CN105085560A - Aluminum compound based on pyrrole derivatives, preparation method of aluminum compound and polylactic acid preparation method - Google Patents

Aluminum compound based on pyrrole derivatives, preparation method of aluminum compound and polylactic acid preparation method Download PDF

Info

Publication number
CN105085560A
CN105085560A CN201510602740.7A CN201510602740A CN105085560A CN 105085560 A CN105085560 A CN 105085560A CN 201510602740 A CN201510602740 A CN 201510602740A CN 105085560 A CN105085560 A CN 105085560A
Authority
CN
China
Prior art keywords
aluminum compound
formula
preparation
och
poly
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.)
Pending
Application number
CN201510602740.7A
Other languages
Chinese (zh)
Inventor
高波
李东霓
李艳伟
李艳辉
段潜
王恒国
沈贤德
司振君
万玉春
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changchun University of Science and Technology
Original Assignee
Changchun University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Changchun University of Science and Technology filed Critical Changchun University of Science and Technology
Priority to CN201510602740.7A priority Critical patent/CN105085560A/en
Publication of CN105085560A publication Critical patent/CN105085560A/en
Pending legal-status Critical Current

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention provides an aluminum compound based on pyrrole derivatives, a preparation method of the aluminum compound and a polylactic acid preparation method. The molecular structure of the aluminum compound is shown as the formula (I). The aluminum compound is prepared through reaction of m-xylylenediamine and the pyrrole derivatives. On one hand, the aluminum compound serves as a catalyst with aluminum as central atoms and has high catalytic reaction activity during lactide ring-opening polymerization catalysis, and high polymerization reaction activity is obtained; on the other hand, a ligand has proper steric hindrance, an ideal stereoscopic effect is obtained, and stereoscopic selectivity of racemization lactide ring-opening polymerization is improved. The invention further provides the polylactic acid preparation method. Polylactic acid obtained by catalyzing racemic lactide through the aluminum compound is polylactic acid with isotactic heterogeneous major components, and polylactic acid with 72.0% of isotaxy components is obtained. Please see the formula in the specification.

Description

A kind of based on the preparation method of pyrrole derivative aluminum compound and preparation method thereof with poly(lactic acid)
Technical field
The invention belongs to catalytic field, particularly a kind of based on the preparation method of pyrrole derivative aluminum compound and preparation method thereof with poly(lactic acid).
Background technology
Poly(lactic acid) (being also polylactide) is a kind of environmentally friendly macromolecular material synthesized by chemistry or biological method, due to its biodegradability, CO2 emissions after a procedure as waste at least reduces 60% than the CO2 emissions of traditional general plastics, therefore, this material is widely used in packaging, bio-pharmaceuticals, medical treatment and industrial or agricultural field.Raw material in the present invention can come from the renewable resources of replacement petroleum resources as corn or beet; the poly(lactic acid) derived product of preparation can be that degradable plastics (replaces the non-degradable plastics such as conventional polyethylene; be conducive to protection of the environment); clinical nail; slow releasing pharmaceutical, tissue engineering bracket and operating sutures etc.Synthesizing polylactic acid generally takes two kinds of polyreaction modes, i.e. rac-Lactide (cyclic dimer of lactic acid) ring-opening polymerization and direct polycondensation of lactic acid reaction.Wherein, the poly(lactic acid) of high molecular is only by utilizing the mode of rac-Lactide ring-opening polymerization to obtain, have some documents at present and patent reports rac-Lactide ring-opening polymerization and prepare poly(lactic acid), such as patent publication No. is two parts of United States Patent (USP)s of 5235031 and 5357034.
There are three kinds of steric isomers in rac-Lactide: levorotatory lactide (LLA), dextrorotation rac-Lactide (DLA) and Study of Meso-Lactide (meso-LA), and its molecular formula is as figure below:
Levorotatory lactide and the dextrorotation rac-Lactide of equivalent are mixed to form rac-lactide.
The steric configuration of polylactide affects the mechanical property of macromolecular material, mechanical property and degradation property.The catalyzer that rac-Lactide ring-opening polymerization was used is in the past some tin compounds, as tin chloride and stannous octoate.Under tin compound catalysis, optically pure levorotatory lactide (L-LA), dextrorotation rac-Lactide (D-LA) respectively ring-opening polymerization obtains isotactic poly-levorotatory lactide and poly-dextrorotation rac-Lactide respectively, and two kinds of polylactides are the lower crystalline polymer of fusing point.But rac-lactide ring-opening polymerization under tin compound or aluminum isopropylate catalysis obtains is the random polylactide of amorphism.Compare with amorphism polylactide, use temperature a wider range of crystallinity polylactide, close to melt temperature.Therefore need exploitation one class to have stereoselective ring-opening polymerization catalyst to rac-lactide polymerization, catalysis rac-lactide is polymerized and obtains crystalline polylactic acid.
Up to the present, catalyzer about the ring-opening polymerization of rac-lactide stereoselectivity has some to report, nitrogenous Al catalysts (Salbinap) AlOMe reported as Spassky etc. is by 2,2'-diaminostilbene, 1'-naphthyl naphthalene and salicylic aldehyde condensation obtain part, and then react obtained with aluminum isopropylate; Tolman etc. report based on carbenes zinc catalyst, be that NCN carbenes and zinc ethyl react, then with benzylalcohol react obtain.But activity (monomer conversion 31 ~ 82%) and the stereoselectivity (59 ~ 70%) of the above catalyst rac-Lactide ring-opening polymerization reported are all lower.Also do not occur utilizing m-xylene diamine and pyrrole derivative to react in prior art and prepare aluminum compound containing pyrroles and use it for the report that catalyzing ring-opening polymerization of lactide prepares poly(lactic acid).
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of based on the preparation method of pyrrole derivative aluminum compound and preparation method thereof with poly(lactic acid), and this aluminum compound catalyzing ring-opening polymerization of lactide generates poly(lactic acid) and has high reaction activity and comparatively highly selective.
The invention provides a kind of based on pyrrole derivative aluminum compound, shown in (I):
In formula (I), R is-CH 3,-CH 2cH 3,-OCH 3,-OCH 2cH 3,-OCH 2cH 2cH 3,-OCH (CH 3) 2or-OCH 2ph, wherein Ph is aryl radical;
R 1, R 2and R 3independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-(CH 2) 3cH 3,-Cl ,-Br ,-NO 2,-SiPh 3,-Si (CH 2cH 3) 3,-Si (CH 3) 3or adamantyl, wherein Ph is aryl radical;
R 4be selected from-H or-CH 3.
The invention provides a kind of preparation method of the aluminum compound based on pyrrole derivative, comprise the following steps:
By the part of formula (II) structure and Al (R ') 3react in a solvent, obtain the aluminum compound of formula (III) structure:
R ' is-CH 3or-CH 2cH 3;
R 1, R 2and R 3independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-(CH 2) 3cH 3,-Cl ,-Br ,-NO 2,-SiPh 3,-Si (CH 2cH 3) 3,-Si (CH 3) 3or adamantyl, wherein Ph is aryl radical;
R 4be selected from-H or-CH 3.
Preferably, also comprise: the aluminum compound of described formula (III) structure and R 〞 H are reacted in a solvent, obtains the aluminum compound of formula (IV) structure;
R 〞 is-OCH 3,-OCH 2cH 3,-OCH 2cH 2cH 3,-OCH (CH 3) 2or-OCH 2ph, wherein Ph is aryl radical;
R 1, R 2and R 3independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-(CH 2) 3cH 3,-Cl ,-Br ,-NO 2,-SiPh 3,-Si (CH 2cH 3) 3,-Si (CH 3) 3or adamantyl, wherein Ph is aryl radical;
R 4be selected from-H or-CH 3.
Preferably, the part of described formula (II) structure and Al (R ') 3mol ratio be 1:1.
Preferably, the part of described formula (II) structure and Al (R ') 3the temperature of reaction of reaction is 50 DEG C ~ 110 DEG C, and the reaction times is 3 ~ 40h.
Preferably, the aluminum compound of described formula (III) structure and the mol ratio of R 〞 H are 1:1.
Preferably, the part of described formula (II) structure is prepared according to following steps:
The pyrrole derivative replaced in formula (V) and formula (VI) m-xylene diamine are reacted the new part of one that generation obtains formula (II) structure;
Formula (V), R 1, R 2and R 3independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-(CH 2) 3cH 3,-Cl ,-Br ,-NO 2,-SiPh 3,-Si (CH 2cH 3) 3,-Si (CH 3) 3or adamantyl, wherein Ph is aryl radical;
R 4be selected from-H or-CH 3;
The invention provides a kind of preparation method of poly(lactic acid), comprise the following steps:
The aluminum compound of rac-Lactide and formula (I) structure is reacted in a solvent, obtains poly(lactic acid);
In formula (I), R is-CH 3,-CH 2cH 3,-OCH 3,-OCH 2cH 3,-OCH 2cH 2cH 3,-OCH (CH 3) 2or-OCH 2ph, wherein Ph is aryl radical;
R 1, R 2and R 3independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-(CH 2) 3cH 3,-Cl ,-Br ,-NO 2,-SiPh 3,-Si (CH 2cH 3) 3,-Si (CH 3) 3or adamantyl, wherein Ph is aryl radical;
R 4be selected from-H or-CH 3.
Preferably, the aluminum compound of described formula (I) structure and the mol ratio of rac-Lactide are 1:50 ~ 1:500.
Preferably, it is 20 DEG C ~ 110 DEG C that temperature is carried out in the reaction of described polyreaction, and the reaction times is 18 ~ 96h.
Beneficial effect of the present invention
The invention provides a kind of based on pyrrole derivative aluminum compound, the structure of this aluminum compound is such as formula shown in (I).Compound in structural formula of the present invention (I) has large volume on the one hand and obtains large sterically hindered, makes it to the Selective long-range DEPT of rac-Lactide ring-opening polymerization, improves the three-dimensional regularity of polymerisate space structure; Centered by metallic aluminium, atom also enhances the catalytic performance of the polyreaction of catalyzer on the other hand.
The present invention also provides a kind of preparation method based on pyrrole derivative aluminum compound, this aluminum compound utilizes m-xylene diamine and pyrrole derivative to react obtained first, the method preparation flow is simple, and the aluminum compound catalysis poly(lactic acid) prepared has comparatively high reaction activity and selectivity.
The present invention also provides a kind of preparation method of poly(lactic acid), the aluminum compound of rac-Lactide and formula (I) structure reacts and obtains by this method in a solvent, experimental result shows that the poly(lactic acid) that aluminum compound catalysis rac-lactide of the present invention obtains is the full poly(lactic acid) accounting for main component with isomery, the polymkeric substance that the aluminum isopropylate catalyzing ring-opening polymerization of lactide that selectivity ratios is commonly used obtains is well a lot, and the poly(lactic acid) isotaxy composition obtained can reach for 72.0% (as described in Example 17).
Accompanying drawing explanation
Fig. 1 is the same core decoupling nucleus magnetic hydrogen spectrum (CDCl that poly(lactic acid) is prepared in the ring-opening polymerization of aluminum isopropylate catalysis rac-lactide 3).
Fig. 2 is the same core decoupling nucleus magnetic hydrogen spectrum (CDCl of the poly(lactic acid) of preparation in embodiment 17 3).
Fig. 3 is the nucleus magnetic hydrogen spectrum figure (CDCl of the poly(lactic acid) of preparation in embodiment 20 3).
Embodiment
The invention provides a kind of aluminum compound containing pyrrole group, its structure is such as formula shown in (I):
In formula (I), R is-CH 3,-CH 2cH 3,-OCH 3,-OCH 2cH 3,-OCH 2cH 2cH 3,-OCH (CH 3) 2or-OCH 2ph, wherein Ph is aryl radical;
R 1, R 2and R 3independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-(CH 2) 3cH 3,-Cl ,-Br ,-NO 2,-SiPh 3,-Si (CH 2cH 3) 3,-Si (CH 3) 3or adamantyl, wherein Ph is aryl radical;
R 4be selected from-H or-CH 3.
In the present invention, centered by the aluminum compound one side metallic aluminium in structural formula (I), catalyst atom has greater catalytic reactive behavior, obtains comparatively satisfied polymerization activity; Having applicable volume obtains desirable steric restriction on the other hand, makes enhancing to the selectivity of rac-Lactide ring-opening polymerization, directly obtains the regularity of higher polymerisate three-dimensional arrangement.
Selectively, when R is-CH 3or-CH 2cH 3time, the invention provides a kind of preparation method based on pyrrole derivative aluminum compound, comprise the following steps: by the part of formula (II) structure and Al (R ') 3react in a solvent, obtain the aluminum compound of formula (III) structure.Wherein, described solvent is organic solvent well known to those skilled in the art, is preferably tetrahydrofuran (THF) or toluene.
R 1,r 2,r 3and R 4selection affect the selection of solvent, work as R 1,r 2and R 3be selected from-H ,-Cl ,-Br or-NO 2, R 4be selected from-H or-CH 3time, reaction solvent is preferably tetrahydrofuran (THF); R 1, R 2and R 3independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-(CH 2) 3cH 3,-Cl ,-Br ,-NO 2,-SiPh 3,-Si (CH 2cH 3) 3,-Si (CH 3) 3or adamantyl, wherein Ph is aryl radical, and wherein Ph is aryl radical, R 4be selected from-H or-CH 3time, reaction solvent is preferably toluene.
R ' is-CH 3or-CH 2cH 3;
R 1, R 2and R 3independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-(CH 2) 3cH 3,-Cl ,-Br ,-NO 2,-SiPh 3,-Si (CH 2cH 3) 3,-Si (CH 3) 3or adamantyl, wherein Ph is aryl radical;
R 4be selected from-H or-CH 3.
Al described in the present invention (R ') 3be preferably Al (CH 3) 3or Al (CH 2cH 3) 3.R ' in formula (III) is from Al (R ') 3.Described Al (R ') 3be preferably 1:1 with the mol ratio of formula (II) structural compounds, the compounds of this invention is metallic compound, and this ratio can ensure that a metal active centres forms coordinate bond with two C=N functional groups simultaneously.
Described part and Al (R ') 3the temperature of reaction of reaction is preferably 70 ~ 90 DEG C, and the selection of reaction solvent is depended in the selection of temperature, is more preferably 72 ~ 86 DEG C, and the reaction times is 10 ~ 40h, is preferably 32h.
Wherein, the part of described formula (II) structure is preferably prepared according to following steps: m-xylene diamine in the pyrrole derivative replaced in formula (V) and formula (VI) is reacted the class part that generation obtains formula (II) structure;
In formula (V), R 1, R 2and R 3independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-(CH 2) 3cH 3,-Cl ,-Br ,-NO 2,-SiPh 3,-Si (CH 2cH 3) 3,-Si (CH 3) 3or adamantyl, wherein Ph is aryl radical;
R 4be selected from-H or-CH 3.
M-xylene diamine in the pyrrole derivative replaced in formula (V) and formula (VI) is reacted, back flow reaction 5 ~ 14h in dehydrated alcohol, be preferably 8h, the mol ratio of the pyrrole derivative replaced in described formula (V) and the middle m-xylene diamine of formula (VI) is 2:1 ~ 3:1, is preferably 2.5:1.
Selectively, when R is-OCH 3,-OCH 2cH 3,-OCH 2cH 2cH 3,-OCH (CH 3) 2or-OCH 2during Ph, the invention provides the another kind of preparation method based on pyrrole derivative aluminum compound, this preparation method continues reaction on the basis of the aluminum compound preparation process of above-mentioned formula (III) structure, obtains the aluminum compound that substituted radical is different.This preparation method is on the basis of above-mentioned steps, further comprising the steps of: the aluminum compound of described formula (III) structure and R 〞 H are reacted in a solvent, obtain the aluminum compound of formula (IV) structure.Described solvent is organic solvent well known to those skilled in the art, is preferably tetrahydrofuran (THF) or toluene.Described R 〞 H is preferably CH 3oH, CH 3cH 2oH, CH 3cH 2cH 2oH, (CH 3) 2cHOH or PhCH 2oH.
R 〞 is-OCH 3,-OCH 2cH 3,-OCH 2cH 2cH 3,-OCH (CH 3) 2or-OCH 2ph;
R 1, R 2and R 3independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-(CH 2) 3cH 3,-Cl ,-Br ,-NO 2,-SiPh 3,-Si (CH 2cH 3) 3,-Si (CH 3) 3or adamantyl, wherein Ph is aryl radical;
R 4be selected from-H or-CH 3.
Wherein, the mol ratio of described R 〞 H and formula (III) structure aluminum compound is preferably 1:1.
The temperature that described formula (III) structure aluminum compound and R 〞 H react is preferably 25 ~ 100 DEG C, and be more preferably 70 DEG C, the reaction times is preferably 1.0 ~ 18h, is more preferably 8h.
Present invention also offers a kind of preparation method of poly(lactic acid), comprise the following steps: the aluminum compound of rac-Lactide and formula (I) structure is reacted in a solvent, obtains poly(lactic acid).Described solvent is organic solvent well known to those skilled in the art, is preferably tetrahydrofuran (THF) or toluene.
Wherein, formula (I) structure aluminum compound is the catalyzer that rac-Lactide polymerization generates in poly(lactic acid) reaction.The mol ratio of this catalyzer and rac-Lactide is 1:50 ~ 1:500, preferably 1:50 ~ 1:300.
In the present invention, the temperature of reaction of rac-Lactide polyreaction is 40 ~ 110 DEG C, and the reaction times is 20 ~ 96h, preferably 24 ~ 80h.This reaction is preferably carried out under the condition of anhydrous and oxygen-free, can reduce the generation of side reaction.
In order to further illustrate the present invention, be described in detail the invention provides a kind of preparation method based on pyrrole derivative aluminum compound and preparation method thereof and poly(lactic acid) below in conjunction with embodiment.
Reagent used in following examples is commercially available.
Embodiment 1 structural formula is the synthesis of the ligand i Ia of II
IIa:R 1＝R 2＝R 3＝R 4＝-H
Under nitrogen protection, by Va (R in V formula 1=R 2=R 3=R 4=-H, 0.238g, being dissolved in 15mL dehydrated alcohol of m-xylene diamine (0.136g, 1.00mmol) 2.50mmol) and in VI formula, after being heated to backflow 8h. cool to room temperature, concentrated, the thick product of gained uses column chromatography, and eluent is sherwood oil: ethyl acetate (volume ratio is 12:1), and obtaining straight product IIa is yellow solid, output is 0.233g, and productive rate is 80.5%.
Utilize mass spectrograph to analyze the ligand i Ia obtained in embodiment 1, obtain result: MZNDI-TOF (THF), m/z=290.30.
Utilize ultimate analysis to analyze the ligand i Ia obtained in embodiment 1, obtain result:
Elem.Anal.Calc.(％):C,74.46；H,6.25；N,19.30.Found:C,74.39；H,6.21；N,19.17.
Embodiment 2 structural formula is the synthesis of the ligand i Ib of II
IIb：R 1＝R 2＝R 3＝-CH 3,R 4＝-H
Under nitrogen protection, by Vb (R in V formula 1=R 2=R 3=-Me, R 4=-H, 0.343g, 2.50mmol) and VI formula in being dissolved in 20mL toluene of m-xylene diamine (0.136g, 1.00mmol), add the p-methyl benzenesulfonic acid of catalytic amount, be heated to the 12h that refluxes.After cool to room temperature, concentrated, the thick product of gained uses column chromatography, and eluent is sherwood oil: ethyl acetate (volume ratio is 18:1), obtaining straight product IIb is yellow solid, and output is 0.289g, and productive rate is 77.3%.
Utilize mass spectrograph to analyze the ligand i Ib obtained in embodiment 2, obtain result: MZNDI-TOF (THF), m/z=374.20.
Utilize ultimate analysis to analyze the ligand i Ib obtained in embodiment 2, obtain result:
Elem.Anal.Calc.(％):C,76.97；H,8.07；N,14.96.Found:C,76.90；H,8.02；N,14.85.
Embodiment 3 structural formula is the synthesis of the ligand i Ic of II
IIc：R 1＝- tBu,R 2＝R 3＝-H,R 4＝-CH 3
By Vc (R in V formula 1=- tbu, R 2=R 3=-H, R 4=-CH 3, 0.413g, 2.50mmol) and VI formula in m-xylene diamine (0.136g, 1.00mmol) be dissolved in 20.0mL toluene, add the p-methyl benzenesulfonic acid of catalytic amount, be heated to reflux 18h.Concentrated, the thick product of gained uses column chromatography, and eluent is sherwood oil: ethyl acetate (volume ratio is 20:1), obtaining straight product IIc is yellow solid, and output is 0.326, and productive rate is 75.7%.
Utilize mass spectrograph to analyze the ligand i Ic obtained in embodiment 3, obtain result: MZNDI-TOF (THF), m/z=430.3.
Utilize ultimate analysis to analyze the ligand i Ic obtained in embodiment 3, obtain result:
Elem.Anal.Calc.(％):C,78.10；H,8.89；N,13.01.Found:C,78.17；H,8.94；N,13.11.
Embodiment 4 structural formula is the synthesis of the aluminum compound Ia-1 ~ Ia-3 of I
Ia-1：R 1＝R 2＝R 3＝R 4＝-H，R＝-CH 3；
Ia-2：R 1＝R 2＝R 3＝R 4＝-H，R＝-OCH(CH 3) 2；
Ia-3：R 1＝R 2＝R 3＝R 4＝-H，R＝-OCH 2Ph。
4.1 under high pure nitrogen protection, is that IIa tetrahydrofuran solution and the 5.0mL concentration of 2.0mol/L is the AlMe of 2.0mol/L by 5.0mL concentration 3tetrahydrofuran solution mix and blend, 35 DEG C of reaction 12h, are down to room temperature, remove volatile matter, obtain aluminum compound Ia-1 through cold well decompression.
The aluminum compound Ia-1 obtained in 10.0mmol4.1 is dissolved in toluene by 4.2, adds 10.0mmol Virahol, obtains aluminum compound Ia-2.
The aluminum compound Ia-1 obtained in 10.0mmol4.1 is dissolved in toluene by 4.3, adds 10.0mmol phenylcarbinol, obtains aluminum compound Ia-3.Utilize ultimate analysis to analyze the aluminum compound Ia-1 ~ Ia-3 obtained in embodiment 4, the constituent content obtaining them is respectively:
Ia-1:Elem.Anal.Calc.(％):C,69.08；H,5.80；N,16.96.Found:C,66.14；H,5.91；N,17.10.
Ia-2:Elem.Anal.Calc.(％):C,67.36；H,6.19；N,14.96.Found:67.44；H,6.15；N,15.02.
Ia-3:Elem.Anal.Calc.(％):C,71.08；H,5.49；N,13.26.Found:C,71.11；H,5.52；N,13.29.
Embodiment 5 structural formula is the aluminum compound Ib-1 ~ Ib-3 of I
Ib-1：R 1＝R 2＝R 3＝-CH 3,R 4＝-H,R＝-CH 3；
Ib-2：R 1＝R 2＝R 3＝-CH 3,R 4＝-H,R＝-OCH(CH 3) 2；
Ib-3：R 1＝R 2＝R 3＝-CH 3,R 4＝-H,R＝-OCH 2Ph.
The preparation method of 5.1 aluminum compound Ib-1 is identical with Ia-1, and wherein difference is: IIa tetrahydrofuran solution is changed to IIb tetrahydrofuran solution.
The aluminum compound Ib-1 obtained in 10mmol5.1 is dissolved in toluene by 5.2, adds 10mmol Virahol, obtains aluminum compound Ib-2.
The aluminum compound Ib-1 obtained in 10mmol5.1 is dissolved in toluene by 5.3, adds 10mmol benzylalcohol, obtains aluminum compound Ib-3.
Utilize ultimate analysis to analyze the aluminum compound Ib-1 ~ Ib-3 obtained in embodiment 5, the constituent content obtaining them is respectively:
Ib-1:Elem.Anal.Calc.(％):C,72.44；H,7.54；N,13.52.Found:C,72.35；H,7.47；N,13.46.
Ib-2:Elem.Anal.Calc.(％):C,70.72；H,7.69；N,12.22.Found:C,70.65；H,7.63；N,12.14.
Ib-3:Elem.Anal.Calc.(％):C,73.49；H,6.96；N,11.06.Found:C,73.55；H,6.89；N,11.00.
Embodiment 6 structural formula is the aluminum compound Ic-1 ~ Ic-3 of I
Ic-1：R 1＝- tBu,R 2＝R 3＝-H,R 4＝-CH 3，R＝-CH 3；
Ic-2：R 1＝- tBu,R 2＝R 3＝-H,R 4＝-CH 3，R＝-OCH(CH 3) 2；
Ic-3：R 1＝- tBu,R 2＝R 3＝-H,R 4＝-CH 3，R＝-OCH 2Ph。
The preparation method of 6.1 aluminum compound Ic-1 is identical with Ia-1, and wherein difference is: the tetrahydrofuran solution tetrahydrofuran solution of IIa being changed to IIc.
The aluminum compound Ic-1 obtained in 8mmol6.1 is dissolved in toluene by 6.2, adds 8mmol Virahol, obtains aluminum compound Ic-2.
The aluminum compound Ic-1 obtained in 8mmol6.1 is dissolved in toluene by 6.3, adds 8mmol benzylalcohol, obtains aluminum compound Ic-3.
Utilize ultimate analysis to analyze the aluminum compound Ic-1 ~ Ic-3 obtained in embodiment 6, the constituent content obtaining them is respectively:
Ic-1:Elem.Anal.Calc.(％):C,74.01；H,8.35；N,11.90.Found:C,74.12；H,8.47；N,11.82.
Ic-2:Elem.Anal.Calc.(％):C,72.34；H,8.42；N,10.89.Found:C,72.24；H,8.31；N,10.77.
Ic-3:Elem.Anal.Calc.(％):C,74.70；H,7.70；N,9.96.Found:C,74.81；H,7.82；N,9.84.
Embodiment 7
Under the condition of anhydrous and oxygen-free, by the rac-lactide that 5.00mmol recrystallization is crossed, the aluminum compound Ia-1 obtained in 0.05mmol embodiment 4 is dissolved in the tetrahydrofuran (THF) of 100mL, 70 DEG C of stirring reaction 20h, add ice-cold ethanol cancellation and be obtained by reacting white polymer, filter, vacuum-drying 35h, obtain 0.705g poly(lactic acid), monomer conversion is 98.1%.
Be marker with polystyrene, utilize gel permeation chromatography (GPC) to analyze the poly(lactic acid) obtained in embodiment 7, the number-average molecular weight obtaining poly(lactic acid) is 2.38 ten thousand.
Embodiment 8
Under the condition of anhydrous and oxygen-free, by the rac-lactide that 5.00mmol recrystallization is crossed, the aluminum compound Ia-2 obtained in 0.05mmol embodiment 4 is dissolved in the tetrahydrofuran (THF) of 100mL, 70 DEG C of stirring reaction 20h, add ice-cold ethanol cancellation and be obtained by reacting polymkeric substance, filter, vacuum-drying 36h, obtain 0.704g poly(lactic acid), monomer conversion is 97.8%.
Be standard substance with polystyrene, utilize gel permeation chromatography to analyze the poly(lactic acid) obtained in embodiment 8, the number-average molecular weight obtaining poly(lactic acid) is 2.30 ten thousand.
Embodiment 9
Preparation method is identical with embodiment 8, and difference is that catalyzer is the aluminum compound Ia-3 obtained in embodiment 4, and obtain 0.693g poly(lactic acid), monomer conversion is 96.3%.
Be marker with polystyrene, utilize gel permeation chromatography to analyze the poly(lactic acid) obtained in embodiment 9, the number-average molecular weight obtaining poly(lactic acid) is 2.41 ten thousand.
Embodiment 10
Under the condition of anhydrous and oxygen-free, the aluminum compound Ib-1 obtained in the rac-lactide crossed by 3.50mmol recrystallization, 0.07mmol embodiment 5 mixes with 70mL tetrahydrofuran (THF), 70 DEG C of stirring reaction 40h, add ice-cold ethanol cancellation and be obtained by reacting polymkeric substance, filter, vacuum-drying 35h, obtains 0.483g poly(lactic acid), and monomer conversion is 95.9%.
Be standard substance with polystyrene, utilize gel permeation chromatography to analyze the poly(lactic acid) obtained in embodiment 10, the number-average molecular weight obtaining poly(lactic acid) is 1.45 ten thousand.
Embodiment 11
Preparation method is identical with embodiment 10, and difference is that catalyzer is the aluminum compound Ib-2 obtained in enforcement 5, and obtain 0.490g poly(lactic acid), monomer conversion is 97.0%.
Be marker with polystyrene, utilize gel permeation chromatography to analyze the poly(lactic acid) obtained in embodiment 11, the number-average molecular weight obtaining poly(lactic acid) is 1.60 ten thousand.
Embodiment 12
Preparation method is identical with embodiment 10, and difference is that catalyzer is the aluminum compound Ib-3 obtained in embodiment 5, and obtain 0.477g poly(lactic acid), monomer conversion is 94.7%.
Be marker with polystyrene, utilize gel permeation chromatography to analyze the poly(lactic acid) obtained in embodiment 12, the number-average molecular weight obtaining poly(lactic acid) is 1.52 ten thousand.
Embodiment 13
Under the condition of anhydrous and oxygen-free, the aluminum compound Ib-1 obtained in the rac-lactide crossed by 40.0mmol recrystallization, 0.08mmol embodiment 5 is dissolved in 200mL toluene, 100 DEG C of stirring reaction 48h, add ice-cold ethanol cancellation and be obtained by reacting polymkeric substance, filter, vacuum-drying 35h, obtains 5.20g poly(lactic acid), and monomer conversion is 90.3%.
Be standard substance with polystyrene, utilize gel permeation chromatography to analyze the poly(lactic acid) obtained in embodiment 13, the number-average molecular weight obtaining poly(lactic acid) is 8.13 ten thousand.
Embodiment 14
Preparation method is identical with embodiment 13, and difference is that catalyzer is the aluminum compound Ib-2 obtained in embodiment 5, and obtain 5.11g poly(lactic acid), monomer conversion is 88.7%.
Be standard substance with polystyrene, utilize gel permeation chromatography to analyze the poly(lactic acid) obtained in embodiment 14, the number-average molecular weight obtaining poly(lactic acid) is 7.99 ten thousand.
Embodiment 15
Preparation method is identical with embodiment 14, and difference is that catalyzer is the aluminum compound Ib-3 obtained in embodiment 5, and obtain 5.31g poly(lactic acid), monomer conversion is 92.3%.
Be marker with polystyrene, utilize gel permeation chromatography to analyze the poly(lactic acid) obtained in the present embodiment, the number-average molecular weight obtaining poly(lactic acid) is 7.34 ten thousand.
Embodiment 16
Preparation method is identical with embodiment 13, and difference is that catalyzer is the aluminum compound Ib-3 obtained in embodiment 5, and obtain 5.35g poly(lactic acid), monomer conversion is 92.9%.
Be standard substance with polystyrene, utilize gel permeation chromatography to analyze the poly(lactic acid) obtained in embodiment 16, the number-average molecular weight obtaining poly(lactic acid) is 7.42 ten thousand.
Embodiment 17
Under the condition of anhydrous and oxygen-free, the aluminum compound Ic-1 obtained in the rac-lactide crossed by 5.0mmol recrystallization, 0.05mmol embodiment 6 is dissolved in 50.0mL toluene, 80 DEG C of stirring reaction 56h, add ice-cold ethanol cancellation and be obtained by reacting polymkeric substance, filter, vacuum-drying 35h, obtains 6.98g poly(lactic acid), and monomer conversion is 97.0%.
The stereoselectivity of aluminum compound catalysis rac-lactide polymerization of the present invention can be confirmed by same core decoupling nucleus magnetic hydrogen spectrum, shown in Fig. 1 and Fig. 2, Fig. 1 be the poly(lactic acid) that the ring-opening polymerization of aluminum isopropylate catalysis rac-lactide obtains same core decoupling nucleus magnetic hydrogen spectrum (25 DEG C, CDCl 3), the non-constant of selectivity; Fig. 2 be the poly(lactic acid) obtained in embodiment 17 same core decoupling nucleus magnetic hydrogen spectrum (25 DEG C, CDCl 3).Can calculate from Fig. 1 and Fig. 2, the poly(lactic acid) isotaxy composition obtained in embodiment 17 is 72.0%, illustrates that aluminum compound catalysis poly(lactic acid) of the present invention has higher selectivity.
Be standard substance with polystyrene, utilize gel permeation chromatography to analyze the poly(lactic acid) obtained in embodiment 17, the number-average molecular weight obtaining poly(lactic acid) is 2.45 ten thousand.
Embodiment 18
Preparation method is identical with embodiment 17, and difference is that catalyzer is the aluminum compound Ic-2 obtained in embodiment 6, and obtain 6.41g poly(lactic acid), monomer conversion is 89.1%.。
Be standard substance with polystyrene, utilize gel permeation chromatography to analyze the poly(lactic acid) obtained in embodiment 18, the number-average molecular weight obtaining poly(lactic acid) is 2.40 ten thousand.
Embodiment 19
Preparation method is identical with embodiment 17, and difference is that catalyzer is the aluminum compound Ic-3 obtained in embodiment 6, and obtain 6.60g poly(lactic acid), monomer conversion is 91.7%.
Be standard substance with polystyrene, utilize gel permeation chromatography to analyze the poly(lactic acid) obtained in embodiment 19, the number-average molecular weight obtaining poly(lactic acid) is 2.35 ten thousand.
Embodiment 20
Under the condition of anhydrous and oxygen-free, the aluminum compound Ic-2 obtained in 5.0mmol levorotatory lactide, 0.10mmol embodiment 18 is dissolved in 100mL tetrahydrofuran (THF), after 60 DEG C of stirring reaction 120h, add in the ethanol of 2 degrees centigrade and obtain polymkeric substance after sedimentation, filter, vacuum-drying 35h, obtains 0.71g poly(lactic acid), and monomer conversion is 98.6%.300,000,000 nucleus magnetic hydrogen spectrums of poly(lactic acid) are shown in Fig. 3, and condition is CDCl 3as deuterated solvent, test at 25 DEG C.
Be standard substance with polystyrene, utilize gel permeation chromatography to analyze the poly(lactic acid) obtained in embodiment 20, the number-average molecular weight obtaining poly(lactic acid) is 1.21 ten thousand, and fusing point is 178.2 DEG C.
The above is only the preferred embodiments of the invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (10)

1. based on an aluminum compound for pyrrole derivative, shown in (I):
In formula (I), R is-CH 3,-CH 2cH 3,-OCH 3,-OCH 2cH 3,-OCH 2cH 2cH 3,-OCH (CH 3) 2or-OCH 2ph, wherein Ph is aryl radical;
R 1, R 2and R 3independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-(CH 2) 3cH 3,-Cl ,-Br ,-NO 2,-SiPh 3,-Si (CH 2cH 3) 3,-Si (CH 3) 3or adamantyl, wherein Ph is aryl radical;
R 4be selected from-H or-CH 3.
2. based on a preparation method for pyrrole derivative aluminum compound, it is characterized in that, comprise the following steps:
By the part of formula (II) structure and Al (R ') 3react in a solvent, obtain the aluminum compound of formula (III) structure:
R ' is-CH 3or-CH 2cH 3;
R 1, R 2and R 3independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-(CH 2) 3cH 3,-Cl ,-Br ,-NO 2,-SiPh 3,-Si (CH 2cH 3) 3,-Si (CH 3) 3or adamantyl, wherein Ph is aryl radical;
R 4be selected from-H or-CH 3.
3. a kind of preparation method based on pyrrole derivative aluminum compound according to claim 2, is characterized in that, further comprising the steps of:
By the aluminum compound of described formula (III) structure and R, " H reacts in a solvent, obtains the aluminum compound of formula (IV) structure;
R 〞 is-OCH 3,-OCH 2cH 3,-OCH 2cH 2cH 3,-OCH (CH 3) 2or-OCH 2ph, wherein Ph is aryl radical; R 1, R 2and R 3independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-(CH 2) 3cH 3,-Cl ,-Br ,-NO 2,-SiPh 3,-Si (CH 2cH 3) 3,-Si (CH 3) 3or adamantyl, wherein Ph is aryl radical;
R 4be selected from-H or-CH 3.
4. a kind of preparation method based on pyrrole derivative aluminum compound according to claim 2, is characterized in that, the part of described formula (II) structure and Al (R ') 3mol ratio be 1:1.
5. a kind of preparation method based on pyrrole derivative aluminum compound according to claim 2, is characterized in that, the part of described formula (II) structure and Al (R ') 3the temperature of reaction of reaction is 20 ~ 110 DEG C, and the reaction times is 2 ~ 80h.
6. a kind of preparation method based on pyrrole derivative aluminum compound according to claim 3, is characterized in that, the aluminum compound of described formula (III) structure and the mol ratio of R 〞 H are 1:1.
7. a kind of preparation method based on pyrrole derivative aluminum compound according to claim 2, is characterized in that, the part of described formula (II) structure is prepared according to following steps:
M-xylene diamine in the pyrrole derivative replaced in formula (V) and formula (VI) is reacted the part that generation obtains formula (II) structure;
In formula (V), R 1, R 2and R 3independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-(CH 2) 3cH 3,-Cl ,-Br ,-NO 2,-SiPh 3,-Si (CH 2cH 3) 3,-Si (CH 3) 3or adamantyl, wherein Ph is aryl radical; R 4be selected from-H or-CH 3.
8. a preparation method for poly(lactic acid), is characterized in that, comprises following steps:
The aluminum compound of rac-Lactide and formula (I) structure is reacted in a solvent, obtains poly(lactic acid);
In formula (I), R is-CH 3,-CH 2cH 3,-OCH 3,-OCH 2cH 3,-OCH 2cH 2cH 3,-OCH (CH 3) 2or-OCH 2ph, wherein Ph is aryl radical;
R 1, R 2and R 3independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-(CH 2) 3cH 3,-Cl ,-Br ,-NO 2,-SiPh 3,-Si (CH 2cH 3) 3,-Si (CH 3) 3or adamantyl, wherein Ph is aryl radical;
R 4be selected from-H or-CH 3.
9. the preparation method of a kind of poly(lactic acid) according to claim 8, is characterized in that, the aluminum compound of formula (I) structure and the mol ratio of rac-Lactide are 1:50 ~ 1:500.
10. the preparation method of a kind of poly(lactic acid) according to claim 8, is characterized in that, temperature of reaction is 40 ~ 110 DEG C, and the reaction times is 10 ~ 96h.
CN201510602740.7A 2015-09-21 2015-09-21 Aluminum compound based on pyrrole derivatives, preparation method of aluminum compound and polylactic acid preparation method Pending CN105085560A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510602740.7A CN105085560A (en) 2015-09-21 2015-09-21 Aluminum compound based on pyrrole derivatives, preparation method of aluminum compound and polylactic acid preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510602740.7A CN105085560A (en) 2015-09-21 2015-09-21 Aluminum compound based on pyrrole derivatives, preparation method of aluminum compound and polylactic acid preparation method

Publications (1)

Publication Number Publication Date
CN105085560A true CN105085560A (en) 2015-11-25

Family

ID=54566972

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510602740.7A Pending CN105085560A (en) 2015-09-21 2015-09-21 Aluminum compound based on pyrrole derivatives, preparation method of aluminum compound and polylactic acid preparation method

Country Status (1)

Country Link
CN (1) CN105085560A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108191904A (en) * 2018-01-03 2018-06-22 长春理工大学 A kind of achirality aluminium compound and its synthetic method and polylactic acid synthetic method
CN115521329A (en) * 2022-08-30 2022-12-27 山东理工大学 Catalyst for lactide ring-opening polymerization and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101302181A (en) * 2007-05-09 2008-11-12 北京化工大学 Synthesis and application of four-chelate diamine pyrrole ligand compound
CN101704831A (en) * 2009-11-04 2010-05-12 北京师范大学 Chiral aluminum complex, preparation method thereof and application thereof in catalyzing stereoselectivity polymerization of lactide
CN104710447A (en) * 2015-03-13 2015-06-17 长春理工大学 Pyrrole group-containing chiral aluminum complex and preparation method thereof as well as preparation method of polylactic acid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101302181A (en) * 2007-05-09 2008-11-12 北京化工大学 Synthesis and application of four-chelate diamine pyrrole ligand compound
CN101704831A (en) * 2009-11-04 2010-05-12 北京师范大学 Chiral aluminum complex, preparation method thereof and application thereof in catalyzing stereoselectivity polymerization of lactide
CN104710447A (en) * 2015-03-13 2015-06-17 长春理工大学 Pyrrole group-containing chiral aluminum complex and preparation method thereof as well as preparation method of polylactic acid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HONGZHI DU ET AL.: "Polymerization of Lactide Using Achiral Bis(pyrrolidene) Schiff BaseAluminum Complexes", 《MACROMOLECULES》 *
HUGO F.SAUCEDO AZPEITIA ET AL.: "Synthesis and characterization of aluminum complexes incorporating Schiff base ligands derived from pyrrole-2-carboxaldehyde", 《MAIN GROUP CHEMISTRY》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108191904A (en) * 2018-01-03 2018-06-22 长春理工大学 A kind of achirality aluminium compound and its synthetic method and polylactic acid synthetic method
CN115521329A (en) * 2022-08-30 2022-12-27 山东理工大学 Catalyst for lactide ring-opening polymerization and preparation method and application thereof
CN115521329B (en) * 2022-08-30 2023-08-15 山东理工大学 Catalyst for lactide ring-opening polymerization and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN103421034B (en) The preparation method of Chiral aluminum compound and preparation method thereof and poly(lactic acid)
Garces et al. Heteroscorpionate magnesium alkyls bearing unprecedented apical σ-C (sp3)–Mg bonds: heteroselective ring-opening polymerization of rac-lactide
CN102491874B (en) Metallic alkoxy complex, catalyst composition and preparation method of poly-caprolactone or poly-lactide
Huang et al. Well-defined sterically hindered zinc aryloxides: Excellent catalysts for ring-opening polymerization of ɛ-caprolactone and l-lactide
CN102268030B (en) Nitrogen-containing bisphenol oxygen-based ligand binuclear aluminum compound and preparation method and application thereof
CN103864659B (en) Chiral imines phenol oxygen base zinc, magnesium compound and its preparation method and application
CN104710447B (en) A kind of preparation method of chiral aluminum complex containing pyrrole group and preparation method thereof and PLA
Huang et al. Magnesium and zinc complexes bearing NNO-tridentate ketiminate ligands: synthesis, structures and catalysis in the ring-opening polymerization of lactides
Fagerland et al. Modulating the thermal properties of poly (hydroxybutyrate) by the copolymerization of rac-β-butyrolactone with lactide
CN105085560A (en) Aluminum compound based on pyrrole derivatives, preparation method of aluminum compound and polylactic acid preparation method
Jiang et al. Phenoxy-imine/-amide aluminum complexes with pendant or coordinated pyridine moieties: Solvent effects on structural type and catalytic capability for the ROP of cyclic esters
Gao et al. Stereoselective ring-opening polymerization of rac-lactides catalyzed by titanium complexes containing N, N-bidentate phenanthrene derivatives
CN104311582A (en) Schiff base zinc compound, preparation method of schiff base zinc compound, and preparation method of polylactic acid
Wheaton et al. Electron deficient zinc complexes: Enhanced lactide polymerization activity achieved through rational ligand design
CN101759712A (en) Novel asymmetric diamidino aluminum compound as well as preparation method and application thereof
CN104230725A (en) Amino phenol ligand magnesium/zinc complex, and preparation method and application thereof
CN108864166B (en) Oxazoline metal compound, preparation method thereof and application thereof as catalyst
CN105175441A (en) Aluminum compound based on cis-1,2-cyclohexane diamine derivative and preparation method and application
CN103254220B (en) The preparation method of Chiral zinc compound, its preparation method and poly(lactic acid)
CN113321676B (en) Tetrahydropyrrole diamine bridged bisphenol rare earth metal complex and preparation and application thereof
CN106380478B (en) A kind of preparation method of three metal centers schiff bases aluminium compound, preparation method, application and polylactic acid
Li et al. Preparation of star-shaped functionalized polylactides by metal porphyrin complexes as both catalysts and cocatalysts
CN102250131A (en) Dialkoxy aluminum complexe coordinated by beta-diketiminato ligand, its preparation method and application in epsilon-caprolactone ring-opening polymerisation
KR101864005B1 (en) Catalyst for polymerization of monomer having a ring-type ester group, and method of forming polymer using the catalyst
CN108912010A (en) A kind of schiff bases manganese compound, preparation method and its application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20151125