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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- CN1814644A CN1814644A CN 200610016622 CN200610016622A CN1814644A CN 1814644 A CN1814644 A CN 1814644A CN 200610016622 CN200610016622 CN 200610016622 CN 200610016622 A CN200610016622 A CN 200610016622A CN 1814644 A CN1814644 A CN 1814644A
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- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000002685 polymerization catalyst Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims description 6
- 125000002587 enol group Chemical group 0.000 title description 36
- -1 D-lactide Chemical compound 0.000 claims abstract description 72
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 40
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 34
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000004626 polylactic acid Substances 0.000 claims abstract description 3
- 150000002085 enols Chemical class 0.000 claims abstract 10
- 239000002262 Schiff base Substances 0.000 claims abstract 5
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims abstract 4
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 claims abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 74
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000000126 substance Substances 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000000921 elemental analysis Methods 0.000 description 20
- 238000001953 recrystallisation Methods 0.000 description 18
- 229960001701 chloroform Drugs 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 229960004217 benzyl alcohol Drugs 0.000 description 5
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- 230000000707 stereoselective effect Effects 0.000 description 2
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 description 1
- YJSATLBWFLERNZ-MDZDMXLPSA-N 2-[(e)-2-(2-aminophenyl)ethenyl]aniline Chemical compound NC1=CC=CC=C1\C=C\C1=CC=CC=C1N YJSATLBWFLERNZ-MDZDMXLPSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012967 coordination catalyst Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
本发明涉及一种烯醇式丙交酯开环聚合催化剂及其制备方法，还涉及到用这种催化剂聚合丙交酯，包括左旋丙交酯，右旋丙交酯，内消旋丙交酯，外消旋丙交酯以及左旋丙交酯和右旋丙交酯之间任意比例的混合物的方法。本发明中的催化剂是指：烯醇式席夫碱与乙基铝反应生成的产物及其衍生物。它们对外消旋丙交酯的聚合有立体选择性，可以聚合外消旋丙交酯得到结晶性聚乳酸。The present invention relates to a kind of enol type lactide ring-opening polymerization catalyst and its preparation method, also relate to using this catalyst to polymerize lactide, including L-lactide, D-lactide, meso-lactide , racemic lactide and mixtures of any ratio between L-lactide and D-lactide. The catalyst in the present invention refers to: the product and its derivatives formed by the reaction of enol Schiff base and ethylaluminum. They have stereoselectivity for the polymerization of racemic lactide, and can polymerize racemic lactide to obtain crystalline polylactic acid.
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.
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| WO2010022685A1 (en) | 2008-09-01 | 2010-03-04 | 南京工业大学 | Preparation method of polylactic acid by catalysis of carbene derivatives |
| 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 |
| US9040653B2 (en) | 2008-09-01 | 2015-05-26 | Nanjing University Of Technology | Ring-opening polymerization of cyclic compounds catalyzed by carbene derivatives |
| 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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| 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 | Cyclic ester ring-opening polymerization catalyst and preparation method |
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| WO2010022685A1 (en) | 2008-09-01 | 2010-03-04 | 南京工业大学 | Preparation method of polylactic acid by catalysis of carbene derivatives |
| 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 |
| 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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