CN104327261A - Preparation method of polylactide - Google Patents
Preparation method of polylactide Download PDFInfo
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- CN104327261A CN104327261A CN201410608985.6A CN201410608985A CN104327261A CN 104327261 A CN104327261 A CN 104327261A CN 201410608985 A CN201410608985 A CN 201410608985A CN 104327261 A CN104327261 A CN 104327261A
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Abstract
The invention discloses a preparation method of polylactide, which comprises the following steps: mixing a catalyst, an organic solvent, an alcohol cocatalyst and lactide, and carrying out polymerization ring-opening reaction under the waterless and oxygen-free conditions in an inert gas protective atmosphere; and after the reaction, treating the reaction product to obtain the polylactide, wherein the catalyst is a methyl aluminum complex of a tetradentate nitrogen oxygen ligand disclosed as Formula I, and the alcohol cocatalyst is benzalcohol or isopropanol. The method has the advantages of simple technique, high reaction rate and mild conditions; by adopting the special-structure catalyst with excellent performance, the product has the advantages of high molecular weight controllability, high yield and narrow molecular weight distribution; the polymerization reaction conditions can be controlled to regulate the three-dimensional structure and molecular weight of the polymers to obtain the polymers of which the molecular weight ranges from 2000 to 170000; and the product has wide selectivity, can satisfy different demands, and has favorable market prospect.
Description
Technical field
The present invention relates to a kind of preparation method of polylactide, be specifically related to a kind of with the preparation method of the aluminum complex of the new quad-tree index polylactide that is catalyzer.
Background technology
The biodegradated polymer materals such as polylactide had both had the feature of conventional polymer material, do not pollute the environment after a procedure again, and medically also have been widely used, as the aspects such as medicine controlled releasing, surgical sutures, bone fracture internal fixation material are studied widely.
The structure of polylactide material and molecular weight have a great impact its purposes, such as, as propping material, require high molecular and high mechanical strength, and as medicinal film material, then tackling medicine has permeability.Can molecular weight distribution be controlled by controllable polymerization method, obtain the polymkeric substance of narrow molecular weight distribution and measurable molecular weight.Now, the catalyzer major part for polylactide synthesis is metal complexes, by can regulate and control the stereoselectivity of catalyzer to the adjustment of part, obtains the polymkeric substance that three-dimensional regularity is high, can better play its machinery, physics and degradation property.Therefore, in order to obtain the more and better polymkeric substance that we need, just need the catalyzer developing different performance to improve three-dimensional regularity and the molecular weight of polymkeric substance.Because metallic aluminium catalyzer has excellent catalytic effect, there is good stereoselectivity, find the focus that suitable Al catalysts is research all the time.
Summary of the invention
The invention provides a kind of preparation method of polylactide, the method is with the aluminium trimethide title complex of four tooth nitrogen oxygen parts for catalyzer, and mild condition, technique is simple, and products therefrom productive rate is high, narrow molecular weight distribution, molecular weight controllability are good.
Technical solution of the present invention is as follows:
A kind of four tooth nitrogen oxygen parts, have as shown in the formula the structural formula shown in II, in formula, R is hydrogen or halogen;
。
In above-mentioned four tooth nitrogen oxygen parts, halogen is preferably fluorine or bromine.
The preparation method of above-mentioned four tooth nitrogen oxygen parts, comprise the following steps: by raw material A (N, N '-dimethyl-N, N '-diphenyl ethylene diamine) be dissolved in anhydrous diethyl ether, slowly n-Butyl Lithium is dripped at 0 DEG C, slowly be raised to room temperature reaction 12 hours, cool to 0 DEG C after reaction, slowly drip the phenyl aldehyde of phenyl aldehyde or replacement, be raised to room temperature, react 12 hours, then add water stopped reaction, separatory collects organic phase, obtains thick product, thick product, through recrystallizing methanol, obtains four tooth nitrogen oxygen parts (formula II).
Reaction formula is as follows:
In above-mentioned preparation method, the consumption of the phenyl aldehyde of n-Butyl Lithium, phenyl aldehyde or replacement is 2 times of molar weights of raw material A.
Above-mentioned part and aluminium trimethide react, and can form the aluminium trimethide title complex of four tooth nitrogen oxygen parts, it has as shown in the formula the structural formula shown in I, and in formula, R is hydrogen or halogen;
In the aluminium trimethide title complex of above-mentioned four tooth nitrogen oxygen parts, halogen is preferably fluorine or bromine.
The preparation method of the aluminium trimethide title complex of above-mentioned four tooth nitrogen oxygen parts, comprise the following steps: with four tooth nitrogen oxygen parts shown in formula II for part, part is joined in organic solvent, at-20 ~ 0 DEG C, add the trimethyl aluminium of equimolar amount, after adding, reaction solution is risen to room temperature naturally, be then warming up to 80 DEG C of reaction 12h, solvent is pumped after having reacted, obtain thick product, thick product recrystallization, obtains the aluminium trimethide title complex (formula I) of four tooth nitrogen oxygen parts.Reaction formula is as follows:
In above-mentioned preparation method, react and carry out under protection of inert gas.
In above-mentioned preparation method, described organic solvent is the saturated alkane of C5 ~ C10 or aromatic hydrocarbon or haloalkane organic solvent, is preferably toluene, tetrahydrofuran (THF) or chloroform.
In above-mentioned preparation method, consumption of organic solvent should be 5 ~ 20 times of reaction raw materials total mass.
In above-mentioned preparation method, recrystallization solvent for use is normal hexane.
The aluminium trimethide title complex of the present invention four tooth nitrogen oxygen part can be used as the catalyzer of rac-Lactide ring-opening polymerization, when the aluminium trimethide title complex of the present invention four tooth nitrogen oxygen part is used as the catalyzer of rac-Lactide ring-opening polymerization, speed of reaction is very fast, and can obtain the lactone of molecular weight within the scope of 2000-170000 according to demand, molecular weight controllability is high.When substituent R in title complex is hydrogen, title complex is high as catalyst activity, the time used when catalyzing and synthesizing the polyester of same molecular amount is short, substituent R is that fluorine takes second place, substituent R is that the bromine time used is the longest, this shows sterically hinderedly have certain influence to catalyst activity, and along with sterically hindered increase, the activity of catalyzer decreases.Catalyzer of the present invention also has good stereoselectivity, and experiment shows, when R is fluorine, stereoselectivity is best, and bromine takes second place, and hydrogen is minimum, and this illustrates that the stereoselectivity of substituent electron attraction more powerful catalyst is higher.
During with the aluminium trimethide title complex of the present invention four tooth nitrogen oxygen part for catalyzer; the preparation method of polylactide comprises the following steps: catalyzer, organic solvent, alcohol promotor and rac-Lactide are mixed; polymerization ring-opening reaction is carried out under anhydrous and oxygen-free and protection of inert gas; after reaction, reactant is processed, obtain polylactide.
In above-mentioned preparation method, add cold methanol purifying polylactide after the process carried out reactant refers to reaction, obtain the polylactide after purifying.
In above-mentioned preparation method, alcohol promotor is benzylalcohol or Virahol.
In above-mentioned preparation method, described rac-Lactide is levorotatory lactide or rac-lactide.
In above-mentioned preparation method, the mol ratio of rac-Lactide and catalyzer is 30 ~ 2000:1, preferred 500-1000:1; The mol ratio of alcohol promotor and catalyzer is 1 ~ 4:1.
In above-mentioned preparation method, polymeric reaction temperature is 20 ~ 120 DEG C, is preferably 20-70 DEG C; Time is 3-24 hour, and preferably 6 is little of 15 hours.
In above-mentioned preparation method, reacting organic solvent used is toluene, chloroform or tetrahydrofuran (THF), preferred toluene.
In above-mentioned preparation method, cause the polymerization of rac-Lactide using the aluminium trimethide title complex of the present invention four tooth nitrogen oxygen part as catalyzer, thus obtain a series of polylactide.The molecular weight Mn of the final gained polylactide of the present invention is between 2000 ~ 170000, by regulating the reaction conditions amount ratio etc. of cocatalyst (lactide monomer and the catalyzer also), can obtain the polymkeric substance of different molecular weight ranges, and molecular weight distribution is narrow.
The invention provides a kind of preparation method of polylactide, the aluminium trimethide title complex of N, N, O, O quad-tree index that the method is special with structure, catalytic activity is good is catalyzer, speed of reaction is fast, polyreaction can occur at a lower temperature, mild condition, and the product of available different molecular weight, molecular weight of product controllability is good, productive rate is high, metal residual is few, narrow molecular weight distribution.In addition, polymerization technology is simple, can adopt common solution polymerization process, by the control of polymeric reaction condition, three-dimensional arrangement and the molecular weight of polymkeric substance can be regulated and controled, obtain the polymkeric substance of molecular weight from 2 thousand to ten seven ten thousand, selectivity is wide, meets the different needs, has good market outlook.
Accompanying drawing explanation
Fig. 1 is the crystal schematic diagram of the novel four tooth nitrogen oxygen parts of the present invention, and wherein R is hydrogen.
Embodiment
Further illustrate the present invention below by specific embodiment, but the present invention is not limited to this, concrete protection domain see claim.
The present invention's raw material A used can prepare voluntarily by method disclosed in prior art, and following embodiment raw material A used adopts document " Emil Fr hlich; Darstellung von N, N '-Dialkyl-methylendiaryl-diaminen und Homologen, Chemische Berichte; Vol. 40; (1907); P. 764 ", method obtains; step is: by 1; the methylphenylamine of 2-ethylene dibromide and its 2 moles of times amount reacts 12 hours under 100 DEG C of conditions; obtain purple mixture; mixture obtains white solid through pillar layer separation (petrol ether/ethyl acetate=10/1); be raw material A, productive rate 81wt%.
prepare four tooth nitrogen oxygen parts
According to following route synthesizing new four tooth nitrogen oxygen part, the following formula II of structural formula of gained part, simply exemplifies the preparation process of several part below.Preferred part R is hydrogen, fluorine, bromine.
embodiment 1
Ligand structure formula used as above formula II, wherein R is hydrogen, and reaction process is: be dissolved in 30 mL anhydrous diethyl ethers, 0 by raw material A (N, N '-dimethyl-N, N '-diphenyl ethylene diamine) (8.30 g, 34.6 mmol)
oc slowly drips the n-Butyl Lithium of raw material A twice molar weight, is slowly raised to room temperature reaction after 12 hours, cools to 0
oc, slowly drips the phenyl aldehyde (7.34 g, 69.2 mmol) of raw material A twice molar weight, be raised to room temperature and react 12 hours later, add water stopped reaction after reaction, separatory collects organic phase, obtain thick product, obtain straight product 10.52 g through recrystallizing methanol, productive rate 67%.
Characterize products obtained therefrom, result is as follows:
Results of elemental analyses: C, 79.69; H, 7.18; N, 6.24 %.
1H NMR (400 MHz, CDCl
3)
δ7.36–7.29 (m, 8H, Ar–
H), 7.27–7.22 (m, 4H, Ar–
H), 7.20–7.16 (m, 2H, Ar–
H), 7.15–7.09 (m, 2H, Ar–
H), 7.06 (dd,
J= 7.7, 1.5 Hz, 2H, Ar–
H), 6.02(s, 2H, ArCHO
H), 5.98 (s, 2H, ArC
HOH), 2.98 (s, 4H, NC
H 2), 2.48 (s, 6H, C
H 3).
13C NMR (100 MHz, CDCl
3)
δ150.49, 144.08, 139.35, 129.54, 128.43, 128.14, 126.98, 126.77, 125.62, 122.40, 74.00, 54.98, 44.64.
As can be seen from above characterization result, it is the part of hydrogen that products obtained therefrom is R in formula II.
The crystal schematic diagram of products obtained therefrom as shown in Figure 1.
embodiment 2
Ligand structure formula used as above formula II, wherein R is fluorine, and reaction process is: be dissolved in 30 mL anhydrous diethyl ethers, 0 by raw material A (7.60 g, 31.6 mmol)
oc slowly drips the n-Butyl Lithium of raw material A twice molar weight, is slowly raised to room temperature reaction after 12 hours, cools to 0
oc, slowly drips the o fluorobenzaldehyde (7.82 g, 63.2 mmol) of raw material A 2 times of molar weights, be raised to room temperature and react 12 hours later, add water stopped reaction after reaction, separatory collects organic phase, obtain thick product, obtain straight product 12.03 g through recrystallizing methanol, productive rate 78%.
Characterize products obtained therefrom, result is as follows:
Results of elemental analyses: C, 73.79; H, 6.25; N, 5.81 %.
1H NMR (400 MHz, CDCl
3)
δ7.59 (t,
J= 7.6 Hz, 2H, Ar–
H), 7.30–7.24 (m, 4H, Ar–
H), 7.17 (t,
J = 8.0 Hz, 3H, Ar–
H), 7.08 (dd,
J = 9.2, 4.0 Hz, 2H, Ar–
H), 7.04–6.98 (m, 3H, Ar–
H), 6.91 (d,
J = 7.7 Hz, 2H, Ar–
H), 6.49 (s, 2H, ArC
HOH), 6.23(s, 2H, ArCHO
H) 3.18 (s, 4H, NC
H 2), 2.72 (s, 6H, C
H 3).
13C NMR (100 MHz, CDCl
3)
δ161.24, 158.79, 138.78, 130.57, 128.80, 128.66, 128.40, 125.90, 124.17, 122.24, 115.17, 114.95, 67.33, 55.12, 44.91.
As can be seen from above characterization result, it is the part of fluorine that products obtained therefrom is R in formula II.
embodiment 3
Ligand structure formula used as above formula II, wherein R is bromine, and reaction process is: be dissolved in 30 mL anhydrous diethyl ethers, 0 by raw material A (6.50 g, 27.0 mmol)
oc slowly drips the n-Butyl Lithium of raw material A twice molar weight, is slowly raised to room temperature reaction after 12 hours, cools to 0
oc, slowly drips the o-bromobenzaldehye (9.91 g, 54.0 mmol) of raw material A 2 times of molar weights, be raised to room temperature and react 12 hours later, add water stopped reaction after reaction, separatory collects organic phase, obtain thick product, obtain straight product 6.92 g through recrystallizing methanol, productive rate 42%.
Characterize products obtained therefrom, result is as follows:
Results of elemental analyses: C, 59.12; H, 4.87; N, 4.65%.
1H NMR (400 MHz, CDCl
3)
δ7.66 (dd,
J= 7.7, 1.3 Hz, 2H, Ar–
H), 7.53 (d,
J= 1.1 Hz, 2H, Ar–
H), 7.36 (t,
J = 7.7 Hz, 2H, Ar–
H), 7.28 (d,
J= 3.3 Hz, 2H, Ar–
H), 7.22–7.13 (m, 2H, Ar–
H), 7.01 (d,
J= 4.5 Hz, 2H, Ar–
H), 6.67 (d,
J = 7.6 Hz, 2H, Ar–
H), 6.45 (br, 2H, ArCHO
H) 6.33 (s, 2H, ArC
H), 3.22 (s, 4H, NC
H 2), 2.82 (s, 6H, C
H 3).
13C NMR (100 MHz, CDCl
3)
δ150.85，141.74, 138.73, 132.46, 129.38, 128.82, 128.79, 128.16, 127.57, 125.76, 123.26, 122.00, 71.56, 54.99, 44.60.
As can be seen from above characterization result, it is the part of bromine that products obtained therefrom is R in formula II.
prepare the aluminium trimethide title complex of four tooth nitrogen oxygen parts
The aluminium trimethide title complex of nitrogen oxygen coordination reacts by part (formula II) and trimethyl aluminium the title complex generated, the structural formula of its part is as shown in the formula II, the following formula I of complex structure formula, illustrates to the catalyzer that different ligands obtains below, and preferred part R is hydrogen, fluorine, bromine.
embodiment 4
Part used is part prepared by embodiment 1, R is hydrogen, and reaction process is: under nitrogen atmosphere, by part (0.52 g, 1.1 mmol) be dissolved in 10 mL toluene, at 0 DEG C, add the trimethyl aluminium of equimolar amount, be slowly raised to room temperature, be heated to 80 DEG C of reactions 12 hours, except desolventizing, crude product hexane recrystallization, obtains straight product 0.49 g, productive rate 91%.
Characterize products obtained therefrom, result is as follows:
Results of elemental analyses: C, 75.63; H, 6.79; N, 5.74 %.
1H NMR (400 MHz, CDCl
3)
δ7.42 (d, J = 7.9 Hz, 4H, Ph–
H), 7.35 (d, J = 5.7 Hz, 8H, Ph–
H), 7.28 (s, 2H, Ph–
H), 7.19 (m, 2H, Ph–
H), 7.18 (m, 2H, Ph–
H), 5.00 (s, 2H, PhC
HO), 4.07 (t, J = 6.5 Hz, 4H, NC
H 2), 2.35 (s, 6H, C
H 3), –1.22 (s, 3H, Al–C
H 3).
13C NMR (101 MHz, CDCl
3)
δ151.06, 132.89, 131.30, 130.06, 129.62, 129.10, 128.37, 125.36, 120.05, 118.20, 53.33, 40.71, 21.54, –9.11.
As can be seen from above characterization result, it is the title complex of hydrogen that products obtained therefrom is R in formula I.
embodiment 5
Part used is part prepared by embodiment 2, R is fluorine, and reaction process is: under nitrogen atmosphere, by part (0.71 g, 1.40 mmoL) be dissolved in 15 mL tetrahydrofuran (THF)s, at-20 DEG C, add equimolar amount trimethyl aluminium, be slowly raised to room temperature, be heated to 80 DEG C of reactions 12 hours, except desolventizing, crude product hexane recrystallization, obtains straight product 0.65 g, productive rate 87%.
Characterize products obtained therefrom, result is as follows:
Results of elemental analyses: C, 70.51; H, 5.97; N, 5.41 %.
1H NMR (400 MHz, CDCl
3, 293K):
δ7.89 (d,
J= 2.9 Hz, 2H, Ar–
H), 7.82 (d,
J= 2.8 Hz, 2H, Ph–
H), 7.64 –7.56(m, 4H, Ph–
H), 7.43–7.38 (m, 8H, Ph–
H), 7.24 (m, 2H, PhC
HO), 3.15 (s, 2H, NC
H 2), 3.03 (s, 2H, NC
H 2), 2.45 (s, 6H, C
H 3), –1.19 (s, 6H, AlC
H 3).
13C NMR (101 MHz, CDCl
3, 293K):
δ198.97, 154.91, 142.45, 141.26 140.54, 138.52, 137.08, 135.17, 127.01, 122.41, 121.71, 118.33, 53.50, 45.22, 12.35, –9.10.
As can be seen from above characterization result, it is the title complex of fluorine that products obtained therefrom is R in formula I.
embodiment 6
Part used is part prepared by embodiment 3, R is bromine, and reaction process is: under nitrogen atmosphere, by part (0.93 g, 1.50 mmoL) be dissolved in 15 mL tetrahydrofuran (THF)s, at 0 DEG C, add equimolar amount trimethyl aluminium, be slowly raised to room temperature, be heated to 50 DEG C of reactions 12 hours, except desolventizing, crude product hexane recrystallization, obtains straight product 0.80 g, productive rate 81 %.
Characterize products obtained therefrom, result is as follows:
Results of elemental analyses: C, 57.32; H, 4.84; N, 4.39 %.
1H NMR (400 MHz, CDCl
3)
δ7.77 (d,
J= 7.6 Hz, 2H, Ph–
H), 7.54 (d,
J= 7.0 Hz, 2H, Ph–
H), 7.48 – 7.38 (m, 5H, Ph–
H), 7.27 (d,
J= 7.8 Hz, 7H, Ph–
H), 6.99 – 6.92 (m, 2H, PhC
HO), 2.90 (s, 2H, NC
H 2), 2.51 (s, 2H, NC
H 2), 2.38 (s, 6H, C
H 3), –1.21 (s, 3H, Al–C
H 3).
13C NMR (101 MHz, CDCl
3)
δ198.19, 151.06, 137.91, 132.89, 131.30, 129.91, 129.10, 128.37, 125.36, 122.68, 120.05, 118.20, 53.33, 40.71, 21.54, –9.11.
As can be seen from above characterization result, it is the title complex of bromine that products obtained therefrom is R in formula I.
embodiment 7
Part used is part prepared by embodiment 1, R is hydrogen, and reaction process is: under nitrogen atmosphere, by part (0.52 g, 1.1 mmol) be dissolved in 10 mL hexanes, at 5 DEG C, add the trimethyl aluminium of 1.2 times of molar weights, be slowly raised to room temperature, be heated to 100 DEG C of reactions 12 hours, except desolventizing, crude product hexane recrystallization, obtains straight product, productive rate 82%.
embodiment 8
Part used is part prepared by embodiment 2, R is fluorine, and reaction process is: under nitrogen atmosphere, by part (0.71 g, 1.40 mmoL) be dissolved in 15 mL tetracol phenixin, at-20 DEG C, add 1.2 times of molar weight trimethyl aluminiums, be slowly raised to room temperature, be heated to 60 DEG C of reactions 12 hours, except desolventizing, crude product hexane recrystallization, obtains straight product, productive rate 71%.
the application of aluminum complex
embodiment 9
React under anhydrous and oxygen-free and protection of inert gas; first adding the rac-lactide of catalyzer, 40 mL tetrahydrofuran (THF)s, 50 μm of ol benzylalcohols and 50 mmol that 25 μm of ol R are hydrogen by order in the ampulla after the baking of high pure nitrogen gas washing, then 20 are placed in
oin the environment of C, react stopped reaction after 12 hours, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 7.06 grams, molecular weight 6.6 ten thousand, molecular weight distribution is 1.13, stereoselectivity (Pr=0.70), yield 98 %.
embodiment 10
React under anhydrous and oxygen-free and protection of inert gas; first adding the rac-lactide of catalyzer, 40 mL tetrahydrofuran (THF)s, 50 μm of ol benzylalcohols and 50 mmol that 25 μm of ol R are fluorine by order in the ampulla after the baking of high pure nitrogen gas washing, then 20 are placed in
oin the environment of C, react stopped reaction after 13 hours, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain product, molecular weight 6.7 ten thousand, molecular weight distribution is 1.11, stereoselectivity (Pr=0.76), yield 98 %.
embodiment 11
React under anhydrous and oxygen-free and protection of inert gas; first adding the rac-lactide of catalyzer, 40 mL tetrahydrofuran (THF)s, 50 μm of ol benzylalcohols and 50 mmol that 25 μm of ol R are bromine by order in the ampulla after the baking of high pure nitrogen gas washing, then 20 are placed in
oin the environment of C, react stopped reaction after 16 hours, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain product, molecular weight 6.6 ten thousand, molecular weight distribution is 1.12, stereoselectivity (Pr=0.72), yield 97%.
embodiment 12
React under anhydrous and oxygen-free and protection of inert gas; first adding the rac-lactide of catalyzer, 30 mL toluene, 25 μm of ol benzylalcohols and 25 mmol that 25 μm of ol R are hydrogen by order in the ampulla after the baking of high pure nitrogen gas washing, then 60 are placed in
oin the oil bath of C, react stopped reaction after 7 hours, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 3.53 grams, molecular weight 10.5 ten thousand, molecular weight distribution is 1.13, stereoselectivity (Pr=0.60), yield 98%.
embodiment 13
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the rac-lactide of catalyzer, 30 mL tetrahydrofuran (THF)s, 25 μm of ol benzylalcohols and 25 mmol that 25 μm of ol R are fluorin radical base by order in the ampulla after the baking of high pure nitrogen gas washing, then 60 are placed in
oreact 8 hours stopped reaction in the oil bath of C, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 3.50 grams, molecular weight 10.1 ten thousand, molecular weight distribution is 1.12, stereoselectivity (Pr=0.62) yield 97%.
embodiment 14
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the rac-lactide of catalyzer, 30 mL chloroforms, 25 μm of ol benzylalcohols and 25 mmol that 25 μm of ol R are bromine group by order in the ampulla after the baking of high pure nitrogen gas washing, then 60 are placed in
oreact 10 hours stopped reaction in the oil bath of C, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 3.50 grams, molecular weight 11.0 ten thousand, molecular weight distribution is 1.13, stereoselectivity (Pr=0.61) yield 97%.
embodiment 15
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the rac-lactide of catalyzer, 30 mL tetrahydrofuran (THF)s, 50 μm of ol Virahols and 42 mmol that 25 μm of ol R are hydrogen by order in the ampulla after the baking of high pure nitrogen gas washing, then 50 are placed in
oreact 14 hours stopped reaction in the oil bath of C, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 5.81 grams, molecular weight 8.5 ten thousand, molecular weight distribution is 1.11, stereoselectivity (Pr=0.64), yield 96%.
embodiment 16
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the rac-lactide of catalyzer, 30 mL toluene, 50 μm of ol benzylalcohols and 38 mmol that 25 μm of ol R are hydrogen by order in the ampulla after the baking of high pure nitrogen gas washing, then 70 are placed in
oreact 19 hours stopped reaction in the oil bath of C, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 5.31 grams, molecular weight 10.7 ten thousand, molecular weight distribution is 1.13, yield 97%.
embodiment 17
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the levorotatory lactide of catalyzer, 30 mL toluene, 100 μm of ol benzylalcohols and 17 mmol that 25 μm of ol R are hydrogen by order in the ampulla after the baking of high pure nitrogen gas washing, then 90 are placed in
oreact 13 hours stopped reaction in the oil bath of C, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 2.33 grams, molecular weight 4.3 ten thousand, molecular weight distribution is 1.14, yield 95%.
embodiment 18
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the levorotatory lactide of catalyzer, 15 mL toluene, 75 μm of ol benzylalcohols and 10 mmol that 25 μm of ol R are hydrogen by order in the ampulla after the baking of high pure nitrogen gas washing, then 120 are placed in
oreact 13 hours stopped reaction in the oil bath of C, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 1.40 grams, molecular weight 6.8 ten thousand, molecular weight distribution is 1.09, yield 97%.
embodiment 19
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the rac-lactide of catalyzer, 10 mL toluene, 35 μm of ol benzylalcohols and 4 mmol that 35 μm of ol R are fluorine by order in the ampulla after the baking of high pure nitrogen gas washing, then 20 are placed in
oin the environment of C, react 18 hours stopped reaction, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 0.56 gram, molecular weight 8.9 ten thousand, molecular weight distribution is 1.10, stereoselectivity (Pr=0.74) yield 97 %.
embodiment 20
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the rac-lactide of catalyzer, 10 mL toluene, 200 μm of ol benzylalcohols and 3 mmol that 100 μm of ol R are bromine by order in the ampulla after the baking of high pure nitrogen gas washing, then 20 are placed in
oin the environment of C, react 24 hours stopped reaction, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 0.42 gram, molecular weight 0.7 ten thousand, molecular weight distribution is 1.13, stereoselectivity (Pr=0.72), yield 96%.
embodiment 21
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the levorotatory lactide of catalyzer, 20 mL toluene, 15 μm of ol benzylalcohols and 8 mmol that 15 μm of ol R are hydrogen group by order in the ampulla after the baking of high pure nitrogen gas washing, then 70 are placed in
oreact 19 hours stopped reaction in the oil bath of C, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 1.11 grams, molecular weight 16.5 ten thousand, molecular weight distribution is 1.12, yield 96%.
embodiment 22
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the levorotatory lactide of catalyzer, 30 mL tetrahydrofuran (THF)s, 100 μm of ol benzylalcohols and 25 mmol that 25 μm of ol R are hydrogen by order in the ampulla after the baking of high pure nitrogen gas washing, then 50 are placed in
oreact 16 hours stopped reaction in the oil bath of C, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 3.53 grams, molecular weight 10.9 ten thousand, molecular weight distribution is 1.08, yield 98%.
embodiment 23
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the levorotatory lactide of catalyzer, 40 mL chloroforms, 100 μm of ol Virahols and 50 mmol that 25 μm of ol R are hydrogen group by order in the ampulla after the baking of high pure nitrogen gas washing, then 20 are placed in
oreact 22 hours stopped reaction in the oil bath of C, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 6.92 grams, molecular weight 7.3 ten thousand, molecular weight distribution is 1.13, yield 96%.
embodiment 24
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the levorotatory lactide of catalyzer, 25 mL toluene, 75 μm of ol benzylalcohols and 25 mmol that 25 μm of ol R are hydrogen by order in the ampulla after the baking of high pure nitrogen gas washing, then 120 are placed in
oreact 14 hours stopped reaction in the oil bath of C, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 3.50 grams, molecular weight 15.7 ten thousand, molecular weight distribution is 1.12, yield 97%.
embodiment 25
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the levorotatory lactide of catalyzer, 30 mL toluene, 100 μm of ol Virahols and 25 mmol that 25 μm of ol R are fluorine by order in the ampulla after the baking of high pure nitrogen gas washing, then 70 are placed in
oreact 17 hours stopped reaction in the oil bath of C, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 3.42 grams, molecular weight 9.1 ten thousand, molecular weight distribution is 1.14, yield 95%.
embodiment 26
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the levorotatory lactide of catalyzer, 15 mL toluene, 100 μm of ol benzylalcohols and 3 mmol that 100 μm of ol R are bromine by order in the ampulla after the baking of high pure nitrogen gas washing, then 70 are placed in
oreact 14 hours stopped reaction in the oil bath of C, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 0.42 gram, molecular weight 1.1 ten thousand, molecular weight distribution is 1.10, yield 96%.
comparative example 1
Raw material A (8.30 g, 34.6 mmol) is dissolved in 30 mL anhydrous diethyl ethers, 0
oc slowly drips the n-Butyl Lithium of raw material A twice molar weight, is slowly raised to room temperature reaction after 12 hours, cools to 0
oc, slowly drip the benzophenone (69.2 mmol) of raw material A twice molar weight, be raised to room temperature and react 12 hours later, water stopped reaction is added after reaction, obtain the compound being insoluble in usual vehicle, DMF and DMSO is difficult to dissolve, and the unknown compound obtained can only be dissolved in acid, cannot carry out necessary sign to it.
comparative example 2
Raw material A (8.30 g, 34.6 mmol) is dissolved in 30 mL anhydrous diethyl ethers, 0
oc slowly drips the n-Butyl Lithium of raw material A twice molar weight, is slowly raised to room temperature reaction after 12 hours, cools to 0
oc, slowly drip the dry acetone (69.2 mmol) of raw material A twice molar weight, be raised to room temperature and react 12 hours later, add water stopped reaction after reaction, the compound productive rate obtained is very low (lower than 5%), does not have using value.
Claims (10)
1. the preparation method of a polylactide, it is characterized in that comprising the following steps: catalyzer, organic solvent, alcohol promotor and rac-Lactide are mixed, under anhydrous and oxygen-free and protection of inert gas, carry out polymerization ring-opening reaction, after reaction, reactant is processed, obtain polylactide; Described catalyzer is for structural formula is as shown in the formula the aluminium trimethide title complex of four tooth nitrogen oxygen parts shown in I, and in formula, R is hydrogen or halogen, and described alcohol promotor is benzylalcohol or Virahol;
。
2. preparation method according to claim 1, is characterized in that: the mol ratio of rac-Lactide and catalyzer is 30 ~ 2000:1, and the mol ratio of alcohol promotor and catalyzer is 1 ~ 4:1.
3. preparation method according to claim 1 and 2, is characterized in that: described catalyzer adopts following methods to obtain:
The preparation of (1) four tooth nitrogen oxygen part
By N, N '-dimethyl-N, N '-diphenyl ethylene diamine is dissolved in anhydrous diethyl ether, at 0 DEG C, slowly drip n-Butyl Lithium, be slowly raised to room temperature reaction 12 hours, after reaction, cool to 0 DEG C, slowly drip the phenyl aldehyde of phenyl aldehyde or replacement, be raised to room temperature, react 12 hours, then add water stopped reaction, separatory collects organic phase, obtain thick product, thick product, through recrystallizing methanol, obtains four tooth nitrogen oxygen parts; Described part has as shown in the formula the structural formula shown in II, and in formula, R is hydrogen or halogen;
(2) preparation of catalyzer
The four tooth nitrogen oxygen parts that step (1) is obtained join in organic solvent, the trimethyl aluminium of equimolar amount is added at-20 ~ 0 DEG C, after adding, reaction solution is risen to room temperature naturally, then 80 DEG C of reaction 12h are warming up to, pump solvent after having reacted, obtain thick product, thick product normal hexane recrystallization, obtain the aluminium trimethide title complex of four tooth nitrogen oxygen parts, i.e. catalyzer; Described title complex has as shown in the formula the structural formula shown in I, and in formula, R is hydrogen or halogen;
。
4. preparation method according to claim 3, is characterized in that: in formula I and formula II, described halogen is fluorine or bromine.
5. preparation method according to claim 3, is characterized in that: in catalyst preparation process, and in step (1), the structural formula of the phenyl aldehyde of described replacement is
, wherein R halogen.
6. preparation method according to claim 3, is characterized in that: in catalyst preparation process, and in step (1), the add-on of the phenyl aldehyde of n-Butyl Lithium, phenyl aldehyde or replacement is N, 2 times of molar weights of N '-dimethyl-N, N '-diphenyl ethylene diamine.
7. preparation method according to claim 3, is characterized in that: in catalyst preparation process, in step (2), reacts and carries out under protection of inert gas.
8. preparation method according to claim 3, is characterized in that: in catalyst preparation process, and in step (2), described organic solvent is toluene, tetrahydrofuran (THF) or chloroform; Consumption of organic solvent is 5 ~ 20 times of reaction raw materials total mass.
9. preparation method according to claim 1, is characterized in that: polymeric reaction temperature is 20 ~ 120 DEG C, and the time is 3-24 hour.
10. preparation method according to claim 1, is characterized in that: polyreaction organic solvent used is toluene, chloroform or tetrahydrofuran (THF).
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| CN108003183A (en) * | 2017-12-12 | 2018-05-08 | 济南大学 | A kind of method of aluminium compound catalysis caprolactone polymerization using the coordination of four tooth nitrogen oxygen |
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| CN102924292A (en) * | 2012-11-06 | 2013-02-13 | 济南大学 | Chiral tetra-amino aniline ligand, aluminum compound thereof, preparation method and application |
| CN102924293A (en) * | 2012-11-06 | 2013-02-13 | 济南大学 | Four-chain amido anilino group ligand, aluminium compound of ligand, preparation method of ligand and application of ligand |
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| CN102924293A (en) * | 2012-11-06 | 2013-02-13 | 济南大学 | Four-chain amido anilino group ligand, aluminium compound of ligand, preparation method of ligand and application of ligand |
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| CN107973815A (en) * | 2017-12-12 | 2018-05-01 | 泰山医学院 | Asymmetric aluminum complex of the derivative containing acetylacetone,2,4-pentanedione and its preparation method and application |
| CN108003183A (en) * | 2017-12-12 | 2018-05-08 | 济南大学 | A kind of method of aluminium compound catalysis caprolactone polymerization using the coordination of four tooth nitrogen oxygen |
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