JP6285465B2 - ポリエステルの新規精製方法 - Google Patents
ポリエステルの新規精製方法 Download PDFInfo
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- JP6285465B2 JP6285465B2 JP2015558490A JP2015558490A JP6285465B2 JP 6285465 B2 JP6285465 B2 JP 6285465B2 JP 2015558490 A JP2015558490 A JP 2015558490A JP 2015558490 A JP2015558490 A JP 2015558490A JP 6285465 B2 JP6285465 B2 JP 6285465B2
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- polyester
- resin
- polymer
- solvent
- lactic acid
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- 238000000034 method Methods 0.000 title claims description 41
- 229920000728 polyester Polymers 0.000 title claims description 40
- 238000000746 purification Methods 0.000 title description 3
- 229920005989 resin Polymers 0.000 claims description 48
- 239000011347 resin Substances 0.000 claims description 48
- 229920000642 polymer Polymers 0.000 claims description 37
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 30
- 229920001429 chelating resin Polymers 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 28
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 16
- 235000014655 lactic acid Nutrition 0.000 claims description 15
- 239000004310 lactic acid Substances 0.000 claims description 15
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 15
- 239000003957 anion exchange resin Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229920001610 polycaprolactone Polymers 0.000 claims description 7
- 239000004632 polycaprolactone Substances 0.000 claims description 7
- 150000003512 tertiary amines Chemical class 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 150000003335 secondary amines Chemical group 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 102100021935 C-C motif chemokine 26 Human genes 0.000 claims description 3
- 101000897493 Homo sapiens C-C motif chemokine 26 Proteins 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000007738 vacuum evaporation Methods 0.000 claims description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 2
- 235000014121 butter Nutrition 0.000 claims 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 39
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000003141 primary amines Chemical group 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000004704 ultra performance liquid chromatography Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 4
- 125000001188 haloalkyl group Chemical group 0.000 description 4
- 229920005990 polystyrene resin Polymers 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229920000962 poly(amidoamine) Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011877 solvent mixture Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- -1 alkyl radical Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- OZZQHCBFUVFZGT-UHFFFAOYSA-N 2-(2-hydroxypropanoyloxy)propanoic acid Chemical compound CC(O)C(=O)OC(C)C(O)=O OZZQHCBFUVFZGT-UHFFFAOYSA-N 0.000 description 1
- ZNOVTXRBGFNYRX-UHFFFAOYSA-N 2-[[4-[(2-amino-5-methyl-4-oxo-1,6,7,8-tetrahydropteridin-6-yl)methylamino]benzoyl]amino]pentanedioic acid Chemical compound C1NC=2NC(N)=NC(=O)C=2N(C)C1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 ZNOVTXRBGFNYRX-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 125000004948 alkyl aryl alkyl group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 239000013583 drug formulation Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- SENLDUJVTGGYIH-UHFFFAOYSA-N n-(2-aminoethyl)-3-[[3-(2-aminoethylamino)-3-oxopropyl]-[2-[bis[3-(2-aminoethylamino)-3-oxopropyl]amino]ethyl]amino]propanamide Chemical compound NCCNC(=O)CCN(CCC(=O)NCCN)CCN(CCC(=O)NCCN)CCC(=O)NCCN SENLDUJVTGGYIH-UHFFFAOYSA-N 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G63/88—Post-polymerisation treatment
- C08G63/90—Purification; Drying
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Biological Depolymerization Polymers (AREA)
- Detergent Compositions (AREA)
Description
・重合体の機械的性質、特に弾性の低下;
・使用(用途)。重合体の合成の最後は、概して高温で行われるが、このとき、残留ラクチドが、押出中に昇華して工具を汚染する可能性がある;
・重合体の安定性。水分が存在すると、ラクチドは容易に加水分解され、乳酸が生じる。PHの局所的低下のために、PLAの分解が自己触媒される;
・配合物中での新たな副生成物の形成。ラクチドは、求核官能基(特に第一級アミン官能基)を有する活性成分の官能基と反応して、対応するラクチル−ラクテートを形成する可能性がある。
(ii)単数または複数の第一級および/または第二級アミン官能基が導入された樹脂およびPAMAMデンドリマーから選択される官能化材料を、溶媒中のポリエステルへ加える工程。
(iii)官能化材料を除去する工程;
(iv)溶媒を除去する工程。
S−L (I)
式中、Lは、直鎖または分岐鎖のC1〜C15アルキル鎖であり、
鎖中、1個または複数の炭素原子が、窒素原子で置換されるが、ただし隣り合う(連続した)2個の炭素原子は両方を窒素原子で置換することはできず、かつ
少なくとも1個の末端炭素原子が窒素原子で置換されており、
およびSは、適切な支持体(担体)である。
(i)弱塩基性アニオン交換樹脂を、溶媒中のポリエステルに加える工程。
(a)溶媒中で、単量体を酸性触媒と接触させる工程;
(b)得られたポリエステルを、上記に記載された工程(i)に従って処理する工程;
(c)得られたポリエステルを、上記に記載された工程(ii)〜(iv)に従って処理する工程;
重合体の合成は、溶液(ジクロロメタン混合液(DCM/トルエン)中、開始剤および酸性触媒の存在下)で行う。反応の最後に、反応媒体を塩基性樹脂(Amberlyst(登録商標) 21)で処理して触媒を除去する。そのため、アミノ官能基を含有する樹脂を用いる工程が追加されている。反応溶媒を濾過および減圧下で除去して、触媒および単量体を含まないPLAを回収する。
残留ラクチドを0.41%含有する極低分子量のPLAのバッチで、3種類の異なる樹脂を試験した。
(2−アミノエチル)ポリスチレン樹脂(樹脂1、0.8〜1.2mmol/g)
N−(2−アミノエチル)−アミノエチルポリスチレン樹脂(樹脂2、3.1〜3.5mmol/g)
トリス−(2−アミノエチル)−アミンポリスチレン樹脂(樹脂3、3.0mmol/g)
1グラムのPLAを7/3のDCM/トルエン混合液10ml中で溶液として、この溶液を、不活性雰囲気中、周囲温度で18時間、50mg(4.0当量)の実施例1の樹脂3の存在下で撹拌する。
D,L−ラクチドを重量で1.0%含有するPLGA(Mn=5680、PDI=1.72)850mgを、5/3のDCM/トルエン混合液に50/50で溶解させ、この溶液を、周囲温度で18時間、75mg(3当量)の樹脂2の存在下で撹拌する。
トルエンおよびジクロロメタンを、不活性雰囲気下、活性化モレキュラーシーブを上で乾燥させる。ラクチドを蒸留トルエンに加えて、不活性雰囲気下で再結晶させる。ドデカノールを減圧下で乾燥させる。トリフルオロメタンスルホン酸を真空蒸留する。Amberlyst(登録商標) 21樹脂をP2O5の存在下で、真空乾燥させ、そして不活性雰囲気下で貯蔵する。
SEC: Mw=957g/mol、IP=1.18
UPLC: 残留ラクチド濃度:0.37%
SEC: Mw=952g/mol、IP=1.18
UPLC: 残留ラクチド濃度:0.08%
Claims (13)
- 不純物含有ポリエステルを精製する方法であって、該不純物はポリエステルの重量に対して少なくとも0.1%の残留単量体を含み、少なくとも以下の工程を含む方法:
(ii)複数の第一級アミン官能基が導入された樹脂から選択される官能化材料を、溶媒中の該ポリエステルに加える工程、
ただし、前記ポリエステルは、ポリカプロラクトン(PCL)、乳酸重合体(PLA)、乳酸とグリコール酸の重合体(PLGA)、およびグリコール酸重合体(PGA)から選択され、
前記単量体は、それぞれ、カプロラクトン、乳酸、乳酸とグリコール酸、及びグリコール酸から選択された、方法。 - 前記樹脂が、さらに、複数の第二級アミン官能基が導入された樹脂である、請求項1に記載の方法。
- 以下の工程:
(iii)前記官能化材料を除去する工程;
(iv)前記溶媒を除去する工程、
をさらに含む、請求項1または請求項2に記載の方法。 - 前記ポリエステルは、乳酸重合体(PLA)、または乳酸とグリコール酸の重合体(PLGA)である、請求項1〜3のいずれか1項に記載の方法。
- 工程(ii)で用いる前記官能化樹脂は、以下の式(I):
S−L (I)
(ただし、式中、Lは、直鎖または分岐鎖のC1〜C15アルキル鎖またはアラルキル鎖であり、鎖中、1個または複数の炭素原子が、窒素原子で置換されるが、
隣り合う2個の炭素原子は両方を窒素原子で置換することはできず、かつ
少なくとも1個の末端炭素原子が窒素原子で置換されており、
およびSは、適切な支持体である)
を有している、請求項1〜4のいずれかに記載の方法。 - Sは、ポリスチレン支持体またはポリスチレン−ジビニルベンゼン支持体である、請求項5に記載の方法。
- 工程(iii)は、濾過により行われる、請求項3〜6のいずれか1項に記載の方法。
- 工程(iv)は、乾燥により、好ましくは真空エバポレーションにより行われる、請求項3〜7のいずれか1項に記載の方法。
- 不純物含有ポリエステルを精製する請求項1〜8のいずれか1項に記載の方法であって、該不純物はポリエステルの重量に対して少なくとも0.1%の残留触媒をさらに含んでおり、以下の工程:
(i)第三級アミン型アニオン交換樹脂を、溶媒中の該ポリエステルに加える工程、
をさらに含む、方法。 - 工程(i)を繰り返して2回目を行う、請求項9に記載の方法。
- 前記第三級アミン型アニオン交換樹脂は、Amberlyst(登録商標) A21、Dowex(商標) 66、Amberlite FPA53、Amberlite FPA55、Amberlite CR5550、またはIMAC HP661樹脂から選択される、請求項9または10に記載の方法。
- 前記アニオン交換樹脂は、その後、濾過により除去される、請求項9〜11のいずれか1項に記載の方法。
- ポリエステル(共)重合方法であって、以下の工程:
(a)溶媒中で、単量体を酸性触媒と接触させる工程;
(b)該得られたポリエステルを、請求項9〜12に記載された工程(i)に従って処理する工程;
(c)該得られたポリエステルを、請求項1〜8に記載された工程(ii)〜(iv)に従って処理する工程;
を含む、方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1351657A FR3002537B1 (fr) | 2013-02-26 | 2013-02-26 | Nouveau procede de purification de polyesters |
FR1351657 | 2013-02-26 | ||
PCT/EP2014/053600 WO2014131747A1 (fr) | 2013-02-26 | 2014-02-25 | Nouveau procédé de purification de polyesters |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2016513161A JP2016513161A (ja) | 2016-05-12 |
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EP (1) | EP2961786B1 (ja) |
JP (1) | JP6285465B2 (ja) |
KR (1) | KR20150125681A (ja) |
CN (1) | CN105026458B (ja) |
AU (1) | AU2014222813B2 (ja) |
BR (1) | BR112015019150B1 (ja) |
CA (1) | CA2902114C (ja) |
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ES (1) | ES2636839T3 (ja) |
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US5338822A (en) * | 1992-10-02 | 1994-08-16 | Cargill, Incorporated | Melt-stable lactide polymer composition and process for manufacture thereof |
US6160173A (en) * | 1996-10-09 | 2000-12-12 | Cargill Incorporated | Process for the recovery of lactic acid esters and amides from aqueous solutions of lactic acid and/or salts thereof |
JPH10168175A (ja) * | 1996-12-10 | 1998-06-23 | Mitsui Chem Inc | 脂肪族ポリエステルの精製方法 |
FR2867698B1 (fr) * | 2004-03-16 | 2007-11-16 | Beaufour Ipsen S C R A S | Systeme catalttique de (co) oligomerisation du lactide et du glycolide |
BRPI0707404B1 (pt) * | 2006-01-31 | 2018-05-29 | Purac Biochem B.V. | Método para a purificação de um polímero reabsorvível a partir de monômeros residuais |
JP2008106084A (ja) * | 2006-10-23 | 2008-05-08 | Maruzen Petrochem Co Ltd | 半導体リソグラフィー用共重合体、組成物並びに該共重合体の製造方法 |
FR2967415B1 (fr) * | 2010-11-15 | 2012-11-30 | Ipsen Pharma Sas | Procede de preparation de polymeres etoiles |
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EA201591584A1 (ru) | 2016-03-31 |
CN105026458A (zh) | 2015-11-04 |
ZA201505571B (en) | 2016-09-28 |
FR3002537A1 (fr) | 2014-08-29 |
AU2014222813A1 (en) | 2015-09-17 |
EP2961786A1 (fr) | 2016-01-06 |
UA115468C2 (uk) | 2017-11-10 |
US20160002398A1 (en) | 2016-01-07 |
EP2961786B1 (fr) | 2017-05-10 |
WO2014131747A1 (fr) | 2014-09-04 |
BR112015019150A2 (pt) | 2017-07-18 |
AU2014222813B2 (en) | 2017-02-02 |
BR112015019150B1 (pt) | 2020-11-17 |
JP2016513161A (ja) | 2016-05-12 |
KR20150125681A (ko) | 2015-11-09 |
CA2902114C (fr) | 2020-10-27 |
ES2636839T3 (es) | 2017-10-09 |
SA515360941B1 (ar) | 2016-10-17 |
HK1217208A1 (zh) | 2016-12-30 |
FR3002537B1 (fr) | 2015-04-24 |
MX362421B (es) | 2019-01-17 |
MX2015010408A (es) | 2015-12-01 |
CA2902114A1 (fr) | 2014-09-04 |
EA030748B1 (ru) | 2018-09-28 |
SG11201506110PA (en) | 2015-09-29 |
CN105026458B (zh) | 2017-06-16 |
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