CN1814644A - Enol form lactide open-ring polymerization catalyst and its preparing method and use - Google Patents
Enol form lactide open-ring polymerization catalyst and its preparing method and use Download PDFInfo
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Abstract
This invention relates to an enol form lactide open loop polymerized catalyst and its preparation method and also a method for polymerizing lactide by the catalyst including levo-lactied, right handed lactide, meso-lactide, dl-lactide and a mixer of any proportions between levo-lactide and right handed lactide, in which, the catalyst refers to the product reacted by an enol form Schiff base and Alethyl and their derivation.
Description
Technical field
The present invention relates to a kind of enol form lactide open-ring polymerization catalyst and preparation method thereof, and the method for using this catalyzer stereoselectivity polymerization rac-Lactide.
Background technology
Poly(lactic acid) is a kind of very important have good biocompatibility, Biodegradable Polymers.It had both had the characteristics of traditional common plastics, did not pollute the environment after use is discarded again, and also had been widely used at medical field, so obtained development at full speed in recent years.
Rac-Lactide has three kinds of steric isomers: levorotatory lactide, dextrorotation rac-Lactide and Study of Meso-Lactide.Their structure is as follows respectively:
Dextrorotation rac-Lactide levorotatory lactide Study of Meso-Lactide
Poly(lactic acid) generally is to be obtained by the rac-Lactide ring-opening polymerization, and the ring-opening polymerization that has had a large amount of patents and scientific and technical literature to disclose various rac-Lactides prepares poly(lactic acid).For example, United States Patent (USP) 5235031,5357034 has been reported the rac-Lactide ring-opening polymerization.
The catalyzer that the ring-opening polymerization of rac-Lactide is adopted usually has aluminum isopropylate, stannous octoate etc.The disadvantage of the catalyzer that these are traditional is that the rac-Lactide of isomorphism type is not had selectivity, when coming polymerization rac-lactide and Study of Meso-Lactide with them, can only obtain non-crystalline polymer.But non-crystalline polymer is in the above easy deformation of second-order transition temperature, and the use temperature of crystalline polymer can this means that the crystalline poly(lactic acid) has the use temperature scope wideer than noncrystalline poly(lactic acid) near melt temperature.This just needs exploitation, and 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)
Nomura (Nuo Mula) etc. has reported a kind of catalyzer, is to obtain Schiff's base by a part quadrol or a part propylene diamine and 3,5 substituted salicylic aldehyde condensations of two molecules to obtain catalyzer by a part Schiff's base and the reaction of a part aluminium triethyl then.(Nomura.N.; Ishii.R.; Akakura.M.; Aoi.K.J.Am.Chem.Soc.2002,124,5938-5939. American Chemical Society meeting will, 2002 124 volumes, 5938-5939 page or leaf)
But all catalyzer of having reported all are to obtain Schiff's base by the salicylic aldehyde of salicylic aldehyde or replacement and diamine reaction.
Summary of the invention
First purpose of the present invention provides a kind of enol form lactide open-ring polymerization catalyst;
Second purpose of the present invention provides a kind of preparation method of enol form lactide open-ring polymerization catalyst;
The 3rd purpose of the present invention provides a kind of application method of enol form lactide open-ring polymerization catalyst.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.
Aluminum alkyls and aluminum alkoxide can the catalysis rac-Lactide ring-opening polymerization, and to the polymerization of rac-Lactide have higher stereoselective all be the big coordination catalysts of some steric hindrances, based on this idea, the invention provides a kind of enol form lactide open-ring polymerization catalyst, have following structure:
The catalyzer that obtains based on a part quadrol and two molecule methyl ethyl diketone condensations is expressed as follows with structural formula I:
Come the different R of expression I with 1a, 1b, 1c, 1d and 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;
The catalyzer that obtains based on a part 1-methyl ethylenediamine and two molecule methyl ethyl diketone condensations is expressed as follows with structural formula II:
Come the different R of expression II with 2a, 2b, 2c, 2d and 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;
The catalyzer that obtains based on a part m-xylene diamine and two molecule methyl ethyl diketone condensations is expressed as follows with structural formula II I:
Represent the R that formula III is different with 3a, 3b, 3c, 3d and 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;
Based on a part quadrol and two molecule 1s, 1, the catalyzer that the condensation of 1-trifluoroacetylacetone obtains is expressed as follows with structural formula IV:
Come the different R of expression IV with 4a, 4b, 4c, 4d and 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.
Second purpose of the present invention provides a kind of preparation method of enol form lactide open-ring polymerization catalyst, and its step and condition are as follows;
(a) be raw material with enol form Schiff's base and aluminium triethyl or corresponding alcohol, described enol form Schiff's base is selected from the compound with following enol-type structure formula 1,2,3 or 4.
Structural formula 1:
Structural formula 2:
Structural formula 3:
Structural formula 4:
(b) under protection of inert gas, be dissolved in enol form Schiff's base described in (a) 1,2,3 or 4 in the toluene respectively, aluminium triethyl toluene solution under protection of inert gas is joined respectively in the toluene solution of enol form Schiff's base 1,2,3 or 4, and the mol ratio of enol form 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, its vacuum tightness is 0.1MPa, obtains the enol form lactide open-ring polymerization catalyst of the 4a of the 3a of 2a, III of 1a, II that structural formula of the present invention is I or IV respectively;
(d) structural formula that again (c) is obtained respectively is that the enol form lactide open-ring polymerization catalyst of the 4a of the 3a of 2a, III of 1a, II of I or IV is dissolved in the 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 4e enol form lactide open-ring polymerization catalyst of the 4d of the 4b of IV, the 4c of IV, IV or IV.
It is as follows to come the polymerization rac-Lactide to obtain the method steps and the condition of poly(lactic acid) with enol form lactide open-ring polymerization catalyst of the present invention:
(a) under the anhydrous and oxygen-free condition, mixed rac-Lactide and enol form lactide open-ring polymerization catalyst of the present invention that recrystallization is crossed, it is the 1/40-1/300 of rac-Lactide that this catalyzer adds molar weight.
(b) toluene is joined in the rac-Lactide and enol form lactide open-ring polymerization catalyst miscellany of the present invention that above-mentioned recrystallization crosses, make rac-Lactide concentration be the solution of 0.5mmol/mL, the oil bath that this solution is put into 70 ℃ is also stirred, and polymerization time is 7-60 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 in 90 ℃ the oil bath and stirs, and 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, 60.41; H, 8.33; N, 10.06; Measured value: C, 61.05; H, 8.67; N, 10.51.
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 enol form lactide open-ring polymerization catalyst (557mg 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, 55.70; H, 7.55; N, 9.99; Measured value: C, 55.93; H, 7.28; N, 10.20.
The results of elemental analyses of the 1c of I, calculated value: C, 57.13; H, 7.88; N, 9.52; Measured value: C, 57.35; H, 7.62; N, 9.81.
The results of elemental analyses of the 1d of I, calculated value: C, 58.43; H, 8.17; N, 9.08; Measured value: C, 58.24; H, 8.40; N, 9.24.
The results of elemental analyses of the 1e of I, calculated value: C, 64.03; H, 7.07; N, 7.86; Measured value: C, 59.86; H, 7.25; N, 7.77.
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, 61.62; H, 8.62; N, 9.58; Measured value: C, 60.82; H, 8.40; N, 10.06.
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, 57.13; H, 7.88; N, 9.52; Measured value: C, 57.42; H, 7.53; N, 9.89.
The results of elemental analyses of the 2c of II, calculated value: C, 58.43; H, 8.17; N, 9.08; Measured value: C, 58.80; H, 7.95; N, 9.31.
The results of elemental analyses of the 2d of II, calculated value: C, 59.61; H, 8.44; N, 8.69; Measured value: C, 59.28; H, 8.49; N, 9.05.
The results of elemental analyses of the 2e of II, calculated value: C, 64.85; H, 7.35; N, 7.56; Measured value: C, 64.65; H, 7.63; N, 7.82.
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 the 3a of product III with embodiment 1.Results of elemental analyses, calculated value: C, 67.78; H, 7.68; N, 7.90; Measured value: C, 67.30; H, 7.34; N, 8.32.
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, 64.03; H, 7.07; N, 7.86; Measured value: C, 59.85; H, 7.40; N, 7.63.
The results of elemental analyses of the 3c of III, calculated value: C, 64.85; H, 7.35; N, 7.56; Measured value: C, 64.66; H, 7.53; N, 7.86.
The results of elemental analyses of the 3d of III, calculated value: C, 65.61; H, 7.60; N, 7.29; Measured value: C, 65.81; H, 7.56; N, 7.60.
The results of elemental analyses of the 3e of III, calculated value: C, 69.43; H, 6.76; N, 6.48; Measured value: C, 69.85; H, 6.43; N, 6.28.
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, 43.53; H, 4.44; N, 7.25; Measured value: C, 43.08; H, 4.52; N, 7.63.
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, 40.22; H, 3.89; N, 7.22; Measured value: C, 40.48; H, 3.95; N, 7.41.
The results of elemental analyses of the 4c of IV, calculated value: C, 41.80; H, 4.26; N, 6.96; Measured value: C, 41.62; H, 4.53; N, 7.12.
The results of elemental analyses of the 4d of IV, calculated value: C, 43.28; H, 4.60; N, 6.73; Measured value: C, 43.15; H, 4.82; N, 6.92.
The results of elemental analyses of the 4e of IV, calculated value: C, 49.15; H, 4.12; N, 6.03; Measured value: C, 49.36; H, 3.94; N, 6.25.
Embodiment 9: the rac-lactide ring-opening polymerization of the 1a of catalyst I
Under the anhydrous and oxygen-free condition, rac-lactide (the 1.5g that recrystallization is crossed, 10.4mmol) and the 1a (48.15mg of enol form lactide open-ring polymerization catalyst I of the present invention, 0.173mmol) mixed, toluene is joined in the rac-Lactide and enol form lactide open-ring polymerization catalyst miscellany of the present invention that above-mentioned recrystallization crosses, 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 19 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 1.2g poly(lactic acid), was standard substance with the polystyrene, and the number-average molecular weight that GPC records product is 0.7 ten thousand, and this polymkeric substance is crystalline, and fusing point is 160 ℃.
Embodiment 10: the rac-lactide ring-opening polymerization of the 1b of catalyst I
Change the 1a of the catalyst I among the embodiment 9 1b of catalyst I into, other conditions can obtain poly(lactic acid) 1.2g with embodiment 9, and number-average molecular weight is 0.75 ten thousand, and fusing point is 160 ℃.
Embodiment 11: the rac-lactide ring-opening polymerization of the 1c of catalyst I
Change the 1a of the catalyst I among the embodiment 9 1c of catalyst I into, other conditions can obtain poly(lactic acid) 1.3g with embodiment 9, and number-average molecular weight is 0.77 ten thousand, and fusing point is 159 ℃.
Embodiment 12: the rac-lactide ring-opening polymerization of the 1d of catalyst I
Change the 1a of the catalyst I among the embodiment 9 1d of catalyst I into, other conditions can obtain poly(lactic acid) 1.1g with embodiment 9, and number-average molecular weight is 0.73 ten thousand, and fusing point is 161 ℃.
Embodiment 13: the rac-lactide ring-opening polymerization of the 1e of catalyst I
Change the 1a of the catalyst I among the embodiment 9 1e of catalyst I into, other conditions can obtain poly(lactic acid) 1.0g with embodiment 9, and number-average molecular weight is 0.72 ten thousand, and fusing point is 158 ℃.
Embodiment 14: the rac-lactide ring-opening polymerization of the 2a of catalyst I I
Under the anhydrous and oxygen-free condition, rac-lactide (the 1.5g that recrystallization is crossed, 10.4mmol) and the 2a (15.2mg of enol form lactide open-ring polymerization catalyst II of the present invention, 0.052mmol) mixed, toluene is joined in the rac-Lactide and enol form lactide open-ring polymerization catalyst miscellany of the present invention that above-mentioned recrystallization crosses, 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 60 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 1.2g poly(lactic acid), was standard substance with the polystyrene, and the number-average molecular weight that GPC records product is 2.5 ten thousand, and this polymkeric substance is crystalline, and fusing point is 167 ℃.
Embodiment 15: the rac-lactide ring-opening polymerization of the 2b of catalyst I I
Change the 2a of the catalyst I I among the embodiment 14 2b of catalyst I I into, other conditions can obtain poly(lactic acid) 1.2g with embodiment 14, and number-average molecular weight is 2.3 ten thousand, and fusing point is 165 ℃.
Embodiment 16: the rac-lactide ring-opening polymerization of the 2c of catalyst I I
Change the 2a of the catalyst I I among the embodiment 14 2c of catalyst I I into, other conditions can obtain poly(lactic acid) 1.0g with embodiment 14, and number-average molecular weight is 2.2 ten thousand, and fusing point is 162 ℃.
Embodiment 17: the rac-lactide ring-opening polymerization of the 2d of catalyst I I
Change the 2a of the catalyst I I among the embodiment 14 2d of catalyst I I into, other conditions can obtain poly(lactic acid) 1.1g with embodiment 14, and number-average molecular weight is 2.6 ten thousand, and fusing point is 164 ℃.
Embodiment 18: the rac-lactide ring-opening polymerization of the 2e of catalyst I I
Change the 2a of the catalyst I I among the embodiment 14 2e of catalyst I I into, other conditions can obtain poly(lactic acid) 1.2g with embodiment 14, and number-average molecular weight is 2.8 ten thousand, and fusing point is 165 ℃.
Embodiment 19: the rac-lactide ring-opening polymerization of the 3a of catalyst I II
Under the anhydrous and oxygen-free condition, rac-lactide (the 1.5g that recrystallization is crossed, 10.4mmol) and the 3a (24.6mg of enol form lactide open-ring polymerization catalyst III of the present invention, 0.07mmol) mixed, toluene is joined in the rac-Lactide and enol form lactide open-ring polymerization catalyst miscellany of the present invention that above-mentioned recrystallization crosses, 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 (30ml) dissolve polymer, be settled out polymkeric substance with excessive second.Polymkeric substance vacuum-drying at room temperature 48 hours, its vacuum tightness was 0.1MPa at last, obtained the 1.0g poly(lactic acid), was standard substance with the polystyrene, and the number-average molecular weight that GPC records product is 1.9 ten thousand.
Embodiment 20: the rac-lactide ring-opening polymerization of the 3b of catalyst I II
Change the 3a of the catalyst I II among the embodiment 19 3b of catalyst I II into, other conditions can obtain poly(lactic acid) 1.2g with embodiment 19, and number-average molecular weight is 20,000.
Embodiment 21: the rac-lactide ring-opening polymerization of the 3c of catalyst I II
Change the 3a of the catalyst I II among the embodiment 19 3c of catalyst I II into, other conditions can obtain poly(lactic acid) 1.1g with embodiment 19, and number-average molecular weight is 2.1 ten thousand.
Embodiment 22: the rac-lactide ring-opening polymerization of the 3d of catalyst I II
Change the 3a of the catalyst I II among the embodiment 19 3d of catalyst I II into, other conditions can obtain poly(lactic acid) 1.2g with embodiment 19, and number-average molecular weight is 20,000.
Embodiment 23: the rac-lactide ring-opening polymerization of the 3e of catalyst I II
Change the 3a of the catalyst I II among the embodiment 19 3e of catalyst I II into, other conditions can obtain poly(lactic acid) 1.4g with embodiment 19, and number-average molecular weight is 2.2 ten thousand.
Embodiment 24: the rac-lactide ring-opening polymerization of the 4a of catalyst I V
Under the anhydrous and oxygen-free condition, rac-lactide (the 1.5g that recrystallization is crossed, 10.4mmol) and the 4a (57.9mg of enol form lactide open-ring polymerization catalyst IV of the present invention, 0.15mmol) mixed, toluene is joined in the rac-Lactide and enol form lactide open-ring polymerization catalyst miscellany of the present invention that above-mentioned recrystallization crosses, 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 7 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), was standard substance with the polystyrene, and the number-average molecular weight that GPC records product is 10,000, and this polymkeric substance is crystalline, and fusing point is 168 ℃.
Embodiment 25: the rac-lactide ring-opening polymerization of the 4b of catalyst I V
Change the 4a of the catalyst I V among the embodiment 24 4b of catalyst I V into, other conditions can obtain poly(lactic acid) 1.2g with embodiment 24, and number-average molecular weight is 0.9 ten thousand, and this polymkeric substance is crystalline, and fusing point is 166 ℃.
Embodiment 26: the rac-lactide ring-opening polymerization of the 4c of catalyst I V
Change the 4a of the catalyst I V among the embodiment 24 4c of catalyst I V into, other conditions can obtain poly(lactic acid) 1.3g with embodiment 24, and number-average molecular weight is 1.1 ten thousand, and this polymkeric substance is crystalline, and fusing point is 168 ℃.
Embodiment 27: the rac-lactide ring-opening polymerization of the 4d of catalyst I V
Change the 4a of the catalyst I V among the embodiment 24 4d of catalyst I V into, other conditions can obtain poly(lactic acid) 1.4g with embodiment 24, and number-average molecular weight is 0.9 ten thousand, and this polymkeric substance is crystalline, and fusing point is 165 ℃.
Embodiment 28: the rac-lactide ring-opening polymerization of the 4e of catalyst I V
Change the 4a of the catalyst I V among the embodiment 24 4e of catalyst I V into, other conditions can obtain poly(lactic acid) 1.3g with embodiment 24, and number-average molecular weight is 1.2 ten thousand, and this polymkeric substance is crystalline, and fusing point is 163 ℃.
Embodiment 29: the levorotatory lactide ring-opening polymerization of the 1a of catalyst I
Under the anhydrous and oxygen-free condition, levorotatory lactide (the 2g that recrystallization is crossed, 13.9mmol) and the 1a (12.9mg of enol form lactide open-ring polymerization catalyst I of the present invention, 0.046mmol) mixed, toluene is joined in the rac-Lactide and enol form lactide open-ring polymerization catalyst miscellany of the present invention that above-mentioned recrystallization crosses, 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 19 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 1.8g poly(lactic acid), was standard substance with the polystyrene, and the number-average molecular weight that GPC records product is 40,000, and this polymkeric substance is crystalline, and fusing point is 155 ℃.
Embodiment 30: 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 (48.4mg of enol form lactide open-ring polymerization catalyst II of the present invention, 0.15mmol) mixed, toluene is joined in the rac-Lactide and enol form lactide open-ring polymerization catalyst miscellany of the present invention that above-mentioned recrystallization crosses, 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 60 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), was standard substance with the polystyrene, and the number-average molecular weight that GPC records product is 10,000, and this polymkeric substance is crystalline, and fusing point is 152 ℃.
Embodiment 31: 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 (60.3mg of enol form lactide open-ring polymerization catalyst catalyst I V of the present invention, 0.15mmol) mixed, toluene is joined in the rac-Lactide and enol form lactide open-ring polymerization catalyst miscellany of the present invention that above-mentioned recrystallization crosses, 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 7 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), was standard substance with the polystyrene, and the number-average molecular weight that GPC records product is 1.1 ten thousand.
Embodiment 32: the mixture ring-opening polymerization of the levorotatory lactide of the 4c of catalyst I V and 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) with the 4c (60.3mg of enol form lactide open-ring polymerization catalyst catalyst I V of the present invention, 0.15mmol) mixed, toluene is joined in the rac-Lactide and enol form lactide open-ring polymerization catalyst miscellany of the present invention that above-mentioned recrystallization crosses, 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 7 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), was standard substance with the polystyrene, and the number-average molecular weight that GPC records product is 0.9 ten thousand.
Claims (3)
1, a kind of enol form lactide open-ring polymerization catalyst, it comprises the compound of following structural formula,
Structural formula I is as follows:
Come the different R of expression I with 1a, 1b, 1c, 1d and 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;
Structural formula II is as follows:
Come the different R of expression II with 2a, 2b, 2c, 2d and 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;
Structural formula II I is as follows:
Represent the R that formula III is different with 3a, 3b, 3c, 3d and 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;
Structural formula IV is as follows:
Come the different R of expression IV with 4a, 4b, 4c, 4d and 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.
2, the preparation method of enol form lactide open-ring polymerization catalyst as claimed in claim 1, preparation process and condition are as follows:
(a) the enol form Schiff's base is selected from the compound with following enol-type structure:
(b) under protection of inert gas, be dissolved in enol form Schiff's base described in (a) 1,2,3 or 4 in the toluene respectively, aluminium triethyl toluene solution under protection of inert gas is joined respectively in the toluene solution of enol form Schiff's base 1,2,3 or 4, and the mol ratio of enol form 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, its vacuum tightness is 0.1MPa, obtains the enol form lactide open-ring polymerization catalyst of the 4a of the 3a of 2a, III of 1a, II that structural formula of the present invention is I or IV respectively;
(d) structural formula that again (c) is obtained respectively is that the enol form lactide open-ring polymerization catalyst of the 4a of the 3a of 2a, III of 1a, II of I or IV is dissolved in the 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 4e enol form lactide open-ring polymerization catalyst of the 4d of the 4b of IV, the 4c of IV, IV or IV.
3, enol form lactide open-ring polymerization catalyst as claimed in claim 1 is applied to rac-Lactide, comprise levorotatory lactide, the dextrorotation rac-Lactide, Study of Meso-Lactide, the polymeric method method of the mixture of arbitrary proportion is as follows between rac-lactide and levorotatory lactide and the dextrorotation rac-Lactide:
(a) under the anhydrous and oxygen-free condition, mixed rac-Lactide and enol form lactide open-ring polymerization catalyst of the present invention that recrystallization is crossed, it is the 1/40-1/300 of rac-Lactide that this catalyzer adds molar weight;
(b) toluene is joined in the rac-Lactide and enol form lactide open-ring polymerization catalyst miscellany of the present invention that above-mentioned recrystallization crosses, make rac-Lactide concentration be the solution of 0.5mmol/mL, the oil bath that this solution is put into 70 ℃ is also stirred, and polymerization time is 7-60 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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| WO2010022683A1 (en) | 2008-09-01 | 2010-03-04 | 南京工业大学 | Method for preparing polylactic acid and products thereof using a twin-screw extruder |
| WO2010022685A1 (en) | 2008-09-01 | 2010-03-04 | 南京工业大学 | Preparation method of polylactic acid by catalysis of carbene derivatives |
| US9040653B2 (en) | 2008-09-01 | 2015-05-26 | Nanjing University Of Technology | Ring-opening polymerization of cyclic compounds catalyzed by carbene derivatives |
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| CN107955146A (en) * | 2017-12-12 | 2018-04-24 | 济南大学 | Utilize the method for the chiral aluminum complex catalysis lactide polymerization containing acetylacetone,2,4-pentanedione derivative |
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| GB0228888D0 (en) * | 2002-12-11 | 2003-01-15 | Johnson Matthey Plc | Polymerisation reaction and catalyst therefor |
| CN1212343C (en) * | 2003-11-27 | 2005-07-27 | 中国科学院长春应用化学研究所 | Catalyst for ring-opening polymerization of cyclic ester and preparation method thereof |
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| WO2010022683A1 (en) | 2008-09-01 | 2010-03-04 | 南京工业大学 | Method for preparing polylactic acid and products thereof using a twin-screw extruder |
| WO2010022685A1 (en) | 2008-09-01 | 2010-03-04 | 南京工业大学 | Preparation method of polylactic acid by catalysis of carbene derivatives |
| US8241545B2 (en) | 2008-09-01 | 2012-08-14 | Nanjing Universty of Technology | Method of making polylactic acid and its products |
| US9029497B2 (en) | 2008-09-01 | 2015-05-12 | Nanjing University Of Technology | Method of making polylactic acid using carbene derivatives as the catalyst |
| US9040653B2 (en) | 2008-09-01 | 2015-05-26 | Nanjing University Of Technology | Ring-opening polymerization of cyclic compounds catalyzed by carbene derivatives |
| US11015021B2 (en) | 2017-04-28 | 2021-05-25 | Nanjing Tech University | Method for preparation of a polyester |
| CN107936238A (en) * | 2017-12-12 | 2018-04-20 | 泰山医学院 | Utilize the method for the asymmetric aluminum complex catalysis glycolide polymerization of the derivative containing acetylacetone,2,4-pentanedione |
| CN107955146A (en) * | 2017-12-12 | 2018-04-24 | 济南大学 | Utilize the method for the chiral aluminum complex catalysis lactide polymerization containing acetylacetone,2,4-pentanedione derivative |
| CN108084411A (en) * | 2017-12-12 | 2018-05-29 | 济南大学 | Utilize the method for the chiral aluminum complex catalysis glycolide polymerization containing acetylacetone,2,4-pentanedione derivative |
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