WO2011045546A2 - Synthèse de polyuréthane par autocondensation - Google Patents
Synthèse de polyuréthane par autocondensation Download PDFInfo
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- WO2011045546A2 WO2011045546A2 PCT/FR2010/052190 FR2010052190W WO2011045546A2 WO 2011045546 A2 WO2011045546 A2 WO 2011045546A2 FR 2010052190 W FR2010052190 W FR 2010052190W WO 2011045546 A2 WO2011045546 A2 WO 2011045546A2
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- 0 CC(C*)C(C)C(C)C1C(C)CCC1 Chemical compound CC(C*)C(C)C(C)C1C(C)CCC1 0.000 description 2
Classifications
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- 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
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C247/00—Compounds containing azido groups
- C07C247/20—Compounds containing azido groups with azido groups acylated by carboxylic acids
- C07C247/22—Compounds containing azido groups with azido groups acylated by carboxylic acids with the acylating carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
Definitions
- the present invention relates to the synthesis of polyurethane by self-condensation. It also relates to new monomers and their methods of preparation and their use for the synthesis of polyurethane.
- Polyurethanes are among the most important polymeric materials and have many useful properties for various applications, such as machinery, coatings and paints, insulation materials, elastic fibers, flexible foams and medical devices.
- polyurethane chemistry allows the synthesis of different types of polymeric materials such as foams (flexible and rigid), thermoplastics, interpenetrating polymer networks (IPN) and segmented polyurethanes, depending on the polyol, the isocyanate and the polymerization method used.
- foams flexible and rigid
- thermoplastics thermoplastics
- IPN interpenetrating polymer networks
- segmented polyurethanes depending on the polyol, the isocyanate and the polymerization method used.
- Vegetable oils are triglycerides and have in their structure most of the time at least one unsaturated fatty acid (Petrovic, Z. Polymer Rev.ews, 2008, 48, 109).
- the use of enzymes or chemicals to modify the structure of the fatty acid and introduce functional groups has long been known (Leitheiser, RH, Peloza, C.C., Lyon, C., KJ Ceilular Plastics 1969, 5, 346, Ehrich, A.
- Polyurethanes are conventionally prepared by the reaction of polyols with isocyanates.
- Isocyanates are very reactive and chemically toxic. It is therefore desirable to implement a process for the preparation of polyurethanes by a route without isocyanates ("non-isocyanate" route).
- the first type of process is the self-condensation method in which an AB type monomer contains hydroxyl and azide groups (Kumar, A., Ramakrishnan, S. Chem., Commun., 1993, 1453, Kumar, A .; Ramakrishnan, SJ Polym Sci .: Part A Polym Chem, 1996, 34, 839, Ranganathan, T., Ramesh, C. Kumar, A. Chem Commun, 2004, 154).
- the other type of process is ring opening of cyclic carbonates with amines (Ochiai, B, Satoh, Y, Endo, T, J. Polym, Sci, Part A: Polym Chem., 39, 4091, 2001). ).
- the present invention therefore aims to provide a new process for the preparation of polyurethane by a route without isocyanates.
- the object of the present invention is to provide a process for the preparation of polyurethane carried out in the absence of isocyanates, said method permitting a stoichiometric control.
- the present invention also aims to provide novel reaction monomers for the preparation of polyurethanes in the absence of isocyanates.
- the present invention relates to compounds of formula (I) below:
- R 1 represents a linear or branched alkyl group comprising from 1 to 20 carbon atoms, optionally substituted by one or more substituents OR a , R a representing a hydrogen atom or an alkyl group comprising from 1 to 20; carbon atoms, said R 1 group possibly containing one or more unsaturations;
- a represents a single or a double bond
- R 2 represents a hydrogen atom, a group OR a , R a representing a hydrogen atom or an alkyl group comprising from 1 to 20 carbon atoms, or a linear or branched alkyl group comprising from 1 to 20; carbon atoms, substituted by an OH group,
- R 2 represents a radical of formula - (OCH 2 CH 2 ) n -OH or -CH 2 - (CH 2 OCH 2 ) n -CH 3 , n representing an integer from 1 to 100, preferably from 6 to 50, and preferably equal to 6, 13 or 45;
- R 3 represents, when a is a single bond, a hydrogen atom or, when a is a double bond, R 3 is absent;
- R 4 represents a hydrogen atom or a group OR b , R b representing a hydrogen atom or an alkyl group comprising from 1 to 20 carbon atoms, or a linear or branched alkyl group comprising from 1 to 20; carbon atoms, substituted by an OH group,
- R 4 represents a radical of formula - (OCH 2 CH 2 ) n -OH or -CH 2 - (CH 2 OCH 2 ) n -CH 3 , n representing an integer from 1 to 100, preferably from 6 to 50, and preferably equal to 6, 13 or 45;
- R 5 represents, when a is a single bond, a hydrogen atom or, when a is a double bond, R 5 is absent;
- - Ai represents a divalent alkylene radical, linear or branched, comprising from 1 to 20 carbon atoms, said alkylene radical optionally containing one or more unsaturations.
- the radical Ai comprises one or more unsaturations
- a step of further functionalization of the compound of formula (I) mentioned above makes it possible to introduce chemical modifications on the unsaturation (s).
- Ri comprises one or more unsaturations
- a step of further functionalization of the compound of formula (I) above makes it possible to introduce chemical modifications on the unsaturation (s).
- the "alkyl" radicals represent saturated hydrocarbon radicals, in a straight or branched chain, comprising from 1 to 20 atoms, in particular from 1 to 12 carbon atoms, preferably from 1 to 10 carbon atoms, and even preferably from 1 to 5 carbon atoms (they can typically be represented by the formula C n H 2 n + 1, n being the number of carbon atoms).
- They are branched or substituted by one or more alkyl radicals mention may be made especially of the isopropyl, tert-butyl, 2-ethylhexyl, 2-methylbutyl, 2-methylpentyl, 1-methylpentyl and 3-methylheptyl radicals.
- alkyl also refers to cycloalkyl radicals which are saturated or partially unsaturated, nonaromatic, mono-, bi- or tricyclic hydrocarbon radicals comprising from 3 to 20 carbon atoms, and preferably from 3 to 10 carbon atoms. carbon, such as in particular cyclopropyl, cyclopentyl, cyclohexyl or adamantyl, and the corresponding rings containing one or more unsaturations.
- alkyl radicals may be substituted by one or more substituents.
- substituents there may be mentioned the following groups: amino, hydroxy, thio, halogen, carboxyl, alkyl, alkoxy, alkylthio, alkylcarbonyl, alkylcarboxyl, alkylamino, aryloxy, arylalkoxy, cyano, trifluoromethyl, alkylsulfonyl, carboxy or carboxyalkyl.
- alkoxy radicals according to the present invention are radicals of formula -O-alkyl, the alkyl group being as defined previously.
- alkylthio refers to a -S-alkyl group, the alkyl group being as defined above.
- alkylamino refers to -NH-alkyl, the alkyl group being as defined above.
- alkylcarbonyl refers to a -CO-alkyl group, the alkyl group being as defined above.
- alkylcarboxyl refers to a -COO-alkyl group, the alkyl group being as defined above.
- alkylsulfonyl refers to a group -SO 2 -alkyl, the alkyl group being as defined above.
- halogen atoms mention is made more particularly of fluorine, chlorine, bromine and iodine atoms.
- aryloxy refers to a -O-aryl group, the aryl group being as defined above.
- arylalkoxy refers to an aryl-alkoxy group, the aryl and alkoxy groups being as defined above.
- carboxyalkyl refers to a HOOC-alkyl- group, the alkyl group being as defined above.
- carboxyalkyl groups there may be mentioned in particular carboxymethyl or carboxyethyl.
- arylalkyl When an alkyl radical is substituted with an aryl group, the term “arylalkyl” or “aralkyl” radical is used.
- the "arylalkyl” or “aralkyl” radicals are aryl-alkyl radicals, the aryl and alkyl groups being as defined above.
- arylalkyl radicals mention may especially be made of the benzyl or phenethyl radical.
- These arylalkyl groups may be substituted by one or more substituents.
- substituents there may be mentioned the following groups: amino, hydroxy, thio, halogen, carboxyl, alkyl, alkoxy, alkylthio, alkylcarbonyl, alkylcarboxyl, alkylamino, aryloxy, arylalkoxy, cyano, trifluoromethyl, alkylsulfonyl, carboxy or carboxyalkyl.
- alkylene radicals represent radicals (also called alkylidenes) derived from alkanes whose two terminal hydrogen atoms have been removed.
- alkylene radicals When said alkylene radicals are linear, they may be represented by the formula - (CH 2 ) n -.
- R 1 represents an alkyl group, in particular comprising 8 carbon atoms.
- R 1 can also advantageously represent an alkyl group substituted with an OH group, and more particularly a CH 3 (CH 2 ) 5 CH (OH) CH 2 group .
- R 2 represents a group
- R 2 may also advantageously represent H.
- R 4 represents an alkoxy group OR b , R b represents an alkyl group, and more particularly R 4 may represent an OMe group.
- R 4 may also advantageously represent H.
- the present invention relates to compounds of formula (I) as defined above, in which at least one of the groups R 1, R 2 and R 4 comprises an OH or alkoxy group. According to another advantageous embodiment, the present invention relates to compounds of formula (I) as defined above, in which, when a represents a single bond, at least one of the groups R 2 and R 4 comprises an OH group. or alkoxy.
- the present invention also relates to the preferred compounds of formula (1-1) below:
- R 1 represents a linear or branched alkyl group comprising from 1 to 20 carbon atoms, optionally substituted by one or more substituents OR a , R a representing a hydrogen atom or an alkyl group comprising from 1 to 20 atoms carbon, said R 1 group possibly containing one or more unsaturations;
- R 2 represents a hydrogen atom, a group OR a , R a representing a hydrogen atom or an alkyl group comprising from 1 to 20 carbon atoms, or a linear or branched alkyl group comprising from 1 to 20; carbon atoms, substituted by an OH group, or R 2 represents a radical of formula - (OCH 2 CH 2 ) n - OH or - CH 2 - (CH 2 OCH 2 ) n --CH 3 , n representing an integer inclusive from 1 to 100, preferably from 6 to 50, and preferably equal to 6, 13 or 45;
- R 3 represents a hydrogen atom
- R 4 represents a hydrogen atom or a group OR b , R b representing a hydrogen atom or an alkyl group comprising from 1 to 20 carbon atoms, or a linear or branched alkyl group comprising from 1 to 20; carbon atoms, substituted by an OH group, or R 4 represents a radical of formula - (OCH 2 CH 2 ) n -OH or -CH 2 - (CH 2 OCH 2 ) n -CH 3 , n representing an integer inclusive from 1 to 100, preferably from 6 to 50, and preferably equal to 6, 13 or 45;
- R 5 represents a hydrogen atom
- - A ! represents a divalent alkylene radical, linear or branched, comprising from 1 to 20 carbon atoms, said alkylene radical optionally containing one or more unsaturations.
- the compounds of formula (1-1) correspond to compounds of formula (I) as defined above, in which a represents a single bond.
- the present invention relates to compounds of formula (I-1) as defined above, in which at least one of the groups R 2 and R 4 comprises an OH or alkoxy group.
- the present invention also relates to preferred compounds of formula
- R 1 represents a linear or branched alkyl group comprising from 6 to 12 carbon atoms
- R a represents a hydrogen atom or an alkyl group comprising from 1 to 12 carbon atoms
- R b represents a hydrogen atom or an alkyl group comprising 1 to 12 carbon atoms
- - A ! represents a divalent alkylene radical, linear or branched, comprising from 6 to 12 carbon atoms.
- the compounds of formula (I-2) correspond to compounds of formula (I) as defined above, wherein a represents a single bond, R 3 is H, R 2 is OR a, R 4 is group OR b and R 5 is H.
- the present invention relates to the compounds of formula (I-2) as defined above, in which R a is H.
- the present invention relates to the compounds of formula (I-2) as defined above, in which R b is a methyl group.
- the present invention relates to the compounds of formula (I-2) as defined above, in which is an alkylene radical, in particular linear, comprising 7 carbon atoms.
- the present invention relates to the compounds of formula (I-2) as defined above, in which R 1 is an alkyl group, in particular a linear group, comprising 8 carbon atoms.
- the present invention also relates to the preferred compound of formula (I-3) below:
- This compound is hereinafter referred to as HMODAz. It is the azide of 10-hydroxy-9-methoxyoctadecanoyl which is a new type AB monomer obtained from sunflower oil.
- the present invention also relates to compounds of formula
- R 1 represents a linear or branched alkyl group comprising from 1 to 20 carbon atoms, optionally substituted by one or more substituents OR a , R a representing a hydrogen atom or an alkyl group comprising from 1 to 20 atoms carbon, said R 1 group possibly containing one or more unsaturations;
- R 2 represents a hydrogen atom, a group OR a , R a representing a hydrogen atom or an alkyl group comprising from 1 to 20 carbon atoms, or a linear or branched alkyl group comprising from 1 to 20; carbon atoms, substituted by an OH group, or R 2 represents a radical of formula - (OCH 2 CH 2 ) n - OH or - CH 2 - (CH 2 OCH 2 ) n --CH 3 , n representing an integer inclusive from 1 to 100, preferably from 6 to 50, and preferably equal to 6, 13 or 45;
- R 4 represents a hydrogen atom or a group OR b , R b representing a hydrogen atom or an alkyl group comprising from 1 to 20 carbon atoms, or a linear or branched alkyl group comprising from 1 to 20; carbon atoms, substituted by an OH group, or R 4 represents a radical of formula - (OCH 2 CH 2 ) n -OH or -CH 2 - (CH 2 OCH 2 ) n -CH 3 , n representing an integer inclusive from 1 to 100, preferably from 6 to 50, and preferably equal to 6, 13 or 45;
- - A ! represents a divalent alkylene radical, linear or branched, comprising from 1 to 20 carbon atoms, said alkylene radical optionally containing one or more unsaturations.
- the compounds of formula (I-4) correspond to compounds of formula (I) as defined above, in which a represents a double bond and R 3 and R 5 are absent.
- R 2 represents H.
- R 4 represents H.
- R 1 represents a linear or branched alkyl group comprising from 6 to 12 carbon atoms, optionally substituted by an OH group,
- - A ! represents a divalent alkylene radical, linear or branched, comprising from 6 to 12 carbon atoms.
- the compounds of formula (I-5) correspond to compounds of formula (I) as defined above, in which a represents a double bond, R 3 and R 5 are absent and R 2 and R 4 are H.
- R 1 is an alkyl group substituted with an OH group.
- R 6 represents a linear or branched alkyl group comprising from 1 to 12 carbon atoms.
- This compound is referred to hereafter as HODEAz. It is the azide of 12-hydroxy-octadec-9-ecanoyl which is a new type AB monomer obtained from castor oil.
- the present invention also relates to a process for preparing a compound of formula (I) as defined above, comprising a reaction step of a compound of formula (II) below:
- the reaction step of the compound of formula (II) mentioned above is carried out in two steps: the first step consists in reacting the compound (II) with ethyl chloroformate in the presence of triethylamine in a THF / water mixture for 2 hours at 0 ° C and the second step is then to react the intermediate compound obtained at the end of the first step with sodium azide in water for 4 hours at 0 ° C.
- the present invention also relates to the use of a compound of formula (I) as defined above, for the preparation of polyurethane.
- the present invention relates to the use of a compound of formula (I-2) or (I-3), for the preparation of polyurethane corresponding to the following formula (III-1):
- a 1; R ! and R b being as defined above for formula (I-2), and m representing an integer from 2 to 50,000, and preferably from 2 to 10,000, especially from 2 to 5,000, and preferably from 2 to 50. More particularly, the present invention relates to the use of a compound of formula (1-3) as defined above, for the preparation of polyurethane corresponding to the following formula (III-1 -1):
- m is an integer from 2 to 50,000, and preferably from 2 to 10,000, especially from 2 to 5,000, and more preferably from 2 to 50.
- the present invention also relates to the use of a compound of formula (I), and more particularly of a compound of formula (I-4), (I-5), (I-6) or (I-7) for the preparation of polyurethane having the following formula (III-2):
- R 6 and A 1 being as defined above for formula (I-6), and
- n representing an integer from 2 to 50,000, and preferably from 2 to
- the present invention relates to the use of a compound of formula (I-7) as defined above, for the preparation of polyurethane corresponding to the following formula (III-2-1):
- m is an integer from 2 to 50,000, and preferably from 2 to 10,000, especially from 2 to 5,000, and more preferably from 2 to 50.
- the present invention also relates to the use of a compound of formula (I), and more particularly of a compound of formula (1-4), (1-5), (1-6) or (I-7) for the preparation of polyurethane having the following formula (111-3):
- m is an integer from 2 to 50,000, and preferably from 2 to 10,000, especially from 2 to 5,000, and more preferably from 2 to 50.
- R 6 and A ! being as defined above for the formula (I-6).
- the present invention relates to the use of a compound of formula (I-7) as defined above, for the preparation of polyurethane corresponding to the following formula (III-3-1):
- m is an integer from 2 to 50,000, and preferably from 2 to 10,000, especially from 2 to 5,000, and more preferably from 2 to 50.
- the present invention also relates to a process for the preparation of polyurethane, in particular corresponding to any one of the formulas (III-1), (III-1 - 1), (III-2) or (III-2), comprising a step of self-condensation of a compound of formula (I) as defined above at a temperature ranging from 50 ° to 100 ° C., preferably at ⁇ ' ⁇ , for a period of 1 hour to 48 hours; hours, preferably for 24 hours.
- the present invention also relates to a process for the preparation of polyurethane, especially having any of formulas (III-3) or (III-3-1), comprising the following steps:
- R 1, R 2 , R 3, R 4 , 5, A 1 and a are as defined above in formula (I), and
- the first step of this process is carried out under reflux for 4 hours.
- Figure 1 shows an FTIR spectrum (Fourier Transform Infrared Spectroscopy) of polymerization samples of HMODAz (5) after different polymerization times.
- Figure 2 shows the proton NMR spectrum (1 H-NMR) of polymerization samples of HMODAz (5) at different time intervals.
- Figure 3 shows SEC (Size Exclusion Chromatography) analyzes of HMODAz (Compound 5) polymerization samples as a function of time.
- FIG. 4 represents the DSC (Differential Scanning Calorimetry) thermograms of polyurethanes (6) (compound of formula (III-1 -1)) and (9) (compound of formula (III-2-1) )).
- Figure 5 shows the proton NMR spectrum (1 H-NMR) of polyurethane derived from ricinoleic acid (1 1).
- the monomer (5) is obtained from a natural source: sunflower oil which is transesterified with methanol in the presence of MgO as a catalyst.
- This HMODAz monomer is synthesized according to a method in five main steps.
- Methyl 10-hydroxy-9-methoxyoctadecanoate (3) (4.0 g, 0.012 mol) was dissolved in 1N methanolic potassium hydroxide solution (100 mL) (Aldrich) and refluxed for 12 h. . The methanol was removed from the reaction mixture and the crude product was dissolved in 100 mL of water. The aqueous solution was neutralized with hydrochloric acid (Aldrich) and the product was extracted with 3 x 50 mL of dichloromethane (J.T.Baker). The dichloromethane solution was washed with 3 x 50 mL of water and dried over anhydrous sodium sulfate (J.T.Baker). The dichloromethane solution was filtered and the solvent was removed to obtain the intermediate compound 4.
- 1N methanolic potassium hydroxide solution 100 mL
- Aldrich methanolic potassium hydroxide solution
- the aqueous solution was neutralized with hydrochloric acid
- the monomer HMODAz (5) is a self-condensable monomer with a secondary hydroxyl group and an acyl azide group as a precursor of the isocyanate function.
- Ricinoleic acid is a C18 fatty acid comprising an OH group with a C9 double bond in the cis configuration.
- the polyurethane synthesis according to the present invention is based on the self-condensation of sodium azide and hydroxyl groups. This technique has the following advantages: i) the reaction proceeds smoothly by simple heating of the monomer in a One pot 'process and ii) no optimization of molar ratios is necessary.
- Figures 1 and 2 show respectively the FTIR and H-NMR spectra of the progression of the polymerization and Figure 3 represents the SEC spectrum of the control of the reaction.
- the FTIR spectra of the samples show that as the polymerization time increases, the intensity of the isocyanate band (2270 cm- 1 ) decreases accordingly while the intensity of the NH band (3338 cm- 1 ) increases because of polyurethane formation.
- the carbonyl band of the acyl azide at 1720 cm- 1 moves at lower frequencies (1695 cm- 1 ) because of the formation of the urethane linkage.
- Figure 4 shows DSC thermograms for polyurethanes derived from HMODAz (5) and HODEAz (8) by self-condensation at a heating rate of 10min.
- the glass transition temperature of the polyurethane synthesized from HMODAz is -20 ° C and the glass transition temperature of the polyurethane synthesized from HODEAz is -48 ° C. It is therefore interesting to note that these polyurethanes have low glass transition temperatures (below room temperature). Such polyurethanes can thus be coupled with other rigid block polymers to prepare thermoplastic elastomers.
- Example 6 Synthesis of Polyurethane from Ricinoleic Acid
- the AB type monomer (hereinafter compound) was prepared according to the reaction scheme described above:
- Transurethanization is a non-isocyanate and solvent-free route used for the synthesis of polyurethanes. It consists of a condensation between bisurethanes (AA) and diols (BB) in the presence of a catalyst.
- the transurethanization polycondensation was carried out at 130 ° C in the presence of titanium tetrabutoxide as a two-stage catalyst.
- the reaction was carried out at 130 ° C. by stirring under nitrogen flow for 4 hours to obtain oligomers.
- the second step was carried out at
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EP10785118.0A EP2488484B1 (fr) | 2009-10-15 | 2010-10-15 | Synthèse de polyuréthane par autocondensation |
US13/502,284 US9133305B2 (en) | 2009-10-15 | 2010-10-15 | Polyurethane synthesis by means of self-condensation |
JP2012533681A JP5615372B2 (ja) | 2009-10-15 | 2010-10-15 | 自己縮合によるポリウレタン合成 |
CA2777644A CA2777644C (fr) | 2009-10-15 | 2010-10-15 | Synthese de polyurethane par autocondensation |
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FR0957223A FR2951448B1 (fr) | 2009-10-15 | 2009-10-15 | Synthese de polyurethane par autocondensation |
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US9062160B1 (en) | 2014-01-23 | 2015-06-23 | International Business Machines Corporation | Catalyst-free methods of forming polyurethanes from pentafluorophenyl carbonates |
US9676893B2 (en) * | 2015-09-23 | 2017-06-13 | International Business Machines Corporation | Polyurethane materials formed from epoxidized plant oils |
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US2334476A (en) * | 1940-09-04 | 1943-11-16 | Du Pont | Unsaturated isocyanate |
US2764599A (en) * | 1951-07-14 | 1956-09-25 | Goodyear Tire & Rubber | Para tertiary butyl benzoyl azide |
US3376127A (en) * | 1965-07-08 | 1968-04-02 | Pittsburgh Plate Glass Co | Aquatic herbicidal methods |
US3725450A (en) * | 1970-10-05 | 1973-04-03 | Gen Mills Chem Inc | Process for the preparation of isocyanates from acyl azides |
JPH10139748A (ja) * | 1996-11-08 | 1998-05-26 | Chugoku Marine Paints Ltd | 新規なアミンイミド化合物 |
US6767922B2 (en) * | 2000-03-14 | 2004-07-27 | Smithkline Beecham Corporation | IL-8 receptor antagonists |
KR101225223B1 (ko) * | 2008-04-29 | 2013-01-22 | 에프. 호프만-라 로슈 아게 | 4-다이메틸아미노부티르산 유도체 |
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---|---|
FR2951448B1 (fr) | 2012-09-07 |
EP2488484B1 (fr) | 2016-12-07 |
FR2951448A1 (fr) | 2011-04-22 |
JP2013508468A (ja) | 2013-03-07 |
CA2777644C (fr) | 2019-04-16 |
WO2011045546A3 (fr) | 2011-07-07 |
CA2777644A1 (fr) | 2011-04-21 |
US20120264901A1 (en) | 2012-10-18 |
JP5615372B2 (ja) | 2014-10-29 |
EP2488484A2 (fr) | 2012-08-22 |
US9133305B2 (en) | 2015-09-15 |
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