EP2147001A2 - Catalyst and method for polymerization and copolymerization of lactide - Google Patents
Catalyst and method for polymerization and copolymerization of lactideInfo
- Publication number
- EP2147001A2 EP2147001A2 EP08734573A EP08734573A EP2147001A2 EP 2147001 A2 EP2147001 A2 EP 2147001A2 EP 08734573 A EP08734573 A EP 08734573A EP 08734573 A EP08734573 A EP 08734573A EP 2147001 A2 EP2147001 A2 EP 2147001A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- lactide
- represented
- polymerization
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims description 16
- 238000007334 copolymerization reaction Methods 0.000 title abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 239000012634 fragment Substances 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 3
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 23
- 239000003446 ligand Substances 0.000 claims description 15
- -1 hydrocarbon radicals Chemical class 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 7
- 239000000539 dimer Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 claims 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 claims 1
- 150000005840 aryl radicals Chemical class 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229920002988 biodegradable polymer Polymers 0.000 abstract description 2
- 239000004621 biodegradable polymer Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract 1
- 239000002685 polymerization catalyst Substances 0.000 abstract 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910019092 Mg-O Inorganic materials 0.000 description 5
- 229910019395 Mg—O Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical group N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 4
- 238000012552 review Methods 0.000 description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 4
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910000071 diazene Inorganic materials 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 150000002680 magnesium Chemical class 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 150000001398 aluminium Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001432 poly(L-lactide) Polymers 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000005838 radical anions Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000002424 x-ray crystallography Methods 0.000 description 2
- KILURZWTCGSYRE-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]alumanyloxypent-3-en-2-one Chemical compound CC(=O)\C=C(\C)O[Al](O\C(C)=C/C(C)=O)O\C(C)=C/C(C)=O KILURZWTCGSYRE-LNTINUHCSA-K 0.000 description 1
- JBCIVYVLDKPKDM-UHFFFAOYSA-N 1-n,2-n-bis[2,6-di(propan-2-yl)phenyl]acenaphthylene-1,2-diimine Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N=C(C=1C2=C3C=CC=C2C=CC=1)C3=NC1=C(C(C)C)C=CC=C1C(C)C JBCIVYVLDKPKDM-UHFFFAOYSA-N 0.000 description 1
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 241000204102 Pseudonocardiaceae Species 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- QAZYYQMPRQKMAC-FDGPNNRMSA-L calcium;(z)-4-oxopent-2-en-2-olate Chemical compound [Ca+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O QAZYYQMPRQKMAC-FDGPNNRMSA-L 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000002290 germanium Chemical class 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229940050168 zinc lactate Drugs 0.000 description 1
- 235000000193 zinc lactate Nutrition 0.000 description 1
- 239000011576 zinc lactate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
Definitions
- the invention relates to a method and catalysts for polymerization and copolymerization of lactide.
- the polylactides can be consumed by microorganisms, for example Pseudonocardiaceae (Applied Microbiology and Biotechnology, 2006, 72, 244).
- Pseudonocardiaceae Applied Microbiology and Biotechnology, 2006, 72, 244.
- the methods for preparation of polylactides are investigated intensively in many industrial and academic research centres in the world.
- Syndiotactic polylactide has been obtained using chiral aluminium alkoxides (USA Pat. 6608170).
- aluminium-alkyl complexes act also as catalyst in the ring-opening polymerisation of lactide (USA Pat. 6376643).
- Some group 11 , 12 and 14 metal complexes bearing tridentate ligands provide for the formation of the polylactide.
- the aims of the invention are the following: (1 ) an increasing the catalyst activity in the lactide polymerization process; (2) a shortening of the polymerization process duration; (3) an improvement of the conversion rates; (4) a conduction of the polymerization at ambient temperatures. Also the invention aims on the preparation of magnesium, calcium, strontium, barium, zinc, aluminium, gallium and germanium complexes, which can be used as catalysts of chemical processes, and especially for polymerisation of lactide.
- the indicated aims of the invention are achieved via the following items:
- a central metal atom of a catalyst is oxophilic and thus is able to coordinate oxygen atom of the lactide and open its ring;
- the conformational ⁇ rigid ligand belongs to ligands of variable oxidation state and thus may accept/donate electrons within the chemical reactions, including those with lactide.
- the rigid ligand of a catalyst may have a chiral carbon atom, thus providing for a control of microstructure of a polylactide formed.
- a contact of a catalyst with monomer leads to formation of polymer in the temperature range from 0 to + 250 0 C.
- the invented catalysts can be prepared in 2 to 3 stages from commercially available starting materials.
- the invented catalysts are neither toxic, nor explosive or flammable.
- the polylactide prepared combining rac-lactide and the invented catalysts always has a stereoblock microstructure, and combining L-lactide and the invented catalysts - isotactic microstructure. Novelty of the present invention is confirmed by the absence in the prototype and other publications combination of high catalytic activity, high molecular weight and stereoregularity of formed polylactide.
- Figure 1 presents the general scheme of ring-opening polymerization of lactide.
- Figure 5 shows a field of methine proton signals in 1 H NMR spectra of L-lactide and the poly-L-lactide prepared thereof using catalysts shown in Figure 2.
- Figure 6 shows a field of methine proton signals in 1 H NMR spectrum (spin-spin coupling suppressed) of poly-rac-lactide prepared using catalysts shown in Figure 2.
- Table 1 summarizes the X-ray crystallography data for the catalysts depicted in Figures 2, 3 and 4. Main bond distances and angles in molecules of these catalysts are summarized in Table 2.
- Table 3 details of the polymerization processes and the some characteristics of the polylactides obtained are presented.
- the catalyst for polymerization and (co)polymerization of lactide comprising metal compound, represented by the general formula:
- M - metal selected from group Zn(II), Mg(II), Ca(II), Sr(II), Ba(II), AI(III), Ga(III), Ge(II)
- R 1 M R 2 - hydrocarbon radicals or substituted hydrocarbon radicals
- R 3 one or two of alkyl, aryl or heterocyclic radicals
- Catalysts shown in Figures 2 and 4 represent monomeric four-coordinate magnesium complexes.
- dpp-BIAN 1 ,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) chelates metal atoms.
- Distances Mg-O(THF) and Mg-O(Et 2 O) in both molecules are almost the same ( Figure 2: 2.0617(10); Figure 4: 2.0728(12) A).
- Catalyst depicted in Figure 3 has a centro-symmetric dimer structure formed via bridging ferf-butyl groups.
- Distances Mg(1 )-N(1 ) and Mg(1 )-N(2) (2.084, 2.133 A, respectively) somewhat shorter than those in catalysts presented in Figure 2 and 4.
- Comparison of the C-N and C-C bond length in diimine moieties of catalysts ( Figures 2, 3 and 4) with those in other dpp-BIAN magnesium complexes, as well as in free diimine dpp-BIAN indicates radical-anionic character of dpp-BIAN ligand.
- distances C(1 )-N(1 ) and C(2)-N(2) in catalyst in Figure 2 (1.3345(17) and 1.3328(16) A) and in catalyst in Figure 4 (1.339(2) and 1.333(2) A) are elongated compare to the free diimine dpp-BIAN (both C-N 1.28 A), but shortened compare to those in (dpp-BIAN)Mg(THF) 3 (European Journal of Inorganic Chemistry 2003, 3336), which contains dpp-BIAN dianion (1.401(6) and 1.378(7) A).
- distances C(1 )-C(2) in catalysts in Figure 2 and 4 (1.4480(17) and 1.439(2) A, correspondingly) elongated in comparison with (dpp-BIAN)Mg(THF) 3 (1.389(7) A; European Journal of Inorganic Chemistry 2003, 3336)), and shortened compare to free dpp-BIAN (1.534(6) A; Izvestiya Akademii Nauk, Seriya Chimicheskaya 2004, Ne 12, 2634.).
- Examples 1-3 describe variants of catalysts preparation
- examples 4 and 5 represent the use of the prepared catalysts for lactide polymerization as well as some basic properties of the polymers formed. All the manipulations on the synthesis, isolation and identification of the catalysts have been carried out either in the Glovebox, or using standard Schlenk technique.
- Example 5 Polymerization of rac-lactide using catalyst depicted in Figure 2.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2007114954/04A RU2355694C2 (ru) | 2007-04-20 | 2007-04-20 | Катализатор получения полилактидов и способ его синтеза |
| PCT/EE2008/000006 WO2008128548A2 (en) | 2007-04-20 | 2008-04-16 | Catalyst and method for polymerization and copolymerization of lactide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2147001A2 true EP2147001A2 (en) | 2010-01-27 |
Family
ID=39835376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP08734573A Withdrawn EP2147001A2 (en) | 2007-04-20 | 2008-04-16 | Catalyst and method for polymerization and copolymerization of lactide |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP2147001A2 (ru) |
| RU (1) | RU2355694C2 (ru) |
| WO (1) | WO2008128548A2 (ru) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0807607D0 (en) | 2008-04-25 | 2008-06-04 | Imp Innovations Ltd | Catalyst |
| RU2478107C2 (ru) * | 2009-12-25 | 2013-03-27 | Государственное образовательное учреждение высшего профессионального образования Российский химико-технологический университет им. Д.И. Менделеева (РХТУ им. Д.И. Менделеева) | Способ получения биоразлагаемого полимера |
| EP2559725B1 (de) * | 2011-08-19 | 2024-05-08 | Uhde Inventa-Fischer GmbH | Verfahren und Vorrichtung zur Rückgewinnung von Lactid aus Polylactid bzw. Glycolid aus Polyglycolid |
| GB201308978D0 (en) * | 2013-05-17 | 2013-07-03 | Imp Innovations Ltd | Method for producing polymers and block copolymers |
| GB201514506D0 (en) | 2015-08-14 | 2015-09-30 | Imp Innovations Ltd | Multi-block copolymers |
| GB201515350D0 (en) | 2015-08-28 | 2015-10-14 | Econic Technologies Ltd | Method for preparing polyols |
| CN109400777B (zh) * | 2018-11-09 | 2021-01-22 | 河北师范大学 | 基于苊醌双亚胺配体的钒配合物及其制备方法和应用 |
| CN109879810B (zh) * | 2019-03-13 | 2022-10-28 | 华东理工大学 | 一种咪唑环取代的氨基酚氧基锌络合物及其制备方法和应用 |
| RU2726362C1 (ru) * | 2019-11-12 | 2020-07-13 | Акционерное общество "Государственный Ордена Трудового Красного Знамени научно-исследовательский институт химии и технологии элементоорганических соединений" (АО "ГНИИХТЭОС") | Способ получения полилактидов |
| CN112625054B (zh) * | 2020-12-28 | 2022-10-28 | 华东理工大学 | 一种吲哚环取代的氨基酚氧基锌络合物及其制备方法和应用 |
| CN113307820B (zh) * | 2021-05-13 | 2022-10-25 | 华东理工大学 | 一种喹啉环取代的氨基酚氧基锌络合物及其制备方法和应用 |
| CN114874250B (zh) * | 2022-06-07 | 2023-11-14 | 山西大学 | 一种吡啶基含n配位的双金属铝配合物及制备方法和应用 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6133402A (en) * | 1998-08-04 | 2000-10-17 | Cornell Research Foundation, Inc. | Polycarbonates made using high activity catalysts |
| US6316590B1 (en) * | 1999-11-10 | 2001-11-13 | Cornell Research Foundation, Inc. | Synthesis of stereospecific and atactic poly(lactic acid)s |
| GB0027530D0 (en) * | 2000-11-10 | 2000-12-27 | Imperial College | Polymerisation initiator |
| DE102004037201B3 (de) * | 2004-07-30 | 2005-09-08 | Forschungszentrum Karlsruhe Gmbh | Zinkkomplex substituierter 2-Amido-Acrylsäure-Iminoester und dessen Verwendung |
| KR100724550B1 (ko) * | 2004-12-16 | 2007-06-04 | 주식회사 엘지화학 | 이중 금속 아연 착화합물과 이를 촉매로 사용한폴리카보네이트의 제조 방법 |
-
2007
- 2007-04-20 RU RU2007114954/04A patent/RU2355694C2/ru not_active IP Right Cessation
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2008
- 2008-04-16 WO PCT/EE2008/000006 patent/WO2008128548A2/en active Application Filing
- 2008-04-16 EP EP08734573A patent/EP2147001A2/en not_active Withdrawn
Non-Patent Citations (1)
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| See references of WO2008128548A3 * |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2355694C2 (ru) | 2009-05-20 |
| RU2007114954A (ru) | 2008-10-27 |
| WO2008128548A3 (en) | 2008-12-18 |
| WO2008128548A2 (en) | 2008-10-30 |
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