WO2016061666A1 - Formulations from glycerol-based polyesters and their blends with plastics and methods of making those - Google Patents

Formulations from glycerol-based polyesters and their blends with plastics and methods of making those Download PDF

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Publication number
WO2016061666A1
WO2016061666A1 PCT/CA2015/000549 CA2015000549W WO2016061666A1 WO 2016061666 A1 WO2016061666 A1 WO 2016061666A1 CA 2015000549 W CA2015000549 W CA 2015000549W WO 2016061666 A1 WO2016061666 A1 WO 2016061666A1
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glycerol
acid
resin composition
based polyester
poly
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PCT/CA2015/000549
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French (fr)
Inventor
Amar Kumar MOHANTY
Manjusri Misra
Oscar Enrique VALERIO GONZALES
Christopher Pond
Tessa HORVATH
Gildas COATIVY
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University Of Guelph
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Publication of WO2016061666A1 publication Critical patent/WO2016061666A1/en

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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
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation

Definitions

  • the present invention relates to the synthesis of oligomeric and polymeric esters from glycerol and carboxylic acids and its use in thermoplastic polymeric blends as impact or toughness enhancers.
  • Glycerol is a molecule containing three hydroxy! groups on its structure. It was previously obtained in the 1940's as a derivative of petroleum resources, and since the last decade, it can be obtained In mass as a by-product of the biodiesel industry (Martin & Richter, 2011). in spite of the intensive utilization of glycerol in many fields of applications such as food, personal care and tobacco products, the increase of biodiesel productions could lead to a leftover of glycerol (Behr, Biting, Irawadl, Leschinski, & Lindner, 2008) and a drop of its price. Consequently, new applications for this molecule have to be found to limit the surplus.
  • glycerol An interesting and economically viable application field for glycerol is the synthesis of biopolyesters through a polycondensation reaction with mono or dicarboxylic acids and their derivatives. Due to the trifunctionality of glycerol, this route can lead to the synthesis of both crosslinked and uncrosslinked polymeric materials according to the synthesis conditions, which will ultimately determine the suitability of a glycerol based polyester in different application fields.
  • US Pat. No. 7,722,804 B2 describes the synthesis of crosslinked glycerol based materials for its use in biomedical applications.
  • US Pat. No. 7,148.293 B2 describes the synthesis of uncrosslinked glycerol based materials and its use as additives in adhesive, coatings and paint formulations.
  • WO2009/146109 describes a plasticlzing agent for biopolymer matrices consisting of a compatibilizing unit and a polyester plasticizing unit.
  • the compatlbilizing unit consists of a lower alkyl organic acid having a C3 to C7 alkyl backbone, while the polyester plasticizing unit is formed from monomers that consists of a multifunctional alcohol, a saturated or unsaturated aliphatic anhydride or its equivalent, and optionally, a saturated aromatic anhydride or its equivalent.
  • the polyester plasticizing unit may optionally include one or more difunctlonal alcohol, such as glycol, every single example included in this document includes both glycerin and diethylene glycol. That is, WO2009/146109 does not enable the synthesis of a plasticizing unit consisting only of glycerin.
  • WO2012/038441 describes the synthesis and application of an impact modifier tor biodegradable polymers such as poly lactic acid.
  • an impact modifier tor biodegradable polymers such as poly lactic acid.
  • the authors employed acrylic monomers derived from petroleum resources for the synthesis. That is, the Impact modifier synthesized is not a biobased product and furthermore does not employ glycerol as a monomer in the synthesis of the impact modifier.
  • Biodiesel derived refined glycerol with a higher degree of purity (higher than 95%) is proposed as monomer for the synthesis of elastomeric like polymeric materials for being used in improvement of toughness or impact properties of commercially available biopoiymers such as poly lactic acid (PLA) or poly butylene succinate (PBS) in normal or reactive extrusion mode in presence of free radical initiators.
  • PLA poly lactic acid
  • PBS poly butylene succinate
  • glycerol can be used to make biocompatible poly (glycerol sebacate) (Wang, Ameer, Sheppard, & Langer, 2002) and more over it was shown that the obtained elastomer exhibit shape memory properties (Cai & Liu, 2008). After a shape memory creation procedure consisting in stretching the material above a temperature of transition Ttmu, the material can keep its shape below Ttmns, and recover Its Initial shape above Ttrans. Such a property can be used to make low invasive surgery for example.
  • the present application is a glycerol based polyester, the glycerol based polyester including (i) glycerol as the only alcohol in the polyester, (ii) at least one saturated dicarboxylic acid, and (iii) at least one unsaturated dicarboxylic acid or a derivative thereof.
  • the glycerol based polyester further includes a monocarboxylic acid having a C16 to C18 alkyi chain.
  • the molar ratio of glycerol to dicarboxylic acid is in the range from about 0.32 to about 1.28.
  • the saturated dicarboxylic acid is selected from succinic acid, glutaric acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid and decanedloic acid.
  • the unsaturated dicarboxylic acid or derivative thereof has an alkyi chain of at least 4 atoms of carbon.
  • the unsaturated dicarboxylic acid or derivative thereof is selected from maleic anhydride or fumaric acid or their derivatives.
  • the present invention provides for a resin composition
  • a resin composition comprising a glycerol based polyester according to any one of the previous embodiments and a polymer or a polymeric blend.
  • the polymer or polymeric blend include biopolymers, and wherein the biopolymers are selected from poly (lactic acid), poly (butylene succinate), poly (hydroxy butyrate co valerate) or a combination thereof.
  • the resin composition includes between 1-50% by weight of the glycerol-based polyester.
  • the resin composition of the present invention is created by reactive extrusion in presence of a free radical Initiator leading to the crosslinking of the glycerol based polyester within the polymeric blend.
  • the free radical initiator is an organic free radical initiator selected from 2,5-Bis(tert-butylperoxy)- 2,5-dimethylhexane or dicumyl peroxide.
  • the polymer or polymeric blend include non-biobased polymers.
  • the resin composition further includes an additive, a biofiller, a nucleating agent, clay or a combination thereof.
  • the resin composition further includes a biofiber.
  • the biofiber is selected from miscanthus, switch grass, agro-residues, hemp, jute, kenaf or a combination thereof.
  • the additive is selected from epoxidized soy bean oil, polymeric methylene diphenyl dilsocyanate, isocyanate terminated prepolymer, titanate and silane.
  • the present invention in another embodiment, relates to a method for preparing a glycerol based polyester, the method including reacting glycerol with at least one saturated dicarboxylic acid and at least one unsaturated dicarboxylic acid or a derivative thereof, wherein the glycerol is the only alcohol used in the reaction.
  • the method further includes adding a rnonocarboxylic acid having a C16 to C18 alkyl chain.
  • the rnonocarboxylic acid is added in the range of 15 to 50 wt%.
  • the reacting includes microwavlng the glycerol with the at least one saturated dicarboxylic acid.
  • the molar ratio of glycerol to dicarboxylic acid Is in the range from about 0.32 to about 1.28.
  • the saturated dicarboxylic acid is selected from succinic acid, glutaric acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid and decanedioic acid.
  • the unsaturated dicarboxylic acid or derivative thereof is selected from maleic anhydride orfumaric acid.
  • the glycerol is provided as crude glycerol, technical glycerol or pure glycerol.
  • the glycerol based polyester is synthesized using glycerol of different purities.
  • the purity of the glycerol ranges between 15 to 99 wt% glycerol content.
  • the present invention in another embodiment, relates to a method of producing a resin composition, the method including blending a polymer with the glycerol based polyester of the previous embodiments.
  • polymer is a single polymer or a blend of polymers.
  • the polymer is selected ' from poly (lactic acid), poly (butylene succinate), poly (hydroxy butyrate co valerate), nylon, polyvinyl chloride, polystyrene, polyethylene, polypropylene, polyacrylonitrile, PVB, silicone, or a combination thereof.
  • the resin composition is produced by blending between 1-50 wt% of the glycerol based polyester and between 50-99 wt% of the biodegradable polymer.
  • the free radical Initiator is organic, and wherein the organic free radical initiator is selected from 2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane or dicumyl peroxide.
  • the glycerol is provided as crude glycerol.
  • the method further includes adding an organic free radical initiator, an additive, a biofiller, a nucleating agent, or a combination thereof. In another embodiment of the method for producing a resin composition of the present invention, the method further includes adding a bioflber.
  • the biofiber is selected from miscanthus, switch grass, agro-residues, hemp, jute, kenaf or combination thereof.
  • the additive is selected from epoxidized soy bean oil, polymeric methylene diphenyl diisocyanate, isocyanate terminated prepolymer, titanate and silane.
  • the present invention in another embodiment, is a resin composition.
  • the resin composition in one embodiment, includes a glycerol based polyester and a polymer or a polymeric blend, wherein the glycerol based polyester comprises: (i) crude glycerol as the only alcohol in the glycerol based polyester, and (ii) at least one saturated dicarboxylic acid.
  • the polymer is selected from poly
  • lactic acid poly (butylene succinate), poly (hydroxy butyrate co valerate), nylon, polyvinyl chloride, polystyrene, polyacrylonitrile, polyvinyl butyral (PVB), silicone, polypropylene and polyethylene or a combination thereof.
  • polyvinyl chloride polystyrene, polyacrylonitrile, polyvinyl butyral (PVB), silicone, polypropylene and polyethylene or a combination thereof.
  • PVB polyvinyl butyral
  • the glycerol in one embodiment of the glycerol based polyesters or the resin compositions of the present invention, is crude glycerol.
  • the glycerol has a purity range from 1% to 99%.
  • the present invention in another embodiment, provides for a shape memory polymeric composition produced by reacting a glycerol as the only alcohol in the composition, at least one saturated dicarboxylic acid and at least one unsaturated dicarboxylic acid.
  • the reaction further includes reacting a monoacid.
  • the shape memory polymeric composition has shape memory such that when the polymeric composition is deformed at a temperature above temperature of transition (TVare) of the composition and the temperature is then lowered to a temperature below the Tvans, the polymeric composition retains its deformed shape, and when the temperature is then raised above the Ttnns the polymeric composition returns substantially to its original shape, wherein the Tuans of the polymeric composition is between room temperature (21 °C) and 37°C.
  • FIG. 1 Flow chart illustrating the preparation of glycerol based polyester and the blending of the glycerol based polyester with a polymer in accordance to one
  • FIG.2 Flow chart illustrating the preparation of a glycerol based polyester and the blending of the glycerol based polyester with a polymeric blend in accordance to another embodiment of the present invention.
  • FIG.3 Flow chart illustrating the preparation of a glycerol based polyester and the blending of the glycerol based polyester with a polymeric blend in accordance to another embodiment of the present invention.
  • FIG.4 Flow chart illustrating the synthesis of a glycerol based polyester and the blending of the glycerol based polyester with a polymeric blend in accordance to yet another embodiment of the present invention.
  • FIG. 5 Calorimetric study of biopolyester made of glycerol, sebacic acid and stearic acid (1:1 :0.5) (top curve A) and a biopolyester made of sebacic acid and glycerol without the use of monoacid (1 -.1 :0) (bottom curve B).
  • Panel A is a photograph of the material prior to the shape memory creation procedure.
  • Panel B is a photograph of the material after having been stored 12 hours without stress at room temperature in a sealed bag.
  • Panel C is a photograph of the material after shape recovery.
  • FIG. 7 Photomicrographs of PGSseb-4 under cooling at 10°C/min (*50) under polarized light at: a) 9°C, b) 37°C and c) 50°C.
  • Biobased means a plant-made molecule that is either directly expressed from plants, such as sugars, starches or fats, or fermented from plant-made molecules. Although glycerol may be obtained by transesteriflcation (chemical reaction), the raw materials used to obtain glycerol are biobased, as such glycerol obtained by transesterification may also be considered biobased. Biopolymer” refers to a polymer made from plant derived molecules.
  • PES poly (glycerol succinate)
  • liquid poly glycerol succinate co maleate
  • liquid poly glycerol succinate co fumarate
  • PESeb poly (glycerol sebacate)
  • PLA poly (lactic acid)
  • the present invention relates to the use of glycerol or crosslinkable glycerol based polyesters as materials for the modification of biodegradable and nonbiodegradable plastic matrices that may result in an improvement in the toughness or impact behavior of commercially biodegradable and non-biodegradable plastic matrices by melt compounding with glycerol based polyesters.
  • glycerol based polyesters of the present invention contain unsaturation sites which can be further reacted during an extrusion process.
  • the reactivity of these unsaturated glycerol based polyesters may be triggered on the extrusion process by using free radical initiators.
  • a thermoplastic polymeric blend with a cross-linked included microphase may be produced leading to improvement of toughness or impact properties of the material.
  • the crosslinking of glycerol based polyesters on the extrusion process can help in reducing migration of the additive from within the matrix in order to maintain the mechanical performance with time.
  • saturated dicarboxylic acids employed for the synthesis of glycerol based polyesters include dicarboxylic acids having C4-C1B alkyl chain.
  • unsaturated dicarboxylic acids and their derivatives include maleic anhydride and fumaric acid, the latter being produced from biobased sources leading to the synthesis of a biobased glycerol polyester.
  • the glycerol based polyester of the present invention may be used for modification of polymeric blend systems as described herein below.
  • the polyesters, including plasticlzers, of the present invention may be synthesized using a combination of an alcohol and acid molecules.
  • the alcohol molecules may include glycerol of different purities and sources.
  • the acid molecules include an organic saturated dicarboxylic acid with a carbon chain length of C4 to C10 and an organic unsaturated dicarboxylic add or its derivatives with a carbon chain length of at least C4. That is, the organic saturated dicarboxylic acid may have a carbon chain length of C4, C5, C6 C7, C8, C9 or C10.
  • the acid molecules may also include an organic monocarboxylic acid. In one embodiment the organic monocarboxylic acid may have a carbon chain length of C12- C18, preferably C18.
  • the molar ratio of alcohol to dicarboxylic acid molecules may be in a range of about 0.32 to about 1.28.
  • the molar ratio of hydroxyl to carboxyl functionalities from glycerol and total acid molecules respectively may be in a range of about 0.48 to about 1.92.
  • a molar ratio of 1:0.5:0.5 mol glycerol/succinic acid/maleic anhydride may be used.
  • Monocarboxylic acid molecules may be added to some formulations to limit or avoid the formation of crosslinking during the synthesis and to improve the compatibility. When monocarboxylic acid molecules are employed, these may be added in a range of 15-50wt%.
  • the glycerol based polyester of the present invention which may be biobased, may be synthesized using a polycondensation reaction.
  • the polycondensation reaction may be performed in different systems such as in a temperature controlled stirred glass reactor or a microwave oven.
  • a microwave oven may be used for polyester synthesis.
  • Such microwaving synthesis may require substantial less time as compared to glass vessel-based reaction system.
  • the glycerol used to synthesize the polyester of the present invention may be obtained from any source, and the purity of the glycerol may range anywhere from about 1% to 99% of glycerol content. Preferably, the purity of glycerol may range from about 15% to about 99%.
  • the glycerol used to synthesize the polyester of the present invention may be crude glycerol. When reactivity is desired, it may be preferable to use glycerol of higher purity such as technical glycerol.
  • Glycerol may be the only alcohol used to create, make or synthesize the polyester of the present invention.
  • the polyester, the resins (described below) and articles of the present invention may be made just with glycerol as the only alcohol and be free of glycols and/or other alcohols.
  • the glycerol based polyesters of the present invention may be used both as a tough polymer for modification of plastics trough blending and/or as shape memory materials.
  • the polyesters of the present invention may be used as blending additives for polymers, including non-biodegradable such as nylon, polyvinyl chloride, polystyrene, polyacry!onitrile, polyvinyl butyral (PVB), silicone, polypropylene and polyethylene and/or biodegradable polymers such as PLA, PBS, PHBV or combinations thereof in the production of blends or resins.
  • the polymers may be provided as single polymers or as a blend of polymers.
  • the percentage of glycerol-based polyester in the final resins or blends of the present invention may range anywhere from about 1wt% to about 50wt%, and any range there in between.
  • the method of producing the blend with the glycerol based polyester and the polymeric blend may be carried out in the presence of a free radical initiator, including an organic free radical initiator, to induce cross-linking.
  • a free radical initiator including an organic free radical initiator
  • a combination of glycerol/succinic acid/maleic anhydride can achieve a good balance between reactivity (crosslinkable) and thermal properties needed for a successful toughening of PLA
  • a molar ratio of 1:0.5:0.5 grycerol:succinic acid:maleic anhydride may be used, however other molar ratios may also be used.
  • organic free radical initiators include 2,5-Bis(ter-butylperoxy)-2,5- dimethylhexane or dicumyl peroxide or another organic peroxide.
  • the blends of glycerol based polyesters and polymeric blends of the present invention may be reinforced with impact modifiers.
  • the blends of the present invention may be compounded with short biofiber/bio-filler such as miscanthus, switch grass, agro-residues, hemp, jute, kenaf or combinations thereof and so forth for creating a number of novel biobased, and in some cases compostable, rigid composite materials.
  • the blends of the present invention may also include additives and/or nucleating agents, talc, carbon black and/or clay and so forth.
  • Additive refers to an additive that could be added to a system but without inducing crosslinking.
  • additives include epoxidized soy bean oil, polymeric methylene diphenyl diisocyanate, isocyanate terminated prepolymer, titanate and silane.
  • the blends of the present invention may be molded into a molded article.
  • blends of the present Invention may be extruded into an extruded article, like a sheet.
  • FIGs. 1-4 Non-limiting examples of the process of preparing GBPs and blends of the present application are illustrated in FIGs. 1-4.
  • a new reactive extrusion pathway is provided in the present work which allows the crosslinking of the glycerol based polyester within the polymeric blend in the presence of organic peroxides as free radical initiators. This can be advantageous in reducing migration of the glycerol based polyester as compared with normal blending of glycerol based polyesters and a biodegradable polymer such as the work presented by Gu ef a/. (Gu sf a/., 2008).
  • glycerol based polyesters using different glycerol sources and its blends with polymers.
  • the synthesis of glycerol based polyesters has been previously reported using pure glycerol (more than 99 wt% glycerol).
  • the polyesters are synthesized using glycerol of different purities ranging from 15 to 99 wt% glycerol content.
  • the blends of crude glycerol based polyesters with biodegradable and non-biodegradable polymers have not been reported so far.
  • Microwave produced polyester can substantially decrease the time of production of the polyester itself and Its blends with thermoplastics like PLA.
  • glycerol based polyesters are blended with polymeric blends in the absence of solvents such as polyethers, and no enzymes or catalysts may be used.
  • ASTM D638, ASTM D790 and ASTM D256 were adopted for tensile, flexural and impact testing respectively, impact specimens were notched 40 h prior to test. Flexural and tensile properties were tested in an lnstron3382 universal testing machine (Instron, USA), impact properties were tested in an Izod Impact tester equipped with a 0-5X0.05 ft lbs hammer. ASTM D648 was adopted for heat deflection temperature (HDT) measurements using a Q800 dynamic mechanical analyzer (TA instruments, USA).
  • HDT heat deflection temperature
  • glycerol and pure succinic acid were employed as the reactants.
  • 120 grams of reactant mixture was placed in a glass beaker agitated by a magnetic stirrer.
  • the molar ratio of reactants was set at one of the following: 0.32, 0.64, 0.85, 1.07 or 1.28 mol glycerol/mol succinic acid.
  • the temperature was increased to 180°C and kept constant throughout the reaction. Water produced was evaporated from the open beaker allowing the equilibrium to favor product formation.
  • the reaction was finished after stirring was stopped due to a sudden increase in viscosity caused by extensive crosslinking.
  • PGS poly (glycerol succinate) followed by the molar ratio of reactants employed for its synthesis (MR: moi glycerol/mol succinic acid).
  • PGS products were blended with poly (butylene succinate) PBS (Biocosafe 1903, Xinfu, China) at 70/30 wt% PBS/PGS using a DSM twin screw extruder. Both materials were previously dried at 80°C for 5 h.
  • the blend of PGS products and PBS was processed at 150°C for 2 minutes at 100 rpm, followed by Injection molding into molds at 30°C shaped in conformity with test specimens defined in ASTM standards.
  • Tables 1 and 2 summarizes the synthesis conditions and mechanical properties of the 70/30 PBS/PGS blends respectively.
  • Example 2 Crude glycerol based gel polyesters and their blends with poly (butylene succinate) or poly (lactic acid)
  • PGS poly (glycerol succinate) preceded by the glycerol source employed for its synthesis
  • PGS products were blended with poly (butylene succinate) PBS (Biocosafe 1903, Xinfu, China) or poly (lactic acid) PLA (Ingeo 3251 D, Natureworks, USA) at different weight ratios using a DSM twin screw extruder.
  • Example 3 Technical glycerol based liquid polyesters and their blends with poly (lactic acid)
  • LPGS liquid poly (glycerol succinate) followed by the molar ratio of reactants employed for its synthesis (MR: mol glycerol/mol succinic acid).
  • LPGS products were blended with poly (lactic acid) PLA (Ingeo 3251 D, Natureworks, USA) or poly (butylene succinate) PBS (Biocosafe 1903, Xirrfu, China) or a combination thereof using a DSM twin screw extruder. All materials were previously dried at 80°C for 5 h.
  • Example 4 Technical glycerol based liquid polyesters synthesized from mixed dicarboxylic acids or derivatives and their blends with poly (lactic acid) PLA or poly (butylene succinate) PBS.
  • LPGSM or LPGSF stands for liquid poly (glycerol succinate co-maleate) or liquid poly (glycerol succinate co-fumarate) followed by the molar ratio of succinic acid to maleic anhydride employed for its synthesis (e.g LPGSMA 50/50 stands for liquid poly (glycerol succinate co-maleate) synthesized using 50/50 mol ratio of succinic acld/maleic anhydride).
  • Liquid products were blended with poly (lactic acid) PLA (Ingeo 3251 D, Natureworks, USA) or poly (butylene succinate) PBS (Biocosafe 1903, Xinfu, China) or a combination thereof using a DSM twin screw extruder.
  • the addition of organic peroxide initiator (Luperox, Sigma-Aldrich, USA) was performed in some formulations in a range of 0.1 to 0.2 phr.
  • PLA and PBS were previously dried at 80°C for 5 h.
  • the blend of LPGS and PLA or PBS was processed at 180*C for 2 minutes at 100 rpm, followed by injection molding into molds at 30 P C shaped in conformity with test specimens defined in ASTM standards.
  • Tables 1 (Examples 4a - 4d) and 2 (Examples 4a - 4k) summarizes the synthesis conditions and mechanical properties of the obtained blends respectively.
  • Example 5 Microwave synthesis of pure glycerol based polyesters and its blends with PLA
  • the PLA/PGSeb mix was blended using a Haake polyiab Mixer at 180°C during 4 minutes at 50 rpm.
  • the product was dried, thermo-molded at 180°C In sheets and subsequently grinded, dried again, and finally extruded using a DSM explorer twin screw extruder (100 rpm, 180°C, 4 minutes of residence time).
  • Tables 1 and 2 summarizes the synthesis conditions and mechanical properties of the obtained blends respectively.
  • Example 6 Microwave synthesis of polyester using mono and dicarboxylic acids as acid molecules and their blends with PLA in multi-step processing.
  • glycerol was used as alcohol molecule. Sebacic acid was used as dicarboxylic acid molecule whereas stearic acid was used as monocarboxylic acid molecule. Briefly, 40 g of glycerol were manually blended with 88 g of sebacic acid in a beaker. The mixture was then put in a labscale microwave oven under stirring at 180°C. Water produced during the reaction was removed by the system of ventilation of the microwave oven. The reaction was stopped after one hour of microwaving. At this point 27.7 g of the solution was removed and 46.3 g of stearic acid (fatty acid with 18 carbons) was added.
  • Example 7 Microwave synthesis of polyester using mono and dicarboxylic acids as acid molecules and their blends with poly (lactic acid) in single step processing
  • glycerol was used as alcohol molecule. Sebacic acid was used as dicarboxylic acid molecule whereas stearic acid was used as monocarboxyiic acid molecule. Briefly, 30 g of glycerol was blended manually with 66 g of sebacic acid (10 carbons) and 46 g of stearic acid (18 carbons). The blend was then put in a labscale microwave oven under stirring at 180°C for 3 h 35 mln (until magnetic stirring was stopped due to a sudden increment in viscosity). The water produced by the reaction was removed by the system of ventilation of the microwave oven.
  • the obtained product (PGSeb-3) was dried in an oven at 80°C during 4 hours and PLA was dried separately 6 hours at 80 e C, Then the PGSeb-3 was cut in small pieces and fed with PLA directly in DSM extruder in order to obtain 80/20 wt% of PLA/PGSeb-3 in the final blend. The extrusion process was kept at 180°C during 4 minutes.
  • Tables 1 and 2 (Example 7) summarizes the synthesis conditions and mechanical properties of the obtained blends respectively.
  • Example 8 Microwave mono-step synthesis of polyester using mono and dicarboxylic acids (glycerol/sebacic acid/stearic acid: 1/1/0.5) as acid molecules and its blends with PLA by twin screw extrusion
  • mono and dicarboxylic acids glycerol/sebacic acid/stearic acid: 1/1/0.5
  • glycerol was used as alcohol molecule. Sebacic acid was used as dicarboxylic acid molecule whereas stearic acid was used as monocarboxylic acid molecule. Briefly, 21.1 g of glycerol was blended manually with 46.3 g of sebacic acid (10 carbons) and 32.5 g of stearic acid (18 carbons) in a 200 ml_ beaker. The blend was then put in a labscale microwave oven under stirring at 180°C for 3 h 45 mln ⁇ 15 mln (until magnetic stirring was stopped due to a sudden increment in viscosity). A silicon lid with a hole was put on the top of the beaker to prevent reagent lost.
  • the water produced by the reaction was removed by the system of ventilation of the microwave oven.
  • the obtained product was called (PGSeb-4).
  • PLA and PHBV were dried 6 hours at 80°C prior to extrusion.
  • the PGSeb-4 was cut in small pieces and fed with PLA and PHBV directly in DSM extruder in order to obtain blend having a content of PGSeb-4 ranging from 0 to 20%.
  • the extrusion process was kept at 180°C during 4 minutes.
  • Tables 1 (Example 8) and 2 (Examples 8a - 8c) summarizes the synthesis conditions and mechanical properties of the obtained blends respectively.
  • Example 9 Synthesis with Dean-Stark apparatus heating system and oven of polyester using mono and dicarboxylic acids (glycerol/sebacic acid/stearic acid: 1/1/0.5) as acid molecules and their blends with PLA by twin screw extrusion.
  • mono and dicarboxylic acids glycerol/sebacic acid/stearic acid: 1/1/0.5
  • glycerol was used as alcohol molecule. Sebacic acid was used as dicarboxylic acid molecule whereas stearic acid was used as monocarboxylic acid molecule. Briefly, 41.9g of glycerol was blended manually with 92.2 g of sebacic acid (10 carbons) and 65 g of stearic acid (18 carbons) and then placed In a four neck 1L glass reactor equipped with temperature controller, stirrer and a condenser connected to a Dean-Stark apparatus to collect water produced In the reaction. The reaction was performed at 180°C for 4 h. The product was then placed in an oven during 4 h 30 min at 130 4 C under vacuum on a Teflon sheet.
  • Example 10 Microwave mono-step synthesis of polyester using mono and dicarboxylic acids (glycerol/sebacic acid/stearic acid: 1/1/0.23) as acid molecules and their blends with PLA and PHBV by twin screw extrusion
  • mono and dicarboxylic acids glycerol/sebacic acid/stearic acid: 1/1/0.23
  • glycerol was used as alcohol molecule.
  • Sebaclc acid was used as dicarboxylic acid molecule whereas stearic acid was used as monocarboxylic acid molecule.
  • 25.6 g of glycerol was blended manually with 56.2 g of sebacic acid (10 carbons) and 18.2 g of stearic acid (18 carbons) In a 250 mL beaker.
  • the blend was then put in a labscale microwave oven under stirring at 180°C for 2 h 30 mln (until magnetic stirring was stopped due to a sudden increment In viscosity).
  • a silicon lid with a hole was put on the top of the beaker to prevent reagent lost.
  • the water produced by the reaction was removed by the system of ventilation of the microwave oven.
  • the obtained product was called (PGSeb-6).
  • PLA and PHBV were dried 6 hours at 80°C prior to extrusion.
  • the PGSeb-6 was cut in small pieces and fed with PLA and PHBV directly in DSM extruder in order to obtain blend having a content of PGSeb-6 ranging from 0 to 18%.
  • the extrusion process was kept at 180°C during 4 minutes.
  • Tables 1 ((Example 10) and 2 (Examples 10a - 10c) summarizes the synthesis conditions and mechanical properties of the obtained blends respectively.
  • Example 11 Microwave multi-step synthesis of polyester using mono and dicarboxylic acids (glycerol/sebacic acid/stearic acid: 1/1/0.23) acid molecules and PLA (10% in mass) and its blend with PLA by twin screw extrusion
  • glycerol was used as alcohol molecule. Sebacic acid was used as dlcarboxyllc acid molecule whereas stearic acid was used as monocarboxylic acid molecule. Briefly, 25.6 g of glycerol was blended manually with 56.2 g of sebacic acid (10 carbons) and 18.2 g of stearic acid (18 carbons) in a 250 mL beaker. The blend was then put in a labscale microwave oven under stirring at 180°C for 1h.
  • PLA (10% in mass of the whole mass after synthesis) dried pellets were added inside the solution, and the reaction was kept at 180 e C during 1 h 10 mln (until magnetic stirring was stopped due to a sudden increment In viscosity). During all the synthesis, a silicon lid with a hole was put on the top of the beaker to prevent reagent lost The water produced by the reaction was removed by the system of ventilation of the microwave oven. The obtained product was called (PGSeb-7). PLA was dried 6 hours at 80*C prior to extrusion.
  • Example 12 Microwave mono-step synthesis of polyester using mono and dicarboxylic acids (glycerol/sebacic acid/palmitic acid: 1/1/0.5) and its blends with PLA by twin screw extrusion
  • mono and dicarboxylic acids glycerol/sebacic acid/palmitic acid: 1/1/0.5
  • glycerol was used as alcohol molecule. Sebacic acid was used as dicarboxylic acid molecule whereas stearic acid was used as monocarboxylic acid molecule. Briefly, 30.12 g of glycerol was blended manually with 65.93 g of sebacic acid (10 carbons) and 41.94 g of palmitic acid (16 carbons) in a 250 mL beaker. The blend was then put in a labscale microwave oven under stirring at 180°C 4 h 55 min (until magnetic stirring was stopped due to a sudden increment in viscosity). A silicon lid with a hole was put on the top of the beaker to prevent reagent lost. The water produced by the reaction was removed by the system of ventilation of the microwave oven.
  • PGSeb-8 The obtained product was called (PGSeb-8).
  • PLA was dried 6 hours at 80°C prior to extrusion. Then the PGSeb-8 was cut in small pieces and fed with PLA directly in DSM extruder in order to obtain blend having a content of 20% of PGSeb-8. The extrusion process was kept at 180°C during 4 minutes.
  • Tables 1 and 2 (Examples 12) summarizes the synthesis conditions and mechanical properties of the obtained blends respectively.
  • Example 13 Technical glycerol based liquid polyesters synthesized from mixed dicarboxylic acids and their blends and biocomposites with poly (butylene succinate) PBS.
  • Liquid product was blended with poly (butylene succinate) ⁇ (Bfocosafe 1903, Xlnfu, China) using a DSM twin screw extruder in the presence of 0.2 phr of an organic peroxide initiator (Luperox, Sigma-Aldrich, USA).
  • the obtained PBS/LPGSMA blend was pelletized and stored in a sealed plastic bag until further use.
  • biocomposites of PBS/LPGSMA blend as matrix and Miscanthus fiber (fiber average length 4 mm) were fabricated on DSM twin screw extruder. Miscanthus fibers were dried at 80°C for 5 h until reaching a moisture content of around 2.5%.
  • Example 13 Microwave synthesis of polyester PGSeb-4 using mono and dicarboxylic acids as acid molecules in single step to make polymers having shape memory and birefringent properties
  • glycerol was used as alcohol molecule.
  • Sebaclc acid was used as dicarboxylic acid molecule whereas stearic acid was used as monocarboxylic acid molecule.
  • 21.1 g of glycerol was blended manually with 46.3 g of sebacic acid (10 carbons) and 32.5 g of stearic acid (18 carbons) in a 250 mL beaker covered by a silicon lid with a hole. The blend was then put in a labscale microwave oven under stirring at 180°C for 3 h 45 min ⁇ 15 min (until magnetic stirring was stopped due to a sudden increment in viscosity).Calorimetric study was performed to compare PGSeb- 4with poly (glycerol sebacate).
  • curves are presented on FIG. 5, they show that poly (glycerol sebacate) (curve B of FIG. 5) has a melting point at 5 "C as it was observed previously in literature (Jaafar, Ammar, Jedlicka, Pearson, & Coulter, 2010), while the product containing fatty acid (curve A of FIG. 5) present a peak at 29°C.
  • Shape memory creation procedure, storage and recovery were conducted as follow (FIG. 6).
  • the material 2.9 ⁇ 0.5 cm length) (FIG. 6 A) was immersed in water bath at 37°C and stretched up to 169 ⁇ 7% (7.6 ⁇ 1.2 cm length). After, the material was removed and kept under stress during 1 minute at room temperature.
  • the product PGS-Seb 4 exhibits also birefringent properties which are dependents of the temperature (FIG. 7) and which could be used for optical applications.

Abstract

A method for the synthesis of crosslinked and uncrosslinked glycerol-based polyesters is described. The method comprises polymerizing glycerol as the only alcohol in the polyester and at least one saturated dicarboxylic acid such as succinic acid or sebacic acid, optionally with one or more unsaturated dicarboxylic acid or derivative thereof, such as fumaric acid or maleic anhydride, and optionally with a monocarboxylic acid such as palmitic acid or stearic acid. These bio-based polyesters can be used as impact or toughness enhancers in thermoplastic polymeric blends, for example with biopolymers such as polylactic acid or polybutylene succinate. The glycerol-based polyesters also have applications as shape-memory materials having a temperature of transition (Ttrans) between 21°C and 37°C.

Description

TITLE OF THE INVENTION
Formulations from Glycerol-based polyesters and their blends with plastics and
Methods of Making those
FIELD OF THE INVENTION
The present invention relates to the synthesis of oligomeric and polymeric esters from glycerol and carboxylic acids and its use in thermoplastic polymeric blends as impact or toughness enhancers.
BACKGROUND OF THE INVENTION
Glycerol is a molecule containing three hydroxy! groups on its structure. It was previously obtained in the 1940's as a derivative of petroleum resources, and since the last decade, it can be obtained In mass as a by-product of the biodiesel industry (Martin & Richter, 2011). in spite of the intensive utilization of glycerol in many fields of applications such as food, personal care and tobacco products, the increase of biodiesel productions could lead to a leftover of glycerol (Behr, Biting, Irawadl, Leschinski, & Lindner, 2008) and a drop of its price. Consequently, new applications for this molecule have to be found to limit the surplus.
An interesting and economically viable application field for glycerol is the synthesis of biopolyesters through a polycondensation reaction with mono or dicarboxylic acids and their derivatives. Due to the trifunctionality of glycerol, this route can lead to the synthesis of both crosslinked and uncrosslinked polymeric materials according to the synthesis conditions, which will ultimately determine the suitability of a glycerol based polyester in different application fields. For example, US Pat. No. 7,722,804 B2 describes the synthesis of crosslinked glycerol based materials for its use in biomedical applications. On the other hand, US Pat. No. 7,148.293 B2 describes the synthesis of uncrosslinked glycerol based materials and its use as additives in adhesive, coatings and paint formulations.
WO2009/146109 describes a plasticlzing agent for biopolymer matrices consisting of a compatibilizing unit and a polyester plasticizing unit. The compatlbilizing unit consists of a lower alkyl organic acid having a C3 to C7 alkyl backbone, while the polyester plasticizing unit is formed from monomers that consists of a multifunctional alcohol, a saturated or unsaturated aliphatic anhydride or its equivalent, and optionally, a saturated aromatic anhydride or its equivalent. Although WO2009/146109 states that the polyester plasticizing unit may optionally include one or more difunctlonal alcohol, such as glycol, every single example included in this document includes both glycerin and diethylene glycol. That is, WO2009/146109 does not enable the synthesis of a plasticizing unit consisting only of glycerin.
WO2012/038441 describes the synthesis and application of an impact modifier tor biodegradable polymers such as poly lactic acid. In this work the authors employed acrylic monomers derived from petroleum resources for the synthesis. That is, the Impact modifier synthesized is not a biobased product and furthermore does not employ glycerol as a monomer in the synthesis of the impact modifier.
It would be an advancement in the art to use glycerol from different sources as the only alcohol for the synthesis of polymeric plasticizers or impact modifiers for bioplastics, as opposed to previous products, such as those described in WO2009/146109, synthesized from a combination of glycerol and other alcohols. Gu ef ai provided an early example of this concept by using a glycerol based polyester as toughening agent for poly (lactic acid) (PLA) (Gu ef a/., 2008). Upon the addition of 15 and 30 wt% of glycerol based polyester to PLA the authors demonstrated an increase of the elongation at break of the material from 7% for neat PLA to 155 and 143% respectively. In spite of these encouraging results the authors did not provided further work concerning the use of different synthesis strategies, monomers or processing conditions on the mechanical performance of PLA/glycerol based materials blends. Furthermore, using low molecular weight additives for PLA modification tends to create leaching problems when the additive is expelled to the surface of the material with aging. If the glycerol based material is susceptible of being crosslinked during the extrusion process, it may reduce these leaching problems.
Additionally according to the drfferents grade of glycerol varying from crude glycerol to pure glycerol different uses are proposed (Zhou, Beltramini, Fan, & Lu, 2008). Crude glycerol containing often less than 50% of glycerol has low comercial value due to its impurity. The use of this inexpensive feedstock as monomer to synthesize cheap polyester fillers for poly (butylene succinate) (PBS) aiming to reduce the price of the obtained biobased-blend Is explored in this work. Biodiesel derived refined glycerol with a higher degree of purity (higher than 95%) is proposed as monomer for the synthesis of elastomeric like polymeric materials for being used in improvement of toughness or impact properties of commercially available biopoiymers such as poly lactic acid (PLA) or poly butylene succinate (PBS) in normal or reactive extrusion mode in presence of free radical initiators.
Regarding the use of glycerol based polyesters as shape memory materials, studies revealed that glycerol can be used to make biocompatible poly (glycerol sebacate) (Wang, Ameer, Sheppard, & Langer, 2002) and more over it was shown that the obtained elastomer exhibit shape memory properties (Cai & Liu, 2008). After a shape memory creation procedure consisting in stretching the material above a temperature of transition Ttmu, the material can keep its shape below Ttmns, and recover Its Initial shape above Ttrans. Such a property can be used to make low invasive surgery for example. However, the stimulus responsible of shape recovery of poly (glycerol sebacate) which is in this case, the melting of the polymer or the crossing of its glass transition, happened at a temperature lower than room temperature preventing the storage of temporary shape (Cai & Liu, 2008). Consequently, strategies to increase the temperature of transition Tirana responsible of the shape recovery at a temperature higher than room temperature were successfully developed by making nanocomposite (Wu, Frydrych, O'Kelly, & Chen, 2014) or by adding glycol in the synthesis of poly (glycerol sebacate) (Liu & Cai, 2009). It would be an advancement in the art to have a temperature Tirana between room temperature and the human body temperature, while avoiding the use of nanoparticles or the use of glycol.
SUMMARY OF THE INVENTION
In accordance to the present invention, there Is provided the following embodiments.
In one embodiment, the present application is a glycerol based polyester, the glycerol based polyester including (i) glycerol as the only alcohol in the polyester, (ii) at least one saturated dicarboxylic acid, and (iii) at least one unsaturated dicarboxylic acid or a derivative thereof.
In one embodiment of the present invention the glycerol based polyester further includes a monocarboxylic acid having a C16 to C18 alkyi chain.
In another embodiment of the glycerol based polyester of the present invention the molar ratio of glycerol to dicarboxylic acid is in the range from about 0.32 to about 1.28.
In another embodiment of the glycerol based polyester of the present invention the saturated dicarboxylic acid is selected from succinic acid, glutaric acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid and decanedloic acid.
In another embodiment of the glycerol based polyester of the present invention the unsaturated dicarboxylic acid or derivative thereof has an alkyi chain of at least 4 atoms of carbon.
In another embodiment of the glycerol based polyester of the present invention the unsaturated dicarboxylic acid or derivative thereof is selected from maleic anhydride or fumaric acid or their derivatives.
In another embodiment, the present invention provides for a resin composition comprising a glycerol based polyester according to any one of the previous embodiments and a polymer or a polymeric blend.
In one embodiment of the resin composition of the present invention the polymer or polymeric blend include biopolymers, and wherein the biopolymers are selected from poly (lactic acid), poly (butylene succinate), poly (hydroxy butyrate co valerate) or a combination thereof.
In another embodiment of the resin composition of the present invention the resin composition includes between 1-50% by weight of the glycerol-based polyester.
In another embodiment of the resin composition of the present invention the resin composition is created by reactive extrusion in presence of a free radical Initiator leading to the crosslinking of the glycerol based polyester within the polymeric blend.
In another embodiment of the resin composition of the present invention the free radical initiator is an organic free radical initiator selected from 2,5-Bis(tert-butylperoxy)- 2,5-dimethylhexane or dicumyl peroxide.
In another embodiment of the resin composition of the present invention the polymer or polymeric blend include non-biobased polymers.
In another embodiment of the resin composition of the present invention the resin composition further includes an additive, a biofiller, a nucleating agent, clay or a combination thereof.
In another embodiment of the resin composition of the present invention the resin composition further includes a biofiber.
In another embodiment of the resin composition of the present invention the biofiber is selected from miscanthus, switch grass, agro-residues, hemp, jute, kenaf or a combination thereof.
In another embodiment of the resin composition of the present invention the additive is selected from epoxidized soy bean oil, polymeric methylene diphenyl dilsocyanate, isocyanate terminated prepolymer, titanate and silane. The present invention, in another embodiment, relates to a method for preparing a glycerol based polyester, the method including reacting glycerol with at least one saturated dicarboxylic acid and at least one unsaturated dicarboxylic acid or a derivative thereof, wherein the glycerol is the only alcohol used in the reaction.
In one embodiment of the method for preparing a glycerol based polyester of the present invention, the method further includes adding a rnonocarboxylic acid having a C16 to C18 alkyl chain.
In another embodiment of the method for preparing a glycerol based polyester of the present invention, the rnonocarboxylic acid is added in the range of 15 to 50 wt%.
In another embodiment of the method for preparing a glycerol based polyester of the present invention, the reacting includes microwavlng the glycerol with the at least one saturated dicarboxylic acid.
In another embodiment of the method for preparing a glycerol based polyester of the present invention, the molar ratio of glycerol to dicarboxylic acid Is in the range from about 0.32 to about 1.28.
In another embodiment of the method for preparing a glycerol based polyester of the present invention, the saturated dicarboxylic acid is selected from succinic acid, glutaric acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid and decanedioic acid.
In another embodiment of the method for preparing a glycerol based polyester of the present invention, the unsaturated dicarboxylic acid or derivative thereof is selected from maleic anhydride orfumaric acid.
In another embodiment of the method for preparing a glycerol based polyester of the present invention, the glycerol is provided as crude glycerol, technical glycerol or pure glycerol.
In another embodiment of the method for preparing a glycerol based polyester of the present invention, the glycerol based polyester is synthesized using glycerol of different purities. In another embodiment of the method for preparing a glycerol based polyester of the present Invention, the purity of the glycerol ranges between 15 to 99 wt% glycerol content.
The present invention, in another embodiment, relates to a method of producing a resin composition, the method including blending a polymer with the glycerol based polyester of the previous embodiments.
In one embodiment of the method for producing a resin composition of the present invention, polymer is a single polymer or a blend of polymers.
In another embodiment of the method for producing a resin composition of the present invention, the polymer is selected' from poly (lactic acid), poly (butylene succinate), poly (hydroxy butyrate co valerate), nylon, polyvinyl chloride, polystyrene, polyethylene, polypropylene, polyacrylonitrile, PVB, silicone, or a combination thereof.
In another embodiment of the method for producing a resin composition of the present Invention, the resin composition is produced by blending between 1-50 wt% of the glycerol based polyester and between 50-99 wt% of the biodegradable polymer.
In another embodiment of the method for producing a resin composition of the present invention, wherein the resin composition is created by reactive extrusion in presence of a free radical initiator leading to the crosslinking of the glycerol based polyester.
In another embodiment of the method for producing a resin composition of the present invention, the free radical Initiator is organic, and wherein the organic free radical initiator is selected from 2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane or dicumyl peroxide.
in another embodiment of the method for producing a resin composition of the present invention, the glycerol is provided as crude glycerol.
In another embodiment of the method for producing a resin composition of the present invention, the method further includes adding an organic free radical initiator, an additive, a biofiller, a nucleating agent, or a combination thereof. In another embodiment of the method for producing a resin composition of the present invention, the method further includes adding a bioflber.
In another embodiment of the method for producing a resin composition of the present invention, the biofiber is selected from miscanthus, switch grass, agro-residues, hemp, jute, kenaf or combination thereof.
In another embodiment of the method for producing a resin composition of the present invention, the additive is selected from epoxidized soy bean oil, polymeric methylene diphenyl diisocyanate, isocyanate terminated prepolymer, titanate and silane.
The present invention, in another embodiment, is a resin composition. The resin composition, in one embodiment, includes a glycerol based polyester and a polymer or a polymeric blend, wherein the glycerol based polyester comprises: (i) crude glycerol as the only alcohol in the glycerol based polyester, and (ii) at least one saturated dicarboxylic acid.
In one embodiment of the resin composition, the polymer is selected from poly
(lactic acid), poly (butylene succinate), poly (hydroxy butyrate co valerate), nylon, polyvinyl chloride, polystyrene, polyacrylonitrile, polyvinyl butyral (PVB), silicone, polypropylene and polyethylene or a combination thereof.
in one embodiment of the glycerol based polyesters or the resin compositions of the present invention, the glycerol is crude glycerol.
In one embodiment of the glycerol based polyesters or the resin compositions of the present invention, the glycerol has a purity range from 1% to 99%.
The present invention, in another embodiment, provides for a shape memory polymeric composition produced by reacting a glycerol as the only alcohol in the composition, at least one saturated dicarboxylic acid and at least one unsaturated dicarboxylic acid. In one aspect of this embodiment, the reaction further includes reacting a monoacid. In one embodiment of the shape memory polymeric composition of the previous two embodiments, the shape memory polymeric composition has shape memory such that when the polymeric composition is deformed at a temperature above temperature of transition (TVare) of the composition and the temperature is then lowered to a temperature below the Tvans, the polymeric composition retains its deformed shape, and when the temperature is then raised above the Ttnns the polymeric composition returns substantially to its original shape, wherein the Tuans of the polymeric composition is between room temperature (21 °C) and 37°C. BRIEF DESCRIPTION OF THE DRAWINGS
The following figures illustrate various aspects and preferred and alternative embodiments of the invention.
FIG. 1: Flow chart illustrating the preparation of glycerol based polyester and the blending of the glycerol based polyester with a polymer in accordance to one
embodiment of the present invention.
FIG.2: Flow chart illustrating the preparation of a glycerol based polyester and the blending of the glycerol based polyester with a polymeric blend in accordance to another embodiment of the present invention.
FIG.3: Flow chart illustrating the preparation of a glycerol based polyester and the blending of the glycerol based polyester with a polymeric blend in accordance to another embodiment of the present invention.
FIG.4: Flow chart illustrating the synthesis of a glycerol based polyester and the blending of the glycerol based polyester with a polymeric blend in accordance to yet another embodiment of the present invention.
FIG. 5: Calorimetric study of biopolyester made of glycerol, sebacic acid and stearic acid (1:1 :0.5) (top curve A) and a biopolyester made of sebacic acid and glycerol without the use of monoacid (1 -.1 :0) (bottom curve B).
FIG. 6: Shape memory creation procedure and shape recovery of a material of the present invention in water bath at 37°C (bar = 1cm). Panel A is a photograph of the material prior to the shape memory creation procedure. Panel B is a photograph of the material after having been stored 12 hours without stress at room temperature in a sealed bag. Panel C is a photograph of the material after shape recovery.
FIG. 7: Photomicrographs of PGSseb-4 under cooling at 10°C/min (*50) under polarized light at: a) 9°C, b) 37°C and c) 50°C.
DESCRIPTION OF THE INVENTION
Definitions
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this Invention belongs. Also, unless indicated otherwise, except within the claims, the use of "or" includes "and" and vice versa. Non-limiting terms are not to be construed as limiting unless expressly stated or the context clearly indicates otherwise (for example "including", "having" and "comprising" typically indicate "including without limitation"). Singular forms including in the claims such as "a", "an" and the" include the piural reference unless expressly stated otherwise. In order to aid in the understanding and preparation of the within invention, the following illustrative, non-limiting, examples are provided. All numerical designations, e.g., dimensions, temperatures and weight, including ranges, are approximations that typically may be varied (+) or (-) by increments of 0.1, 1.0, or 10.0. as appropriate. All numerical designations may be understood as preceded by the term "about." The priority document as well as all documents cited, are incorporated by reference.
"Biobased" means a plant-made molecule that is either directly expressed from plants, such as sugars, starches or fats, or fermented from plant-made molecules. Although glycerol may be obtained by transesteriflcation (chemical reaction), the raw materials used to obtain glycerol are biobased, as such glycerol obtained by transesterification may also be considered biobased. Biopolymer" refers to a polymer made from plant derived molecules.
List of Abbreviations
"GBP" glycerol based polyester
"PGS" poly (glycerol succinate)
IPGS" liquid poly (glycerol succinate)
"LPGSMA" liquid poly (glycerol succinate co maleate)
"LPGSFA" liquid poly (glycerol succinate co fumarate)
"PGSeb" poly (glycerol sebacate)
"PBS" poly (butylene succinate)
"PLA" poly (lactic acid)
"PHBV poly (hydroxy butyrate co valerate)
Overview
The present invention relates to the use of glycerol or crosslinkable glycerol based polyesters as materials for the modification of biodegradable and nonbiodegradable plastic matrices that may result in an improvement in the toughness or impact behavior of commercially biodegradable and non-biodegradable plastic matrices by melt compounding with glycerol based polyesters.
Provided herein is a new and inventive utilization of saturated dicarboxylic acid monomers in combination with unsaturated dicarboxylic acids or their derivatives for synthesizing glycerol based polyesters. The cross-linkable glycerol based polyesters of the present invention contain unsaturation sites which can be further reacted during an extrusion process. The reactivity of these unsaturated glycerol based polyesters may be triggered on the extrusion process by using free radical initiators. As a result, a thermoplastic polymeric blend with a cross-linked included microphase may be produced leading to improvement of toughness or impact properties of the material. Moreover, the crosslinking of glycerol based polyesters on the extrusion process can help in reducing migration of the additive from within the matrix in order to maintain the mechanical performance with time. Examples of saturated dicarboxylic acids employed for the synthesis of glycerol based polyesters include dicarboxylic acids having C4-C1B alkyl chain. Examples of unsaturated dicarboxylic acids and their derivatives include maleic anhydride and fumaric acid, the latter being produced from biobased sources leading to the synthesis of a biobased glycerol polyester.
The glycerol based polyester of the present invention may be used for modification of polymeric blend systems as described herein below.
Polyesters
The polyesters, including plasticlzers, of the present invention, which may be biobased or non-biobased, may be synthesized using a combination of an alcohol and acid molecules. The alcohol molecules may include glycerol of different purities and sources. The acid molecules include an organic saturated dicarboxylic acid with a carbon chain length of C4 to C10 and an organic unsaturated dicarboxylic add or its derivatives with a carbon chain length of at least C4. That is, the organic saturated dicarboxylic acid may have a carbon chain length of C4, C5, C6 C7, C8, C9 or C10. The acid molecules may also include an organic monocarboxylic acid. In one embodiment the organic monocarboxylic acid may have a carbon chain length of C12- C18, preferably C18. The molar ratio of alcohol to dicarboxylic acid molecules may be in a range of about 0.32 to about 1.28. The molar ratio of hydroxyl to carboxyl functionalities from glycerol and total acid molecules respectively may be in a range of about 0.48 to about 1.92. In one embodiment, a molar ratio of 1:0.5:0.5 mol glycerol/succinic acid/maleic anhydride may be used. Monocarboxylic acid molecules may be added to some formulations to limit or avoid the formation of crosslinking during the synthesis and to improve the compatibility. When monocarboxylic acid molecules are employed, these may be added in a range of 15-50wt%.
Production of Polyester
The glycerol based polyester of the present invention, which may be biobased, may be synthesized using a polycondensation reaction. The polycondensation reaction may be performed in different systems such as in a temperature controlled stirred glass reactor or a microwave oven.
In one embodiment of the present invention a microwave oven may be used for polyester synthesis. Such microwaving synthesis may require substantial less time as compared to glass vessel-based reaction system.
The glycerol used to synthesize the polyester of the present invention may be obtained from any source, and the purity of the glycerol may range anywhere from about 1% to 99% of glycerol content. Preferably, the purity of glycerol may range from about 15% to about 99%. The glycerol used to synthesize the polyester of the present invention may be crude glycerol. When reactivity is desired, it may be preferable to use glycerol of higher purity such as technical glycerol.
Glycerol may be the only alcohol used to create, make or synthesize the polyester of the present invention. As such, the polyester, the resins (described below) and articles of the present invention may be made just with glycerol as the only alcohol and be free of glycols and/or other alcohols.
Production of Resins
The glycerol based polyesters of the present invention may be used both as a tough polymer for modification of plastics trough blending and/or as shape memory materials.
The polyesters of the present invention may be used as blending additives for polymers, including non-biodegradable such as nylon, polyvinyl chloride, polystyrene, polyacry!onitrile, polyvinyl butyral (PVB), silicone, polypropylene and polyethylene and/or biodegradable polymers such as PLA, PBS, PHBV or combinations thereof in the production of blends or resins. The polymers may be provided as single polymers or as a blend of polymers. The percentage of glycerol-based polyester in the final resins or blends of the present invention may range anywhere from about 1wt% to about 50wt%, and any range there in between. Preferably, the method of producing the blend with the glycerol based polyester and the polymeric blend may be carried out in the presence of a free radical initiator, including an organic free radical initiator, to induce cross-linking. A combination of glycerol/succinic acid/maleic anhydride can achieve a good balance between reactivity (crosslinkable) and thermal properties needed for a successful toughening of PLA In one embodiment of the present invention a molar ratio of 1:0.5:0.5 grycerol:succinic acid:maleic anhydride may be used, however other molar ratios may also be used. Examples of organic free radical initiators include 2,5-Bis(ter-butylperoxy)-2,5- dimethylhexane or dicumyl peroxide or another organic peroxide.
The blends of glycerol based polyesters and polymeric blends of the present invention may be reinforced with impact modifiers. The blends of the present invention may be compounded with short biofiber/bio-filler such as miscanthus, switch grass, agro-residues, hemp, jute, kenaf or combinations thereof and so forth for creating a number of novel biobased, and in some cases compostable, rigid composite materials.
The blends of the present invention may also include additives and/or nucleating agents, talc, carbon black and/or clay and so forth. Additive refers to an additive that could be added to a system but without inducing crosslinking. Examples of additives include epoxidized soy bean oil, polymeric methylene diphenyl diisocyanate, isocyanate terminated prepolymer, titanate and silane.
The blends of the present invention may be molded into a molded article.
Furthermore, the blends of the present Invention may be extruded into an extruded article, like a sheet.
Non-limiting examples of the process of preparing GBPs and blends of the present application are illustrated in FIGs. 1-4.
Advantages
a) A new reactive extrusion pathway is provided in the present work which allows the crosslinking of the glycerol based polyester within the polymeric blend in the presence of organic peroxides as free radical initiators. This can be advantageous in reducing migration of the glycerol based polyester as compared with normal blending of glycerol based polyesters and a biodegradable polymer such as the work presented by Gu ef a/. (Gu sf a/., 2008).
b) Blending of glycerol based polyesters with polymer blends. The use of polymeric blend system as matrix for the addition of glycerol based polyesters has been explored. Unlike in previous work about modification of single polymer using glycerol based polyesters (Gu ef a/., 2008) we have explored the use of polymeric blends as matrix for modification. This can be advantageous in creating materials with enhanced stiffness-toughness balance and desirable thermal properties, as well as in reducing the cost of the overall product Using a combination of monomers for glycerol based polyester synthesis which permits the crosslinking of this polyester in a reactive extrusion process can decrease the leaching problems when the additive is expelled to the surface of the material with aging. A crosslinkable glycerol based polyester is therefore highly desirable for toughness modification of commercial bioplastics such as PLA and PBS and their blends.
c) Production of glycerol based polyesters using different glycerol sources and its blends with polymers. The synthesis of glycerol based polyesters has been previously reported using pure glycerol (more than 99 wt% glycerol). In the present invention, the polyesters are synthesized using glycerol of different purities ranging from 15 to 99 wt% glycerol content. The blends of crude glycerol based polyesters with biodegradable and non-biodegradable polymers have not been reported so far.
d) Microwave produced polyester can substantially decrease the time of production of the polyester itself and Its blends with thermoplastics like PLA.
e) The glycerol based polyesters are blended with polymeric blends in the absence of solvents such as polyethers, and no enzymes or catalysts may be used.
In order to aid in the understanding and preparation of the within invention, the following illustrative, non-limiting, examples are provided. Examples
Testing conditions
ASTM D638, ASTM D790 and ASTM D256 were adopted for tensile, flexural and impact testing respectively, impact specimens were notched 40 h prior to test. Flexural and tensile properties were tested in an lnstron3382 universal testing machine (Instron, USA), impact properties were tested in an Izod Impact tester equipped with a 0-5X0.05 ft lbs hammer. ASTM D648 was adopted for heat deflection temperature (HDT) measurements using a Q800 dynamic mechanical analyzer (TA instruments, USA).
Molecular weight determinations were conducted in a GPC instrument (Viscotek GPCmax, Malvern instruments, UK) equipped with two columns Styragel HR1 and Styragel HR2 (Waters Corporation, USA) and one PLgel-Mixed E column (Agilent Technologies, USA) connected in series. Tetrahydrofuran was used as solvent at 40°C and a flowrate of 0.3 mL/min. A series of 8 polyethylene glycol standards with molecular weight ranging from 106 to 7830 Da was used for calibration (Easy Vial, Agilent Technologies, USA). Example 1 - Pure glycerol based gel polyesters and their blends with poly
(butylene succinate)
Pure glycerol and pure succinic acid were employed as the reactants. 120 grams of reactant mixture was placed in a glass beaker agitated by a magnetic stirrer. The molar ratio of reactants was set at one of the following: 0.32, 0.64, 0.85, 1.07 or 1.28 mol glycerol/mol succinic acid. The temperature was increased to 180°C and kept constant throughout the reaction. Water produced was evaporated from the open beaker allowing the equilibrium to favor product formation. The reaction was finished after stirring was stopped due to a sudden increase in viscosity caused by extensive crosslinking. Products synthesized at different molar ratios of reactants were designated as PGS which stands for poly (glycerol succinate) followed by the molar ratio of reactants employed for its synthesis (MR: moi glycerol/mol succinic acid). PGS products were blended with poly (butylene succinate) PBS (Biocosafe 1903, Xinfu, China) at 70/30 wt% PBS/PGS using a DSM twin screw extruder. Both materials were previously dried at 80°C for 5 h. The blend of PGS products and PBS was processed at 150°C for 2 minutes at 100 rpm, followed by Injection molding into molds at 30°C shaped in conformity with test specimens defined in ASTM standards. Tables 1 and 2 (Examples 1a - 1e) summarizes the synthesis conditions and mechanical properties of the 70/30 PBS/PGS blends respectively.
Example 2 - Crude glycerol based gel polyesters and their blends with poly (butylene succinate) or poly (lactic acid)
Crude glycerol coming from biodiesel production and pure succinic acid were employed as the reactants. Alternatively, glycerol with different purity was employed as the glycerol source (Table 3). 180 grams of reactant mixture was placed in a four neck 1L glass reactor equipped with temperature controller, stirrer and a condenser connected to a Dean-Stark apparatus to collect water produced in the reaction. The mass ratio of reactants was set in a range of 0.5 to 1.9 g glycerol/g succinic acid (Table 1 examples 2a - 2e). The temperature was increased to 180°C and kept constant throughout the reaction. The reaction was finished after stirring was stopped due to a sudden increase in viscosity caused by extensive crosslinking or the presence of entanglement or after 6 h when no viscosity increase was observed. Products synthesized at different molar ratios of reactants were designated as PGS which stands for poly (glycerol succinate) preceded by the glycerol source employed for its synthesis (e.g. PG-PGS stands for pure glycerol based PGS). PGS products were blended with poly (butylene succinate) PBS (Biocosafe 1903, Xinfu, China) or poly (lactic acid) PLA (Ingeo 3251 D, Natureworks, USA) at different weight ratios using a DSM twin screw extruder. All materials were previously dried at 80DC for 5 h. The blend of PGS and PBS or PLA was processed at 150°C for PBS and 180°C for PLA for 2 minutes at 100 rpm, followed by Injection molding into molds at 30°C shaped in conformity with test specimens defined in ASTM standards. Tables 1 (Examples 2a - 2e) and 2 (Examples 2a - 2h) summarizes the synthesis conditions and mechanical properties of the obtained blends respectively.
Example 3 - Technical glycerol based liquid polyesters and their blends with poly (lactic acid)
Technical glycerol (96 wt% glycerol) and pure succinic acid were employed as the reactants. For the synthesis, 180 grams of reactant mixture was placed in a four neck 1L glass reactor equipped with temperature controller, stirrer and a condenser connected to a Dean-Stark apparatus to collect water produced in the reaction. The molar ratio of reactants was set at one of the following: 0.6, 1 or 1.2 mol glycerol/mol succinic acid. The temperature was increased to 180°C and kept constant throughout the reaction. Reaction was stopped 5 minutes before the gel point formation recorded previously in order to obtain non-crossilnked polymers. Products synthesized at different molar ratios of reactants were designated as LPGS which stands for liquid poly (glycerol succinate) followed by the molar ratio of reactants employed for its synthesis (MR: mol glycerol/mol succinic acid). LPGS products were blended with poly (lactic acid) PLA (Ingeo 3251 D, Natureworks, USA) or poly (butylene succinate) PBS (Biocosafe 1903, Xirrfu, China) or a combination thereof using a DSM twin screw extruder. All materials were previously dried at 80°C for 5 h. The blend of LPGS and PLA or PBS was processed at 180°C for 2 minutes at 100 rpm, followed by injection molding into molds at 30°C shaped in conformity with test specimens defined in ASTM standards. The addition of organic peroxide initiator (Luperox, Sigma-AkJrich, USA) was performed in some formulations in a range of 0.1 to 0.2 phr. Tables 1 (Examples 3a - 3c) and 2 (Examples 3a - 3h) summarizes the synthesis conditions and mechanical properties of the obtained blends respectively.
Example 4 - Technical glycerol based liquid polyesters synthesized from mixed dicarboxylic acids or derivatives and their blends with poly (lactic acid) PLA or poly (butylene succinate) PBS.
Technical glycerol (96 wt% glycerol), maleic anhydride, fumaric acid and pure succinic acid were employed as the reactants. For the synthesis, 180 grams of reactant mixture was placed in a four neck 1L glass reactor equipped with temperature controller, stirrer and a condenser connected to a Dean-Stark apparatus to collect water produced in the reaction. The molar ratio of functionalities was set at 1.5 mol OH/mol COOH. A combination of succinic acid (SA) and maleic anhydride (MA) or fumaric acid chosen from 100/0, 50/50 or 0/100 in mol percentage was employed as the dicarboxylic acid molecules for the synthesis. The temperature was increased to 150°C or 180°C and kept constant throughout the reaction. Reaction was stopped 5 minutes before the gel point formation recorded previously in order to obtain non-crosslinked polymers. Products synthesized at different molar ratios of succinic acid to maleic anhydride or fumaric acid were designated as LPGSM or LPGSF which stands for liquid poly (glycerol succinate co-maleate) or liquid poly (glycerol succinate co-fumarate) followed by the molar ratio of succinic acid to maleic anhydride employed for its synthesis (e.g LPGSMA 50/50 stands for liquid poly (glycerol succinate co-maleate) synthesized using 50/50 mol ratio of succinic acld/maleic anhydride). Liquid products were blended with poly (lactic acid) PLA (Ingeo 3251 D, Natureworks, USA) or poly (butylene succinate) PBS (Biocosafe 1903, Xinfu, China) or a combination thereof using a DSM twin screw extruder. The addition of organic peroxide initiator (Luperox, Sigma-Aldrich, USA) was performed in some formulations in a range of 0.1 to 0.2 phr. PLA and PBS were previously dried at 80°C for 5 h. The blend of LPGS and PLA or PBS was processed at 180*C for 2 minutes at 100 rpm, followed by injection molding into molds at 30PC shaped in conformity with test specimens defined in ASTM standards. Tables 1 (Examples 4a - 4d) and 2 (Examples 4a - 4k) summarizes the synthesis conditions and mechanical properties of the obtained blends respectively.
Example 5 - Microwave synthesis of pure glycerol based polyesters and its blends with PLA
Pure glycerol and sebacic acid were employed as the reactants for the synthesis. 43.3 g of glycerol were manually blended with 88 g of sebacic acid in a glass beaker. The beaker was then put in a labscale microwave oven under stirring at 180eC. Water produced during the reaction was removed by the system of ventilation of the microwave oven. The reaction was stopped when magnetic stirring was stopped due to a sudden increment in viscosity, after 2 h 41 min of microwaving. Then 25 g of this product (PGSeb-1) was blended manually with 270 g of PLA (Ingeo 3251 D, Natureworks, USA) and dried during 6 hours at 80°C to remove the water from the PGSeb and the PLA. The PLA/PGSeb mix was blended using a Haake polyiab Mixer at 180°C during 4 minutes at 50 rpm. The product was dried, thermo-molded at 180°C In sheets and subsequently grinded, dried again, and finally extruded using a DSM explorer twin screw extruder (100 rpm, 180°C, 4 minutes of residence time).Tables 1 and 2 (Example 5) summarizes the synthesis conditions and mechanical properties of the obtained blends respectively.
Example 6 - Microwave synthesis of polyester using mono and dicarboxylic acids as acid molecules and their blends with PLA in multi-step processing.
Pure glycerol was used as alcohol molecule. Sebacic acid was used as dicarboxylic acid molecule whereas stearic acid was used as monocarboxylic acid molecule. Briefly, 40 g of glycerol were manually blended with 88 g of sebacic acid in a beaker. The mixture was then put in a labscale microwave oven under stirring at 180°C. Water produced during the reaction was removed by the system of ventilation of the microwave oven. The reaction was stopped after one hour of microwaving. At this point 27.7 g of the solution was removed and 46.3 g of stearic acid (fatty acid with 18 carbons) was added. Then the mixture was put inside the microwave oven at 180°C for 2 h 40 min (until magnetic stirring was stopped due to a sudden Increment In viscosity). Afterwards, 30 g or 60 g of this product (PGSeb-2) was blended manually with 270 g of PLA or 240 g of PLA and left during 6 hours at 80°C to remove the water of the PGSeb- 2 and the PLA. Finally, the PLA/PGSeb-2 mixture was blended in a Haake po!ylab Mixer at 180°C during 4 minutes at 50 rpm. The product was dried, thermomo!ded at 180°C in sheets and subsequently grinded, dried again, and finally extruded using a DSM explorer twin screw extruder (100 rpm, 180°C, 4 minutes of residence time). Tables 1 (Example 6) and 2 (Examples 6a and 6b) summarizes the synthesis conditions and mechanical properties of the obtained blends respectively.
Example 7 - Microwave synthesis of polyester using mono and dicarboxylic acids as acid molecules and their blends with poly (lactic acid) in single step processing
Pure glycerol was used as alcohol molecule. Sebacic acid was used as dicarboxylic acid molecule whereas stearic acid was used as monocarboxyiic acid molecule. Briefly, 30 g of glycerol was blended manually with 66 g of sebacic acid (10 carbons) and 46 g of stearic acid (18 carbons). The blend was then put in a labscale microwave oven under stirring at 180°C for 3 h 35 mln (until magnetic stirring was stopped due to a sudden increment in viscosity). The water produced by the reaction was removed by the system of ventilation of the microwave oven. The obtained product (PGSeb-3) was dried in an oven at 80°C during 4 hours and PLA was dried separately 6 hours at 80eC, Then the PGSeb-3 was cut in small pieces and fed with PLA directly in DSM extruder in order to obtain 80/20 wt% of PLA/PGSeb-3 in the final blend. The extrusion process was kept at 180°C during 4 minutes. Tables 1 and 2 (Example 7) summarizes the synthesis conditions and mechanical properties of the obtained blends respectively.
Example 8 - Microwave mono-step synthesis of polyester using mono and dicarboxylic acids (glycerol/sebacic acid/stearic acid: 1/1/0.5) as acid molecules and its blends with PLA by twin screw extrusion
Pure glycerol was used as alcohol molecule. Sebacic acid was used as dicarboxylic acid molecule whereas stearic acid was used as monocarboxylic acid molecule. Briefly, 21.1 g of glycerol was blended manually with 46.3 g of sebacic acid (10 carbons) and 32.5 g of stearic acid (18 carbons) in a 200 ml_ beaker. The blend was then put in a labscale microwave oven under stirring at 180°C for 3 h 45 mln ± 15 mln (until magnetic stirring was stopped due to a sudden increment in viscosity). A silicon lid with a hole was put on the top of the beaker to prevent reagent lost. The water produced by the reaction was removed by the system of ventilation of the microwave oven. The obtained product was called (PGSeb-4). PLA and PHBV were dried 6 hours at 80°C prior to extrusion. Then the PGSeb-4 was cut in small pieces and fed with PLA and PHBV directly in DSM extruder in order to obtain blend having a content of PGSeb-4 ranging from 0 to 20%. The extrusion process was kept at 180°C during 4 minutes. Tables 1 (Example 8) and 2 (Examples 8a - 8c) summarizes the synthesis conditions and mechanical properties of the obtained blends respectively.
Example 9 - Synthesis with Dean-Stark apparatus heating system and oven of polyester using mono and dicarboxylic acids (glycerol/sebacic acid/stearic acid: 1/1/0.5) as acid molecules and their blends with PLA by twin screw extrusion.
Pure glycerol was used as alcohol molecule. Sebacic acid was used as dicarboxylic acid molecule whereas stearic acid was used as monocarboxylic acid molecule. Briefly, 41.9g of glycerol was blended manually with 92.2 g of sebacic acid (10 carbons) and 65 g of stearic acid (18 carbons) and then placed In a four neck 1L glass reactor equipped with temperature controller, stirrer and a condenser connected to a Dean-Stark apparatus to collect water produced In the reaction. The reaction was performed at 180°C for 4 h. The product was then placed in an oven during 4 h 30 min at 1304C under vacuum on a Teflon sheet. Finally the temperature was increased to 150°C and the product was kept 10 hours in the same conditions. A yellowish resin was obtained. In parallel, PLA was dried separately 6 hours at 80°C. Then the PGSeb-5 was cut in small pieces and fed with PLA directly in DSM extruder in order to obtain 90/10 wt% of PLA/PGSeb-5 in the final blend. The extrusion process was kept at 180°C during 4 minutes. Tables 1 and 2 (Example 9) summarizes the synthesis conditions and mechanical properties of the obtained blends respectively.
Example 10 - Microwave mono-step synthesis of polyester using mono and dicarboxylic acids (glycerol/sebacic acid/stearic acid: 1/1/0.23) as acid molecules and their blends with PLA and PHBV by twin screw extrusion
Pure glycerol was used as alcohol molecule. Sebaclc acid was used as dicarboxylic acid molecule whereas stearic acid was used as monocarboxylic acid molecule. Briefly, 25.6 g of glycerol was blended manually with 56.2 g of sebacic acid (10 carbons) and 18.2 g of stearic acid (18 carbons) In a 250 mL beaker. The blend was then put in a labscale microwave oven under stirring at 180°C for 2 h 30 mln (until magnetic stirring was stopped due to a sudden increment In viscosity). A silicon lid with a hole was put on the top of the beaker to prevent reagent lost. The water produced by the reaction was removed by the system of ventilation of the microwave oven. The obtained product was called (PGSeb-6). PLA and PHBV were dried 6 hours at 80°C prior to extrusion. Then the PGSeb-6 was cut in small pieces and fed with PLA and PHBV directly in DSM extruder in order to obtain blend having a content of PGSeb-6 ranging from 0 to 18%. The extrusion process was kept at 180°C during 4 minutes. Tables 1 ((Example 10) and 2 (Examples 10a - 10c) summarizes the synthesis conditions and mechanical properties of the obtained blends respectively.
Example 11 - Microwave multi-step synthesis of polyester using mono and dicarboxylic acids (glycerol/sebacic acid/stearic acid: 1/1/0.23) acid molecules and PLA (10% in mass) and its blend with PLA by twin screw extrusion
Pure glycerol was used as alcohol molecule. Sebacic acid was used as dlcarboxyllc acid molecule whereas stearic acid was used as monocarboxylic acid molecule. Briefly, 25.6 g of glycerol was blended manually with 56.2 g of sebacic acid (10 carbons) and 18.2 g of stearic acid (18 carbons) in a 250 mL beaker. The blend was then put in a labscale microwave oven under stirring at 180°C for 1h. Then 9 g of PLA (10% in mass of the whole mass after synthesis) dried pellets were added inside the solution, and the reaction was kept at 180eC during 1 h 10 mln (until magnetic stirring was stopped due to a sudden increment In viscosity). During all the synthesis, a silicon lid with a hole was put on the top of the beaker to prevent reagent lost The water produced by the reaction was removed by the system of ventilation of the microwave oven. The obtained product was called (PGSeb-7). PLA was dried 6 hours at 80*C prior to extrusion. Then the PGSeb-7 was cut in small pieces and fed with PLA directly in DSM extruder in order to obtain blend having a content of 10% and 15% of PGSeb- 7.The extrusion process was kept at 180°C during 4 minutes. Tables 1 (Example 11) and 2 (Examples 11a and 11b) summarizes the synthesis conditions and mechanical properties of the obtained blends respectively.
Example 12 -Microwave mono-step synthesis of polyester using mono and dicarboxylic acids (glycerol/sebacic acid/palmitic acid: 1/1/0.5) and its blends with PLA by twin screw extrusion
Pure glycerol was used as alcohol molecule. Sebacic acid was used as dicarboxylic acid molecule whereas stearic acid was used as monocarboxylic acid molecule. Briefly, 30.12 g of glycerol was blended manually with 65.93 g of sebacic acid (10 carbons) and 41.94 g of palmitic acid (16 carbons) in a 250 mL beaker. The blend was then put in a labscale microwave oven under stirring at 180°C 4 h 55 min (until magnetic stirring was stopped due to a sudden increment in viscosity). A silicon lid with a hole was put on the top of the beaker to prevent reagent lost. The water produced by the reaction was removed by the system of ventilation of the microwave oven. The obtained product was called (PGSeb-8). PLA was dried 6 hours at 80°C prior to extrusion. Then the PGSeb-8 was cut in small pieces and fed with PLA directly in DSM extruder in order to obtain blend having a content of 20% of PGSeb-8. The extrusion process was kept at 180°C during 4 minutes. Tables 1 and 2 (Examples 12) summarizes the synthesis conditions and mechanical properties of the obtained blends respectively.
Example 13 - Technical glycerol based liquid polyesters synthesized from mixed dicarboxylic acids and their blends and biocomposites with poly (butylene succinate) PBS.
Technical glycerol (96 wt% glycerol), maleic anhydride and pure succinic acid were employed as the reactants. For the synthesis, 180 grams of reactant mixture was placed In a four neck 1L glass reactor equipped with temperature controller, stirrer and a condenser connected to a Dean-Stark apparatus to collect water produced in the reaction. The molar ratio of functionalities was set at 1.5 mol OH/mol COOH. A combination of 50/50 succinic acid (SA) and maleic anhydride (MA) In mol percentage was employed as the dicarboxylic acid molecules for the synthesis. The temperature was increased to 150°C and kept constant throughout the reaction. Reaction was stopped 5 minutes before the gel point formation recorded previously in order to obtain non-crosslinked polymers. Liquid product was blended with poly (butylene succinate) ΡΒΘ (Bfocosafe 1903, Xlnfu, China) using a DSM twin screw extruder in the presence of 0.2 phr of an organic peroxide initiator (Luperox, Sigma-Aldrich, USA). The obtained PBS/LPGSMA blend was pelletized and stored in a sealed plastic bag until further use. Subsequently, biocomposites of PBS/LPGSMA blend as matrix and Miscanthus fiber (fiber average length 4 mm) were fabricated on DSM twin screw extruder. Miscanthus fibers were dried at 80°C for 5 h until reaching a moisture content of around 2.5%. The biocomposite was processed at 180°C for 2 minutes at 100 rpm, followed by injection molding into molds at 30DC shaped in conformity with test specimens defined in ASTM standards. Table 2 (Example 13) summarizes the mechanical properties of the obtained biocomposltes. Example 14 - Microwave synthesis of polyester PGSeb-4 using mono and dicarboxylic acids as acid molecules in single step to make polymers having shape memory and birefringent properties
Pure glycerol was used as alcohol molecule. Sebaclc acid was used as dicarboxylic acid molecule whereas stearic acid was used as monocarboxylic acid molecule. Briefly, 21.1 g of glycerol was blended manually with 46.3 g of sebacic acid (10 carbons) and 32.5 g of stearic acid (18 carbons) in a 250 mL beaker covered by a silicon lid with a hole. The blend was then put in a labscale microwave oven under stirring at 180°C for 3 h 45 min ±15 min (until magnetic stirring was stopped due to a sudden increment in viscosity).Calorimetric study was performed to compare PGSeb- 4with poly (glycerol sebacate). The curves are presented on FIG. 5, they show that poly (glycerol sebacate) (curve B of FIG. 5) has a melting point at 5 "C as it was observed previously in literature (Jaafar, Ammar, Jedlicka, Pearson, & Coulter, 2010), while the product containing fatty acid (curve A of FIG. 5) present a peak at 29°C. Shape memory creation procedure, storage and recovery were conducted as follow (FIG. 6). The material (2.9±0.5 cm length) (FIG. 6 A) was immersed in water bath at 37°C and stretched up to 169±7% (7.6±1.2 cm length). After, the material was removed and kept under stress during 1 minute at room temperature. After 12 hours of storage at room temperature in sealed bag, the shape fixity was 86±4% (7.0±1.0 cm length) (FIG. 6 B). After this storage, when it was immersed again in water bath at 37X without any constraint, the shape recovery rate was of 85±6% (3.7±0.4 cm length) (FIG. 6 C).
The product PGS-Seb 4 exhibits also birefringent properties which are dependents of the temperature (FIG. 7) and which could be used for optical applications.
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Table 3. Glycerol sources employed for crude glycerol based PGS synthesis
Glycerol content
Glycerol source in glycerol
source (wt%)
Pure glycerol 99
Technical glycerol 96
Refined glycerol 75
Crude glycerol 1 30
Crude glycerol 2 15
Figure imgf000034_0001
Table 4. Heat deflection temperature (HDT) of selected blend compositions
Figure imgf000034_0002
Through the embodiments that are illustrated and described, the currently contemplated best mode of making and using the Invention is described.
Without further elaboration, it is believed that one of ordinary skill in the art can, based on the description presented herein, utilize the present invention to the full extent.
References Behr, A-, Eilting, J,, hawadi, K., L^escbinski, J., & Lindner, F. (2008). Improved utilisation of renewable resources: New important derivatives of glycerol. Green Chemistry, 7(7(1), 13.
doi:10.1039/b710561d
Cai, W., & Liu, L. (2008). Shape-memory effect of poly (glycerol-sebacate) elastomer. Materials Letters, 52(14), 2171-2173. doi:10.10167j.matlet.2007.11.042
Jaafar, L H., Aaunar, M. M, Jedlidca, S. S., Pearson, R. a., & Coulter, J. P. (2010). Spectroscopic
evaluation,, thermal, and thcmomechanical characterization of poly(glycerol-sebaqate) with variations in curing temperatures and durations. Journal of Materials Science, 45(9), 2525-2529. doi:10.1007/sl0853-010-4259-0
Gu, Li-qin, Yong-feng Li, and Sfcu-jun Cheng. "Modification of Poly (L-Lactidc) by Poly (Glycerol- Sebacate)[J]." Journal of Functional Polymers 3 (2008): 022.
Liu, L., & Cai, W. (2009). Novel copolyester for a shape-memory biodegradable material in vivo.
Materials Letters, (53(20), 1656-1658. doi:10.1016/j.matlet.2009.04.037
Martin, A., & Richter, M. (2011). Oligomerization of glycerol - a critical review. European Journal of Lipid Science and Technology. doi:10.1002/ejlt.201000386
Wang, Y-, Ameer, G. A., Sheppard, B- J., & Langer, R. (2002). A tough biodegradable elastomer. Nature Biotechnology, 20(6), 602-6. doi:10.1038/nbt0602-602
Wu, T., Fiydrych, M., O'Kelly, K., & Chen, B. (2014). PoIyQdycerol sebacate urethane)-CeUulose
Nanocomposites with Water-Active Shape-Memory Effects. Biamacromolecules,
140610141656009. doi:10.102l/bm500507z
Zhou, C. C, Beltramiru, J. N., Fan, Y., & Lu, G. Q. M. (2008). Cheixioselective catalytic conversion of glycerol as a biorenewable source to valuable commodity chemicals. Chemical Society Reviews, 57(3), 527-549. doi:10.1039/b707343g

Claims

CLAIMS What is claimed is:
1. A glycerol based polyester, the glycerol based polyester comprising (i) glycerol as the only alcohol in the polyester, (li) at least one saturated dicarboxylic acid, and (iii) at least one unsaturated dicarboxylic acid or a derivative thereof.
2. The glycerol based polyester of claim 1, wherein the glycerol based polyester further includes a monocarboxylic acid having a C16 to C18 alkyl chain.
3. The glycerol based polyester of claim 1 or claim 2, wherein the molar ratio of glycerol to dicarboxylic acid is in the range from about 0.32 to about 1.28.
4. The glycerol based polyester of claim 1, wherein the saturated dicarboxylic acid is selected from succinic acid, glutaric acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid and decanedioic acid.
5. The glycerol based polyester of claim 1, wherein the unsaturated dicarboxylic acid or derivative thereof has an alkyl chain of at least 4 atoms of carbon.
6. The glycerol based polyester of claim 1, wherein the unsaturated dicarboxylic acid or derivative thereof is selected from maleic anhydride or fumaric acid or their derivatives.
7. A resin composition comprising a glycerol based polyester of claims 1-6 and a polymer or a polymeric blend.
8. The resin composition of claim 7, wherein the polymer or polymeric blend include biopolymers, and wherein the biopolymers are selected from poly (lactic acid), poly (butylene succinate), poly (hydroxy butyrate co valerate) or a combination thereof.
9. The resin composition of claim 7, wherein the resin composition includes between 1-50% by weight of the glycerofbased polyester.
10. The resin composition of claim 7, wherein the resin composition is created by reactive extrusion in presence of a free radical initiator leading to the crosslinking of the glycerol based polyester within the polymeric blend.
11. The resin composition of the claim 10, wherein the free radical initiator is an organic free radical initiator selected from 2,5-Bis(tert-butylperoxy)-2,5- dimethylhexane or dfcumyl peroxide.
12. The resin composition of claim 7, wherein the polymer or polymeric blend include non-biobased polymers.
13. The resin composition of claim 7, wherein the resin composition further includes an additive, a biofiller, a nucleating agent, clay or a combination thereof.
14. The resin composition of claim 7, wherein the resin composition further includes a biofiber.
15. The resin composition of claim 14, wherein the biofiber is selected from miscanthus, switch grass, agro-residues, hemp, jute, kenaf or combination thereof.
16. The resin composition of claim 13, wherein the additive is selected from epoxidized soy bean oil, polymeric methylene diphenyl diisocyanate, Isocyanate terminated prepolymer, titanate and silane.
17. A method for preparing a glycerol based polyester, the method comprising reacting glycerol with at least one saturated dicarboxyllc acid and at least one unsaturated dicarboxyllc acid or a derivative thereof, wherein the glycerol is the only alcohol used In the reaction.
18. The method of claim 17, wherein the method further includes adding a monocarboxylic acid having a C16 to C18 alkyl chain.
19. The method of claim 18, wherein the monocarboxylic acid Is added in the range of 15 to SO wt%.
20. The method of claim 17, wherein the reacting includes microwaving the glycerol with the at least one saturated dicarboxylic acid.
21. The method of claim 17, wherein the molar ratio of glycerol to dicarboxylic acid is in the rage from about 0.32 to about 1.28.
22. The method of claim 17, wherein the saturated dicarboxylic acid is selected from succinic acid, glutaric acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedloic acid and decanedioic acid.
23. The method of claim 17, wherein the unsaturated dicarboxylic acid Is selected from maleic anhydride orfumaric acid.
24. The method of claim 17, wherein the glycerol is provided as crude glycerol, technical glycerol or pure glycerol.
25. The method of claim 17, wherein the glycerol based polyester is synthesized using glycerol of different purities.
26. The method of claim 17, wherein the purity of the glycerol ranges between 15 to 99 wt% glycerol content.
27. A method of producing a resin composition, the method comprising blending a polymer with the glycerol based polyester of claims 1-6.
28. The method of claim 27, wherein polymer is a single polymer or a blend of polymers.
29. The method of claim 27, wherein the polymer is selected from poly (lactic acid), poly (butylene succinate), poly (hydroxy butyrate co valerate), nylon, polyvinyl chloride, polystyrene, polyethylene, polypropylene, polyacrylonitrile, PVB, silicone, or a combination thereof.
30. The method of claim 27, wherein the resin composition is produced by blending between 1-50 wt% of the glycerol based polyester and between 50-99 wt% of the biodegradable polymer.
31. The method of claim 27, wherein the resin composition is created by reactive extrusion in presence of a free radical initiator leading to the crosslinking of the glycerol based polyester.
32. The method of claim 31, wherein the free radical initiator is organic, and wherein the organic free radical initiator is selected from 2,5-Bis(tert-butylperoxy)-2,5- dimethylhexane ordicumyl peroxide.
33. The method of claim 27, wherein the glycerol is provided as crude glycerol.
34. The method of claim 27, wherein the method further includes adding an organic free radical initiator, an additive, a bioflller, a nucleating agent, or a combination thereof.
35. The method of claim 27, wherein the method further includes adding a biafiber.
36. The method of claim 35, wherein the biofiber is selected from miscanthus, switch grass, agro-residues, hemp, jute, kenaf or combination thereof.
37. The method of claim 34, wherein the additive is selected from epoxidized soy bean oil, polymeric methylene diphenyl diisocyanate, isocyanate terminated prepolymer, titanate and silane.
38. A resin composition comprising a glycerol based polyester and a polymer or a polymeric blend, wherein the glycerol based polyester comprises: (i) crude glycerol as the only alcohol in the glycerol based polyester, and (ii) at least one saturated dicarboxylic acid.
39. The resin composition of claim 38, wherein the polymer is selected from poly (lactic acid), poly (butylene succinate), poly (hydroxy butyrate co valerate), nylon, polyvinyl chloride, polystyrene, polyacrylonitrile, polyvinyl butyral (PVB), silicone, polypropylene and polyethylene or a combination thereof.
40. The resin compostion of claim 38, wherein the glycerol is crude glycerol.
41. The resin composition of claim 38, wherein the glycerol has a purity range from 1% to 99%.
42. A shape memory polymeric composition, the shape memory polymeric composition being produced by reaction of a glycerol as the only alcohol in the composition, at least one saturated dicarboxylic acid and at least one unsaturated dicarboxylic acid.
43. The shape memory polymeric composition of claim 42 wherein the reaction further includes a monoacid.
44. The shape memory polymeric composition of claim 42, 43, wherein the shape memory polymeric composition having shape memory such that when the polymeric composition is deformed at a temperature above temperature of transition (Ttrans) of the composition and the temperature is then lowered to a temperature below the Ttrans, the polymeric composition retains its deformed shape, and when the temperature is then raised above the Ttrans the polymeric composition returns substantially to its original shape, wherein the Tirana of the polymeric composition is between room temperature (21 °C) and 37°C.
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CN113278273A (en) * 2020-02-20 2021-08-20 王洁 Degradable microparticle, degradable product containing same and application
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