CN100393771C - Schiff-base aluminium catalyst for lactide open-ring polymerization, and it spreparing method and use - Google Patents
Schiff-base aluminium catalyst for lactide open-ring polymerization, and it spreparing method and use Download PDFInfo
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- CN100393771C CN100393771C CNB2006100166233A CN200610016623A CN100393771C CN 100393771 C CN100393771 C CN 100393771C CN B2006100166233 A CNB2006100166233 A CN B2006100166233A CN 200610016623 A CN200610016623 A CN 200610016623A CN 100393771 C CN100393771 C CN 100393771C
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Abstract
The present invention relates to a Schiff base aluminum catalyst for lactide ring-opening polymerization, a preparation method thereof, a method for polymerizing lactide comprising levorotatory lactide, dextrorotary lactide, mesomeric lactide and racemic lactide with the catalyst and a method for preparing a mixture of any proportion of the levorotatory lactide and the dextrorotary lactide. The catalyst of the present invention is a product and a derivative thereof generated by the reaction of beta-dione Schiff base and aluminium triethide, and the product and the derivative have stereoselectivity to the polymerization of the racemic lactide.
Description
Technical field
The present invention relates to be used for the Schiff's base Al catalysts and the preparation method of rac-Lactide ring-opening polymerization, and the method for using this catalyzer stereoselectivity polymerization rac-Lactide.
Background technology
As a kind of synthetic biodegradable material, poly(lactic acid) has been widely used in biomedicine and the pharmaceutical industry at environment.High molecular weight polylactic acid is generally synthesized by the ring-opening polymerization of rac-Lactide, and lot of documents and patent such as United States Patent (USP) 5235031,5357034 have been reported the rac-Lactide ring-opening polymerization.Rac-Lactide has three kinds of steric isomers: levorotatory lactide, and dextrorotation rac-Lactide and Study of Meso-Lactide, their structure is as follows respectively:
Dextrorotation rac-Lactide levorotatory lactide Study of Meso-Lactide
The use temperature of crystalline polymer can this means that the crystalline poly(lactic acid) has the use temperature scope wideer than amorphous poly(lactic acid) near melt temperature.And this just needs exploitation a kind of polymerization has stereoselective ring-opening polymerization catalyst to rac-Lactide, and its can obtain crystalline polylactic acid by polymerization rac-lactide.
The more existing reports of the catalyzer of rac-Lactide stereoselectivity ring-opening polymerization as: Schiff's base-Al catalysts (Salbinap) AlOMe of Coates reports such as (Ke Tesi) is by a part 2,2 '-diaminostilbene, 1 '-Lian dinaphthyl and two molecule salicylic aldehyde condensations obtain Schiff's base and obtain catalyzer by a part Schiff's base and the reaction of a part aluminum isopropylate then.Ovitt, T.M., Coates, G.W..J.Am.Chem.Soc.2002,124:1316-1326. American Chemical Society meeting will, 2002 124 volumes, 1316-1326 page or leaf.
Zhong (Zhong Zhiyuan) etc. has reported (cyclohexylsalen) AlOiPr catalyzer, be by 1,2-hexamethylene diamino and two molecules 3, the condensation of 5-di-tert-butyl salicylaldehyde obtain Schiff's base and obtain catalyzer by a part Schiff's base and the reaction of a part aluminum isopropylate then.The melting point polymer that obtains is 185 ℃ of Zhong, Z.; Dijkstra.P.J.; Feijen.J.J.Am.Chem.Soc.2003,125,11291-11298. American Chemical Society meeting will, 2003 125 volumes, 11291-11298 page or leaf.
Summary of the invention
First purpose of the present invention provides the Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization;
Second purpose of the present invention provides the preparation method of the Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization;
The 3rd purpose of the present invention provides the application method of the Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization.With this polymerization catalyst rac-Lactide, comprise levorotatory lactide, dextrorotation rac-Lactide, Study of Meso-Lactide, the method for the mixture of arbitrary proportion between rac-lactide and levorotatory lactide and the dextrorotation rac-Lactide.
Schiff's base among the present invention is to utilize beta-diketon and diamine condensation, and the hydroxyl that is produced by the enol-type structure of beta-diketon comes and the aluminium coordination, forms the Schiff's base Al catalysts of pentacoordinate.This with obtain Schiff's base by the salicylic aldehyde of salicylic aldehyde or replacement and diamine reaction and structurally have significantly different with aluminium coordinate catalyzer then.
The invention provides the Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization, have following structure:
1. the Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization that obtains based on a part quadrol and two molecule benzoyl acetone condensations, I is expressed as follows with structural formula:
Come the different R of expression I with 1a, 1b, 1c, 1d or 1e respectively, wherein 1a is: R=CH
2CH
3, 1b is: R=OCH
3, 1c is: R=OCH
2CH
3, 1d is: R=OCH (CH
3)
2, 1e is: R=OCH
2Ph;
2. the Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization that obtains based on a part 1-methyl ethylenediamine and two molecule benzoyl acetone condensations is expressed as follows with structural formula II:
Come the different R of expression II with 2a, 2b, 2c, 2d or 2e respectively, wherein 2a is: R=CH
2CH
3, 2b is: R=OCH
3, 2c is: R=OCH
2CH
3, 2d is: R=OCH (CH
3)
2, 2e is: R=OCH
2Ph;
3. the Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization that obtains based on a part propylene diamine and two molecule benzoyl acetone condensations, I is expressed as follows with structural formula II:
Represent the R that formula III is different with 3a, 3b, 3c, 3d or 3e respectively, wherein 3a is: R=CH
2CH
3, 3b is: R=OCH
3, 3c is: R=OCH
2CH
3, 3d is: R=OCH (CH
3)
2, 3e is: R=OCH
2Ph;
4. based on a part 2,2-dimethyl-1, the Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization that 3-propylene diamine and two molecule benzoyl acetone condensations obtain, IV is expressed as follows with structural formula:
Come the different R of expression IV with 4a, 4b, 4c, 4d or 4e respectively, wherein 4a is: R=CH
2CH
3, 4b is: R=OCH
3, 4c is: R=OCH
2CH
3, 4d is: R=OCH (CH
3)
2, 4e is: R=OCH
2Ph;
5. the Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization that obtains based on a part m-xylene diamine and two molecule benzoyl acetone condensations, V is expressed as follows with structural formula:
Come the different R of expression V with 5a, 5b, 5c, 5d and 5e respectively, wherein 5a is: R=CH
2CH
3, 5b is: R=OCH
3, 5c is: R=OCH
2CH
3, 5d is: R=OCH (CH
3)
2, 5e is: R=OCH
2Ph;
Second purpose of the present invention provides the preparation method of the Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization, and preparation process and condition are as follows:
(a) the used beta-diketon class Schiff's base of the present invention is selected from the compound of the enol-type structure with following structural formula 1,2,3,4 or 5.
Structural formula 1:
Structural formula 2:
Structural formula 3:
Structural formula 4:
Structural formula 5:
(b) under protection of inert gas, be dissolved in the Schiff's base of beta-diketon class described in (a) 1,2,3,4 or 5 in the toluene respectively, aluminium triethyl toluene solution under protection of inert gas is joined respectively in the toluene solution of beta-diketon class Schiff's base 1,2,3,4 or 5, and the mol ratio of beta-diketon class Schiff's base and aluminium triethyl add-on is 1: 1;
(c) put into 90 ℃ oil bath, stirred 10 hours, and reduced to room temperature then, vacuumize and remove volatile matter, vacuum tightness is 0.1MPa, obtains the Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization of the 5a of the 4a of 3a, IV of 2a, III of 1a, II that structural formula of the present invention is I or V respectively;
(d) structural formula that again (c) is obtained respectively is that the Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization of the 5a of the 4a of 3a, IV of 2a, III of 1a, II of I or V is dissolved in toluene, add methyl alcohol, ethanol, Virahol or benzylalcohol with the amounts such as solute of this kind toluene solution respectively to the every kind of toluene solution that obtains, can obtain the 1d of 1c, I of 1b, I that structural formula of the present invention is I or the 1e of I respectively; The 2d of the 2b of II, the 2c of II, II or the 2e of II; The 3d of the 3b of III, the 3c of III, III or the 3e of III; The 4d of the 4b of IV, the 4c of IV, IV or the 4e of IV; The Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization of the 5d of the 5b of V, the 5c of V, V or the 5e of V.
The Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization of the present invention comes the polymerization rac-Lactide to obtain poly(lactic acid), and its using method is as follows:
(a) under the anhydrous and oxygen-free condition, mixed recrystallization rac-Lactide of crossing and the Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization, the add-on of this catalyzer is the 1/35-1/200 (mol ratio) of rac-Lactide;
(b) toluene is joined above-mentioned recrystallization rac-Lactide of crossing and the Schiff's base Al catalysts miscellany that is used for the rac-Lactide ring-opening polymerization, make rac-Lactide concentration be the solution of 0.5mmol/mL, the oil bath that this solution is put into 70-110 ℃ is also stirred, polymerization time is 1.5-31 hour, obtains polymkeric substance;
(c) polymkeric substance that obtains in (b) is dissolved in chloroform soln,, filters with the excess ethyl alcohol precipitation, vacuum-drying at room temperature 48 hours, its vacuum tightness is 0.1MPa, obtains poly(lactic acid).
Have a mind to effect:
Embodiment
Embodiment 1: structural formula is 1a catalyzer synthetic of I
Under the protective condition of rare gas element, be concentration that the 4ml structural formula of 1mol/L is the toluene solution of 1 Schiff's base, with concentration be the AlEt of the 4ml of 1mol/L
3Toluene solution is mixed, puts into 90 ℃ oil bath and stirring, reacts 10 hours, reduces to room temperature then, vacuumizes and removes volatile matter, and its vacuum tightness is 0.1MPa, and obtaining the product structure formula is the 1a catalyzer of I.Results of elemental analyses, calculated value: C, 71.62; H, 6.76; N, 6.96; Measured value: C, 71.40; H, 7.03; N, 6.75.
Embodiment 2: structural formula is 1e catalyzer synthetic of the 1d of 1c, I of 1b, I of I or I
The structural formula that embodiment 1 is obtained is the Schiff's base Al catalysts (805mg that is used for the rac-Lactide ring-opening polymerization of the 1a of I, 2mmol) be dissolved in the toluene, to the methyl alcohol of the toluene solution adding that obtains with the amounts such as solute of this kind toluene solution, can obtain structural formula of the present invention is the 1b catalyzer of I.
If change the methyl alcohol in the present embodiment into ethanol, Virahol or benzylalcohol respectively, other conditions are identical, can obtain the 1d of 1c, I of catalyst I or the 1e of I respectively.
The 1b results of elemental analyses of I, calculated value: C, 68.30; H, 6.23; N, 6.93; Measured value: C, 68.62; H, 6.53; N, 6.42.
The results of elemental analyses of the 1c of I, calculated value: C, 68.88; H, 6.50; N, 6.69; Measured value: C, 68.65; H, 6.31; N, 6.82.
The results of elemental analyses of the 1d of I, calculated value: C, 69.43; H, 6.76; N, 6.48; Measured value: C, 69.25; H, 6.49; N, 6.34.
The results of elemental analyses of the 1e of I, calculated value: C, 72.48; H, 6.08; N, 5.83; Measured value: C, 72.60; H, 5.91; N, 5.62.
Embodiment 3: structural formula is 2a catalyzer synthetic of II
Change the Schiff's base among the embodiment 11 into Schiff's base 2, other conditions can obtain the 2a of product II with embodiment 1.Results of elemental analyses, calculated value: C, 72.09; H, 7.02; N, 6.73; Measured value: C, 72.30; H, 7.43; N, 6.84.
Embodiment 4: structural formula is 2e catalyzer synthetic of the 2d of 2c, II of 2b, II of II or II
Change the 1a of the I among the embodiment 2 2a of II into, other conditions can obtain the 2b of catalyst I I with embodiment 2;
If change the methyl alcohol in the present embodiment into ethanol, Virahol or benzylalcohol respectively, other conditions are identical, can obtain the 2d of 2c, II of catalyst I I or the 2e of II respectively.
The results of elemental analyses of the 2b of II, calculated value: C, 68.88; H, 6.50; N, 6.69; Measured value: C, 68.72; H, 6.40; N, 6.34.
The results of elemental analyses of the 2c of II, calculated value: C, 69.43; H, 6.76; N, 6.48; Measured value: C, 69.59; H, 6.42; N, 6.80.
The results of elemental analyses of the 2d of II, calculated value: C, 69.94; H, 7.00; N, 6.27; Measured value: C, 70.20; H, 7.22; N, 6.09.
The results of elemental analyses of the 2e of II, calculated value: C, 72.86; H, 6.32; N, 5.66; Measured value: C, 72.65; H, 6.12; N, 5.82.
Embodiment 5: structural formula is 3a catalyzer synthetic of III
Change the Schiff's base among the embodiment 11 into Schiff's base 3, other conditions can obtain product 3a with embodiment 1.Results of elemental analyses, calculated value: C, 72.09; H, 7.02; N, 6.73;
Measured value: C, 71.88; H, 7.36; N, 6.75.
Embodiment 6: structural formula is 3e catalyzer synthetic of the 3d of 3c, III of 3b, III of III or III
Change the 1a of I among the embodiment 2 3a of III into, other conditions can obtain the 3b of catalyst I II with embodiment 2;
If change the methyl alcohol in the present embodiment into ethanol, Virahol or benzylalcohol respectively, other conditions are identical, can obtain the 3d of 3c, III of catalyst I II or the 3e of III respectively.
The results of elemental analyses of the 3b of III, calculated value: C, 68.88; H, 6.50; N, 6.69; Measured value: C, 69.02; H, 6.33; N, 6.80.
The results of elemental analyses of the 3c of III, calculated value: C, 69.43; H, 6.76; N, 6.48; Measured value: C, 69.22; H, 6.50; N, 6.71.
The results of elemental analyses of the 3d of III, calculated value: C, 69.94; H, 7.00; N, 6.27; Measured value: C, 69.88; H, 7.21; N, 6.44.
The results of elemental analyses of the 3e of III, calculated value: C, 72.86; H, 6.32; N, 5.66; Measured value: C, 73.02; H, 6.41; N, 5.89.
Embodiment 7: structural formula is 4a catalyzer synthetic of IV
Change the Schiff's base among the embodiment 11 into Schiff's base 4, other conditions can obtain the 4a of product IV with embodiment 1.Results of elemental analyses, calculated value: C, 72.95; H, 7.48; N, 6.30; Measured value: C, 73.32; H, 7.09; N, 6.52.
Embodiment 8: structural formula is 4e catalyzer synthetic of the 4d of 4c, IV of 4b, IV of IV or IV
Change the 1a of I among the embodiment 2 4a of IV into, other conditions can obtain the 4b of catalyst I V with embodiment 2;
If change the methyl alcohol in the present embodiment into ethanol, Virahol or benzylalcohol respectively, other conditions are identical, can obtain the 4d of 4c, IV of catalyst I V or the 4e of IV respectively.
The results of elemental analyses of the 4b of IV, calculated value: C, 69.94; H, 7.00; N, 6.27; Measured value: C, 69.88; H, 6.85; N, 6.50.
The results of elemental analyses of the 4c of IV, calculated value: C, 70.41; H, 7.22; N, 6.08; Measured value: C, 70.32; H, 7.52; N, 6.24.
The results of elemental analyses of the 4d of IV, calculated value: C, 70.86; H, 7.43; N, 5.90; Measured value: C, 70.65; H, 7.29; N, 6.09.
The results of elemental analyses of the 4e of IV, calculated value: C, 73.54; H, 6.75; N, 5.36; Measured value: C, 73.68; H, 6.98; N, 5.72.
Embodiment 9: structural formula is 5a catalyzer synthetic of V
Change the Schiff's base among the embodiment 11 into Schiff's base 5, other conditions can obtain product 5a with embodiment 1.Results of elemental analyses, calculated value: C, 75.29; H, 6.53; N, 5.85; Measured value: C, 74.95; H, 6.90; N, 6.02.
Embodiment 10: structural formula is 5e catalyzer synthetic of the 5d of 5c, V of 5b, V of V or V
Change the 1a of I among the embodiment 2 5a of V into, other conditions can obtain the 5b of catalyst V with embodiment 2;
If change the methyl alcohol in the present embodiment into ethanol, Virahol or benzylalcohol respectively, other conditions are identical, can obtain the 5d of 5c, V of catalyst V or the 5e of V respectively.
The results of elemental analyses of the 5b of V, calculated value: C, 72.48; H, 6.08; N, 5.83; Measured value: C, 72.65; H, 6.26; N, 5.63.
The results of elemental analyses of the 5c of V, calculated value: C, 72.86; H, 6.32; N, 5.66; Measured value: C, 73.05; H, 6.25; N, 5.86.
The results of elemental analyses of the 5d of V, calculated value: C, 73.21; H, 6.54; N, 5.51; Measured value: C, 73.44; H, 6.38; N, 5.63.
The results of elemental analyses of the 5e of V, calculated value: C, 75.52; H, 5.98; N, 5.03 measured values: C, 75.66; H, 5.62; N, 5.26.
Embodiment 11: use the rac-lactide ring-opening polymerization of the 1a of catalyst I
Under the anhydrous and oxygen-free condition, rac-lactide (the 2.0g that recrystallization is crossed, 13.9mmol) and the 1a (80.1mg that is used for the Schiff's base Al catalysts I of rac-Lactide ring-opening polymerization of the present invention, 0.199mmol) mixed, toluene is joined rac-Lactide and the Schiff's base Al catalysts miscellany that is used for the rac-Lactide ring-opening polymerization of the present invention that above-mentioned recrystallization is crossed, the concentration of making rac-Lactide is the solution of 0.5mmol/mL, the oil bath that this solution is put into 70 ℃ is also stirred, reacted 29 hours, with trichloromethane (40ml) dissolve polymer, be settled out polymkeric substance with excess ethyl alcohol.Polymkeric substance vacuum-drying at room temperature 48 hours, its vacuum tightness was 0.1MPa at last, obtained the 1.5g poly(lactic acid).With the polystyrene is standard substance, and the number-average molecular weight that GPC records product is 1.04 ten thousand, and this polymkeric substance is crystalline, and fusing point is 162 ℃.
Embodiment 12: use the rac-lactide ring-opening polymerization of the 1b of catalyst I
Change the 1a of the catalyst I among the embodiment 11 1b of catalyst I into, other conditions can obtain poly(lactic acid) 1.8g with embodiment 11, and number-average molecular weight is 0.9 ten thousand, and fusing point is 160 ℃.
Embodiment 13: use the rac-lactide ring-opening polymerization of the 1c of catalyst I
Change the 1a of the catalyst I among the embodiment 11 1c of catalyst I into, other conditions can obtain poly(lactic acid) 1.7g with embodiment 11, and number-average molecular weight is 1.1 ten thousand, and fusing point is 159 ℃.
Embodiment 14: use the rac-lactide ring-opening polymerization of the 1d of catalyst I
Change the 1a of the catalyst I among the embodiment 11 1d of catalyst I into, other conditions can obtain poly(lactic acid) 1.9g with embodiment 11, and number-average molecular weight is 0.8 ten thousand, and fusing point is 161 ℃.Embodiment 15: use the rac-lactide ring-opening polymerization of the 1e of catalyst I
Change the 1a of the catalyst I among the embodiment 11 1e of catalyst I into, other conditions can obtain poly(lactic acid) 1.7g with embodiment 11, and number-average molecular weight is 0.7 ten thousand, and fusing point is 162 ℃.
Embodiment 16: use the rac-lactide ring-opening polymerization of the 2a of catalyst I I
Under the anhydrous and oxygen-free condition, rac-lactide (the 2.0g that recrystallization is crossed, 13.9mmol) and the 2a (165.3mg that is used for the Schiff's base Al catalysts II of rac-Lactide ring-opening polymerization of the present invention, 0.397mmol) mixed, toluene is joined rac-Lactide and the Schiff's base Al catalysts miscellany that is used for the rac-Lactide ring-opening polymerization of the present invention that above-mentioned recrystallization is crossed, the concentration of making rac-Lactide is the solution of 0.5mmol/mL, the oil bath that this solution is put into 70 ℃ is also stirred, react after 31 hours, with trichloromethane (30ml) dissolve polymer, be settled out polymkeric substance with excess ethyl alcohol.Polymkeric substance vacuum-drying at room temperature 48 hours, its vacuum tightness was 0.1MPa at last, obtained the 1.6g poly(lactic acid), was standard substance with the polystyrene, and the number-average molecular weight that GPC records product is 0.47 ten thousand, and this polymkeric substance is crystalline, and fusing point is 157 ℃.
Embodiment 17: use the rac-lactide ring-opening polymerization of the 2b of catalyst I I
Change the 2a of the catalyst I I among the embodiment 16 2b of catalyst I I into, other conditions can obtain poly(lactic acid) 1.5g with embodiment 16, and number-average molecular weight is 0.5 ten thousand, and fusing point is 158 ℃.
Embodiment 18: use the rac-lactide ring-opening polymerization of the 2c of catalyst I I
Change the 2a of the catalyst I I among the embodiment 16 2c of catalyst I I into, other conditions can obtain poly(lactic acid) 1.6g with embodiment 16, and number-average molecular weight is 0.4 ten thousand, and fusing point is 160 ℃.
Embodiment 19: use the rac-lactide ring-opening polymerization of the 2d of catalyst I I
Change the 2a of the catalyst I I among the embodiment 16 2d of catalyst I I into, other conditions can obtain poly(lactic acid) 1.8g with embodiment 16, and number-average molecular weight is 0.5 ten thousand, and fusing point is 160 ℃.
Embodiment 20: use the rac-lactide ring-opening polymerization of the 2e of catalyst I I
Change the 2a of the catalyst I I among the embodiment 16 2e of catalyst I I into, other conditions can obtain poly(lactic acid) 1.6g with embodiment 16, and number-average molecular weight is 0.48 ten thousand, and fusing point is 161 ℃.
Embodiment 21: use the rac-lactide ring-opening polymerization of the 3a of catalyst I II
Under the anhydrous and oxygen-free condition, rac-lactide (the 2.0g that recrystallization is crossed, 13.9mmol) and the 3a (74.9mg that is used for the Schiff's base Al catalysts III of rac-Lactide ring-opening polymerization of the present invention, 0.18mmol) mixed, toluene is joined rac-Lactide and the Schiff's base Al catalysts miscellany that is used for the rac-Lactide ring-opening polymerization of the present invention that above-mentioned recrystallization is crossed, the concentration of making rac-Lactide is the solution of 0.5mmol/mL, the oil bath that this solution is put into 70 ℃ is also stirred, react after 12 hours, with trichloromethane (35ml) dissolve polymer, be settled out polymkeric substance with excess ethyl alcohol.Polymkeric substance vacuum-drying at room temperature 48 hours, its vacuum tightness was 0.1MPa at last, obtained the 1.8g poly(lactic acid), was standard substance with the polystyrene, and the number-average molecular weight that GPC records product is 1.1 ten thousand, and this polymkeric substance is crystalline, and fusing point is 162 ℃.
Embodiment 22: use the rac-lactide ring-opening polymerization of the 3b of catalyst I II
Change the 3a of the catalyst I II among the embodiment 21 3b of catalyst I II into, other conditions can obtain poly(lactic acid) 1.5g with embodiment 21, and number-average molecular weight is 10,000, and fusing point is 161 ℃.
Embodiment 23: use the rac-lactide ring-opening polymerization of the 3c of catalyst I II
Change the 3a of the catalyst I II among the embodiment 21 3c of catalyst I II into, other conditions can obtain poly(lactic acid) 1.6g with embodiment 21, and number-average molecular weight is 1.1 ten thousand, and fusing point is 161 ℃.
Embodiment 24: use the rac-lactide ring-opening polymerization of the 3d of catalyst I II
Change the 3a of the catalyst I II among the embodiment 21 3d of catalyst I II into, other conditions can obtain poly(lactic acid) 1.6g with embodiment 21, and number-average molecular weight is 10,000, and fusing point is 160 ℃.
Embodiment 25: use the rac-lactide ring-opening polymerization of the 3e of catalyst I II
Change the 3a of the catalyst I II among the embodiment 21 3e of catalyst I II into, other conditions can obtain poly(lactic acid) 1.7g with embodiment 21, and number-average molecular weight is 0.8 ten thousand, and fusing point is 162 ℃.
Embodiment 26: use the rac-lactide ring-opening polymerization of the 4a of catalyst I V
Under the anhydrous and oxygen-free condition, rac-lactide (the 2.0g that recrystallization is crossed, 13.9mmol) and the 4a (51.5mg that is used for the Schiff's base Al catalysts IV of rac-Lactide ring-opening polymerization of the present invention, 0.12mmol) mixed, toluene is joined rac-Lactide and the Schiff's base Al catalysts miscellany that is used for the rac-Lactide ring-opening polymerization of the present invention that above-mentioned recrystallization is crossed, the concentration of making rac-Lactide is the solution of 0.5mmol/mL, the oil bath that this solution is put into 70 ℃ is also stirred, react after 4 hours, with trichloromethane (30ml) dissolve polymer, be settled out polymkeric substance with excess ethyl alcohol.Polymkeric substance vacuum-drying at room temperature 48 hours, its vacuum tightness was 0.1MPa at last, obtained the 1.5g poly(lactic acid).With the polystyrene is standard substance, and the number-average molecular weight that GPC records product is 1.2 ten thousand, and this polymkeric substance is crystalline, and fusing point is 165 ℃.
Embodiment 27: use the rac-lactide ring-opening polymerization of the 4b of catalyst I V
Change the 4a of the catalyst I V among the embodiment 26 4b of catalyst I V into, other conditions can obtain poly(lactic acid) 1.7g with embodiment 26, and number-average molecular weight is 0.9 ten thousand, and this polymkeric substance is crystalline, and fusing point is 166 ℃.
Embodiment 28: use the rac-lactide ring-opening polymerization of the 4c of catalyst I V
Change the 4a of the catalyst I V among the embodiment 26 4c of catalyst I V into, other conditions can obtain poly(lactic acid) 1.8g with embodiment 26, and number-average molecular weight is 1.1 ten thousand, and this polymkeric substance is crystalline, and fusing point is 168 ℃.
Embodiment 29: use the rac-lactide ring-opening polymerization of the 4d of catalyst I V
Change the 4a of the catalyst I V among the embodiment 26 4d of catalyst I V into, other conditions can obtain poly(lactic acid) 1.8g with embodiment 26, and number-average molecular weight is 0.9 ten thousand, and this polymkeric substance is crystalline, and fusing point is 165 ℃.
Embodiment 30: use the rac-lactide ring-opening polymerization of the 4e of catalyst I V
Change the 4a of the catalyst I V among the embodiment 26 4e of catalyst I V into, other conditions can obtain poly(lactic acid) 1.6g with embodiment 26, and number-average molecular weight is 1.2 ten thousand, and this polymkeric substance is crystalline, and fusing point is 165 ℃.
Embodiment 31: use the rac-lactide ring-opening polymerization of the 4a of catalyst I V
Under the anhydrous and oxygen-free condition, rac-lactide (the 2.0g that recrystallization is crossed, 13.9mmol) and the 4a (51.5mg that is used for the Schiff's base Al catalysts IV of rac-Lactide ring-opening polymerization of the present invention, 0.12mmol) mixed, toluene is joined rac-Lactide and the Schiff's base Al catalysts miscellany that is used for the rac-Lactide ring-opening polymerization of the present invention that above-mentioned recrystallization is crossed, the concentration of making rac-Lactide is the solution of 0.5mmol/mL, the oil bath that this solution is put into 90 ℃ is also stirred, react after 2 hours, with trichloromethane (30ml) dissolve polymer, be settled out polymkeric substance with excess ethyl alcohol.Polymkeric substance vacuum-drying at room temperature 48 hours, its vacuum tightness was 0.1MPa at last, obtained the 1.6g poly(lactic acid).With the polystyrene is standard substance, and the number-average molecular weight that GPC records product is 1.1 ten thousand, and this polymkeric substance is crystalline, and fusing point is 162 ℃.
Embodiment 32: use the rac-lactide ring-opening polymerization of the 4a of catalyst I V
Under the anhydrous and oxygen-free condition, rac-lactide (the 2.0g that recrystallization is crossed, 13.9mmol) and the 4a (51.5mg that is used for the Schiff's base Al catalysts IV of rac-Lactide ring-opening polymerization of the present invention, 0.12mmol) mixed, toluene is joined rac-Lactide and the Schiff's base Al catalysts miscellany that is used for the rac-Lactide ring-opening polymerization of the present invention that above-mentioned recrystallization is crossed, the concentration of making rac-Lactide is the solution of 0.5mmol/mL, the oil bath that this solution is put into 110 ℃ is also stirred, react after 1.5 hours, with trichloromethane (30ml) dissolve polymer, be settled out polymkeric substance with excess ethyl alcohol.Polymkeric substance vacuum-drying at room temperature 48 hours, its vacuum tightness was 0.1MPa at last, obtained the 1.3g poly(lactic acid), was standard substance with the polystyrene.The number-average molecular weight that GPC records product is 1.0 ten thousand, and this polymkeric substance is crystalline, and fusing point is 160 ℃.
Embodiment 33: use the rac-lactide ring-opening polymerization of the 5a of catalyst V
Under the anhydrous and oxygen-free condition, rac-lactide (the 2.0g that recrystallization is crossed, 13.9mmol) and the 5a (119.6mg that is used for the Schiff's base Al catalysts V of rac-Lactide ring-opening polymerization of the present invention, 0.25mmol) mixed, toluene is joined rac-Lactide and the Schiff's base Al catalysts miscellany that is used for the rac-Lactide ring-opening polymerization of the present invention that above-mentioned recrystallization is crossed, the concentration of making rac-Lactide is the solution of 0.5mmol/mL, the oil bath that this solution is put into 70 ℃ is also stirred, react after 10 hours, with trichloromethane (35ml) dissolve polymer, be settled out polymkeric substance with excess ethyl alcohol.Polymkeric substance vacuum-drying at room temperature 48 hours, its vacuum tightness was 0.1MPa at last, obtained the 1.7g poly(lactic acid).With the polystyrene is standard substance, and the number-average molecular weight that GPC records product is 0.78 ten thousand.
Embodiment 34: use the rac-lactide ring-opening polymerization of the 5b of catalyst V
Change the 5a of the catalyst V among the embodiment 33 5b of catalyst V into, other conditions can obtain poly(lactic acid) 1.5g with embodiment 33, and number-average molecular weight is 0.8 ten thousand.
Embodiment 35: use the rac-lactide ring-opening polymerization of the 5c of catalyst V
Change the 5a of the catalyst V among the embodiment 33 5c of catalyst V into, other conditions can obtain poly(lactic acid) 1.4g with embodiment 33, and number-average molecular weight is 0.9 ten thousand.
Embodiment 36: use the rac-lactide ring-opening polymerization of the 5d of catalyst V
Change the 5a of the catalyst V among the embodiment 33 5d of catalyst V into, other conditions can obtain poly(lactic acid) 1.5g with embodiment 33, and number-average molecular weight is 1.0 ten thousand.
Embodiment 37: use the rac-lactide ring-opening polymerization of the 5e of catalyst V
Change the 5a of the catalyst V among the embodiment 33 5e of catalyst V into, other conditions can obtain poly(lactic acid) 1.4g with embodiment 33, and number-average molecular weight is 0.8 ten thousand.
Embodiment 38: use the levorotatory lactide ring-opening polymerization of the 1a of catalyst I
Under the anhydrous and oxygen-free condition, levorotatory lactide (the 2.0g that recrystallization is crossed, 13.9mmol) and the 1a (56.3mg that is used for the Schiff's base Al catalysts I of rac-Lactide ring-opening polymerization of the present invention, 0.14mmol) mixed, toluene is joined rac-Lactide and the Schiff's base Al catalysts miscellany that is used for the rac-Lactide ring-opening polymerization of the present invention that above-mentioned recrystallization is crossed, the concentration of making rac-Lactide is the solution of 0.5mmol/mL, the oil bath that this solution is put into 70 ℃ is also stirred, react after 29 hours, with trichloromethane (30ml) dissolve polymer, be settled out polymkeric substance with excess ethyl alcohol.Polymkeric substance vacuum-drying at room temperature 48 hours, its vacuum tightness was 0.1MPa at last, obtained the 1.5g poly(lactic acid).With the polystyrene is standard substance, and the number-average molecular weight that GPC records product is 1.2 ten thousand, and this polymkeric substance is crystalline, and fusing point is 156 ℃.
Embodiment 39: use the dextrorotation rac-Lactide ring-opening polymerization of the 2d of catalyst I I
Under the anhydrous and oxygen-free condition, dextrorotation rac-Lactide (the 1.5g that recrystallization is crossed, 10.4mmol) and the 2d (67.0mg that is used for the Schiff's base Al catalysts II of rac-Lactide ring-opening polymerization of the present invention, 0.15mmol) mixed, toluene is joined rac-Lactide and the Schiff's base Al catalysts miscellany that is used for the rac-Lactide ring-opening polymerization of the present invention that above-mentioned recrystallization is crossed, the concentration of making rac-Lactide is the solution of 0.5mmol/mL, the oil bath that this solution is put into 70 ℃ is also stirred, react after 31 hours, with trichloromethane (30ml) dissolve polymer, be settled out polymkeric substance with excess ethyl alcohol.Polymkeric substance vacuum-drying at room temperature 48 hours, its vacuum tightness was 0.1MPa at last, obtained the 1.0g poly(lactic acid).With the polystyrene is standard substance, and the number-average molecular weight that GPC records product is 1.0 ten thousand, and this polymkeric substance is crystalline, and fusing point is 153 ℃.
Embodiment 40: use the Study of Meso-Lactide ring-opening polymerization of the 4c of catalyst I V
Under the anhydrous and oxygen-free condition, Study of Meso-Lactide (the 1.5g that recrystallization is crossed, 10.4mmol) and the 4c (69.1mg that is used for the Schiff's base Al catalysts IV of rac-Lactide ring-opening polymerization of the present invention, 0.15mmol) mixed, toluene is joined rac-Lactide and the Schiff's base Al catalysts miscellany that is used for the rac-Lactide ring-opening polymerization of the present invention that above-mentioned recrystallization is crossed, the concentration of making rac-Lactide is the solution of 0.5mmol/mL, the oil bath that this solution is put into 70 ℃ is also stirred, react after 4 hours, with trichloromethane (30ml) dissolve polymer, be settled out polymkeric substance with excess ethyl alcohol.Polymkeric substance vacuum-drying at room temperature 48 hours, its vacuum tightness was 0.1MPa at last, obtained the 1.0g poly(lactic acid).With the polystyrene is standard substance, and the number-average molecular weight that GPC records product is 1.1 ten thousand.
Embodiment 41: the levorotatory lactide of the 4c of usefulness catalyst I V and the mixture ring-opening polymerization of dextrorotation rac-Lactide
Under the anhydrous and oxygen-free condition, the levorotatory lactide that recrystallization is crossed and the mixture of dextrorotation rac-Lactide, the additional proportion of left-handed lactide and dextrorotation rac-Lactide is 20/80 (1.5g, 10.4mmol) and the 4c (69.1mg that is used for the Schiff's base Al catalysts IV of rac-Lactide ring-opening polymerization of the present invention, 0.15mmol) mixed, toluene is joined rac-Lactide and the Schiff's base Al catalysts miscellany that is used for the rac-Lactide ring-opening polymerization of the present invention that above-mentioned recrystallization is crossed, the concentration of making rac-Lactide is the solution of 0.5mmol/mL, the oil bath that this solution is put into 70 ℃ is also stirred, react after 3 hours, with trichloromethane (30ml) dissolve polymer, be settled out polymkeric substance with excess ethyl alcohol.Polymkeric substance vacuum-drying at room temperature 48 hours, its vacuum tightness was 0.1MPa at last, obtained the 1.0g poly(lactic acid).With the polystyrene is standard substance, and the number-average molecular weight that GPC records product is 0.9 ten thousand.
Claims (3)
1. Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization, it is respectively the compound with following structural formula,
Structural formula I is as follows:
In the formula, R is 1a:R=CH
2CH
3, R is 1b:R=OCH
3, R is 1c:R=OCH
2CH
3, R is 1d:R=OCH (CH
3)
2Or R is 1e:R=OCH
2Ph;
Structural formula II is as follows:
In the formula, R is 2a:R=Ch
2CH
3, R is 2b:R=OCH
3, R is 2c:R=OCH
2Ch
3, R is 2d:R=OCH (CH
3)
2Or R is 2e:R=OCH
2Ph;
Structural formula II I is as follows:
In the formula, R is 3a:R=CH
2CH
3, R is 3b:R=OCH
3, R is 3c:R=OCH
2CH
3, R is 3d:R=OCH (CH
3)
2Or R is 3e:R=OCH
2Ph;
Structural formula IV is as follows:
In the formula, R is 4a:R=CH
2CH
3, R is 4b:R=OCH
3, R is 4c:R=OCH
2CH
3, R is 4d:R=OCH (CH
3)
2Or R is 4e:R=OCH
2Ph;
Structural formula V is as follows:
In the formula, R is 5a:R=CH
2CH
3, R is 5b:R=OCH
3, R is 5c:R=OCH
2CH
3, R is 5d:R=OCH (CH
3)
2Or R is 5e:R=OCH
2Ph.
2. be used for the preparation method of the Schiff's base Al catalysts of rac-Lactide ring-opening polymerization as claim 1, preparation process is as follows:
(a) beta-diketon class Schiff's base is selected from the compound with following structure:
(b) under protection of inert gas, be dissolved in the Schiff's base of beta-diketon class described in (a) 1,2,3,4 or 5 in the toluene respectively, aluminium triethyl toluene solution under protection of inert gas is joined respectively in the toluene solution of beta-diketon class Schiff's base 1,2,3,4 or 5, and the mol ratio of beta-diketon class Schiff's base and aluminium triethyl add-on is 1: 1;
(c) put into 90 ℃ oil bath, stirred 10 hours, and reduced to room temperature then, vacuumize and remove volatile matter, vacuum tightness is 0.1MPa, obtains the Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization of the 5a of the 4a of 3a, IV of 2a, III of 1a, II that structural formula of the present invention is I or V respectively;
(d) structural formula that again (c) is obtained respectively is that the Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization of the 5a of the 4a of 3a, IV of 2a, III of 1a, II of I or V is dissolved in toluene, add methyl alcohol, ethanol, Virahol or benzylalcohol with the amounts such as solute of this kind toluene solution respectively to the every kind of toluene solution that obtains, can obtain the 1d of 1c, I of 1b, I that structural formula of the present invention is I or the 1e of I respectively; The 2d of the 2b of II, the 2c of II, II or the 2e of II; The 3d of the 3b of III, the 3c of III, III or the 3e of III; The 4d of the 4b of IV, the 4c of IV, IV or the 4e of IV; The Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization of the 5d of the 5b of V, the 5c of V, V or the 5e of V.
3. the purposes of the Schiff's base Al catalysts of rac-Lactide ring-opening polymerization as claimed in claim 1, it is characterized in that, use it for rac-Lactide, comprise levorotatory lactide, the dextrorotation rac-Lactide, Study of Meso-Lactide, polymerization between rac-lactide and levorotatory lactide and the dextrorotation rac-Lactide, its step is as follows:
(a) under the anhydrous and oxygen-free condition, mixed recrystallization rac-Lactide of crossing and the Schiff's base Al catalysts that is used for the rac-Lactide ring-opening polymerization, the mol ratio of the add-on of this catalyzer and the add-on of rac-Lactide is 1/35-1/200;
(b) toluene is joined above-mentioned recrystallization rac-Lactide of crossing and the Schiff's base Al catalysts miscellany that is used for the rac-Lactide ring-opening polymerization, make rac-Lactide concentration be the solution of 0.5mmol/mL, the oil bath that this solution is put into 70-110 ℃ is also stirred, polymerization time is 1.5-31 hour, obtains polymkeric substance;
(c) polymkeric substance that obtains in (b) is dissolved in chloroform soln,, filters with the excess ethyl alcohol precipitation, vacuum-drying at room temperature 48 hours, its vacuum tightness is 0.1MPa, obtains poly(lactic acid).
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| CN101665567B (en) | 2008-09-01 | 2011-11-23 | 南京工业大学 | Method for controlled ring-opening polymerization for ring compound by catalysis of carbine derivatives |
| CN101665566B (en) | 2008-09-01 | 2012-01-04 | 南京工业大学 | Method for preparing polylactic acid and products thereof by utilizing double-screw extruder |
| CN101665565B (en) | 2008-09-01 | 2012-01-04 | 南京工业大学 | Method for preparing polylactic acid through catalysis of carbine derivatives |
| CN101805937B (en) * | 2010-03-18 | 2012-07-25 | 上海同杰良生物材料有限公司 | Filament bundle for degrading cigarette, preparation method thereof, and preparation method of filter stick |
| CN102491874B (en) | 2011-12-08 | 2015-05-20 | 中国科学院长春应用化学研究所 | Metallic alkoxy complex, catalyst composition and preparation method of poly-caprolactone or poly-lactide |
| CN102786544B (en) * | 2012-08-28 | 2015-02-04 | 中国科学院长春应用化学研究所 | Schiff base aluminum compound, preparation process of Schiff base aluminum compound and preparation process of polylactic acid |
| CN102786674B (en) * | 2012-08-28 | 2014-04-30 | 中国科学院长春应用化学研究所 | Schiff base aluminum compound, preparation method thereof and preparation method of polylactic acid |
| CN103421034B (en) * | 2013-08-09 | 2015-10-21 | 中国科学院长春应用化学研究所 | The preparation method of Chiral aluminum compound and preparation method thereof and poly(lactic acid) |
| CN104447830A (en) * | 2014-11-10 | 2015-03-25 | 中国科学院长春应用化学研究所 | Schiff base aluminum compound, preparation method thereof, and preparation method of polylactic acid |
| CN106947067B (en) | 2017-04-28 | 2022-01-04 | 南京工业大学 | Preparation method of polyester |
| CN110003455B (en) * | 2018-01-05 | 2021-09-21 | 中国石油化工股份有限公司 | Catalyst composition and preparation method of polylactide |
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| WO2004052980A1 (en) * | 2002-12-11 | 2004-06-24 | Johnson Matthey Plc | Polymerisation reaction and catalyst therefor |
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Effective date of registration: 20090911 Address after: No. 43 worker Road, Jiaojiang District, Zhejiang, Taizhou Patentee after: Zhejiang Hisun Biological Material Co., Ltd. Address before: No. 5625 Renmin Street, Jilin, Changchun Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences |