, be then placed in 110
oin the oil bath of C, react the caprolactone adding 10 mmol after 40 minutes, react and add a small amount of water termination reaction and dissolve polymer after 40 minutes, with methanol extraction, washing several, ambient temperature in vacuum is dry, obtains 2.3 grams, molecular weight 67.2 ten thousand, molecular weight distribution 1.31, yield 89%.
Claims (10)
1. a chiral amino anilino zn cpds, is characterized in that: structural formula as shown in the formula shown in I, R in 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
1for methyl or ethyl, R
2for methyl or ethyl.
3. the synthetic method of chiral amino anilino zn cpds according to claim 1 and 2, comprises the following steps:
(1) part is prepared: raw material N, N-dialkylamine benzaldehyde and (1R, 2R)-cyclohexanediamine in organic solvent condensation reaction are occurred, and temperature of reaction is 40 ~ 70
oc, the reaction times is 2 ~ 24 hours, obtains the Schiff's base shown in formula a after reaction through 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) prepare chiral amino anilino zn cpds: chiral amino anilino part and zinc alkyl(s) are reacted in organic solvent, temperature of reaction is 0 ~ 120
oc, the reaction times is 1 ~ 36 hour, through concentrated, that recrystallization obtains formula I structure chiral amino anilino zn cpds after reaction; Schiff's base and amido anilino ligand structure formula as follows, R in formula
1alkyl for C1-C4 straight or branched structure:
。
4. preparation method according to claim 3, is characterized in that: the mol ratio of N, 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, is characterized in that: in condensation reaction, and the temperature of condensation reaction is 50 ~ 70
oc, the reaction times is 3 ~ 12 hours; In reduction reaction, the temperature of reduction reaction is 20 ~ 70
oc, the reaction times is 2 ~ 12 hours; In 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, is characterized in that: described zinc alkyl(s) molecular formula is Zn (R
2)
2, R
2for the alkyl of C1 ~ C4 straight or branched structure.
7. preparation method according to claim 3, is characterized in that: the organic solvent that condensation reaction is used in step (1) is one in tetrahydrofuran (THF), methyl alcohol, hexane, ethanol and chloroform or two kinds; The organic solvent that in step (1), reduction reaction is used is that tetrahydrofuran (THF) is or/and ether; In step (2), organic solvent used is one in tetrahydrofuran (THF), toluene, hexane, benzene, chloroform and methylene dichloride or two kinds; In step (1) and (2), recrystallization solvent used is hexane.
8. the application of the chiral amino anilino zn cpds described in a claim 1 or 2, 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 rac-lactide.
9. application according to claim 8, it is characterized in that, cyclic lactone ring-opening polymerization comprises the following steps: chiral amino anilino zn cpds catalyzer, organic solvent, alcohol promotor and cyclic lactone are mixed, under anhydrous and oxygen-free and protection of inert gas, carry out polymerization ring-opening reaction, after reaction, reactant is carried out processing to obtain polylactone; Alcohol promotor is benzylalcohol or Virahol.
10. application according to claim 9, is characterized in that: polyreaction organic solvent used is toluene, methylene dichloride or tetrahydrofuran (THF); Cyclic lactone and chiral amino anilino zn cpds catalyst molar ratio are 20 ~ 2000:1, and the mol ratio of alcohol promotor and chiral amino anilino zn cpds catalyzer is 2 ~ 6:1; Polymeric reaction temperature is 20 ~ 115 DEG C, and the time is 5-1440 minute.
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