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WO2017147708A1 - Polyesters dérivés de sources renouvelables, contenant des monomères à chaîne ramifiée, leurs procédés de production et leur utilisation - Google Patents

Polyesters dérivés de sources renouvelables, contenant des monomères à chaîne ramifiée, leurs procédés de production et leur utilisation Download PDF

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WO2017147708A1
WO2017147708A1 PCT/CA2017/050280 CA2017050280W WO2017147708A1 WO 2017147708 A1 WO2017147708 A1 WO 2017147708A1 CA 2017050280 W CA2017050280 W CA 2017050280W WO 2017147708 A1 WO2017147708 A1 WO 2017147708A1
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formula
monomers
polymer composition
reaction mixture
polyesters
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Suresh Narine
Shaojun Li
Laziz BOUZIDI
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Trent University
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Trent University
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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
    • 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

Definitions

  • the disclosure generally provides polyesters derived from renewable sources, such as certain natural oils.
  • the polyesters disclosed herein contain monomers that introduce branching into the backbone of the polymer.
  • the disclosure also provides methods of making such polyesters.
  • the disclosure also provides certain uses of such polyesters.
  • the medium chain homologue poly(nonane lactone) derived from natural oils has been shown to exhibit improved thermal properties compared to poly(s-caprolactone) (PCL) and has been suggested as potential replacement for petroleum derived PCL in drug delivery applications.
  • polyesters in this series are short chain homologues, such as poly (glycolic acid), poly (3 -hydroxy propionic acid), poly(4-hydroxy butyrate) etc., which suffer from poor thermal stability, low melting points, and consequently, poor melt processibility.
  • Long chain polyester homologues have recently attracted significant interest as potential new degradable analogues of linear polyethylene (PE).
  • Linear PE is one of the best- known commodity polymers, but due to its hydrophobicity and molecular size, is nonbiodegradable. PE is used in large volumes for household products and packaging applications because of its adequate mechanical properties and its relatively lower cost compared to engineering polymers. Recent efforts have indicated that the PE-like properties of the long chain polyester homologues, along with biodegradability, present ecological advantages by offering alternative solutions to the PE commodity waste problem.
  • U.S. Patent Application Publication No. 2015/0065682 describes the preparation of certain ⁇ -hydroxyl fatty acids (e.g., with carbon number of 9, 13 and 18) by employing ozone to oxidize an unsaturated fatty acid, or by the cross-metathesis of fatty acids and fatty alcohols followed by hydrogenation in the presence of Ni catalyst and prepared their poly(o hydroxyl fatty acid)s by melt polycondensation.
  • these linear polyesters presented a high tensile strength but, in some cases, due to their high degree of crystallinity, the polyesters showed pronounced brittleness, thereby limiting their use in many applications, such as coatings.
  • the disclosure provides polymer compositions, comprising one or more polyester polymers comprising constitutional units formed from a reaction mixture, the reaction mixture comprising: (a) one or more monomers of formula (I):
  • R 2 and R 3 are independently a hydrogen atom or Ci-6 alkyl.
  • a series of branched poly ( ⁇ -hydroxyl fatty acid) polyesters have been prepared from methyl ⁇ -hydroxyl fatty acid esters including methyl ⁇ -hydroxynonanoate, methyl ⁇ -hydroxytridecanoate and methyl ⁇ -hydroxyoctadecanoate using a green melt poly condensation route.
  • the branches were implanted by random polymerization of the methyl ⁇ -hydroxyl fatty acid esters and 2-butyl-2-ethyl-l,3- propanediol.
  • a diacid methyl ester including dimethyl azelate, dimethyl adipate or dimethyl octadecanedioate, was used in amounts to make the ratio of OH and COOH unity.
  • the reaction was conducted under vacuum (initially at 300 mbar, and then at 20 mbar) at a gradually increasing temperature (from 80 °C to 200 °C) to avoid the evaporation of the monomers.
  • the structure of polyesters and their branches have been confirmed by ⁇ -NMR.
  • the ratio of the branched structures to the ⁇ -hydroxyl fatty acid structures (simply ratio of branches) in the polyesters was also determined by 1H- NMR.
  • Figure 5 shows the ⁇ -NMR spectrum for the PEn 7 m 2 -0.1 polyester.
  • Figure 8 shows the ⁇ -NMR spectrum for the PEn 7 mi 4 -0.2 polyester.
  • Figure 9 shows the ⁇ -NMR spectrum for the PEnnm 2 -0.1 polyester.
  • Figure 10 shows the H-NMR spectrum for the PEnnm 2 -0.2 A polyester.
  • Figure 11 shows the H-NMR spectrum for the PEnnm 2 -0.2 B polyester.
  • Figure 12 shows the ⁇ -NMR spectrum for the PEnnm 2 -0.3 polyester.
  • Figure 13 shows the ⁇ -NMR spectrum for the PEnnm 5 -0.1 polyester.
  • Figure 14 shows the H-NMR spectrum for the PEnnm 5 -0.2 polyester.
  • Figure 15 shows the H-NMR spectrum for the PEnnm 5 -0.3 polyester.
  • Figure 17 shows the H-NMR spectrum for the PEnnmi 4 -0.2 polyester.
  • Figure 18 shows the X H-NMR spectrum for the PEnnmi 4 -0.3 polyester.
  • Figure 19 shows the X H-NMR spectrum for the PEni 6 m 2 -0.2 polyester.
  • Figure 20 shows the DTG curves for certain PEn z m x -y polyesters.
  • Figure 21 shows the DTG curves for PEn -2 m 5 and PEnnm 5 -0.2 polyesters.
  • Figure 28 shows the mechanical properties of branched polyesters as a function of the enthalpy of melting, (a) Young's modulus; (b) Stress at break; (c) strain. Dashed lines are guides for the eye.
  • Figure 29 shows the strain - stress curve of the PEnnm 2 -0.2 B polyester.
  • polymer refers to a substance having a chemical structure that includes the multiple repetition of constitutional units formed from substances of
  • polymer includes soluble and/or fusible molecules having chains of repeat units, and also includes insoluble and infusible networks.
  • monomer refers to a substance that can undergo a polymerization reaction to contribute constitutional units to the chemical structure of a polymer.
  • polyester refers to a polymer comprising two or more ester linkages. Other types of linkages can be included, however. In some embodiments, at least 80%, or at least 90%, or at least 95% of the linkages in the polyester are ester linkages.
  • the term can refer to an entire polymer molecule, or can also refer to a particular polymer sequence, such as a block within a block copolymer.
  • dihydroxyl polyester refers to a polyester having two or more free hydroxyl groups, e.g., at the terminal (e.g., reacting) ends of the polymer (i.e., a "dihydroxyl-terminated polyester”). In some embodiments, such polyesters have exactly two free hydroxyl groups.
  • alcohol or “alcohols” refer to compounds having the general formula: R-OH, wherein R denotes any organic moiety (such as alkyl, aryl, or silyl groups), including those bearing heteroatom-containing substituent groups. In certain embodiments, R denotes alkyl, alkenyl, aryl, or alcohol groups. In certain embodiments, the term “alcohol” or “alcohols” may refer to a group of compounds with the general formula described above, wherein the compounds have different carbon lengths.
  • hydroxyl refers to a -OH moiety. In some cases, an alcohol can have more than two or more hydroxyl groups. As used herein, "diol” and “polyol” refer to alcohols having two or more hydroxyl groups.
  • group refers to a linked collection of atoms or a single atom within a molecular entity, where a molecular entity is any constitutionally or isotopically distinct atom, molecule, ion, ion pair, radical, radical ion, complex, conformer etc., identifiable as a separately distinguishable entity.
  • mixture refers broadly to any combining of two or more compositions.
  • the two or more compositions need not have the same physical state; thus, solids can be “mixed” with liquids, e.g., to form a slurry, suspension, or solution. Further, these terms do not require any degree of homogeneity or uniformity of composition. This, such “mixtures” can be homogeneous or heterogeneous, or can be uniform or non- uniform. Further, the terms do not require the use of any particular equipment to carry out the mixing, such as an industrial mixer.
  • natural oil or "lipid” refers to oils derived from various plants or animal sources. These terms include natural oil derivatives, unless otherwise indicated. The terms also include modified plant or animal sources (e.g., genetically modified plant or animal sources), unless indicated otherwise. Examples of natural oils include, but are not limited to, vegetable oils, algae oils, fish oils, animal fats, tall oils, derivatives of these oils, combinations of any of these oils, and the like.
  • vegetable oils include rapeseed oil (canola oil), coconut oil, com oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm kernel oil, rung oil, jatropha oil, mustard seed oil, penny cress oil, camelina oil, hempseed oil, and castor oil.
  • animal fats include lard, tallow, poultry fat, yellow grease, and fish oil.
  • Tall oils are by-products of wood pulp manufacture.
  • the natural oil or natural oil feedstock comprises one or more unsaturated glycerides (e.g., unsaturated triglycerides).
  • natural oil derivatives refers to the compounds or mixtures of compounds derived from a natural oil using any one or combination of methods known in the art. Such methods include but are not limited to saponification, fat splitting,
  • natural oil derivatives include gums, phospholipids, soapstock, acidulated soapstock, distillate or distillate sludge, fatty acids and fatty acid alkyl ester (e.g. non-limiting examples such as 2-ethylhexyl ester), hydroxy substituted variations thereof of the natural oil.
  • the natural oil derivative may be a fatty acid methyl ester ("FAME") derived from the glyceride of the natural oil.
  • alkyl refers to a straight or branched chain saturated hydrocarbon having 1 to 30 carbon atoms, which may be optionally substituted, as herein further described, with multiple degrees of substitution being allowed.
  • alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl, n-pentyl, neopentyl, n-hexyl, and 2-ethylhexyl.
  • the "alkyl” group can be bivalent, in which case, the group can be described as an "alkylene” group.
  • multi-atom bivalent species are to be read from left to right.
  • D is defined as -OC(O)-
  • the resulting group with D replaced is: A-OC(0)-E and not A-C(0)0-E.
  • the disclosure provides polymer compositions, comprising one or more polyester polymers comprising constitutional units formed from a reaction mixture, the reaction mixture comprising (a) one or more monomers of formula (I):
  • reaction mixture further comprises constitutional units formed from aliphatic dibasic acids or esters thereof.
  • any suitable monomers of formula (I) or combination of monomers of formula (I) can be used.
  • Compounds, such as those of formula (I) can be referred to as " ⁇ -hydroxy aliphatic acids” or “ ⁇ -hydroxy aliphatic esters,” depending on whether the a-end of the compound is a carboxylic acid group or an acid or ester group, respectively.
  • the monomers of formula (I) are acids, such that R 1 is a hydrogen atom.
  • the monomers of formula (I) are esters, for example, if R 1 is Ci_6 alkyl, such as methyl or ethyl. In some embodiments, R 1 is methyl.
  • the monomers of formula (I) can be present in the reaction mixture in any suitable combination.
  • the reaction mixture comprises monomers of formula (I) where p is 8, monomers of formula (I) where p is 12, monomers of formula (I) where p is 17, or any combination thereof.
  • the reaction mixture comprises monomers of formula (I) where p is 8.
  • the reaction mixture comprises monomers of formula (I) where p is 12.
  • the reaction mixture comprises monomers of formula (I) where p is 17. In some such
  • the reaction mixture comprises monomers of formula (I) where p is 8 and monomers of formula (I) where p is 12. In some such embodiments, the reaction mixture comprises monomers of formula (I) where p is 8 and monomers of formula (I) where p is 17. In some such embodiments, the reaction mixture comprises monomers of formula (I) where p is 12 and monomers of formula (I) where p is 17. In some such embodiments, the reaction mixture comprises monomers of formula (I) where p is 8, monomers of formula (I) where p is 12, and monomers of formula (I) where p is 18.
  • ⁇ -hydroxy aliphatic acids/esters besides those of formula (I) can be present. Even so, in some such embodiments, the monomers of formula (I) (according to any of the aforementioned embodiments) make up at least 50 percent by weight, or at least 60% by weight, or at least 70% by weight, or at least 80% by weight, or at least 90% by weight, or at least 95% by weight, or at least 97% by weight, or at least 99% by weight, of the ⁇ -hydroxy aliphatic acids/esters present in the reaction mixture, based on the total weight of ⁇ -hydroxy aliphatic acids/esters present in the reaction mixture.
  • X 1 is a branched-chain Cs -14 alkylene, or a branched-chain C 7-12 alkylene.
  • the monomers of formula (II) can have any suitable degree of branching (i.e., the number of carbon atoms covalently bound to three or four other carbon atoms.
  • X 1 comprises one branching point. In some such embodiments, the carbon atom at that branching point is covalently bound to four other carbon atoms.
  • X 1 is represented by the following formula:
  • G 1 is -CH 2 -;
  • G 2 is a direct bond or is -CH 2 -, -CH 2 -CH 2 -, or -CH 2 -CH 2 -CH 2 -;
  • G 3 is a direct bond or -C(G 7 )(G 8 )-;
  • G 4 is a direct bond or is -CH 2 -, -CH 2 -CH 2 -, or -CH 2 -CH 2 -CH 2 -;
  • G and G are independently a hydrogen atom or Ci-6 alkyl, wherein at least one of G 5 and G 6 is not a hydrogen atom; and
  • G 7 and G 8 are independently a hydrogen atom or Ci-6 alkyl, wherein at least one of G 7 and G 8 is not a hydrogen atom.
  • G 2 is a direct bond. In some such embodiments, G 2 is -CH 2 -. In some such embodiments of any of the aforementioned embodiments, G 3 is a direct bond. In some such embodiments of any of the aforementioned embodiments, G is or -C(G 7 )(G 8 )-. In some such embodiments, G is a hydrogen atom. In some other such embodiments, G 7 is methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, pentyl, or isobutyl. In some such embodiments of any of the aforementioned embodiments, G 8 is a hydrogen atom.
  • G 8 is methyl, ethyl, propyl, isopropyl, butyl, sec- butyl, isobutyl, pentyl, or isobutyl.
  • G 4 is a direct bond.
  • G 4 is -CH 2 -. In some other such embodiments of any of the aforementioned embodiments, G 4 is
  • G 5 is a hydrogen atom. In some other such embodiments of any of the aforementioned
  • G 5 is methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, pentyl, or isobutyl. In some further such embodiments, G 5 is methyl, ethyl, propyl, or butyl. In some embodiments of any of the aforementioned embodiments, G 6 is a hydrogen atom. In some other such embodiments of any of the aforementioned embodiments, G 6 is methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, pentyl, or isobutyl. In some further such embodiments, G 6 is methyl, ethyl, propyl, or butyl. In some embodiments, G 5 is ethyl and G ⁇ is butyl.
  • the monomer of formula (II) is 2-butyl-2-ethyl-l,3-propanediol.
  • the polyesters comprise constitutional units formed from a reaction mixture that further comprises a C6-22 aliphatic dibasic acid or ester thereof.
  • the reaction mixture further comprising one or more monomers of formula (III):
  • R 2 and R 3 are independently a hydrogen atom or Ci-6 alkyl.
  • the reaction mixture can contain any combination of monomers of formula (III).
  • the reaction mixture comprises monomers of formula (III) where q is 4, monomers of formula (III) where q is 7, monomers of formula (III) where q is 10, monomers of formula (III) where q is 16, or any combinations thereof.
  • the reaction mixture comprises monomers of formula (III) where q is 4.
  • the reaction mixture comprises monomers of formula (III) where q is 7. In some
  • the reaction mixture comprises monomers of formula (III) where q is 10. In some embodiments, the reaction mixture comprises monomers of formula (III) where q is 16.
  • R 2 and R 3 are a hydrogen atom.
  • R 2 and R 3 are Ci-6 alkyl, such as methyl.
  • any suitable amount of monomers of formula (III) can be included in the reaction mixture.
  • the molar ratio of monomers of formula (II) to monomers of formula (III) ranges from 1 :3 to 3: 1, or from 1 :2 to 2: 1, or from 1.5 : 1 to 1 : 1.5, or from 1.2: 1 to 1 : 1.2.
  • the monomers of formula (I) can have any suitable ratio to the monomers of formula (II) and the monomers of formula (III).
  • the molar ratio of monomers of formula (I) to monomers of formula (II) ranges from 1 : 1 to 25: 1, or from 2: 1 to 20: 1 , or from 3: 1 to 15: 1, or from 4: 1 to 12: 1.
  • the molar ratio of (a) monomers of formula (I) to (b) the sum of monomers of formula (II) and monomers of formula (III) ranges from 1 : 1 to 20: 1, or from 1 : 1 to 15: 1, or from 2: 1 to 10: 1.
  • the polyester consists entirely or almost entirely of monomers of formula (I) and monomers of formula (II).
  • the reaction mixture consists essentially of monomers of formula (I) and monomers of formula (II).
  • the polyester consists entirely or almost entirely of monomers of formula (I), monomers of formula (II), and monomers of formula (III).
  • the reaction mixture consists essentially of monomers of formula (I), monomers of formula (II), and monomers of formula (III).
  • the resulting polyesters can have certain desirable physical properties.
  • the one or more polyesters lose no more than 5 percent of their weight upon heating to a temperature of at least 300 °C, or to a temperature of at least 320 °C, or to a temperature of at least 340 °C.
  • the one or more polyesters have a Young's modulus of at least 200 MPa, or at least 250 MPa, or at least 300 MPa, or at least 350 MPa, or at least 400 MPa.
  • the one or more polyesters have a strain at break of at least 10%, or at least 20%, or at least 50%, or at least 100%, or at least 150%, or at least 200%, or at least 250%.
  • polyesters disclosed herein can be synthesized by any suitable means, although some means may be more desirable than others. Suitable synthetic methodologies are disclosed in the Examples, below. The claims to the compounds, or to compositions including the compounds, are not limited in any way by the synthetic method used to make the compounds.
  • Erucic acid (90% purity), methyl oleate (70% purity), oleyl alcohol (85% purity), Raney nickel 2800 (slurry in water), Ti(IV) isopropoxide [Ti(OiPr) 4 ] (99.99% purity), Grubbs 2nd generation catalyst, 2-butyl-2-ethyl-l,3-propanediol (99% purity), dimethyl azelate and dimethyl adipate were purchased from Sigma-Aldrich. Methyl ⁇ - hydroxynonanoate and methyl
  • ⁇ -NMR spectra were recorded in CDC1 3 on a Varian Unity-INOVA at 499.695 MHz. All spectra were obtained using an 8.6 pulse with 4 transients collected in 16,202 points. Datasets were zero-filled to 64 000 points, and a line broadening of 0.4 Hz was applied prior to Fourier transformation. The spectra were processed using ACD Labs NMR Processor, version 12.01. H chemical shifts are internally referenced to CDCI 3 (7.26 ppm). Physical Characterization
  • the static mechanical properties of the polymer films were determined at room temperature using a Texture Analyzer (TA HD, Texture Technologies Corp., Robbinsville, NJ, USA) equipped with a 2-kg load cell. The measurements were performed following the ASTM D882 standard procedure. The sample was stretched at a rate of 5 mm min 1 from a gauge of 35 mm.
  • TA HD Texture Technologies Corp., Robbinsville, NJ, USA
  • the branched polyesters were prepared from methyl ⁇ -hydroxyl fatty acids, 2-butyl- 2-ethyl-l,3-propanediol by a polycondensation reaction, as shown in Figure 1.
  • the recipe for the polymerizations is provided in Table 1.
  • the amount of dimethyl diacid ester was adjusted to realize an equal ratio of OH:COOH suitable for achieving high molecular weight.
  • the procedure follows: A+B+C (from Figure 1) was heated to 80 °C and catalyst (Ti(OiPr) 4 ) with a concentration 5.1 ⁇ 1/2 g monomers was added under stirring at 1000 rpm.
  • the reaction was continued for 1 h at 80 °C, then 1 h at 100 °C, 2h at 120 °C, 2 h at 140 °C, and overnight at 160 °C with a vacuum of 300 mbar, and then 2 h at 180 °C, and 4 to 6 h at 200 °C with a vacuum of 20 mbar.
  • the nominal stirring speed was adjusted gradually during the reaction from 1000 rpm at the start of the reaction to 300 rpm depending on the viscosity of the reaction system.
  • the reaction was terminated at the last step of
  • the relative number of the branches can be estimated by the ratio of -CH 2 0- at 4.07 ppm to the
  • the thermal stability of the achieved branched polyesters was determined by thermal gravimetric analysis (TGA).
  • TGA thermal gravimetric analysis
  • the derivative of the TGA (DTG) curves of branched polyesters of the present work are provided in Figure 20.
  • the DTG curves of PEn -2 m 5 and PEnnm 5 -0.2 which exemplify the thermal degradation behavior of all these polyesters are shown in Fig. 2.
  • TGA data T 53 ⁇ 4 : temperature at 5% weight loss, T° n : extrapolated onset of degradation temperature, T m 2 : peak temperatures of the DTG, TR: thermal degradation temperature range and Ash: ash content (%) after thermal degradation) of all the polyesters of the present work are provided in Table 4.
  • the onset temperature of degradation or T 5% in Table 2) was higher than 300 °C for all the branched polyesters. This is a high enough temperature for the safe thermal processing of these materials. As exemplified in Fig.
  • polyesters presented a one-step degradation with a DTG peak at 358 °C and 449 °C, respectively.
  • polyesters showed two steps in this temperature range due to the different ester linkages formed from hydroxyl group from ⁇ - hydroxyl fatty acids or from 2-butyl-2-ethyl-l,3-propanediol.
  • the second step occurred at -440 °C to 480 °C, with a weight loss of less than 15%, related to the clearance of the carbon-carbon bonds.
  • Most of the samples contained less than 2 % ash after the thermal degradation was complete.
  • the thermal properties were determined by DSC.
  • the DSC data are provided in Table 5.
  • the data of Fig. 22 showing the heating DSC thermograms (2 nd cycle) of the polyesters with C6, C9 and C18 diacid methyl ester, namely PEn -2 m 2 , PEn -2 m 5 and PEn -2 mi 4 and reveal the effect of the 2-butyl-2-ethyl-l,3-propanediol branches on the crystallinity of the diacid fatty acid chain.
  • Fig. 22 showing the heating DSC thermograms (2 nd cycle) of the polyesters with C6, C9 and C18 diacid methyl ester, namely PEn -2 m 2 , PEn -2 m 5 and PEn -2 mi 4 and reveal the effect of the 2-butyl-2-ethyl-l,3-propanediol branches on the crystallinity of the diacid fatty acid chain.
  • melting behavior including melting point (T m ), melting enthalpy and glass transition temperature (T ) of the degree of branching, ⁇ -hydroxyl fatty acid chain length (n) and diacid methyl ester chain length (m) is shown in Figs. 23-25, respectively.
  • the viscosity of the reaction system is directly related to molecular weight, and can therefore be used as a very good indicator to determine the point at which the polymerization reaction can be terminated to achieve high molecular weight polymers and improved elastomeric properties.

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  • 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)

Abstract

L'invention concerne d'une manière générale des polyesters dérivés de sources renouvelables, telles que certaines huiles naturelles. Dans certains modes de réalisation, les polyesters selon l'invention contiennent des monomères qui introduisent une ramification dans le squelette du polymère. L'invention concerne également des procédés de production de ces polyesters. L'invention concerne en outre certaines utilisations de ces polyesters.
PCT/CA2017/050280 2016-03-02 2017-03-02 Polyesters dérivés de sources renouvelables, contenant des monomères à chaîne ramifiée, leurs procédés de production et leur utilisation Ceased WO2017147708A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2020260312A1 (fr) 2019-06-25 2020-12-30 Institut National De Recherche Pour L'agriculture, L'alimentation Et L'environnement Procédé de préparation d'un élastomère à partir d'un acide gras hydroxylé et élastomère obtenu par un tel procédé

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EP0801088A1 (fr) * 1996-04-12 1997-10-15 Witco Polyester polyol, mousse de polyuréthane obtenue à partir dudit polyester polyol et son utilisation
CA2869333A1 (fr) * 2012-04-11 2013-10-17 The Lubrizol Corporation Dispersants derives de polyesters d'acides gras hydroxyles et dispersants a base de polyalkylene glycol
US20140051780A1 (en) * 2012-08-16 2014-02-20 Synthezyme Llc COPOLYESTERS HAVING REPEAT UNITS DERIVED FROM w-HYDROXY FATTY ACIDS
US20150018260A1 (en) * 2012-02-28 2015-01-15 Petroliam Nasional Berhad Lubricant composition of matter and methods of preparation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0801088A1 (fr) * 1996-04-12 1997-10-15 Witco Polyester polyol, mousse de polyuréthane obtenue à partir dudit polyester polyol et son utilisation
US20150018260A1 (en) * 2012-02-28 2015-01-15 Petroliam Nasional Berhad Lubricant composition of matter and methods of preparation
CA2869333A1 (fr) * 2012-04-11 2013-10-17 The Lubrizol Corporation Dispersants derives de polyesters d'acides gras hydroxyles et dispersants a base de polyalkylene glycol
US20140051780A1 (en) * 2012-08-16 2014-02-20 Synthezyme Llc COPOLYESTERS HAVING REPEAT UNITS DERIVED FROM w-HYDROXY FATTY ACIDS

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020260312A1 (fr) 2019-06-25 2020-12-30 Institut National De Recherche Pour L'agriculture, L'alimentation Et L'environnement Procédé de préparation d'un élastomère à partir d'un acide gras hydroxylé et élastomère obtenu par un tel procédé
FR3097867A1 (fr) * 2019-06-25 2021-01-01 Institut National Polytechnique De Toulouse Procédé de préparation d’un élastomère à partir d’un acide gras hydroxylé et élastomère obtenu par un tel procédé
CN114729110A (zh) * 2019-06-25 2022-07-08 法国国家农业,食品与环境研究院 由羟基化脂肪酸制备弹性体的方法和通过这样的方法获得的弹性体
CN114729110B (zh) * 2019-06-25 2023-09-22 法国国家农业,食品与环境研究院 由羟基化脂肪酸制备弹性体的方法和通过这样的方法获得的弹性体
US12497482B2 (en) 2019-06-25 2025-12-16 Centre National De La Recherche Scientifique Method for preparing an elastomer from a hydroxylated fatty acid and elastomer obtained by such a method

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