CN1544504A - Catalyst for ring-opening polymerization of cyclic ester and preparation method thereof - Google Patents
Catalyst for ring-opening polymerization of cyclic ester and preparation method thereof Download PDFInfo
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- CN1544504A CN1544504A CNA2003101158211A CN200310115821A CN1544504A CN 1544504 A CN1544504 A CN 1544504A CN A2003101158211 A CNA2003101158211 A CN A2003101158211A CN 200310115821 A CN200310115821 A CN 200310115821A CN 1544504 A CN1544504 A CN 1544504A
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- CN
- China
- Prior art keywords
- lactide
- rac
- opening polymerization
- cyclic esters
- schiff
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- -1 cyclic ester Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000007151 ring opening polymerisation reaction Methods 0.000 title claims description 22
- 239000003054 catalyst Substances 0.000 title abstract description 16
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 11
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004411 aluminium Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 43
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 41
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 22
- 125000004122 cyclic group Chemical group 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 239000004626 polylactic acid Substances 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 238000003808 methanol extraction Methods 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 5
- AVKUERGKIZMTKX-NJBDSQKTSA-N ampicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=CC=C1 AVKUERGKIZMTKX-NJBDSQKTSA-N 0.000 description 3
- 229920006125 amorphous polymer Polymers 0.000 description 2
- 230000000707 stereoselective effect Effects 0.000 description 2
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form 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
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a category of cyclic ester open loop polymerization catalyst and method for preparation, it also relates to the process for polymerizing racemic lactide by using these catalysts, wherein the catalysts are the product of the reaction between Schiff's base and aluminium triethide or aluminium isopropoxide, they exhibit stereoselectivity to the polymerization of racemic lactide, thus crystallinity polylactic acid can be obtained through polymerizing racemic lactide.
Description
Technical field
The present invention relates to class cyclic esters ring-opening polymerization catalyst and preparation method thereof, and the method for using this class catalyzer stereoselectivity polymerization rac-lactide.
Technical background
From point of view of environment protection, it is biodegradable needing polymkeric substance, abandons and pollutes to reduce refuse.Poly(lactic acid) is a kind of have good biocompatibility, Biodegradable Polymers, compares with polyolefine, and from the environmental protection aspect, it has unrivaled excellent specific property.Simultaneously, at medical field, the application of poly(lactic acid) also more and more widely, for example: it can be used as suture line, nail, bone rod, medicine sustained release carrier.
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 and rare earth compound etc.These traditional catalyzer do not have selectivity to the rac-Lactide of isomorphism type not, when coming the polymerization rac-lactide with them, can only obtain amorphous polymer.But amorphous 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 amorphous poly(lactic acid) near melt temperature.Therefore, the needs exploitation is a kind of, and polymerization has stereoselective cyclic esters ring-opening polymerization catalyst to rac-Lactide, and its can obtain crystalline polylactic acid by polymerization rac-lactide.
Summary of the invention
The purpose of this invention is to provide a class cyclic esters ring-opening polymerization catalyst;
Another object of the present invention provides the preparation method of a class cyclic esters ring-opening polymerization catalyst;
The 3rd purpose of the present invention provides the application of a class cyclic esters ring-opening polymerization catalyst.
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 catalyzer of some steric hindrances, based on this idea, the present invention has selected a class cyclic esters ring-opening polymerization catalyst, and they have following structure:
With Salepen (
tBu) AlEt represents;
With Salepen (
tBu) AlO
iPr represents;
With Schiff's base, aluminium triethyl or aluminum isopropylate is raw material, and preparation process is as follows:
(a) under protection of inert gas, Schiff's base, aluminium triethyl or aluminum isopropylate are dissolved in the toluene, wherein Schiff's base is meant the compound with following structure:
With Salmpen (
tBu) H
2Expression;
(b) control Schiff's base and aluminium triethyl or with the mol ratio of aluminum isopropylate be 1: 1, under agitation condition, they mixing;
(c) temperature control 50-120 ℃, stir, cooling vacuumizes and removes volatile matter then, obtains Schiff's base-aluminum compound, and gained Schiff's base-aluminum compound is exactly a cyclic esters ring-opening polymerization catalyst of the present invention.
Cyclic esters ring-opening polymerization catalyst of the present invention, stereoselectivity polymerization rac-lactide obtains crystalline polylactic acid, and its polymerization process is as follows:
(a) under the anhydrous and oxygen-free condition, mixed rac-lactide and cyclic esters ring-opening polymerization catalyst that recrystallization is crossed, the add-on of catalyzer is the 1/50-1/600 (mol ratio) of rac-lactide, wherein, rac-lactide is meant that be the product that mixing in 1: 1 forms by levorotatory lactide and dextrorotation rac-Lactide with mol ratio, and the structure of levorotatory lactide and dextrorotation rac-Lactide is as follows respectively:
The dextrorotation rac-Lactide,
Levorotatory lactide
(b) add toluene and stirring in (a), the controlled polymerization temperature is 50-120 ℃, and polymerization time is 6-96 hour;
(c) with polymkeric substance in (b) molten be dichloromethane solution, with excessive methanol precipitation, filtration, vacuum-drying at room temperature obtains poly(lactic acid).
Embodiment
By embodiment the present invention is carried out more detailed explanation below, still, should be appreciated that these embodiment only are in order to explain the present invention, rather than the present invention is limited.Any change of on basis of the present invention, having done, substitute or modify and all do not exceed the spirit and scope of the present invention.
Embodiment 1: catalyst S almpen (
tBu) AlEt, synthetic
Stir and the protective condition of rare gas element under, the Schiff's base Salmpen of 4ml (
tBu) H
2The AlEt of toluene solution (1mol/L) and 4ml
3Toluene solution (1mol/L) is mixed, and 80 ℃ of temperature controls stirred 48 hours, lowers the temperature then, vacuumizes and removes volatile matter, obtain product S almpen (
tBu) AlEt 2.24g, productive rate are 95.1%.Results of elemental analyses,
Calculated value: C, 75.47; H, 9.76; N, 4.76; Measured value: C, 75.52; H, 9.59; N, 4.88.
Embodiment 2: catalyst S almpen (
tBu) AlO
iPr's is synthetic
Except the AlEt in the example 1
3Change aluminum isopropylate into, temperature of reaction changes into outside 120 ℃, and other step is identical with example 1, obtain product S almpen (
tBu) AlO
iPr 2.31g, productive rate are 93.3%.Results of elemental analyses, calculated value: C, 73.75; H, 9.61; N, 4.53; Measured value: C, 73.98; H, 9.87; N, 4.16.
Embodiment 3: catalyst S alepen (
tBu) AlEt's is synthetic
Except the Schiff's base in the example 1 is changed into Salepen (
tBu) H
2, temperature of reaction changes into outside 50 ℃, other step is identical with example 1, obtain product S alepen (
tBu) AlEt 2.38g, productive rate are 96.5%.Results of elemental analyses, calculated value: C, 75.93; H, 9.97; N, 4.54; Measured value: C, 75.97; H, 10.21; N, 4.66.
Embodiment 4: catalyst S alepen (
tBu) AlO
iPr's is synthetic
Except the AlEt in the example 3
3Change into outside the aluminum isopropylate, other step is identical with example 3, obtain product S alepen (
tBu) AlO
iPr 2.49g, productive rate are 96.2%.Results of elemental analyses, calculated value: C, 74.26; H, 9.82; N, 4.33; Measured value: C, 73.90; H, 9.97; N, 4.52.
Embodiment 5: catalyst S alpen (
tBu) AlO
iPr's is synthetic
Except the Schiff's base in the example 2 is changed into Salpen (
tBu) H
2Outward, other step is identical with example 2, obtain product S alpen (
tBu) AlO
iPr 2.25g, productive rate are 95.2%.Results of elemental analyses, calculated value: C, 73.18; H, 9.38; N, 4.74; Measured value: C, 73.50; H, 9.56; N, 4.94.
Embodiment 6.
Under the protection of high-purity argon gas, add in proper order in the ampere bottle of handling through anhydrous and oxygen-free earlier rac-lactide (2.88g, 20mmol), catalyst S almpen (
tBu) (235.5mg 0.4mmol) with 40ml toluene, places 70 ℃ of oil baths to the ampere bottle to AlEt again, reacts after 12 hours, with methylene dichloride (60ml) dissolve polymer, goes out polymkeric substance with the q.s methanol extraction.Polymkeric substance vacuum-drying at room temperature 48 hours, obtaining the 2.5g polymkeric substance at last, is standard substance with the polystyrene, and the number-average molecular weight that GPC records product is 1.6 ten thousand, and this polymkeric substance is crystalline, and fusing point is 190 ℃.
Embodiment 7.
Under the protection of high-purity argon gas, add in proper order in the ampere bottle of handling through anhydrous and oxygen-free earlier rac-lactide (5.76g, 40mmol), catalyst S almpen (
tBu) (235.5mg 0.4mmol) with 80ml toluene, places 70 ℃ of oil baths to the ampere bottle to AlEt again, reacts after 24 hours, with methylene dichloride (120ml) dissolve polymer, goes out polymkeric substance with the q.s methanol extraction.Polymkeric substance vacuum-drying at room temperature 48 hours, obtaining the 5.0g polymkeric substance at last, is standard substance with the polystyrene, and the number-average molecular weight that GPC records product is 2.2 ten thousand, and this polymkeric substance is crystalline, and fusing point is 192 ℃.
Embodiment 8.
Under the protection of high-purity argon gas, add in proper order in the ampere bottle of handling through anhydrous and oxygen-free earlier rac-lactide (2.88g, 20mmol), catalyst S almpen (
tBu) AlO
i(247.5mg 0.4mmol) with 40ml toluene, places 70 ℃ of oil baths to the ampere bottle to Pr again, reacts after 24 hours, with methylene dichloride (60ml) dissolve polymer, goes out polymkeric substance with the q.s methanol extraction.Polymkeric substance vacuum-drying at room temperature 48 hours, obtaining the 2.4g polymkeric substance at last, is standard substance with the polystyrene, and the number-average molecular weight that GPC records product is 0.83 ten thousand, and this polymkeric substance is crystalline, and fusing point is 201 ℃.
Embodiment 9.
Under the protection of high-purity argon gas, add in proper order in the ampere bottle of handling through anhydrous and oxygen-free earlier rac-lactide (8.65g, 60mmol), catalyst S almpen (
tBu) AlO
i(123.8mg 0.2mmol) with 120ml toluene, places 70 ℃ of oil baths to the ampere bottle to Pr again, reacts after 48 hours, with methylene dichloride (180ml) dissolve polymer, goes out polymkeric substance with the q.s methanol extraction.Polymkeric substance vacuum-drying at room temperature 48 hours, obtaining the 7.5g polymkeric substance at last, is standard substance with the polystyrene, and the number-average molecular weight that GPC records product is 4.2 ten thousand, and this polymkeric substance is crystalline, and fusing point is 188 ℃.
Embodiment 10.
Under the protection of high-purity argon gas, add in proper order in the ampere bottle of handling through anhydrous and oxygen-free earlier rac-lactide (8.65g, 60mmol), catalyst S almpen (
tBu) AlO
i(61.9mg 0.1mmol) with 120ml toluene, places 50 ℃ of oil baths to the ampere bottle to Pr again, reacts after 96 hours, with methylene dichloride (180ml) dissolve polymer, goes out polymkeric substance with the q.s methanol extraction.Polymkeric substance vacuum-drying at room temperature 48 hours, obtaining the 6.6g polymkeric substance at last, is standard substance with the polystyrene, and the number-average molecular weight that GPC records product is 7.9 ten thousand, and this polymkeric substance is crystalline, and fusing point is 190 ℃.
Embodiment 11.
Under the protection of high-purity argon gas, add in proper order in the ampere bottle of handling through anhydrous and oxygen-free earlier rac-lactide (5.76g, 40mmol), catalyst S alepen (
tBu) (123.4mg 0.2mmol) with 80ml toluene, places 70 ℃ of oil baths to the ampere bottle to AlEt again, reacts after 48 hours, with methylene dichloride (120ml) dissolve polymer, goes out polymkeric substance with the q.s methanol extraction.Polymkeric substance vacuum-drying at room temperature 48 hours, obtaining the 5.3g polymkeric substance at last, is standard substance with the polystyrene, and the number-average molecular weight that GPC records product is 3.5 ten thousand, and this polymkeric substance is crystalline, and fusing point is 191 ℃.
Embodiment 12.
Under the protection of high-purity argon gas, add in proper order in the ampere bottle of handling through anhydrous and oxygen-free earlier rac-lactide (5.76g, 40mmol), catalyst S alepen (
tBu) AlO
i(64.6mg 0.1mmol) with 80ml toluene, places 70 ℃ of oil baths to the ampere bottle to Pr again, reacts after 96 hours, with methylene dichloride (120ml) dissolve polymer, goes out polymkeric substance with the q.s methanol extraction.Polymkeric substance vacuum-drying at room temperature 48 hours, obtaining the 4.7g polymkeric substance at last, is standard substance with the polystyrene, and the number-average molecular weight that GPC records product is 6.2 ten thousand, and this polymkeric substance is crystalline, and fusing point is 194 ℃.
Embodiment 13.
Under the protection of high-purity argon gas, add in proper order in the ampere bottle of handling through anhydrous and oxygen-free earlier rac-lactide (5.76g, 40mmol), catalyst S alpen (
tBu) AlO
i(236.3mg 0.4mmol) with 80ml toluene, places 120 ℃ of oil baths to the ampere bottle to Pr again, reacts after 6 hours, with methylene dichloride (120ml) dissolve polymer, goes out polymkeric substance with the q.s methanol extraction.Polymkeric substance vacuum-drying at room temperature 48 hours, obtaining the 5.5g polymkeric substance at last, is standard substance with the polystyrene, and the number-average molecular weight that GPC records product is 2.7 ten thousand, and this polymkeric substance is crystalline, and fusing point is 150 ℃.
Claims (5)
1, a class cyclic esters ring-opening polymerization catalyst, it has following general structure:
Wherein, R is ethyl or isopropoxy, R
1, R
2Be hydrogen, methyl or ethyl.
2, the preparation method of cyclic esters ring-opening polymerization catalyst as claimed in claim 1, preparation process is as follows:
(a) under protection of inert gas, Schiff's base, aluminium triethyl or aluminum isopropylate are dissolved in the toluene;
(b) control Schiff's base and aluminium triethyl or with the mol ratio of aluminum isopropylate be 1: 1, under agitation condition, they mixing;
(c) temperature control 50-120 ℃, stir, cooling vacuumizes and removes volatile matter then, obtains Schiff's base-aluminum compound.
3,, it is characterized in that described Schiff's base is meant the compound with following structure as the preparation method of claim 1,2 described cyclic esters ring-opening polymerization catalysts:
With Salpen (
tBu) H
2Expression;
With Salmpen (
tBu) H
2Expression;
With Salepen (
tBu) H
2Expression;
4, it is as follows that cyclic esters ring-opening polymerization catalyst as claimed in claim 1 is applied to the stereoselectivity polymerization process of rac-lactide:
(a) under the anhydrous and oxygen-free condition, mixed rac-lactide and cyclic esters ring-opening polymerization catalyst that recrystallization is crossed, the add-on of catalyzer is that the mol ratio of rac-lactide is 1/50-1/600;
(b) add toluene and stirring in (a), the controlled polymerization temperature is 50-120 ℃, and polymerization time is 6-96 hour;
(c) with polymkeric substance in (b) molten be dichloromethane solution, with excessive methanol precipitation, filtration, vacuum-drying at room temperature obtains poly(lactic acid).
5, cyclic esters ring-opening polymerization catalyst as claimed in claim 4 is applied to the stereoselectivity polymerization process of rac-lactide, it is characterized in that described rac-lactide is meant that be the product that mixing in 1: 1 forms by levorotatory lactide and dextrorotation rac-Lactide with mol ratio, the structure of levorotatory lactide and dextrorotation rac-Lactide is as follows respectively:
The dextrorotation rac-Lactide,
Levorotatory lactide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310115821 CN1212343C (en) | 2003-11-27 | 2003-11-27 | Catalyst for ring-opening polymerization of cyclic ester and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310115821 CN1212343C (en) | 2003-11-27 | 2003-11-27 | Catalyst for ring-opening polymerization of cyclic ester and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1544504A true CN1544504A (en) | 2004-11-10 |
| CN1212343C CN1212343C (en) | 2005-07-27 |
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393771C (en) * | 2006-03-03 | 2008-06-11 | 中国科学院长春应用化学研究所 | Schiff-base aluminium catalyst for lactide open-ring polymerization, and it spreparing method and use |
| 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 |
| WO2010022684A1 (en) | 2008-09-01 | 2010-03-04 | 南京工业大学 | Method of adjustable and controllable ring-opening polymerization of cyclic compounds by catalysis of carbene derivatives |
| CN102627760A (en) * | 2012-04-12 | 2012-08-08 | 中国科学院长春应用化学研究所 | Catalyst composition and preparation method of polylactic acid |
| CN102786544A (en) * | 2012-08-28 | 2012-11-21 | 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 |
| US9029497B2 (en) | 2008-09-01 | 2015-05-12 | Nanjing University Of Technology | Method of making polylactic acid using carbene derivatives as the catalyst |
| CN105143303A (en) * | 2013-03-18 | 2015-12-09 | 沙特基础工业公司 | Process for preparing a copolymer |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100406491C (en) * | 2006-03-03 | 2008-07-30 | 中国科学院长春应用化学研究所 | Enol form lactide open-ring polymerization catalyst and its preparing method and use |
| CN100406492C (en) * | 2006-03-17 | 2008-07-30 | 中国科学院长春应用化学研究所 | Ring-opening polymerization catalyst for lactide and process for preparing same |
-
2003
- 2003-11-27 CN CN 200310115821 patent/CN1212343C/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393771C (en) * | 2006-03-03 | 2008-06-11 | 中国科学院长春应用化学研究所 | Schiff-base aluminium catalyst for lactide open-ring polymerization, and it spreparing method and use |
| 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 |
| WO2010022684A1 (en) | 2008-09-01 | 2010-03-04 | 南京工业大学 | Method of adjustable and controllable ring-opening polymerization of cyclic compounds 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 |
| CN102627760A (en) * | 2012-04-12 | 2012-08-08 | 中国科学院长春应用化学研究所 | Catalyst composition and preparation method of polylactic acid |
| CN102627760B (en) * | 2012-04-12 | 2014-08-06 | 中国科学院长春应用化学研究所 | Catalyst composition and preparation method of polylactic acid |
| CN102786544A (en) * | 2012-08-28 | 2012-11-21 | 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 |
| 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 |
| CN105143303A (en) * | 2013-03-18 | 2015-12-09 | 沙特基础工业公司 | Process for preparing a copolymer |
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| Publication number | Publication date |
|---|---|
| CN1212343C (en) | 2005-07-27 |
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