CN103254220A - Chiral zinc compound and preparation method thereof as well as preparation method of polylactic acid - Google Patents
Chiral zinc compound and preparation method thereof as well as preparation method of polylactic acid Download PDFInfo
- Publication number
- CN103254220A CN103254220A CN2013102135206A CN201310213520A CN103254220A CN 103254220 A CN103254220 A CN 103254220A CN 2013102135206 A CN2013102135206 A CN 2013102135206A CN 201310213520 A CN201310213520 A CN 201310213520A CN 103254220 A CN103254220 A CN 103254220A
- Authority
- CN
- China
- Prior art keywords
- zinc compound
- formula
- chiral zinc
- preparation
- type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Catalysts (AREA)
Abstract
The invention provides a chiral zinc compound which has the chiral optical activity of S type or R type and is shown in the formula (I). The preparation method of the chiral zinc compound comprises the following step of: reacting a ligand shown in the formula (II) with Zn(R')2 in an organic solvent, thereby obtaining the chiral zinc compound, or reacting a chiral zinc compound as shown in the formula (III) with a monohydric alcohol of C1 to C10 in a solvent, thereby obtaining the chiral zinc compound. The invention also provides a preparation method of a polylactic acid, and the preparation method comprises the step of carrying out ring-opening polymerization of lactide in an organic solvent under the catalytic action of the chiral zinc compound as shown in formula (I), thereby obtaining a crystalline polylactic acid, wherein the lactide is L type lactide, D type lactide or racemic lactide. The chiral zinc compound has an asymmetrical three-dimensional structure and the steric hindrance of the chiral zinc compound is great, so that the lactides all can be opened in ring and polymerized in the same direction; as a result, the selectivity of catalyzing ring-opening polymerization of the lactides is enhanced and the crystalline polylactic acid is obtained. Besides, the chiral zinc compound is high in catalytic activity.
Description
Technical field
The present invention relates to catalyst field, particularly the preparation method of chiral zinc compound, its preparation method and poly(lactic acid).
Background technology
Poly(lactic acid) is a kind of biology class degraded macromolecular of chemical process preparation, and it has a wide range of applications in wrapping material, biological medicine and pharmaceutical industry.The preparation method of poly(lactic acid) has two kinds usually, that is: rac-Lactide (cyclic dimer of lactic acid) ring-opening polymerization and lactic acid direct polymerization.Wherein, high molecular weight polylactic acid generally obtains by the rac-Lactide ring-opening polymerization, and having had lot of documents and patent that relevant report has been carried out in the rac-Lactide ring-opening polymerization now, is that 5235031 United States Patent (USP) and the patent No. are 5357034 United States Patent (USP) as: the patent No..
Rac-Lactide is divided into three kinds of steric isomers: levorotatory lactide (LLA), dextrorotation rac-Lactide (DLA) and Study of Meso-Lactide, and its structure is as follows respectively:
The steric configuration of rac-Lactide has conclusive effect to mechanical property, processing characteristics and the degraded character of polymkeric substance.Rac-Lactide ring-opening polymerization catalyzer commonly used is nontoxic tin catalyst, as tin chloride or stannous octoate.Under the effect of tin series catalysts, optically pure DLA, LLA ring-opening polymerization respectively obtain isotactic poly-dextrorotation rac-Lactide and poly-levorotatory lactide, and it is 180 ℃ crystalline polymer that these two kinds of polymkeric substance are fusing point.But the product of rac-lactide ring-opening polymerization under the same conditions is the amorphism random copolymers.Compare with the amorphism poly(lactic acid), use temperature a wider range of crystalline polymer, can be near melt temperature, therefore needing exploitation, a kind of polymerization has stereoselective ring-opening polymerization catalyst to rac-Lactide, can obtain crystalline polylactic acid by the polymerization rac-lactide.
At present, about the more existing reports of the catalyzer of rac-Lactide stereoselectivity ring-opening polymerization, chirality Al catalysts (Salbinap) AlOMe as reports such as Coates is by a part 2, the 2'-diaminostilbene, 1'-naphthyl naphthalene and two molecule salicylic aldehyde condensations obtain part, are obtained by a part part and the reaction of a part aluminum isopropylate then; (cyclohexylsalen) AlO of report such as Zhong Zhiyuan
iThe Pr catalyzer is by a part 1,2-cyclohexanediamine and two molecules 3, and the condensation of 5-di-tert-butyl salicylaldehyde obtains Schiff's base, is obtained by monovalent Schiff's base and the reaction of monovalent aluminum isopropylate then.But the catalyzer of reporting all is the Al catalysts that obtained by the salicylic aldehyde of salicylic aldehyde or replacement and diamine reaction, and selectivity and the activity of its catalyzed reaction are lower.
Summary of the invention
The technical problem that the present invention solves is to provide the preparation method of a kind of chiral zinc compound, its preparation method and poly(lactic acid), and described chiral zinc compound has stereoselectivity to poly(lactic acid) is synthetic, and the catalytic activity height.
The invention discloses a kind of chiral zinc compound, its chirality optical activity is S type or R type, shown in (I):
Wherein, R is the alkyl of C1～C5 or the alkoxyl group of C1～C10; R
1, R
2Or R
3Be independently selected from respectively-H ,-CH
3,-OCH
3,-CH
2CH
3,-CH (CH
3)
2,-C (CH
3)
3,-F ,-Cl ,-Br or-NO
2
The invention discloses a kind of preparation method of chiral zinc compound, may further comprise the steps:
With the part shown in the formula (II) and Zn (R ')
2In organic solvent, react, obtain the chiral zinc compound shown in the formula (III); The chirality optical activity of the chiral zinc compound shown in the formula (III) is S type or R type; The chirality optical activity of the part shown in the described formula (II) is S type or R type;
Wherein, R
1, R
2Or R
3Be independently selected from respectively-H ,-CH
3,-OCH
3,-CH
2CH
3,-CH (CH
3)
2,-C (CH
3)
3,-F ,-Cl ,-Br or-NO
2
R ' is the alkyl of C1～C5.
Preferably, the part shown in the described formula (II) and Zn (R ')
2Mol ratio be 1:(1～3).
Preferably, the temperature of described reaction is 70 ℃～100 ℃, and the time of reaction is 6～12h.
Preferably, the preparation method of the part shown in the described formula (II) is:
With 2 of S type or R type, the 2'-diaminostilbene, the substituted benzene methyl ether reaction shown in 1'-naphthyl naphthalene and the formula V obtains the described part of formula (II); Described part has chirality;
In the formula V, R
1, R
2Or R
3Be independently selected from respectively-H ,-CH
3,-CH
2CH
3,-CH (CH
3)
2,-C (CH
3)
3,-F ,-Cl ,-Br or-NO
2
The invention discloses a kind of preparation method of chiral zinc compound, may further comprise the steps:
Chiral zinc compound shown in the formula (III) and the monohydroxy-alcohol of C1～C10 are reacted in solvent, obtain the chiral zinc compound shown in the formula (IV); The chirality optical activity of the chiral zinc compound shown in the formula (IV) is S type or R type;
Wherein, wherein, R
1, R
2Or R
3Be independently selected from respectively-H ,-CH
3,-OCH
3,-CH
2CH
3,-CH (CH
3)
2,-C (CH
3)
3,-F ,-Cl ,-Br or-NO
2
R 〞 is the alkoxyl group of C1～C10.
Preferably, the mol ratio of the monohydroxy-alcohol of the chiral zinc compound shown in the described formula (III) and C1～C10 is 1:(1～3).
The invention discloses a kind of preparation method of poly(lactic acid), may further comprise the steps:
Under the chiral zinc compound for catalysis effect shown in the formula (I), ring-opening polymerization takes place in rac-Lactide in organic solvent, obtain crystalline poly(lactic acid);
Described rac-Lactide is L type rac-Lactide, D type rac-Lactide or rac-lactide;
Wherein, R is the alkyl of C1～C5, the alkoxyl group of C1～C10;
R
1, R
2Or R
3Be independently selected from respectively-H ,-CH
3,-OCH
3,-CH
2CH
3,-CH (CH
3)
2,-C (CH
3)
3,-F ,-Cl ,-Br or-NO
2
Preferably, the mol ratio of the described chiral zinc compound of described formula (I) and rac-Lactide is 1:50～1:400.
Preferably, the temperature of reaction of described reaction is 50 ℃～110 ℃, and the reaction times is 0.5～5h.
Compared with prior art, chiral zinc compound of the present invention is S type or R type suc as formula shown in (I).Described chiral zinc compound has asymmetric space multistory structure, and is sterically hindered bigger, makes rac-Lactide all can strengthen the selectivity of catalyzing ring-opening polymerization of lactide according to identical direction ring-opening polymerization.It not only can obtain crystalline poly(lactic acid) by the catalysis rac-lactide, and can catalyzing levorotatory lactide or the dextrorotation rac-Lactide obtain crystalline poly(lactic acid).On the other hand, have zinc in the described chiral zinc compound, metallic zinc ionic stronger than traditional tin and aluminium, in catalytic reaction process, the catalytic activity height.Experimental result shows that the poly(lactic acid) that chiral zinc compound for catalysis of the present invention obtains is that fusing point is 135～179 ℃ crystalline polymer.
Embodiment
In order further to understand the present invention, be described below in conjunction with the preferred embodiment of the invention of embodiment, but should be appreciated that these describe just to further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of chiral zinc compound, its chirality optical activity is S type or R type, shown in (I):
Wherein, R is the alkyl of C1～C5 or the alkoxyl group of C1～C10, is preferably-CH
3,-CH
2CH
3,-OCH
3,-OCH
2CH
3,-OCH (CH
3)
2Or-OCH
2Ph;
R
1, R
2Or R
3Be independently selected from respectively-H ,-CH
3,-OCH
3,-CH
2CH
3,-CH (CH
3)
2,-C (CH
3)
3,-F ,-Cl ,-Br or-NO
2
Chiral zinc compound of the present invention is according to the difference of R group, its preparation method difference.
The invention discloses a kind of preparation method of chiral zinc compound, may further comprise the steps:
With the part shown in the formula (II) and Zn (R ')
2In organic solvent, react, obtain the chiral zinc compound shown in the formula (III); The chirality optical activity of the chiral zinc compound shown in the formula (III) is S type or R type; The chirality optical activity of the part shown in the described formula (II) is S type or R type;
Wherein, R
1, R
2Or R
3Be independently selected from respectively-H ,-CH
3,-OCH
3,-CH
2CH
3,-CH (CH
3)
2,-C (CH
3)
3,-F ,-Cl ,-Br or-NO
2
R ' is the alkyl of C1～C5, is preferably-CH
3,-CH
2CH
3
The present invention is with the part shown in the formula (II) and organic zinc chemical combination Zn (R ')
2Reaction, obtain the chiral zinc compound shown in the formula (III), chiral zinc compound shown in the described formula (III) has identical active structure with the chiral zinc compound shown in the formula (I), just on the zinc with group different, the R ' group of the chiral zinc compound of described method preparation can only be the alkyl of C1～C5.Part shown in the described formula (II) and Zn (R ')
2Mol ratio be preferably 1:(1～3), 1:1 more preferably.Described Zn (R ')
2Be organic zinc compound, described R ' is the alkyl of C1～C5, is preferably methyl or ethyl.
The preparation method of the part shown in the described formula (II) is preferably:
With 2 of S type or R type, the 2'-diaminostilbene, the substituted benzene methyl ether reaction shown in 1'-naphthyl naphthalene and the formula V obtains the described part of formula (II); Described part has chirality;
In the formula V, R
1, R
2Or R
3Be independently selected from respectively-H ,-CH
3,-CH
2CH
3,-CH (CH
3)
2,-C (CH
3)
3,-F ,-Cl ,-Br or-NO
2
Described catalyst for reaction is preferably palladium, and described reaction preferably refluxes in tetrahydrofuran solvent, and the time of described reaction is preferably 5～10 hours, more preferably 7～8 hours.
Prepare in the process of chiral zinc compound in the present invention, described organic solvent is preferably tetrahydrofuran (THF) or toluene.Work as R
1, R
2And R
3Be independently selected from-H ,-F ,-Cl ,-Br or-NO
2The time, reaction solvent is preferably tetrahydrofuran (THF), works as R
1, R
2And R
3Be independently selected from-CH
3,-CH
2CH
3,-CH (CH
3)
2,-C (CH
3)
3The time, reaction solvent is preferably toluene.The temperature of described reaction is preferably 70 ℃～100 ℃, more preferably 79～90 ℃, most preferably is 70 ℃ or 90 ℃.The time of described reaction is preferably 6～12h, and more preferably 6～10h most preferably is 7～8h.
The invention discloses a kind of preparation method of chiral zinc compound, may further comprise the steps:
Chiral zinc compound and R ' ' H shown in the formula (III) are reacted in solvent, obtain the chiral zinc compound shown in the formula (IV); The chirality optical activity of the chiral zinc compound shown in the formula (IV) is S type or R type;
Wherein, wherein, R
1, R
2Or R
3Be independently selected from respectively-H ,-CH
3,-OCH
3,-CH
2CH
3,-CH (CH
3)
2,-C (CH
3)
3,-F ,-Cl ,-Br or-NO
2
R 〞 is the alkoxyl group of C1～C10, is preferably-OCH
3,-OCH
2CH
3,-OCH (CH
3)
2Or-OCH
2Ph.
The present invention is raw material with the monohydroxy-alcohol of the chiral zinc compound shown in the formula (III) and C1～C10, and the chiral zinc compound shown in the described formula (III) is preparation according to the method described above preferably.The monohydroxy-alcohol of described C1～C10 is preferably methyl alcohol, ethanol, Virahol or benzylalcohol, more preferably benzylalcohol or Virahol.The mol ratio of the monohydroxy-alcohol of the chiral zinc compound shown in the described formula (III) and C1～C10 is preferably 1:(1～3), 1:1 more preferably.The organic solvent of described reaction is preferably tetrahydrofuran (THF) or toluene.The described reaction times is rapid, and described two kinds of raw materials mixing gets final product.The present invention is not particularly limited temperature, and room temperature gets final product.
The invention also discloses a kind of preparation method of poly(lactic acid), may further comprise the steps:
Under the chiral zinc compound for catalysis effect shown in the formula (I), ring-opening polymerization takes place in rac-Lactide in organic solvent, obtain crystalline poly(lactic acid);
Described rac-Lactide is L type rac-Lactide, D type rac-Lactide or rac-lactide;
(I)；
Wherein, R is the alkyl of C1～C5, the alkoxyl group of C1～C10; Be preferably-CH
3,-CH
2CH
3,-OCH
3,-OCH
2CH
3,-OCH (CH
3)
2Or-OCH
2Ph; R
1, R
2Or R
3Be independently selected from respectively-H ,-CH
3,-OCH
3,-CH
2CH
3,-CH (CH
3)
2,-C (CH
3)
3,-F ,-Cl ,-Br or-NO
2
The present invention is raw material with the rac-Lactide, and described rac-Lactide can be raw material for L-type rac-Lactide, D-type rac-Lactide or rac-lactide, and the chiral zinc compound shown in the formula (I) is catalyzer.The mol ratio of the described chiral zinc compound of described formula (I) and rac-Lactide is preferably 1:50～1:400, more preferably 1:70～200.The temperature of reaction of described reaction is preferably 50 ℃～110 ℃, more preferably 60～90 ℃.The described reaction times is preferably 0.5～5h, more preferably 2～4h.Described reaction is preferably carried out under the condition of anhydrous and oxygen-free, to avoid or to reduce the generation of side reaction.
The poly(lactic acid) that obtains is detected, and experimental result shows that obtaining the poly(lactic acid) fusing point is 135～179 ℃, all has the crystalline texture of the full same sex.
In order further to understand the present invention, below in conjunction with embodiment the preparation method of chiral zinc compound provided by the invention, its preparation method and poly(lactic acid) is described, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Under nitrogen atmosphere, 0.045g palladium and 0.25g dinaphthalene hexichol phosphorus are dissolved in the 30mL toluene, slowly add 0.75g2-bromoanisole and 1.1374g S type or R type 2,2'-diaminostilbene, 1'-naphthyl naphthalene, add the 0.576g sodium tert-butoxide behind the stirring at room 5min, place 70 ℃ of oil baths to stir 6h behind the stirring at room 10min, behind the cool to room temperature, adding the 40mL ether, wash with salt solution, behind the separatory, the yellow soda ash drying concentrates, the thick product of gained uses column chromatography, eluent is that volume ratio is hexane and the ethyl acetate of 10:1, and comprising 2% triethylamine, the colorless solid that obtains at last is ligand i Ia, it has formula (II) structure, wherein R
1, R
2, and R
3Be H.
Utilize nucleus magnetic resonance that the ligand i Ia that obtains among the embodiment 1 is analyzed, obtain its hydrogen spectrum, the result is as follows:
1H?NMR(400MHz,CDCl
3,25℃):3.52(s,3H,OCH
3),3.68(s,2H,NH
2),5.70(s,1H,NH),6.74-7.90(m,16H).
Utilize mass spectrograph that the ligand i Ia that obtains among the embodiment 1 is analyzed, obtain the result: MALDI-TOF (THF), m/z=390.20.
Utilize ultimate analysis that the ligand i Ia that obtains among the embodiment 1 is analyzed, obtain its each constituent content.
Elem.Anal.(%)：C,83.05;H,5.68;N,7.17.Found:C,83.09;H,5.71;N,7.20。
Embodiment 2
Under nitrogen atmosphere, 0.045g palladium and 0.25g dinaphthalene hexichol phosphorus are dissolved in the 30mL toluene, slowly add 0.82g2-bromo-5-fluoroanisole and 1.1374g S type or R type 2,2'-diaminostilbene, 1'-naphthyl naphthalene, add the 0.576g sodium tert-butoxide behind the stirring at room 5min, place 70 ℃ of oil baths to stir 6h behind the stirring at room 10min, behind the cool to room temperature, adding the 40mL ether, wash with salt solution, behind the separatory, the yellow soda ash drying concentrates, the thick product of gained uses column chromatography, eluent is that volume ratio is hexane and the ethyl acetate of 10:1, and comprising 2% triethylamine, the colorless solid that obtains at last is ligand i Ib, it has formula (II) structure, wherein R
1Be F, R
2, and R
3Be H.
Utilize nucleus magnetic resonance that the ligand i Ib that obtains among the embodiment 2 is analyzed, obtain its hydrogen spectrum, the result is as follows:
1H?NMR(400MHz,CDCl
3,25℃):3.54(s,3H,OCH
3),3.69(s,2H,NH
2),5.56(s,1H,NH),6.50-7.87(m,15H).
Utilize mass spectrograph that the ligand i Ib that obtains among the embodiment 2 is analyzed, obtain the result: MALDI-TOF (THF), m/z=408.20.
Utilize ultimate analysis that the ligand i Ib that obtains among the embodiment 2 is analyzed, obtain its each constituent content.
Elem.Anal.(%)：C,79.39;H,5.18;N,6.86;Found:C,79.36;H,5.15;N,6.79。
Embodiment 3
Under nitrogen atmosphere, 0.045g palladium and 0.25g dinaphthalene hexichol phosphorus are dissolved in the 30mL toluene, slowly add 1.197g2-bromo-4,6-di-t-butyl methyl-phenoxide and 1.1374g S type or R type 2,2'-diaminostilbene, 1'-naphthyl naphthalene, add the 0.576g sodium tert-butoxide behind the stirring at room 5min, place 70 ℃ of oil baths to stir 6h behind the stirring at room 10min, behind the cool to room temperature, adding the 40mL ether, wash with salt solution, behind the separatory, the yellow soda ash drying concentrates, the thick product of gained uses column chromatography, eluent is that volume ratio is hexane and the ethyl acetate of 10:1, and comprising 2% triethylamine, the colorless solid that obtains at last is ligand i Ic.It has formula (II) structure, wherein R
1Be H, R
2, and R
3Be-C (CH
3)
3
Utilize nucleus magnetic resonance that the ligand i Ic that obtains among the embodiment 3 is analyzed, obtain its hydrogen spectrum, the result is as follows:
1H?NMR(400MHz,CDCl
3,25℃):1.29(s,9H,C(CH
3)
3),1.33(s,9H,C(CH
3)
3),3.43(s,3H,OCH
3),3.75(s,2H,NH
2),5.53(s,1H,NH),6.97(s,1H,ArH),7.11-7.87(m,13H)。
Embodiment 4
Under the condition of protection of inert gas, be that IIa tetrahydrofuran solution and the 6mL concentration of 1mol/L is 1mol/L Zn(CH with 6mL concentration
3)
2Tetrahydrofuran solution mix to stir, 70 ℃ of reaction 8h are down to room temperature, vacuumize through cold well and remove volatile matter, obtain chiral zinc compound I a-1.It has formula (I) structure, wherein R
1, R
2And R
3Be H, R is CH
3
Utilize ultimate analysis that the chiral zinc compound I a-1 that obtains among the embodiment 4 is analyzed, obtain its each constituent content.
Ia-1:Elem.Anal.（%）：Calc.C,71.72;H,4.94;N,5.97;Found:C,71.67;H4.90；N,5.95。
Embodiment 5
The chiral zinc compound I a-1 that obtains among the 4mmol embodiment 4 is dissolved in the toluene, adds the 4mmol Virahol, obtain chiral zinc compound I a-2.It has formula (I) structure, wherein R
1, R
2And R
3Be H, R is-OCH (CH
3)
2
Utilize ultimate analysis that the chiral zinc compound I a-2 that obtains among the embodiment 5 is analyzed, obtain its each constituent content.
Ia-2:Elem.Anal.（%）：Calc.C,70.24;H,5.31;N,5.46;Found:C70.28;H5.39；N,6.04。
Embodiment 6
The chiral zinc compound I a-1 that obtains among the 4mmol embodiment 4 is dissolved in the toluene, adds 4mmol benzylalcohol, obtain chiral zinc compound I a-3.It has formula (I) structure, wherein R
1, R
2And R
3Be H, R is-OCH
2Ph.
Utilize ultimate analysis that the chiral zinc compound I a-3 that obtains among the embodiment 6 is analyzed, obtain its each constituent content.
Ia-3:Elem.Anal.（%）：Calc.C,72.79;H,4.85;N,4.99;Found:C72.72;H4.80；N5.99。
Embodiment 7
The preparation method of chiral zinc compounds ib-1 is identical with Ia-1, and wherein difference is: the IIa tetrahydrofuran solution is changed to the IIb tetrahydrofuran solution.Ib-1 has formula (I) structure, wherein R
1Be F, R
2And R
3Be H, R is methyl.
Utilize ultimate analysis that the chiral zinc compounds ib-1 that obtains among the embodiment 7 is analyzed, obtain its each constituent content.
Ib-1:Elem.Anal.（%）：Calc.C,69.07;H,4.55;N,5.75;Found:C69.01;H4.52；N5.69。
Embodiment 8
The chiral zinc compounds ib-1 that obtains among the 4mmol embodiment 7 is dissolved in the toluene, adds the 4mmol Virahol, obtain chiral zinc compounds ib-2.It has formula (I) structure, wherein R
1Be F, R
2And R
3Be H, R is-OCH (CH
3)
2
Utilize ultimate analysis that the chiral zinc compounds ib-2 that obtains among the embodiment 8 is analyzed, obtain its each constituent content.
Ib-2:Elem.Anal.（%）：Calc.C,67.86;H,4.94;N,5.28;Found:C67.80;H4.90；N,5.22。
Embodiment 9
The chiral zinc compounds ib-1 that obtains among the 4mmol embodiment 7 is dissolved in the toluene, adds 4mmol benzylalcohol, obtain chiral zinc compounds ib-3.It has formula (I) structure, wherein R
1Be F, R
2And R
3Be H, R is-OCH
2Ph.
Utilize ultimate analysis that the chiral zinc compounds ib-3 that obtains among the embodiment 9 is analyzed, obtain its each constituent content.
Ib-3:Elem.Anal.（%）：Calc.C,70.53;H,4.53;N,4.84;Found:C70.59;H4.58；N,5.30。
Embodiment 10
The preparation method of chiral zinc compound I c-1 is identical with Ia-1, and wherein difference is: the IIa tetrahydrofuran solution is changed to the IIc tetrahydrofuran solution.Ic-1 has formula (I) structure, wherein R
1Be F, R
2And R
3Be H, R is methyl.
Utilize ultimate analysis that the chiral zinc compound I c-1 that obtains among the embodiment 10 is analyzed, obtain its each constituent content.
Ic-1:Elem.Anal.（%）：Calc.C,74.41;H,6.76;N,4.82;.Found:C,74.37;H6.67；N,4.79。
Embodiment 11
The chiral zinc compound I c-1 that obtains among the 4mmol embodiment 10 is dissolved in the toluene, adds the 4mmol Virahol, obtain chiral zinc compound I c-2.It has formula (I) structure, wherein R
1Be F, R
2And R
3Be H, R is-OCH (CH
3)
2
Utilize ultimate analysis that the chiral zinc compound I c-2 that obtains among the embodiment 11 is analyzed, obtain its each constituent content.
Ic-2:Elem.Anal.（%）：Calc.C,73.01;H,6.93;N,4.48.Found:C,73.08;H6.92；N,4.40。
Embodiment 12
The chiral zinc compound I c-1 that obtains among the 4mmol embodiment 10 is dissolved in the toluene, adds 4mmol benzylalcohol, obtain chiral zinc compound I c-3.It has formula (I) structure, wherein R
1Be F, R
2And R
3Be H, R is-OCH
2Ph.
Utilize ultimate analysis that the chiral zinc compound I c-3 that obtains among the embodiment 12 is analyzed, obtain its each constituent content.
Ic-3:Elem.Anal.（%）：Calc.C,74.93;H,6.44;N,4.16.Found:C,74.88;H6.87；N,4.31。
Embodiment 13
Under the condition of anhydrous and oxygen-free, the chiral zinc compound I a-1 that obtains among the rac-lactide that the 2.08mmol recrystallization is crossed, the 0.015mmol embodiment 4 mixes with the 31mL tetrahydrofuran (THF), 70 ℃ of stirring reaction 3h, add the excess ethanol precipitation polymers, filter, vacuum-drying 24h obtains the 0.25g poly(lactic acid), and its fusing point is 138 ℃.
Be marker with the polystyrene, utilize gel permeation chromatography (GPC) that the poly(lactic acid) that obtains among the embodiment 7 is analyzed, the number-average molecular weight that obtains poly(lactic acid) is 1.9 ten thousand.
Embodiment 14
Under the condition of anhydrous and oxygen-free, the chiral zinc compound I a-2 that obtains among the rac-lactide that the 2.08mmol recrystallization is crossed, the 0.015mmol embodiment 5 mixes with the 31mL tetrahydrofuran (THF), 70 ℃ of stirring reaction 3h, add the excess ethanol precipitation polymers, filter, vacuum-drying 24h obtains the 0.24g poly(lactic acid), and its fusing point is 135 ℃.
Be standard substance with the polystyrene, utilize gel permeation chromatography that the poly(lactic acid) that obtains among the embodiment 8 is analyzed, the number-average molecular weight that obtains poly(lactic acid) is 1.7 ten thousand.
Embodiment 15
The preparation method is identical with embodiment 8, and difference is that catalyzer is the chiral zinc compound I a-3 that obtains among the embodiment 6, obtains the 0.23g poly(lactic acid), and its fusing point is 137 ℃.
Be marker with the polystyrene, utilize gel permeation chromatography that the poly(lactic acid) that obtains in the present embodiment is analyzed, the number-average molecular weight that obtains poly(lactic acid) is 1.6 ten thousand.
Embodiment 16
Under the condition of anhydrous and oxygen-free, the chiral zinc compounds ib-1 that obtains among the rac-lactide that the 3.00mmol recrystallization is crossed, the 0.03mmol embodiment 7 mixes with the 27mL tetrahydrofuran (THF), 50 ℃ of stirring reaction 2h, add the excess ethanol precipitation polymers, filter, vacuum-drying 24h obtains the 0.40g poly(lactic acid), and its fusing point is 138 ℃.
Be standard substance with the polystyrene, utilize gel permeation chromatography that the poly(lactic acid) that obtains in the present embodiment is analyzed, the number-average molecular weight that obtains poly(lactic acid) is 1.60 ten thousand.
Embodiment 17
The preparation method is identical with embodiment 16, and difference is that catalyzer is the chiral zinc compounds ib-2 that obtains in the enforcement 8, obtains the 0.42g poly(lactic acid), and its fusing point is 137 ℃.
Be marker with the polystyrene, utilize gel permeation chromatography that the poly(lactic acid) that obtains in the present embodiment is analyzed, the number-average molecular weight that obtains poly(lactic acid) is 1.64 ten thousand.
Embodiment 18
The preparation method is identical with embodiment 16, and difference is that catalyzer is the chiral zinc compounds ib-3 that obtains among the embodiment 9, obtains the 0.41g poly(lactic acid), and its fusing point is 138 ℃.
Be marker with the polystyrene, utilize gel permeation chromatography that the poly(lactic acid) that obtains in the present embodiment is analyzed, the number-average molecular weight that obtains poly(lactic acid) is 1.80 ten thousand.
Embodiment 19
Under the condition of anhydrous and oxygen-free, the chiral zinc compounds ib-1 that obtains among the rac-lactide that the 6.00mmol recrystallization is crossed, the 0.030mmol embodiment 7 mixes with the 60mL tetrahydrofuran (THF), 50 ℃ of stirring reaction 3h, add the excess ethanol precipitation polymers, filter, vacuum-drying 24h obtains the 0.842g poly(lactic acid), and its fusing point is 140 ℃.
Be standard substance with the polystyrene, utilize gel permeation chromatography that the poly(lactic acid) that obtains in the present embodiment is analyzed, the number-average molecular weight that obtains poly(lactic acid) is 3.34 ten thousand.
Embodiment 20
The preparation method is identical with embodiment 19, and difference is that catalyzer is the chiral zinc compounds ib-2 that obtains among the embodiment 8, obtains the 0.851g poly(lactic acid), and its fusing point is 139 ℃.
Be standard substance with the polystyrene, utilize gel permeation chromatography that the poly(lactic acid) that obtains in the present embodiment is analyzed, the number-average molecular weight that obtains poly(lactic acid) is 3.30 ten thousand.
Embodiment 21
The preparation method is identical with embodiment 19, and difference is that catalyzer is the chiral zinc compounds ib-3 that obtains among the embodiment 9, obtains the 0.844g poly(lactic acid), and its fusing point is 140 ℃.
Be standard substance with the polystyrene, utilize gel permeation chromatography that the poly(lactic acid) that obtains in the present embodiment is analyzed, the number-average molecular weight that obtains poly(lactic acid) is 3.28 ten thousand.
Embodiment 22
Under the condition of anhydrous and oxygen-free, the chiral zinc compound I c-1 that obtains among the rac-lactide that the 4.50mmol recrystallization is crossed, the 0.030mmol embodiment 10 mixes with the 45mL tetrahydrofuran (THF), 60 ℃ of stirring reaction 4h, add the excess ethanol precipitation polymers, filter, vacuum-drying 24h obtains the 0.67g poly(lactic acid), and its fusing point is 138 ℃.
Be standard substance with the polystyrene, utilize gel permeation chromatography that the poly(lactic acid) that obtains in the present embodiment is analyzed, the number-average molecular weight that obtains poly(lactic acid) is 2.87 ten thousand.
Embodiment 23
The preparation method is identical with embodiment 22, and difference is that catalyzer is the chiral zinc compound I c-2 that obtains among the embodiment 11, obtains the 0.65g poly(lactic acid), and its fusing point is 140 ℃.
Be standard substance with the polystyrene, utilize gel permeation chromatography that the poly(lactic acid) that obtains in the present embodiment is analyzed, the number-average molecular weight that obtains poly(lactic acid) is 2.89 ten thousand.
Embodiment 24
The preparation method is identical with embodiment 21, and difference is that catalyzer is the chiral zinc compound I c-3 that obtains among the embodiment 12, obtains the 0.64g poly(lactic acid), and its fusing point is 141 ℃.
Be standard substance with the polystyrene, utilize gel permeation chromatography that the poly(lactic acid) that obtains in the present embodiment is analyzed, the number-average molecular weight that obtains poly(lactic acid) is 2.77 ten thousand.
Embodiment 25
Under the condition of anhydrous and oxygen-free, the chiral zinc compound I c-1 that obtains among the rac-lactide that the 3.00mmol recrystallization is crossed, the 0.030mmol embodiment 10 mixes with the 27mL tetrahydrofuran (THF), 60 ℃ of stirring reaction 4h, add the excess ethanol precipitation polymers, filter, vacuum-drying 24h obtains the 0.40g poly(lactic acid), and its fusing point is 148 ℃.
Be marker with the polystyrene, utilize gel permeation chromatography that the poly(lactic acid) that obtains in the present embodiment is analyzed, the number-average molecular weight that obtains poly(lactic acid) is 1.89 ten thousand.
Embodiment 26
The preparation method is identical with embodiment 25, and difference is that catalyzer is the chiral zinc compound I c-2 that obtains among the embodiment 11, obtains the 0.41g poly(lactic acid), and its fusing point is 141 ℃.
Be marker with the polystyrene, utilize gel permeation chromatography that the poly(lactic acid) that obtains in the present embodiment is analyzed, the number-average molecular weight that obtains poly(lactic acid) is 2.11 ten thousand.
Embodiment 27
The preparation method is identical with embodiment 25, and difference is that catalyzer is the chiral zinc compound I c-3 that obtains among the embodiment 12, obtains the 0.42g poly(lactic acid), and its fusing point is 142 ℃.
Be marker with the polystyrene, utilize gel permeation chromatography that the poly(lactic acid) that obtains in the present embodiment is analyzed, the number-average molecular weight that obtains poly(lactic acid) is 2.30 ten thousand.
Embodiment 28
Under the condition of anhydrous and oxygen-free, the chiral zinc compound I c-1 that obtains among the levorotatory lactide that the 3.02mmol recrystallization is crossed, the 0.021mmol embodiment 10 mixes with the 40.0mL tetrahydrofuran (THF), 70 ℃ of stirring reaction 3h, add the excess ethanol precipitation polymers, filter, vacuum-drying 24h obtains the 0.42g poly(lactic acid), and its fusing point is 145 ℃.
Be standard substance with the polystyrene, utilize gel permeation chromatography that the poly(lactic acid) that obtains in the present embodiment is analyzed, the number-average molecular weight that obtains poly(lactic acid) is 2.96 ten thousand.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be apparent concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments herein.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the wideest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. chiral zinc compound, its chirality optical activity is S type or R type, shown in (I):
Wherein, R is the alkyl of C1～C5 or the alkoxyl group of C1～C10; R
1, R
2Or R
3Be independently selected from respectively-H ,-CH
3,-OCH
3,-CH
2CH
3,-CH (CH
3)
2,-C (CH
3)
3,-F ,-Cl ,-Br or-NO
2
2. the preparation method of a chiral zinc compound may further comprise the steps:
With the part shown in the formula (II) and Zn (R ')
2In organic solvent, react, obtain the chiral zinc compound shown in the formula (III); The chirality optical activity of the chiral zinc compound shown in the formula (III) is S type or R type; The chirality optical activity of the part shown in the described formula (II) is S type or R type;
（II）；
Wherein, R
1, R
2Or R
3Be independently selected from respectively-H ,-CH
3,-OCH
3,-CH
2CH
3,-CH (CH
3)
2,-C (CH
3)
3,-F ,-Cl ,-Br or-NO
2
R ' is the alkyl of C1～C5.
3. preparation method according to claim 2 is characterized in that, the part shown in the described formula (II) and Zn (R ')
2Mol ratio be 1:(1～3).
4. preparation method according to claim 2 is characterized in that, the temperature of described reaction is 70 ℃～100 ℃, and the time of reaction is 6～12h.
5. preparation method according to claim 2 is characterized in that, the preparation method of the part shown in the described formula (II) is:
With 2 of S type or R type, the 2'-diaminostilbene, the substituted benzene methyl ether reaction shown in 1'-naphthyl naphthalene and the formula V obtains the described part of formula (II); Described part has chirality;
In the formula V, R
1, R
2Or R
3Be independently selected from respectively-H ,-CH
3,-CH
2CH
3,-CH (CH
3)
2,-C (CH
3)
3,-F ,-Cl ,-Br or-NO
2
6. the preparation method of a chiral zinc compound may further comprise the steps:
Chiral zinc compound shown in the formula (III) and the monohydroxy-alcohol of C1～C10 are reacted in solvent, obtain the chiral zinc compound shown in the formula (IV); The chirality optical activity of the chiral zinc compound shown in the formula (IV) is S type or R type;
Wherein, wherein, R
1, R
2Or R
3Be independently selected from respectively-H ,-CH
3,-OCH
3,-CH
2CH
3,-CH (CH
3)
2,-C (CH
3)
3,-F ,-Cl ,-Br or-NO
2
R 〞 is the alkoxyl group of C1～C10.
7. preparation method according to claim 2 is characterized in that, the mol ratio of the monohydroxy-alcohol of the chiral zinc compound shown in the described formula (III) and C1～C10 is 1:(1～3).
8. the preparation method of a poly(lactic acid) may further comprise the steps:
Under the chiral zinc compound for catalysis effect shown in the formula (I), ring-opening polymerization takes place in rac-Lactide in organic solvent, obtain crystalline poly(lactic acid);
Described rac-Lactide is L type rac-Lactide, D type rac-Lactide or rac-lactide;
Wherein, R is the alkyl of C1～C5, the alkoxyl group of C1～C10;
R
1, R
2Or R
3Be independently selected from respectively-H ,-CH
3,-OCH
3,-CH
2CH
3,-CH (CH
3)
2,-C (CH
3)
3,-F ,-Cl ,-Br or-NO
2
9. preparation method according to claim 8 is characterized in that, the mol ratio of the described chiral zinc compound of described formula (I) and rac-Lactide is 1:50～1:400.
10. preparation method according to claim 8 is characterized in that, the temperature of reaction of described reaction is 50 ℃～110 ℃, and the reaction times is 0.5～5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310213520.6A CN103254220B (en) | 2013-05-31 | 2013-05-31 | The preparation method of Chiral zinc compound, its preparation method and poly(lactic acid) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310213520.6A CN103254220B (en) | 2013-05-31 | 2013-05-31 | The preparation method of Chiral zinc compound, its preparation method and poly(lactic acid) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103254220A true CN103254220A (en) | 2013-08-21 |
| CN103254220B CN103254220B (en) | 2015-10-07 |
Family
ID=48958481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310213520.6A Active CN103254220B (en) | 2013-05-31 | 2013-05-31 | The preparation method of Chiral zinc compound, its preparation method and poly(lactic acid) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103254220B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467503A (en) * | 2013-09-09 | 2013-12-25 | 中国科学院长春应用化学研究所 | Chiral aluminum compounds with binaphthyl derivatives and preparation method thereof, and preparation method of polylactic acid |
| CN103864659A (en) * | 2014-03-12 | 2014-06-18 | 华东理工大学 | Chiral imine phenol oxyl zinc and magnesium compound as well as preparation method and application thereof |
| CN104211929B (en) * | 2014-08-06 | 2016-01-13 | 中国科学院长春应用化学研究所 | A kind of organic zinc composition catalyst and method for making thereof and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050203A (en) * | 1988-08-08 | 1991-03-27 | 巴特尔纪念研究院 | Come from the degradable thermoplastic plastics of rac-Lactide |
| CN101492441A (en) * | 2006-01-27 | 2009-07-29 | 浙江海正生物材料股份有限公司 | Uses of benzoic acid stannous as catalyst |
| CN101909666A (en) * | 2007-11-13 | 2010-12-08 | 美敦力迷你迈德公司 | Antimicrobial coatings for medical devices and methods for making and using them |
-
2013
- 2013-05-31 CN CN201310213520.6A patent/CN103254220B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050203A (en) * | 1988-08-08 | 1991-03-27 | 巴特尔纪念研究院 | Come from the degradable thermoplastic plastics of rac-Lactide |
| CN101492441A (en) * | 2006-01-27 | 2009-07-29 | 浙江海正生物材料股份有限公司 | Uses of benzoic acid stannous as catalyst |
| CN101909666A (en) * | 2007-11-13 | 2010-12-08 | 美敦力迷你迈德公司 | Antimicrobial coatings for medical devices and methods for making and using them |
Non-Patent Citations (3)
| Title |
|---|
| TINA M. OVITT ET AL.: ""Stereochemistry of Lactide Polymerization with Chiral Catalysts: New Opportunities for Stereocontrol Using Polymer Exchange Mechanisms"", 《J. AM. CHEM. SOC.》 * |
| 华佳捷 等: ""低毒锌类催化剂制备聚乳酸的研究"", 《化学学报》 * |
| 孙俊全 等: ""乙酰基丙酮络合物催化合成聚乳酸"", 《功能高分子学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467503A (en) * | 2013-09-09 | 2013-12-25 | 中国科学院长春应用化学研究所 | Chiral aluminum compounds with binaphthyl derivatives and preparation method thereof, and preparation method of polylactic acid |
| CN103864659A (en) * | 2014-03-12 | 2014-06-18 | 华东理工大学 | Chiral imine phenol oxyl zinc and magnesium compound as well as preparation method and application thereof |
| CN103864659B (en) * | 2014-03-12 | 2016-06-29 | 华东理工大学 | Chiral imines phenol oxygen base zinc, magnesium compound and its preparation method and application |
| CN104211929B (en) * | 2014-08-06 | 2016-01-13 | 中国科学院长春应用化学研究所 | A kind of organic zinc composition catalyst and method for making thereof and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103254220B (en) | 2015-10-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cohen et al. | Copolymerization of cyclohexene oxide and carbon dioxide using (salen) Co (III) complexes: synthesis and characterization of syndiotactic poly (cyclohexene carbonate) | |
| Hung et al. | Efficient initiators for the ring‐opening polymerization of l‐lactide: Synthesis and characterization of NNO‐tridentate Schiff‐base zinc complexes | |
| Otero et al. | Neutral and cationic aluminum complexes supported by acetamidate and thioacetamidate heteroscorpionate ligands as initiators for ring-opening polymerization of cyclic esters | |
| Peckermann et al. | Indium complexes supported by 1, ω-dithiaalkanediyl-bridged bis (phenolato) ligands: synthesis, structure, and controlled ring-opening polymerization of L-lactide | |
| CN100393771C (en) | Schiff-base aluminium catalyst for lactide open-ring polymerization, and it spreparing method and use | |
| Kan et al. | Aluminum methyl, alkoxide and α-alkoxy ester complexes supported by 6, 6′-dimethylbiphenyl-bridged salen ligands: synthesis, characterization and catalysis for rac-lactide polymerization | |
| Yi et al. | Magnesium and calcium complexes containing biphenyl-based tridentate Iminophenolate Ligands for ring-opening polymerization of rac-Lactide | |
| Ghosh et al. | Gallium and indium complexes containing the bis (imino) phenoxide ligand: synthesis, structural characterization and polymerization studies | |
| CN103421034A (en) | Chiral aluminum compound and preparation method thereof and preparation method of polylactic acid | |
| Yi et al. | Magnesium complexes containing biphenyl-based tridentate imino-phenolate ligands for ring-opening polymerization of rac-lactide and α-methyltrimethylene carbonate | |
| CN103864659B (en) | Chiral imines phenol oxygen base zinc, magnesium compound and its preparation method and application | |
| Kireenko et al. | Aluminum complexes based on pyridine substituted alcohols: synthesis, structure, and catalytic application in ROP | |
| Gregson et al. | Titanium–salen complexes as initiators for the ring opening polymerisation of rac-lactide | |
| CN103254220B (en) | The preparation method of Chiral zinc compound, its preparation method and poly(lactic acid) | |
| Steiniger et al. | Synthesis, Structures, and Catalytic Activity of Homo‐and Heteroleptic Ketoiminate Zinc Complexes in Lactide Polymerization | |
| Schäfer et al. | Towards New Robust Zn (II) Complexes for the Ring‐Opening Polymerization of Lactide Under Industrially Relevant Conditions | |
| KR101217954B1 (en) | Group ３ post-metallocene complexes based on bis(naphthoxy)pyridine and bis(naphthoxy)thiophene ligands for the ring-opening polymerisation of polar cyclic monomers | |
| Gallegos et al. | Comparative study of lactide polymerization with lithium, sodium, potassium, magnesium, calcium, and zinc azonaphthoxide complexes | |
| CN104710447B (en) | A kind of preparation method of chiral aluminum complex containing pyrrole group and preparation method thereof and PLA | |
| Gowda et al. | Aryloxy and benzyloxy compounds of zirconium: Synthesis, structural characterization and studies on solvent-free ring-opening polymerization of ɛ-caprolactone and δ-valerolactone | |
| CN107417739B (en) | A kind of schiff bases iron compound, preparation method and its application as catalyst | |
| CN102757457B (en) | Schiff base aluminum compound and preparation method thereof, and preparation method of polylactic acid | |
| Ruiz et al. | Towards a selective synthetic route for cobalt amino acid complexes and their application in ring opening polymerization of rac-lactide | |
| Dammann et al. | Dinuclear tethered pyridine, diimine complexes | |
| Daneshmand et al. | Exploring the reactivity of manganese (iii) complexes with diphenolate-diamino ligands in rac-lactide polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210624 Address after: 241080 6th floor, building 4, Longhu new town south, Sanshan Economic Development Zone, Wuhu City, Anhui Province Patentee after: Pulis Biotechnology Co.,Ltd. Address before: 130022 No. 5625 Renmin Street, Jilin, Changchun Patentee before: Changchun Institute of Applied Chemistry Chinese Academy of Sciences |
|
| TR01 | Transfer of patent right |