WO2010081887A1 - Acide polylactique isotactique et son procede de fabrication - Google Patents
Acide polylactique isotactique et son procede de fabrication Download PDFInfo
- Publication number
- WO2010081887A1 WO2010081887A1 PCT/EP2010/050477 EP2010050477W WO2010081887A1 WO 2010081887 A1 WO2010081887 A1 WO 2010081887A1 EP 2010050477 W EP2010050477 W EP 2010050477W WO 2010081887 A1 WO2010081887 A1 WO 2010081887A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lactide
- poly
- lactic acid
- polylactic acid
- carried out
- Prior art date
Links
- 0 C[C@@](C(O[C@@]1(C)*)=O)OC1=O Chemical compound C[C@@](C(O[C@@]1(C)*)=O)OC1=O 0.000 description 2
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
- C08G63/02—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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
Definitions
- the invention relates to a polymerization process for obtaining an isotactic polymer of lactide.
- the invention also relates to said polymer and its use in known applications, particularly in the field of packaging, textile and durable applications.
- Polylactic acid while being a homopolymer, can differentiate in its structure at its stereoregularity.
- the poly-L-lactic acid, resulting from the polymerization of L-lactide, and the poly-D-lactic acid, resulting from the polymerization of D-lactide, are enantiomers of isotactic stereoregularity, while the polymerization of the meso -lactide provides a syndiotactic polylactic acid.
- US 6,166,169 relates to an aliphatic polyester obtained by polymerization of at least one monomer selected from the group comprising lactides, lactones, cyclic carbonates and cyclic anhydrides.
- the solution polymerization process does not really make it possible to obtain such a polylactic acid polymer at a reasonable economic cost.
- the solution polymerization process has the disadvantage of a generally long reaction time and the need to separate, at the end of the polymerization process, the polymer obtained from the solvent.
- the object of the present invention is to provide a mass polymerization process for obtaining isotactic polylactic acid having a low rate of tacticity defect.
- Yet another object of the present invention is to provide a mass polymerization process for obtaining isotactic polylactic acid having improved rigidity.
- the present invention therefore aims to remedy at least one of the drawbacks mentioned above.
- the bulk polymerization process of the invention is particularly well applicable to an industrial exploitation. Indeed, it allows a fast obtaining of the polymer and allows, with possible drying, direct exploitation of the polymer unlike the solution process after which the polymer obtained must be separated from the solvent, which on the one hand increases the complexity of the polymer. process and on the other hand affects its economic profitability.
- the Applicant has also found that because of its crystallinity, it is possible to dry the polylactic acid according to the invention at higher temperatures and therefore with increased productivity.
- the drying efficiency makes it possible to avoid degradation by hydrolysis of the product during its processing and thus to maintain the mechanical properties of the product.
- This increase in crystallinity also facilitates the steps of packaging and storage of the product.
- the present invention relates to a mass polymerization process for obtaining:
- polylactic acid of configuration L with a number-average molecular mass of between 60,000 and 200,000 having a percentage of D-D dimer unit of formula (la)
- L-lactic acid, or polylactic acid of configuration D having a number-average molecular weight of between 60,000 and 200,000 having a percentage of L-L dimer unit of formula (Ib)
- poly-D-lactic acid between 0 and 2.5% by weight of poly-D-lactic acid, characterized in that the bulk polymerization consisting of contacting, at a temperature of between 170 and 200 ° C., and for a reaction time of between 5 and 75 minutes, corresponding lactide of stereochemical configuration LL or DD having an optical purity of L or D of at least 99, 5% by weight with at least one catalyst system and in the presence of an initiator to form poly-L-lactic acid or poly-D-lactic acid.
- the percentage of dimeric unit LL in a polymer D or dimer unit DD in a polymer L is defined as being "a percentage of insertion defect”.
- the percentage of LD dimer unit and / or DL in an L or D polymer respectively is defined as "percentage of racemization defect" or "percentage of mesolactide equivalent".
- the present invention therefore relates to a mass polymerization process for obtaining an isotactic polylactic acid of L or D configuration which comprises an insertion defect rate of between 0 and 0.5% by weight of polylactic acid and a racemisation defect rate of between 0 and 2.5% by weight of polylactic acid.
- the present invention therefore relates to a mass polymerization process for obtaining isotactic polylactic acid having a low rate of tacticity defect.
- Default tacticity means the sum of the percentage of insertion fault and racemization defect.
- the term "bulk process" is understood to mean any polymerization occurring in the absence of a solvent.
- the present invention also relates to obtaining polylactic acid of L or D configuration according to the method of the invention.
- polylactic acid is equivalent to the term “polylactide acid”.
- poly-L-lactic acid or “poly-L-lactide acid” as used in the invention refers to an isotactic polymer of the general formula (IV) wherein n is an integer between 100 and 100,000:
- insertion defect refers to the incorporation into a homo-polymer of a given stereoregularity of a lactide unit of inverse stereoregularity.
- the lack of insertion into a poly-L-lactic acid refers to the incorporation of DD lactide into the polymeric chain of poly-L-lactic acid, and
- in poly-L-lactide acid refers to the mass ratio of inverse stereoregularity unit along the polymer chain of a given polylactic acid of stereoregularity.
- the "lack of racemization” as used in the invention refers to the incorporation of meso-lactide into the polymeric chain of isotactic polylactic acid or the inversion of the configuration of a asymmetric carbon of lactide during polymerization.
- the term “percentage of racemization defect” therefore refers to the mass proportion of meso-lactide units incorporated into the polylactic acid polymer chain.
- the term “meso-lactide motif” refers to a unit of general formula (II) or (III):
- lactide of stereochemical configuration DD or LL having an optical purity also called L or D isomeric purity of at least 99.5% by weight, preferably from minus 99.8% by weight.
- the L-L lactide used in the process comprises a D-D lactide content of less than 0.2%, and the D-D lactide used in the process comprises an L-L lactide content of less than 0.2%.
- the chemical purity of the starting lactide is such that the residual acidity is less than 20 meq / kg and the residual water is less than or equal to 100 ppm, more preferably less than or equal to 50 ppm.
- reaction time or residence time refers to the lapse of time during which poly-L-lactic acid or poly-D-lactic acid is present in a reactor or a cascade of reactors, in the extruder or any other polymerization equipment that can operate in batch or continuous mode, with or without stirrer.
- said preparation process can be carried out at a temperature of between 170 and 200 ° C., preferably at a temperature of between 170 and 195 ° C., more preferably at a temperature of between 175 and 185 ° C., even more preferably at a temperature of between 175 and 180 ° C.
- Any configuration of the reactor that can promote temperature control, such as, for example, a ratio of exchange surface / reaction volume or any other system known to man of the art will be preferred in the context of the invention.
- said preparation process can be carried out during a reaction time of between 5 and 75 minutes, preferably between 10 and 60 minutes, more preferably between 10 and 45 minutes, even more preferably between 15 and 30 minutes.
- said preparation process can be carried out jointly at a temperature of between 170 and 195 ° C. and during a reaction time of between 10 and 75 minutes, preferably at a temperature of between 170.degree. and 185 ° C and a reaction time of between 15 and 30 minutes, preferably at a temperature between 170 and 180 0 C and a reaction time of between 15 and 25 minutes.
- said preparation process can be carried out in the presence of an inert gas.
- the inert gas may be selected from the group consisting of nitrogen, argon, neon, krypton, xenon, helium.
- the inert gas may be nitrogen or argon, more preferably the inert gas may be nitrogen.
- the inert gas may contain between 0 and 100 ppm of H 2 O, preferentially between 0 and 50 ppm of H 2 O, more preferably between 0 and 10 ppm of H 2 O.
- said inert gas may have a content of in H 2 O less than or equal to 5 ppm.
- said contacting of lactide with the catalytic system and said polymerization reaction can be carried out under atmospheric pressure and in the presence or absence of an inert gas.
- said contacting of lactide with the catalytic system and said mass polymerization reaction can be carried out under vacuum and in the presence or absence of an inert gas.
- Said process may be carried out in batch mode or continuously in a reactor or a cascade of polymerization reactors optionally provided with one or more high-viscosity stirrers or by extrusion in a single, double or multi-screw extruder (or horizontal reactor).
- the process is continuous.
- the process is carried out in a reactor optionally with a high viscosity stirrer.
- Said polymerization process can be carried out under vacuum, at overpressure or at atmospheric pressure.
- the process can be carried out under a vacuum, overpressure or nitrogen sweep, preferably under an overpressure of an inert gas.
- the polymerization is carried out by extrusion in an extruder.
- the process can be performed under an inert gas sweep.
- the polymerization of lactide is carried out up to a conversion of between 80% and the thermodynamic limit, preferably greater than 90%.
- the process of the present invention is carried out in the presence of at least one catalytic system.
- the catalytic system comprises at least one catalyst and optionally at least one cocatalyst.
- the catalyst is of formula (M) (X 1 , X 2 .... X m ) n in which
- M is a metal selected from the group comprising the elements of columns 3 to 12 of the periodic table and the elements Al, Ga, In, Tl, Sn, Pb, Sb and Bi, - X 1 , X 2 , ... .
- X m is a substituent selected from the group consisting o dC 2 alkyl, C 6-30 aryl, oxide, carboxylate, halide, alkoxy and CrC 2 O compounds containing group 15 elements and / or 16 of the periodic table,
- n is an integer from 1 to 6
- n is an integer between 1 and 6.
- alkyl means a linear or branched, saturated hydrocarbon group of 1 to 20 carbon atoms, in particular from 1 to 16 atoms. carbon, in particular from 1 to 12 carbon atoms, in particular from 1 to 10 atoms and more particularly from 1 to 6 carbon atoms.
- radicals such as methyl, ethyl, isopropyl, n-butyl, t-butyl, t-butylmethyl, n-propyl, pentyl, n-hexyl, 2-ethylbutyl, heptyl, octyl, nonyl, or decyl.
- aryl means an aromatic ring comprising from 1 to 3 optionally fused aromatic rings of from 6 to 20 carbon atoms, especially from 6 to 10 carbon atoms.
- aryl groups suitable for the implementation of the invention it is possible to mention phenyl, phenethyl, naphthyl or anthryl.
- alkoxy means a group of general formula R-O- where R is an alkyl group as defined above.
- R is an alkyl group as defined above.
- halide means a chloride, a fluoride, an iodide or a bromide.
- the cocatalyst is of general formula (Y) (R 1 , R 2 ... R q ) s in which - Y is a member selected from the elements of group 15 and / or 16 of the periodic table,
- R 1 , R 2 ... R q is a substituent selected from the group consisting of dC 2 o alkyl, C 6 -C 2 O aryl, oxide, halide, alkoxy, aminoalkyl, thioalkyl, phenyloxy, aminoaryl, thioaryl, and compounds containing the elements of group 15 and / or 16 of the periodic table.
- q is an integer between 1 and 6, and s is an integer from 1 to 6.
- aminoalkyl is understood to mean an alkyl group carrying a group -NR a 2 on its carbon chain where R a is an alkyl, an aryl or a hydrogen.
- thioalkyl means an alkyl group carrying a group R b S- where R b is an alkyl, an aryl or a hydrogen.
- aminoaryl means an aryl group having a unit -NR C 2 where R c is an aryl, an alkyl or a hydrogen.
- thioaryl means an aryl group having a R d S- - where R d is an aryl, an alkyl or a hydrogen.
- the catalytic system comprises tin bis (2-ethylhexanoate) as catalyst and triphenylphosphine PPh 3 as co-catalyst.
- This system catalytic is known and described for example in US 6,166,169.
- the molar ratio between the cocatalyst and the catalyst may be between 1/10 and 10/1, preferably between 1/3 and 3/1. More preferably, the molar ratio between the cocatalyst and the catalyst may be 1/1.
- the molar ratio between the lactide and the catalyst may be between 200/1 and 10,000 / 1, preferably between 1 000/1 and 7.500 / 1, more preferably between 1.500 / 1 and 6.000 / 1.
- the method of the present invention also includes the use of an initiator.
- the initiating agent may be the residual water contained in the lactide, an alcohol or an amine.
- the alcohol or amine may be an aliphatic or aromatic compound of the general formula R 1O - (A) S wherein A is OH or NH 2 and s is 1 or 2, R 10 is alkyl of 1 to 20 carbon atoms or an aryl having 6 to 30 carbon atoms.
- R 10 is an alkyl having 3 to 12 carbon atoms or an aryl having 6 to 10 carbon atoms.
- Amines include isopropylamine and 1, 6 hexanediamine.
- the molar ratio between the lactide and the initiator when the latter is an alcohol or an amine may be between 50/1 and 1,000 / 1, preferably between 100/1 and 750 / 1, more preferably between 200/1 and 600/1.
- the molar ratio between lactide and water can be included in the same ranges as those mentioned when the initiator is an alcohol or an amine.
- the initiator is an alcohol or an amine.
- the present invention also relates to obtaining polylactic acid of L or D configuration by the process of the present invention.
- the polylactic acid of configuration L or D obtainable by the process of the invention has an insertion defect percentage of between 0 and 0.5%, preferably between 0 and 0.3%, more preferentially between 0 and 0.3%. 0 and 0.2% and a percentage of racemisation defect of between 0 and 2.5%, preferably between 0 and 1.5%, more preferably between 0 and 1%. More preferably, the polylactic acid of L or D configuration obtainable by the process of the invention has 0% insertion defect in its polymer chain. Thus, the lack of tacticity of said polylactic acid can only come from a defect of racemization.
- the insertion and racemization defects are detected by carbon 13 nuclear magnetic resonance ( 13 C NMR).
- the low percentage of lack of insertion and racemization within the polymer chain makes it possible to obtain a polylactic acid whose crystallization temperature, observable by differential scanning calorimetry according to the method ISO 1,1357-2, during the cooling after the first heating is between 1 10 and 120 0 C and that observable during cooling after the second heating is between 90 and 100 0 C.
- the polymers thus obtained exhibit improved crystalline behavior and improved thermal resistance.
- the polylactic acid of configuration L or D obtainable by the process of the invention has a number-average molecular weight (Mn) of between 60,000 and 200,000, preferably between 70,000 and 175,000, more preferably between 80,000 and 150,000 when measured by gel permeation chromatography against a polystyrene standard in chloroform at 35 ° C.
- the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is generally between 1, 2 and 2.8.
- the term "percent D-mer” and “percent L-mer” refers respectively to the D-type and L-type monomeric unit found in the polylactide. This percentage is determined by enzymatic method.
- the poly-L-lactide acid obtainable by the process of the invention preferably has a percentage of D-mer less than or equal to 1.75% by weight of poly-L-lactide acid, preferably less than at 1, 5%, more preferably less than 1%.
- the poly-D-lactide acid obtainable by the process of the invention preferably has an L-mer percentage of less than or equal to 1.75% by weight of poly-D-lactide acid, preferably less than at 1, 5%, more preferably less than 1%.
- the present invention also relates to the use of isotactic polylactic acid as obtained for the manufacture of packaging such as packaging films for candies, for the manufacture of disposable objects such as for example cups or for the manufacture of textiles such as for example fibers.
- the present invention also relates to the use of isotactic polylactic acid as obtained in the field of sustainable applications.
- Model PL-LAs were polymerized under mild balloon conditions so as not to cause racemization of PL-LA and to insert D-LA motifs between L-LA motifs.
- Three PL-LA models were prepared: -a PL-LA with 100% L-Lactide.
- PL-LA with a mixture of 95% L-Lactide and 5% D-Lactide PL-LA with a mixture of 90% L-Lactide and 10% D-Lactide.
- Scheme 1 illustrates the insertion of D-Lactide into a polymer chain of PL-LA.
- Scheme 2 illustrates the insertion of meso-Lactide obtained by racemization in a polymer chain of PL-LA.
- Lactides are dimers. Enzymatic analysis makes it possible to measure the totality of the monomer of one of the two optically active enantiomeric forms present in the dimer, such as, for example, the content of D-mer or L-mer in lactide in order to control its purity. This analysis can also be performed on PL-LA and PD-LA after polymerization. One unit of L-LA in the PL-LA will give 100% of L-sea and one unit of D-LA in the PD-LA will give 100% of D-mer. A meso-LA unit will give 50% D-mer and 50% L-sea. So, when racemizing L-LA or D-LA, we will find our in the presence of a meso-LA equivalent.
- Lactide can be represented in the following 2 chiral forms:
- This meso-lactide is not commercially available.
- Scheme 3 illustrates the insertion of D-Lactide and "meso-Lactide” obtained by racemization in a polymeric chain of PL-LA
- the enzymatic method makes it possible to determine the percentage of D-mer (monomeric unit of type D) that we find in the polymeric chain of PL-LA or the percentage of L-mer (monomeric unit of type L) that we find in the chain polymeric PD-LA. At no time, the enzymatic method makes it possible to determine the origin of this monomeric unit: insertion or racemization.
- the distribution of the defects is the following: 67% insertion defects and 33% racemization defects.
- the enzymatic measurement of this sample gives us 30% of D-mer (or 30% by weight of D-LA equivalent) and knowing that 67% of the defects are insertion defects, this corresponds to at 67% of 30% of D-mer, ie 20% of D-mer and thus to 20% of D-LA.
- racemization defects knowing that they are of the order of 33%, this corresponds to 10% of D-mer and 20% of meso-LA equivalent.
- % weight D-LA [] x% D-mer STPI + STPR in which "STPI” represents the total area of the insertion peaks and “STPR" the total surface of the racemization peaks determined by NMR multiplied by the% D - sea determined by enzymatic method.
- The% weight of D-LA thus represents the insertion tacticity.
- % meso-LA weight [[] x% D-mer] x 2
- The% weight meso-LA therefore represents the tacticity of racemization.
- % weight L-LA 100 - (% weight D-LA +% weight meso-LA)
- the stereochemical purity of the poly-L-lactic acid or poly-D-lactic acid of the invention was determined by the respective content of L-mer or D-mer. This determination was made by enzymatic method.
- the principle of the method is as follows: The L-lactate and D-lactate ions are oxidized to pyruvate respectively by L-lactate dehydrogenase and D-lactate dehydrogenase enzymes using nicotinamide adenine dinucleotide (NAD) as a coenzyme. To force the reaction towards the formation of pyruvate, it is necessary to trap this compound by reaction with hydrazine. The increase in optical density at 340 nm is proportional to the amount of L-lactate or D-lactate present in the sample.
- NAD nicotinamide adenine dinucleotide
- the polylactic acid samples were prepared by mixing 25 ml of sodium hydroxide (1 mol / L) with 0.6 g of PLA. The solution was boiled for 8 hours and then cooled. The solution was then brought to neutral pH by addition of hydrochloric acid (1 mol / l), and then deionized water was added in sufficient quantity to reach 200 ml. The samples were then analyzed on a Vital Scientific Selectra Junior analyzer using for the L-mer determination of poly-L-lactide acid, the box entitled "L-lactic acid 5260" marketed by the company Scil and for the determination in D-mer of poly-D-lactide acid, the box entitled "L-lactic acid 5240" marketed by Scil. During the analysis, a reagent blank and a calibration using the "Scil 5460" calibrator are used.
- lactide samples were prepared by mixing 25 ml of sodium hydroxide (1 mol / L) with 0.6 g of lactide. The solution was mixed and left standing for half an hour before being brought to neutral pH by addition of hydrochloric acid (1 mol / l), then deionized water was added in sufficient quantity to arrive at 200 ml.
- NMR Method The presence of insertion and racemization defects was determined by carbon 13 nuclear magnetic resonance (NMR) (Avance, 500 Mhz, 10 mm SELX probe). Samples were prepared from 250 mg of polylactic acid dissolved in 2.5 to 3 ml of CDCl 3 .
- the method of the invention has been applied to prepare various samples of isotactic polylactide.
- the LL stereochemical starting lactide having an isomeric purity greater than 99.5% by weight was contacted with tin (II) bis (2-ethylhexanoate) salt in the presence of triphenylphosphine, PPh 3 .
- the molar ratio of lactide to catalyst (lactide / catalyst) was 4,000.
- the process was carried out under atmospheric pressure with a nitrogen sweep in a horizontal continuous reactor equipped with a stirrer.
- the residual water content of the lactide was between 25 and 50 ppm.
- the polymerization conditions such as temperature, residence time and rotational speed of the stirrer for the various tests are given in Table 1.
- the percentage of L-mer was determined by the enzymatic method.
- the percentage of D-mer was determined by calculation (100% -% L-sea).
- Polymers of poly-L-lactic acid A and B were synthesized in a reactor from L-lactide of optical purity greater than 99.5%, at a temperature of 175 ° C and a residence time of 25%. minutes in the presence of bis (2-ethylhexanoate) tin (II) and triphenylphosphine PPh 3 .
- Example 5 Example 6 Example 7 Example 8 Example 9 (Polymer A) (Polymer B) (Polymer C) (Polymer D) (Polymer E)
- the poly-L-lactic acid polymers A and B according to the invention have little or no insertion defect unlike other polylactic acid polymers. Their percentages of racemization defects (mesolactide equivalent) are also much lower than those of commercial polymers C to E.
- the crystallization temperature of the samples A to E was determined by differential scanning calorimetry according to the method ISO 1,1357-2. According to this method, the samples were heated from 20 0 C to 200 0 C at a rate of 10 ° C per minute, then cooled to 200 0 C to 20 ° C at 20 ° C per minute and then heated to 20 0 C at 200 ° C at 10 ° C per minute.
- the crystallization temperature measured during the second heating of polymers A and B was between 100 and 120 ° C.
- a crystallization phenomenon was also observable during cooling after the first heating between 90 and 100 ° C for said polymers. No temperature of crystallization is observed on the fusion thermograms of the samples of commercial products C to E.
- poly-L-lactic acid was synthesized from LL-lactide of optical purity greater than 99.5%, by twin screw extruder (L / D ratio: 56) to a temperature of 195 ° C for 20 minutes in the presence of bis (2-ethylhexanoate) tin (II) and triphenylphosphine.
- the molar ratio of lactide to catalyst (lactide / catalyst) was 5,000.
- Polymerization of poly-L-lactic acid has been carried out at atmospheric pressure under argon sweep. Octanol was used as initiator.
- the molar ratio of lactide to octanol (lactide / octanol) was 400.
- the amount of L-mer, determined by enzymatic method on the polymer obtained is 99.6%.
- the insertion defect percentage (% DD-LA) is less than 0.2% and the percentage of defect of racemization (% LD-LA) is 0.5%.
- the number average molecular weight is 74,000 and the ratio Mw / Mn is 1.76.
- the crystallization temperature of the polymer obtained was determined according to the same method as that mentioned in Example 3.
- the crystallization temperature measured during the second heating of said polymer was between 100 and 120 ° C.
- a crystallization phenomenon was also observed. observable during cooling after the first heating between 90 and 100 0 C for said polymer.
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)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10701128.0A EP2379619B2 (fr) | 2009-01-16 | 2010-01-15 | Acide polylactique isotactique et son procede de fabrication |
AU2010205657A AU2010205657B2 (en) | 2009-01-16 | 2010-01-15 | Isotactic polylactic acid and method for producing same |
KR1020117016312A KR101314352B1 (ko) | 2009-01-16 | 2010-01-15 | 동일배열 폴리락트산 및 그의 제조 방법 |
US13/143,379 US20110319588A1 (en) | 2009-01-16 | 2010-01-15 | Isotactic polylactic acid and method for producing same |
JP2011545749A JP5611234B2 (ja) | 2009-01-16 | 2010-01-15 | アイソタクチックポリ乳酸と、その製造方法 |
CN201080004751.0A CN102282195B (zh) | 2009-01-16 | 2010-01-15 | 全同立构聚乳酸及其制造方法 |
BRPI1007134 BRPI1007134B1 (pt) | 2009-01-16 | 2010-01-15 | ácido polilático, seu uso e método de fabricação do mesmo |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BEBE2009/0028 | 2009-01-16 | ||
BE2009/0028A BE1018628A3 (fr) | 2009-01-16 | 2009-01-16 | Acide polylactique isotactique et son procede de fabrication. |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010081887A1 true WO2010081887A1 (fr) | 2010-07-22 |
Family
ID=40957683
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2010/050477 WO2010081887A1 (fr) | 2009-01-16 | 2010-01-15 | Acide polylactique isotactique et son procede de fabrication |
Country Status (8)
Country | Link |
---|---|
US (1) | US20110319588A1 (fr) |
EP (1) | EP2379619B2 (fr) |
JP (1) | JP5611234B2 (fr) |
KR (1) | KR101314352B1 (fr) |
CN (1) | CN102282195B (fr) |
BE (1) | BE1018628A3 (fr) |
BR (1) | BRPI1007134B1 (fr) |
WO (1) | WO2010081887A1 (fr) |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012045759A1 (fr) | 2010-10-05 | 2012-04-12 | Futerro S.A. | Fabrication d'articles a base de polylactide par rotomoulage |
WO2013034702A1 (fr) | 2011-09-09 | 2013-03-14 | Total Research & Technology Feluy | Articles rotomoulés comprenant une couche de polyoléfine et de polyester |
WO2013034701A1 (fr) | 2011-09-09 | 2013-03-14 | Total Research & Technology Feluy | Articles rotomoulés multicouches comprenant une couche de polyester |
EP2746318A1 (fr) | 2012-12-18 | 2014-06-25 | Total Research & Technology Feluy | Procédé de préparation de stéréocomplexes à base de PLA |
WO2014202481A1 (fr) | 2013-06-18 | 2014-12-24 | Total Research & Technology Feluy | Composition polymère |
WO2014206996A1 (fr) | 2013-06-27 | 2014-12-31 | Futerro S.A. | Film multicouche comprenant des biopolymères |
WO2015000982A1 (fr) | 2013-07-02 | 2015-01-08 | Total Research & Technology Feluy | Compositions pe-pla pour bouchons et fermetures |
WO2016038181A1 (fr) | 2014-09-11 | 2016-03-17 | Total Research & Technology Feluy | Articles rotomoulés multicouches |
WO2016038182A1 (fr) | 2014-09-11 | 2016-03-17 | Total Research & Technology Feluy | Articles multicouches |
US9676170B2 (en) | 2013-03-05 | 2017-06-13 | Total Research & Technology Feluy | Multilayered rotomoulded articles |
WO2017108577A1 (fr) * | 2015-12-21 | 2017-06-29 | Carbios | Cellules de levure recombinantes produisant de l'acide polylactique et leurs utilisations |
WO2017191089A1 (fr) | 2016-05-03 | 2017-11-09 | Total Research & Technology Feluy | Articles de pla imprimés en 3d |
US9862169B2 (en) | 2013-03-05 | 2018-01-09 | Total Research & Technology Feluy | Rotomoulded articles |
WO2018046503A1 (fr) | 2016-09-06 | 2018-03-15 | Total Research & Technology Feluy | Compositions polymères monovinylaromatiques améliorées comprenant un biopolymère |
WO2018095906A1 (fr) | 2016-11-22 | 2018-05-31 | Total Research & Technology Feluy | Structure multicouche d'acide polylactique-polyéthylène |
US10287561B2 (en) | 2014-10-21 | 2019-05-14 | Carbios | Polypeptide having a polyester degrading activity and uses thereof |
US10385183B2 (en) | 2014-05-16 | 2019-08-20 | Carbios | Process of recycling mixed PET plastic articles |
US10508269B2 (en) | 2015-03-13 | 2019-12-17 | Carbios | Polypeptide having a polyester degrading activity and uses thereof |
US10626242B2 (en) | 2014-12-19 | 2020-04-21 | Carbios | Plastic compound and preparation process |
US10723848B2 (en) | 2015-06-12 | 2020-07-28 | Carbios | Masterbatch composition comprising a high concentration of biological entities |
US10767026B2 (en) | 2016-05-19 | 2020-09-08 | Carbios | Process for degrading plastic products |
EP3922458A1 (fr) | 2020-06-09 | 2021-12-15 | Total Research & Technology Feluy | Produits multicouche pour le conditionnement d'aliments |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017041017A1 (fr) * | 2015-09-02 | 2017-03-09 | Colorado State University Research Foundation | Transformations du méso-lactide |
KR102648698B1 (ko) | 2021-04-16 | 2024-03-15 | 주식회사 엘지화학 | 폴리락트산 내 d-락틱 반복 단위의 함량을 분석하는 방법 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE1008099A3 (fr) * | 1994-03-04 | 1996-01-16 | Brussels Biotech Sa | Production semi-continue de polylactides par ouverture de cycle lactides obtenus a partir de derives d'acide lactique. |
US6166169A (en) | 1996-07-15 | 2000-12-26 | Brussels Biotech | Aliphatic polyesters and/or copolyesters and a process for the production thereof |
WO2001081610A2 (fr) * | 2000-04-20 | 2001-11-01 | Inventa-Fischer Gmbh & Co. Kg | Procede permettant de produire de l'acide polylactique et dispositif correspondant |
JP2005042084A (ja) * | 2003-07-04 | 2005-02-17 | Toyota Central Res & Dev Lab Inc | ポリ乳酸樹脂組成物及びその成形体 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3318153B2 (ja) * | 1995-04-10 | 2002-08-26 | カネボウ株式会社 | ポリ乳酸の製造方法 |
US5747637A (en) * | 1995-09-07 | 1998-05-05 | Mitsui Toatsu Chemicals, Inc. | Bioabsorbable polymer and process for preparing the same |
DE19628472A1 (de) * | 1996-07-15 | 1998-01-29 | Brussels Biotech S A | Aliphatischer Polyester und/oder Copolyester und Verfahren zu seiner Herstellung |
JP3707240B2 (ja) * | 1998-05-08 | 2005-10-19 | トヨタ自動車株式会社 | ポリ乳酸系組成物、それを用いた成形物、フィルム、繊維及び成型品 |
IT1299222B1 (it) * | 1998-05-12 | 2000-02-29 | Mallinckrodt Holding Bv | Maschera personalizzabile, facciale o nasale, per ventilazione non invasiva di pazienti in genere |
US7144634B2 (en) * | 2001-04-30 | 2006-12-05 | Treofan Germany Gmbh & Co. Kg | Polylactic acid (PLA) film having good antistatic properties |
BE1015060A3 (fr) * | 2002-08-06 | 2004-09-07 | Brussels Biotech Nv Sa | Procede de production de polylactide au depart d'une solution d'acide lactique ou d'un de ses derives. |
CA2660352A1 (fr) * | 2006-07-28 | 2008-01-31 | Teijin Limited | Composition de resine, son procede de fabrication et articlemoule |
JP2008069271A (ja) * | 2006-09-14 | 2008-03-27 | Teijin Ltd | ポリラクチドの製造方法 |
JP2008120878A (ja) * | 2006-11-09 | 2008-05-29 | Teijin Ltd | ポリラクチド粉粒体およびそれを含有する組成物 |
US8211986B2 (en) * | 2006-12-28 | 2012-07-03 | Musashino Chemical Laboratory, Ltd. | Method for producing polylactic acid block copolymer |
JP5804672B2 (ja) * | 2007-06-29 | 2015-11-04 | ユニチカ株式会社 | 結晶性ポリ乳酸樹脂組成物およびそれからなる成形体 |
-
2009
- 2009-01-16 BE BE2009/0028A patent/BE1018628A3/fr not_active IP Right Cessation
-
2010
- 2010-01-15 US US13/143,379 patent/US20110319588A1/en not_active Abandoned
- 2010-01-15 WO PCT/EP2010/050477 patent/WO2010081887A1/fr active Application Filing
- 2010-01-15 EP EP10701128.0A patent/EP2379619B2/fr active Active
- 2010-01-15 CN CN201080004751.0A patent/CN102282195B/zh active Active
- 2010-01-15 JP JP2011545749A patent/JP5611234B2/ja active Active
- 2010-01-15 BR BRPI1007134 patent/BRPI1007134B1/pt active IP Right Grant
- 2010-01-15 KR KR1020117016312A patent/KR101314352B1/ko active IP Right Grant
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE1008099A3 (fr) * | 1994-03-04 | 1996-01-16 | Brussels Biotech Sa | Production semi-continue de polylactides par ouverture de cycle lactides obtenus a partir de derives d'acide lactique. |
US6166169A (en) | 1996-07-15 | 2000-12-26 | Brussels Biotech | Aliphatic polyesters and/or copolyesters and a process for the production thereof |
WO2001081610A2 (fr) * | 2000-04-20 | 2001-11-01 | Inventa-Fischer Gmbh & Co. Kg | Procede permettant de produire de l'acide polylactique et dispositif correspondant |
JP2005042084A (ja) * | 2003-07-04 | 2005-02-17 | Toyota Central Res & Dev Lab Inc | ポリ乳酸樹脂組成物及びその成形体 |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Week 200518, Derwent World Patents Index; AN 2005-168289, XP002542699 * |
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012045759A1 (fr) | 2010-10-05 | 2012-04-12 | Futerro S.A. | Fabrication d'articles a base de polylactide par rotomoulage |
WO2013034702A1 (fr) | 2011-09-09 | 2013-03-14 | Total Research & Technology Feluy | Articles rotomoulés comprenant une couche de polyoléfine et de polyester |
WO2013034701A1 (fr) | 2011-09-09 | 2013-03-14 | Total Research & Technology Feluy | Articles rotomoulés multicouches comprenant une couche de polyester |
US10208191B2 (en) | 2011-09-09 | 2019-02-19 | Total Research & Technology Feluy | Rotomolded articles comprising a layer of polyolefin and polyester |
US9862165B2 (en) | 2011-09-09 | 2018-01-09 | Total Research & Technology Feluy | Multilayered rotomoulded articles comprising a layer of polyester |
EP2746318A1 (fr) | 2012-12-18 | 2014-06-25 | Total Research & Technology Feluy | Procédé de préparation de stéréocomplexes à base de PLA |
US9676170B2 (en) | 2013-03-05 | 2017-06-13 | Total Research & Technology Feluy | Multilayered rotomoulded articles |
US9862169B2 (en) | 2013-03-05 | 2018-01-09 | Total Research & Technology Feluy | Rotomoulded articles |
WO2014202481A1 (fr) | 2013-06-18 | 2014-12-24 | Total Research & Technology Feluy | Composition polymère |
US10273356B2 (en) | 2013-06-18 | 2019-04-30 | Total Research & Technology Feluy | Polymer composition |
WO2014206996A1 (fr) | 2013-06-27 | 2014-12-31 | Futerro S.A. | Film multicouche comprenant des biopolymères |
WO2015000982A1 (fr) | 2013-07-02 | 2015-01-08 | Total Research & Technology Feluy | Compositions pe-pla pour bouchons et fermetures |
US10385183B2 (en) | 2014-05-16 | 2019-08-20 | Carbios | Process of recycling mixed PET plastic articles |
WO2016038182A1 (fr) | 2014-09-11 | 2016-03-17 | Total Research & Technology Feluy | Articles multicouches |
WO2016038181A1 (fr) | 2014-09-11 | 2016-03-17 | Total Research & Technology Feluy | Articles rotomoulés multicouches |
US10265924B2 (en) | 2014-09-11 | 2019-04-23 | Total Research & Technology Feluy | Multilayered articles |
US10287561B2 (en) | 2014-10-21 | 2019-05-14 | Carbios | Polypeptide having a polyester degrading activity and uses thereof |
US10626242B2 (en) | 2014-12-19 | 2020-04-21 | Carbios | Plastic compound and preparation process |
US10508269B2 (en) | 2015-03-13 | 2019-12-17 | Carbios | Polypeptide having a polyester degrading activity and uses thereof |
US10723848B2 (en) | 2015-06-12 | 2020-07-28 | Carbios | Masterbatch composition comprising a high concentration of biological entities |
US11198767B2 (en) | 2015-06-12 | 2021-12-14 | Carbios | Process for preparing a biodegradable plastic composition |
US11802185B2 (en) | 2015-06-12 | 2023-10-31 | Carbios | Masterbatch composition comprising a high concentration of biological entities |
WO2017108577A1 (fr) * | 2015-12-21 | 2017-06-29 | Carbios | Cellules de levure recombinantes produisant de l'acide polylactique et leurs utilisations |
US10717996B2 (en) | 2015-12-21 | 2020-07-21 | Carbios | Recombinant yeast cells producing polylactic acid and uses thereof |
RU2758138C2 (ru) * | 2015-12-21 | 2021-10-26 | Карбио | Рекомбинантные клетки дрожжей, продуцирующие полимолочную кислоту, и их использования |
WO2017191089A1 (fr) | 2016-05-03 | 2017-11-09 | Total Research & Technology Feluy | Articles de pla imprimés en 3d |
US10767026B2 (en) | 2016-05-19 | 2020-09-08 | Carbios | Process for degrading plastic products |
US11377533B2 (en) | 2016-05-19 | 2022-07-05 | Carbios | Process for degrading plastic products |
WO2018046503A1 (fr) | 2016-09-06 | 2018-03-15 | Total Research & Technology Feluy | Compositions polymères monovinylaromatiques améliorées comprenant un biopolymère |
WO2018095906A1 (fr) | 2016-11-22 | 2018-05-31 | Total Research & Technology Feluy | Structure multicouche d'acide polylactique-polyéthylène |
EP3922458A1 (fr) | 2020-06-09 | 2021-12-15 | Total Research & Technology Feluy | Produits multicouche pour le conditionnement d'aliments |
Also Published As
Publication number | Publication date |
---|---|
KR20110104038A (ko) | 2011-09-21 |
US20110319588A1 (en) | 2011-12-29 |
JP2012515245A (ja) | 2012-07-05 |
EP2379619A1 (fr) | 2011-10-26 |
BRPI1007134A2 (pt) | 2016-02-23 |
JP5611234B2 (ja) | 2014-10-22 |
EP2379619B2 (fr) | 2017-01-04 |
AU2010205657A1 (en) | 2011-07-28 |
KR101314352B1 (ko) | 2013-10-04 |
CN102282195A (zh) | 2011-12-14 |
EP2379619B1 (fr) | 2013-08-28 |
CN102282195B (zh) | 2015-12-16 |
BE1018628A3 (fr) | 2011-05-03 |
BRPI1007134B1 (pt) | 2019-11-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2379619B1 (fr) | Acide polylactique isotactique et son procede de fabrication | |
EP2401317B1 (fr) | Procédé de production de stéréocomplexes plla/pdla | |
Kemnitzer et al. | Poly (β-hydroxybutyrate) stereoisomers: a model study of the effects of stereochemical and morphological variables on polymer biological degradability | |
EP2118167B1 (fr) | Procédé de préparation de polylactones et polylactames | |
EP2694568B1 (fr) | Procede de fabrication de polycarbonate a partir de derives de dianhydrohexitols portant deux fonctions carbonate d'alkyle | |
WO2011158905A1 (fr) | Procédé de production de poly(acide lactique) | |
BE1019059A3 (fr) | Procede de polymerisation en masse du lactide. | |
FR2953523A1 (fr) | Procede de preparation d'un polymere d'au moins un monomere cyclique | |
Michalak et al. | Oxidative degradation of poly (3-hydroxybutyrate). A new method of synthesis for the malic acid copolymers | |
EP2694569B1 (fr) | Procede de fabrication de polycarbonate a partir de dialkylcarbonate de dianhydrohexitol | |
EP1948710B1 (fr) | Procede de preparation de polyhydroxyalkanoates, polymeres ainsi obtenus, compositions les comprenant, et leurs utilisations | |
US5440007A (en) | Composition of and method for forming high molecular weight predominantly syndiotactic substituted-poly (β-propioesters) | |
EP3068818B1 (fr) | Procédé de synthèse de polyamide | |
EP2365957B1 (fr) | Procédé de préparation de carbonates et d'esters | |
FR3060582A1 (fr) | Procede de preparation de copolymeres polydiene / polylactide par extrusion reactive | |
EP4108776A1 (fr) | Production de biopolymères | |
EP3976705B1 (fr) | Procédé de préparation de polyester aliphatique stabilisé et compositions ainsi obtenues | |
US20230044934A1 (en) | Novel bioplastics | |
FR2790761A1 (fr) | Copolyester aliphatique biodegradable et son procede d'obtention |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080004751.0 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10701128 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 4701/DELNP/2011 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010701128 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010205657 Country of ref document: AU |
|
ENP | Entry into the national phase |
Ref document number: 20117016312 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2011545749 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2010205657 Country of ref document: AU Date of ref document: 20100115 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13143379 Country of ref document: US |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: PI1007134 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: PI1007134 Country of ref document: BR Kind code of ref document: A2 Effective date: 20110713 |