WO2023277718A1 - Résines de polyester insaturé à hautes performances à base de ressources renouvelables - Google Patents

Résines de polyester insaturé à hautes performances à base de ressources renouvelables Download PDF

Info

Publication number
WO2023277718A1
WO2023277718A1 PCT/PT2022/050019 PT2022050019W WO2023277718A1 WO 2023277718 A1 WO2023277718 A1 WO 2023277718A1 PT 2022050019 W PT2022050019 W PT 2022050019W WO 2023277718 A1 WO2023277718 A1 WO 2023277718A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
prepolymer
acid
mol
styrene
Prior art date
Application number
PCT/PT2022/050019
Other languages
English (en)
Inventor
Mateus DE ASSUNÇÃO HOFMANN
João Carlos MOURA BORDADO
Mário Alexandre DE JESUS GARRIDO
João Pedro RAMÔA RIBEIRO CORREIA
Md Abu TOYOB SHAHID
Original Assignee
Instituto Superior Técnico
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Instituto Superior Técnico filed Critical Instituto Superior Técnico
Publication of WO2023277718A1 publication Critical patent/WO2023277718A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • 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
    • C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/547—Hydroxy compounds containing aromatic rings
    • 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
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation

Definitions

  • the present disclosure relates to unsaturated polyester resins based on raw materials that are partially or almost fully derived from renewable resources.
  • the invention allows producing unsaturated polyester resins, which, after curing, have mechanical and thermophysical properties that match or exceed the properties of comparable conventional petrochemical unsaturated polyester resins.
  • Unsaturated polyester resins are thermosetting polymers that can be used to impregnate synthetic fibres in the manufacturing of Fibre-reinforced plastic (FRP) composite materials used in several structural applications. Due to their suitable balance between low cost, versatility of processing, and good mechanical and thermophysical properties, these resins have been among the most often used thermosetting polymers by the FRP composites industry for several years. However, their production still depends significantly on raw materials that are derived from petroleum. The use of petrochemical monomers to manufacture polymers used as consumer products is expected to decrease in the coming years due to the possible depletion of known reserves, the continued rise in crude oil extraction costs, strict governmental regulation around the world in favour of sustainability, and the overall societal demand for more ecological products.
  • FRP Fibre-reinforced plastic
  • the raw materials used for the synthesis of unsaturated polyester resins are dicarboxylic acids, dihydroxyl alcohols and a reactive diluent with at least one vinyl group.
  • a balance between aliphatic and aromatic or cyclic compounds must be kept within the polyester main chain.
  • the viscosity and the mechanical properties of the resins of the present invention are due to a great extent to the molar fractions between the diols 1,3-propanediol and isosorbide (aliphatic and cyclic, respectively).
  • 2,5-furandicarboxylic acid is a potential replacement monomer for oil-derived diacids or anhydrides, such as phthalic anhydride, iso and orthophthalic acid.
  • This furan building block occupies a prominent position among the monomers for condensation polymers, as it often provides higher mechanical strength and glass transition temperature, when compared to the above- mentioned aromatic diacids or even to terephthalic acid.
  • polyesters based on 2,5-furandicarboxylic acid exhibit a semicrystalline structure but crystallize at a slower rate than polyesters containing an aromatic ring. This results in much improved barrier properties against oxygen, carbon dioxide, and water vapour, which could be beneficial for several structural applications, namely, in more aggressive environments.
  • Isosorbide is another building block derived from renewable sources; when used as a monomer, it can provide polyester a balance between high performance and sustainability.
  • Isosorbide is a glycol of cyclic structure that provides rigidity to the unsaturated polyester backbone structure, resulting in polyesters with higher glass transition temperature than conventional aliphatic diols.
  • viscosity is very significantly increased when high isosorbide ratios are incorporated into the polyester backbone, becoming difficult to dilute it with the reactive diluent, most probably due to the presence of polysaccharides formed during the heating of the reactor; this may limit its use in the processing of FRP composite materials that require low viscosities for fibres impregnation.
  • the US20040092703A1 [2] patent reported one route to overcome this limitation by dissolving isosorbide in water prior to being fed into the reactor where polymerization of the polyester occurs. Thus, isosorbide can be readily pumped to the esterification portion of the polyester process.
  • the US8487041B2 [3] patent filed an unsaturated polyester containing isosorbide and itaconic acid, in presence of 1,2-propylene glycol and/or 1,3-propanediol, while maintaining a low viscosity of neat polyester by using a combination of hydroquinone and toluhydroquinone as inhibitors.
  • Example 9 from that patent shows a neat polyester that is fully bio-derived; however, after dilution in styrene, the final content of such resin was 65%. In contrast, no information was provided about the glass transition temperature. The lack of this information limits its range of applicability, especially concerning its use as a matrix for manufacturing FRP composite materials for structural applications, where the glass transition temperature has significant influence on the maximum service temperature that may be considered in the design of the structural object.
  • the resin curing process was carried out with initiators and accelerators suitable for cold moulding processes, which prevents its use in fast moulding processes that require high curing temperatures.
  • aromatic or furan diacid increases the solubility of the unsaturated polyester in vinyl monomers, especially in styrene, which enables storage, handling, and processing of the resin.
  • 1,3-propanediol is a renewable aliphatic diol derived from corn sugar fermentation, which has low viscosity (liquid at room temperature) and is able to adjust the viscosity of polyester with aromatic or rigid cyclic morphology, while maintaining the mechanical and thermophysical properties of the product after curing.
  • the state-of-the-art of polyester resins and patents, such as US20120157618A1 [7] and US20090312485A1 [8] have reported that the use of 1,3-propanediol instead of non-renewable aliphatic diols does not significantly affect the thermophysical properties of unsaturated polyester resins, especially their glass transition temperature.
  • the present invention proposes to use 1,3-propanediol to decrease the viscosity of polyester based on isosorbide, and this approach unexpectedly improves the mechanical and thermophysical properties, when compared to conventional polyester resins based on 1,2-propylene glycol and diethylene glycol.
  • the sustainability of unsaturated polyester can be further increased by replacing maleic anhydride (crude- derived) with fumaric acid.
  • Fumaric acid is non-toxic and naturally formed or can be obtained from agroindustry by products [9-11].
  • the present invention proposes to use only fumaric acid (derived from renewable resources, such as sugar cane bagasse fermentation) as unsaturated monomer in the polyester backbone, since it increases the renewable content of the polyester and, later on, the fumarate double bond is more reactive than the maleate, resulting in a more complete radical polymerization, and lower requirement of post-cure treatment.
  • the balance between thermophysical properties and toughness is determined, among other parameters, mainly by the crosslinking density in the unsaturated polyester backbone.
  • the invention presented herein has surprisingly managed to promote a good balance between glass transition temperature and toughness, by adjusting the ratio between saturated and unsaturated acids in the polyester backbone.
  • polyester shrinkage one of its historic drawbacks compared to other thermosetting resins, has been overcome in the present invention through the incorporation of dimer acid segments in the polyester backbone.
  • Dimer acids are the main product of the oligomerisation (dimerization) of C18 vegetable unsaturated fatty acids, such as tall oil fatty acid, as well as oleic or linoleic, and have been used as a raw material in polyester since the 1920s, especially for the production of alkyd resins for the coating industry.
  • Triglyceride-based acids are rich in aliphatic long chains and have high molecular weight, which contributes to the high incorporation of bio-content in polyester.
  • polyesters comprised of fatty acid dimers present a segmented formation, two or multi-phase structure, and a high ability to deform.
  • dimer acids were found out, with surprise, to decrease the polyester shrinkage, presenting a similar behaviour to low profile additives, especially in mouldings that require high temperatures during processing, while maintaining the thermophysical properties of the cured resin.
  • the resins used as matrix in FRP composites should have low enough viscosity and long enough gel time to guarantee the adequate time for proper impregnation of the reinforcing fibres. Therefore, different variants of the resin composition must be available to allow adjusting it for processes such as pultrusion and vacuum infusion, and for simple lamination processes, such as open mould applications, which are more prone to lower viscosity resins. Excessive resin viscosity can be overcome in different ways; for example, by increasing the amount of styrene to decrease the target viscosity of the polyester resin.
  • a combination of a low absolute viscosity aliphatic diol and a cyclic diol was found to contribute to achieving such balance.
  • a lower absolute viscosity should be governed by the higher aliphatic diol rate, while an increase in the cyclic diol rate gives better thermophysical properties to the resin.
  • the crosslinking density of the prepolymer, saturated and unsaturated dicarboxylic acids ratio must be adjusted over a range of at least 1:2 and at most 1:4.
  • typical reactive diluents used in unsaturated polyester resins such as styrene
  • HAPs Hazardous Air Pollutants
  • VOCs Volatile Organic Compounds
  • methacrylate was reported by US20190031801A1 [13] patent as an alternative to replace styrene, since methacrylate contains polymerizable radicals through double bonds, which provide similar reactivity as styrene, but is less environmentally damaging.
  • HEMA 2- hydroxyethyl methacrylate
  • acrylate polymers are well known for their physical properties, such as toughness, elasticity, resistance to breakage, and quite good oil and heat resistance. At room temperature they behave like rubber, as their glass transition temperature is below room temperature [15].
  • HEMA as a suitable alternative for styrene [16-17].
  • US5747597A [18] document demonstrated the feasibility of replacing styrene with acrylate in unsaturated polyester resin, and document WO 99/23122 [19] also reported styrene free unsaturated polyester resin with HEMA.
  • the bio-based unsaturated polyester backbone that has been developed is incompatible with only HEMA diluent monomer.
  • HEMA has been used together with styrene as diluent monomer with the unsaturated polyester resin, as reactivity between HEMA and styrene has been reported [20].
  • the resin was found to provide better mechanical and thermophysical properties, when compared to conventional unsaturated polyester resin, crosslinked with only styrene.
  • Emphasis has been given to reduce the percentage of styrene in unsaturated polyester resin as much as possible while maintaining the properties required for service condition. The reduction of styrene concentration is an additional advantage of this innovative bio-based unsaturated polyester resin.
  • the present invention discloses acrylic building blocks based on methacrylate carbonyl compounds used to obtain polyester with less styrene content.
  • the use of 2- hydroxyethyl methacrylate is one alternative to decrease styrene content, being reported in this invention.
  • the present invention refers to unsaturated polyester resins incorporating high bio-content by weight, presenting similar or improved mechanical and thermophysical properties in comparison with conventional oil-derived unsaturated polyester resins.
  • the resin of the present invention is suitable for several processing techniques typically used to manufacture FRP composite materials, such as hand-layup, vacuum infusion and pultrusion.
  • This new sustainable unsaturated polyester resin provides an increase in sustainability and versatility, when compared to conventional ones.
  • the present invention discloses a composition comprising unsaturated polyester resins, the resin comprising a prepolymer and at least one reactive diluent; wherein the prepolymer is in an amount of from 50% to 70%, preferably 60% (w/w); and wherein the prepolymer and the at least one reactive diluent are derived from renewable natural resources.
  • the present invention discloses a composition wherein the reactive diluent is a mixture of: styrene and HEMA; styrene, HEMA and pentaerythritol tetraacrylate (PETA); or styrene and PETA.
  • the reactive diluent is a mixture of: styrene and HEMA; styrene, HEMA and pentaerythritol tetraacrylate (PETA); or styrene and PETA.
  • the present invention discloses a composition wherein the maximum amount of styrene in relation to the total amount of unsaturated polyester and reactive diluent is 30% (w/w), preferably 20% (w/w), more preferably 10% (w/w).
  • the present invention discloses a composition comprising styrene at 20% (w/w), HEMA at 10% (w/w) and PETA at 10% (w/w).
  • the present invention discloses a composition wherein the prepolymer is a reaction product obtained by polycondensation of: at least 1,3-propanediol and isosorbide as aliphatic and cyclic polyol, respectively; at least C4 unsaturated dicarboxylic acid or anhydride as unsaturated dicarboxylic acid; or a dimer fatty acid as saturated dicarboxylic acid or a furandicarboxylic acid, both as saturated dicarboxylic acid.
  • the present invention discloses a composition comprising an unsaturated polyester backbone, the unsaturation being originated from bio-based fumaric acid.
  • the present invention discloses a resin or cured resin comprising the composition of the present invention.
  • the present invention discloses a resin or cured resin wherein from 40% to 60% (w/w) comprises ester groups and is derived from renewable sources.
  • the present invention discloses a product comprising the composition, resin or cured resin of the present invention, wherein the tensile strength, modulus of elasticity, and strain at break are greater than or equal to 44 MPa, 2.9 GPa, and 1.5%, respectively.
  • the present invention discloses a product comprising the composition, resin or cured resin of the present invention, wherein the glass transition temperature (Tg) is of at least 51 °C, defined based on dynamic mechanical analysis, namely from the onset of the storage modulus curve decay.
  • Tg glass transition temperature
  • the present invention discloses an object, preferably a structural element comprising the product of the present invention.
  • the present invention discloses a process for obtaining the composition of the present invention comprising the following steps: reacting at least two dicarboxylic acid/anhydride and at least one polyol to obtain a prepolymer; wherein the at least two dicarboxylic acid/anhydride comprise 0 to 1.5 mol % of a C36-dicarboxylic acid; 0 to 16 mol % of a C8-dicarboxylic aromatic acid; 0 to 12 mol % of a furandicarboxylic acid; 31 to 38 mol % of a C4- unsaturated dicarboxylic acid; wherein the at least one polyol comprises 0 to 18 mol % of a C2-aliphatic diol; 17 to 38 mol % of a C3-aliphatic diol; 17 to 18 mol % of a C6-cyclic dihydric alcohol; and wherein mol % is in terms of the total amount of prepolymer
  • the present invention discloses a process further comprising the step of: mixing the prepolymer with at least two reactive diluents comprising (i) 10 to 30 parts of styrene, (ii) 10 to 20 parts of 2-hydroxyetyhl methacrylate and (iii) 10 to 20 parts of pentaerythritol tetraacrylate, to obtain a resin.
  • the present invention discloses a process further comprising the step of: mixing the prepolymer with at least three reactive diluents comprising (i) 10 to 30 parts of styrene, (ii)
  • the present invention discloses a process further comprising the step of: curing the resin by an open moulding process in the presence of an accelerator, preferably a redox agent, to obtain an object or structural part comprising the cured resin.
  • an accelerator preferably a redox agent
  • the present invention discloses a process further comprising the step of: post-curing the cured resin from 80 °C to 120 °C, preferably from 90 °C to 110 °C, even more preferably at 100 °C for at least 4 hours.
  • the present invention discloses a process wherein the accelerator is an amine or an organometallic compound.
  • the present invention discloses a process, wherein the step of mixing the prepolymer to obtain a resin is carried out in the presence of an initiator, preferably comprising a peroxide, to obtain a cured resin.
  • the present invention discloses a process wherein the step of reacting at least two dicarboxylic acid/anhydride and at least one polyol to obtain a prepolymer is carried out in the presence of hydroquinone and/or toluhydroquinone as radical inhibitor.
  • the present invention discloses a process wherein the step of reacting at least two dicarboxylic acid/anhydride and at least one polyol to obtain a prepolymer is carried out in the presence of imidazole or tetraisopropyl titanate as esterification catalysts.
  • the present invention discloses a process wherein the C36-dicarboxylic acid is a dimer acid obtained from dimerization of tall oil.
  • the present invention discloses a process wherein the C4-unsaturated dicarboxylic acid is fumaric acid derived from a non-petrochemical source.
  • the present invention discloses a process wherein the furandicarboxylic acid is 2,5-furandicarboxylic acid obtained from renewable resources.
  • the present invention discloses a process wherein the C6-cyclic dihydric alcohol is 1,4:3,6-dianhydro-D-glucitol or isosorbide derived from natural sugars.
  • the present invention discloses the use of the composition, resin, cured resin or product of the present disclosure in the manufacture of fibre-reinforced polymer composite materials for civil structures, marine, construction and auto-parts structures, aerospace and wind energy industry.
  • the present invention discloses the use of the composition, resin, cured resin or product of the present disclosure in the manufacture by hand- layup, vacuum infusion, filament winding, resin transfer moulding and pultrusion.
  • the prepolymer is a reaction product obtained by polycondensation of (i) at least 1,3-propanediol and isosorbide as aliphatic and cyclic polyol, respectively, (ii) optionally, a dimer fatty acid as saturated dicarboxylic acid, and (iii) at least C4 unsaturated dicarboxylic acid or anhydride as unsaturated dicarboxylic acid.
  • the total amount of saturated acids must be balanced between dimer acids and/or building blocks comprising at least one aromatic dicarboxylic acid, for example, phthalic acid or anhydride, and, optionally, 2,5-furandicarboxylic acid, respectively.
  • aromatic dicarboxylic acid for example, phthalic acid or anhydride
  • 2,5-furandicarboxylic acid respectively.
  • the molar amount of ethylene glycol or other oil-derived dihydric alcohol is at most 33%, in relation to the total amount of glycol to be used in the reaction mixture.
  • the molar amount of 1,3-propanediol is (i) preferably at least 33% and at most 67%, (ii) more preferably at least 50% and at most 67%, and (iii) even more preferably at least 60% and at most 67%, in relation to the total amount of glycol to be used in the reaction mixture.
  • the molar amount of isosorbide is (i) preferably at least 25% and at most one third in percentage, (ii) more preferably at least 28% and at most one third in percentage, and (iii) even more preferably at least 30% and at most one third in percentage, in relation to the total amount of glycol to be used in the reaction mixture.
  • the isosorbide must be diluted prior to being loaded into the reactor, in a solution that comprises at least 15% and at most 30% (w/w) of water, in relation to the total weight of isosorbide to be used in the reaction mixture.
  • the molar amount of 2,5-furandicarboxylic acid relative to the total amount of saturated diacids is (i) preferably at least 50% until the total replacement, (ii) more preferably at least 75% until the total replacement, and (iii) even more preferably the total replacement.
  • the molar amount of dimer fatty acid relative is (i) preferably at most 1.4%, (ii) more preferably at most 1.2%, and (iii) even more preferably at most 1.0%, in relation to the total molar amount of the monomers (diacids and diols) to be used in the reaction mixture.
  • the acid value of the prepolymer is (i) preferably in the range from 35 to 60 mgKOH/g resin, (ii) more preferably in the range from 35 to 55 mgKOH/g resin, and (iii) even more preferably in the range from 35 to 50 mgKOH/g resin.
  • the acid value of the prepolymer is determined by titration according to ISO 2114:2000 [21].
  • the weight average molecular weight (Mw) of the unsaturated polyester is (i) preferably at least 2500 g/mol and at most 7000 g/mol, and (ii) more preferably at least 3500 g/mol and at most 5000 g/mol, and (iii) even more preferably at least 3500 g/mol and at most 4000 g/mol.
  • the number average molecular weight (Mn) of the unsaturated polyester is (i) preferably at least 1200 g/mol and at most 2000 g/mol, and (ii) more preferably at least 1400 g/mol and at most 2000 g/mol, and (iii) even more preferably at least 1500 g/mol and at most 2000 g/mol.
  • the glass transition temperature (Tg) of the unsaturated polyester resins measured from dynamic mechanical analysis (DMA) based on the onset of the storage modulus curve decay, is (i) preferably at least 60 °C, (ii) more preferably at least 65 °C, and (iii) even more preferably at least 70 °C.
  • the prepolymer is advantageously prepared in the presence of at least one radical inhibitor selected from hydroquinone, toluhydroquinone, benzoquinone, or toluhydroquinone, (i) more preferably in the presence of toluhydroquinone, and (ii) even more preferably in the presence of hydroquinone and toluhydroquinone.
  • at least one radical inhibitor selected from hydroquinone, toluhydroquinone, benzoquinone, or toluhydroquinone, (i) more preferably in the presence of toluhydroquinone, and (ii) even more preferably in the presence of hydroquinone and toluhydroquinone.
  • the prepolymer is advantageously prepared in the presence of at least one esterification catalyst, preferably imidazole or tetraisopropyl titanate, more preferably in the presence of imidazole.
  • the unsaturated polyester resin composition comprises more than one reactive diluent, being preferably styrene and acrylate type monomers.
  • a mixture between styrene and 2-hydroxyethyl methacrylate is used as reactive diluent.
  • PETA pentaerythritol tetraacrylate
  • a mixture between styrene, 2-hydroxyethyl methacrylate (HEMA) and pentaerythritol tetraacrylate (PETA) is used as reactive diluent.
  • reactive diluent shall be any substances which reduce the viscosity of an unsaturated polyester resin for processing and become part of the resin during its subsequent curing via copolymerization .
  • the composition of the unsaturated polyester resin comprises at least 60% (w/w) of prepolymer.
  • the maximum amount of styrene in the resin composition is (i) preferably at most 30% (w/w), (ii) more preferably at most 20% (w/w), and (iii) more preferably at most 10% (w/w), in relation to the total amount of unsaturated polyester and reactive diluent present in the resin composition.
  • the amount of HEMA in the resin composition is (i) preferably at least 10% and at most 20% (w/w), (ii) more preferably at least 15% and at most 20% (w/w), and (iii) more preferably 20% (w/w), in relation to the total amount of unsaturated polyester and reactive diluent present in the resin composition .
  • the amount of PETA in the resin composition is (i) preferably at least 10% and at most 20% (w/w), (ii) more preferably at least 15% and at most 20% (w/w), and (iii) more preferably 20% (w/w), in relation to the total amount of unsaturated polyester and reactive diluent present in the resin composition.
  • the resin can be cured using two different processes, depending on the application. In both processes, the resin is cured in the presence of a free radical initiator.
  • the first curing process for cold curing applications, is used in temperature ranges suitable for hand-layup and/or vacuum infusion, when the initiator is a redox, wherein the curing is carried out at a temperature (i) in the range from -10 to 80 °C, (ii) preferably in the range from 0 to 70 °C, and (iii) most preferably in the range from 10 to 60 °C.
  • the present invention describes the use of an organic peroxide as redox agent (initiator), more preferably methyl ethyl ketone peroxide, in combination with at least one accelerator, more preferably cobalt octoate.
  • redox agent initiator
  • accelerator more preferably cobalt octoate.
  • the second curing process is for high temperature curing, for applications such as pultrusion, where an accelerator is optionally required, since the curing process can be achieved for temperatures in the range of at least 170 °C and at most 180 °C.
  • the present invention suggests the use of di-tert-butyl peroxide, di- tert-butyl diperphthalate, di-tert-butyl peroxide, methyl isobutyl ketone peroxide or tert-butyl peroxybenzoate.
  • the synthesis of the prepolymer was prepared by catalysed bulk polycondensation, performed in a four head reactor of 2 litres (with bottom drain valve) equipped with an anchor blade mechanical stirrer, a thermocouple to control heating blanket, a nitrogen inlet (one pimple per second), and a condenser attached to a dean-stark adaptor to collect the water (formed in the reaction, and raw material solubilization) .
  • the following steps must be taken to prepare the prepolymer present in the resin composition : to charge the reactor with isosorbide and water; to charge the reactor with: (i) unsaturated dicarboxylic acid and/or anhydride and, optionally, other diacids;
  • Viscosity test was performed on a Cone & Plate Viscometer Instrument from REL (Research Equipment London Ltd.) / according to ISO 2884-2:2003 [23], which consists of placing only two drops of resin on a surface that is then approached by a rotating cone (constant speed). The viscosity was taken as the average value of 3 measurements.
  • Gel time was used as a parameter to monitor reactivity/time to gelation. Samples with 12 g were placed into glass tubes with 160 mm in length and 16 mm in diameter and tests were performed on a Gelnorm® gel timer instrument.
  • Barcol hardness tests were performed using the Barber Colman Barcol impresser, following ASTM D2583-13 [24]. The testing was conducted within 3 mm of the edge of the specimen. In order to produce an even distribution of force, plate specimens were continuously supported on a stiff, hard, and supportive surface to minimize false data due to bending in the material. Twenty-five tests were conducted on each sample plate. After the test, the average from results was calculated and taken as Barcol hardness.
  • Tensile test specimens with dumb-bell-shape (type 1A) were prepared according to part 2 of ISO 527 [25]. The specimens have a prismatic form with reinforcement at the ends to avoid grip failure. The transition is made with a constant radius of 24 ⁇ 1 mm. Tests were carried out under displacement control, at a speed of 2 mm/min. From the test results, the average values of the tensile properties were obtained, namely, tensile strength, modulus of elasticity, and strain at break.
  • the specimens were subjected to a constant strain amplitude of 15 pm at a constant oscillation frequency of 1 Hz while submitted to a temperature sweep at a constant heating rate of 2 °C/min, starting at -30 °C and ending at 150 °C.
  • the Tg from tan d peak was also determined.
  • Examples 1, 2, 3 and 4 cover the main building blocks currently available namely 2,5-furandicarboxylic acid (FDCA), isosorbide, 1,3-propanediol, dimer acids, showing a considerable improvement when compared to the state of the art by introducing a greater bio-content while maintaining the properties most suitable for the purpose of the resin, which are, inter alia, the basis of a matrix for impregnation of fibers for the manufacture of FRP composites.
  • FDCA 2,5-furandicarboxylic acid
  • isosorbide 1,3-propanediol
  • dimer acids dimer acids
  • Examples 1A to 1C were prepared according to the standard synthesis procedure using the reactants listed in Table 1. These examples focus on the use of different ratios between phthalic anhydride and fumaric acid, without changing the proportions of dihydric diols. Isosorbide, 1,3- propanediol, and fumaric acid were used as raw materials derived from renewable sources, while ethylene glycol and phthalic anhydride were derived from oil-platform. Water was used to dissolve isosorbide prior to the reaction in a corresponding weight of 30% of isosorbide. To perform the curing process, methyl ethyl ketone peroxide and cobalt octoate were used as initiator and accelerator, respectively. Specimens from examples 1A to 1C were post- cured at 100 °C during 4 h to perform mechanical and thermophysical tests.
  • Examples 1A to 1C show that the polyester prepolymer discovered by this invention is capable of containing a high content derived from renewable raw materials, always above 68%, reaching more than 76%.
  • Examples 1A to 1C present acid numbers equal to or lower than 50, which is very similar to those of conventional unsaturated polyesters produced from the oil industry.
  • the resins obtained from examples 1A to 1C present mechanical and thermophysical properties equal to or greater than those of conventional oil-derived unsaturated polyester resins, as can be seen in Table 1.
  • Resins from examples 1A and IB present glass transition temperature equal to or greater than those of oil-derived ones, with the advantage of having a renewable content greater than 44% in weight.
  • Examples 2A and 2B were prepared according to the standard synthesis procedure using the reactants listed in Table 2, where the partial or total replacement of phthalic anhydride by 2,5-furandicarboxylic acid derived from renewable sources were tested. Water was used to dissolve isosorbide prior to the reaction in a corresponding weight of 30% of isosorbide. To perform the curing process, methyl ethyl ketone peroxide and cobalt octoate were used as initiator and accelerator, respectively. Specimens from examples 2A and 2B were post-cured at 100 °C during 4 h to perform mechanical and thermophysical tests.
  • Examples 2A and 2B present a considerable increase in Tg, reaching up to 70 °C, based on the onset of the storage modulus decay; surprisingly, the invention allowed achieving equal or higher mechanical performance than that of oil-derived polyester resins.
  • 2,5- furandicarboxylic acid a bio-derived monomer used almost exclusively by the packaging and paint industry, can be used as a building block for the synthesis of high performance and environmentally friendly unsaturated polyester resins for FRP structural applications.
  • Examples 2A and 2B show that the unsaturated polyester resin developed in this invention achieve high mechanical and thermophysical properties with bio-content up to 55%, reaching almost 60%.
  • Examples 3A and 3B were prepared according to the standard synthesis procedure using the reactants listed in Table 3, where the partial replacement of phthalic anhydride by dimer fatty acid derived from renewable sources was tested. Water was used to dissolve isosorbide prior to the reaction in a corresponding weight of 30% of isosorbide. To perform the curing process, methyl ethyl ketone peroxide and cobalt octoate were used as initiator and accelerator, respectively. Specimens from examples 3A and 3B were post- cured at 100 during 4 h to perform mechanical and thermophysical tests.
  • Examples 3A and 3B show that the invention allows replacing the oil-derived saturated dicarboxylic anhydride (or acid) by using dimer fatty acids derived from tall oil, which increases the amount of renewable content into the invention. Even partially or totally replacing phthalic anhydride, the invention provides, surprisingly, Tg above 60 °C based on the onset of the storage modulus decay.
  • Example 3A and 3B present viscosities and gel times suitable to be used in the manufacturing of composite materials, which require more time to impregnate fibres and need lower shrinkage, such as FRP composites with large dimensions to be used as face sheets of sandwich panels.
  • Examples 4A and 4B were prepared according to the standard synthesis procedure using the reactants listed in Table 4. These examples do not present oil-derived glycols in their formulation. Water was used to dissolve isosorbide prior to the reaction in a corresponding weight of 30% of isosorbide. To perform the curing process, methyl ethyl ketone peroxide and cobalt octoate were used as initiator and accelerator, respectively. Specimens from examples 4A and 4B were post-cured at 100 °C during 4 h to perform mechanical and thermophysical tests.
  • Examples 4A and 4B present bio-based content above 50%, with viscosities similar to those of oil-derived unsaturated polyester resins to be used as polymeric matrices in the FRP composites industry.
  • the invention allows, surprisingly, to use dihydric alcohols fully derived from renewable resources, which can replace their oil- derived counterparts, maintaining or even improving the mechanical properties.
  • polyester resin obtained from example 2B was submitted to a gel time test at 180 °C with 1.0% of tert- Butyl peroxybenzoate (for example trigonox CTM) and 0.5% of methyl isobutyl ketone peroxide (for example trigonox HMaTM) as initiator and accelerator, respectively.
  • the gel time was 1 min and 11 seconds, which shows that the invention allows embodiment based on 2,5-furandicarboxylic acid, which can be used in the pultrusion process.
  • polyester resin obtained from example 3B was submitted to a gel time test at 180 °C with 1.0% of tert- Butyl peroxybenzoate (for example trigonox CTM) and 0.5% of methyl isobutyl ketone peroxide (for example trigonox HMaTM) as initiator and accelerator, respectively.
  • the gel time was 57 seconds, indicating fast reactivity and a very short cure time under high temperatures of the embodiment based on dimer fatty acids. This parameter is important for hot processing techniques, which require reduced shrinkage.
  • polyester resin obtained from example 4A was submitted to a gel time test at 180 °C with 1.0% of tert- Butyl peroxybenzoate (for example trigonox CTM) and 0.5% of methyl isobutyl ketone peroxide (for example trigonox HMaTM) as initiator and accelerator, respectively.
  • the gel time was 1 minute and 10 seconds, showing that the invention can be used in hot processing techniques.
  • the prepolymer obtained in example 4A was incorporated into a mixture of reactive diluents, in a proportion of 60/20/10/10 parts (w/w) of prepolymer, styrene, 2-hydroxyethyl methacrylate and pentaerythritol tetracrylate, respectively, resulting in an unsaturated polyester resin with 54% bio-based content.
  • Catalysts were used to accelerate the curing of the resin, namely, MEKP and cobalt octoate as initiator and accelerator, respectively.
  • After 24 hours at room temperature the resin was post-cured at 100 °C for 4 hours.
  • the cured product had an average Barcol hardness of 25 and tensile modulus of 3.5 GPa.
  • the glass transition temperatures from the onset of the storage modulus curve decay and tan delta peak were 55 °C and 95 °C, respectively .
  • the prepolymer obtained in example 4A was incorporated into a mixture of reactive diluents, in a proportion of 60/20/20 parts (w/w) of prepolymer, styrene and pentaerythritol tetracrylate, respectively, resulting in an unsaturated polyester resin with 58% bio-based content.
  • Catalysts were used to accelerate the curing of the resin, namely, MEKP and cobalt octoate as initiator and accelerator, respectively.
  • the glass transition temperatures from the onset of the storage modulus curve decay and tan delta peak were 51 °C and 126 °C, respectively.
  • ASTM D2583-13a Standard Test Method for Indentation Hardness of Rigid Plastics by Means of a Barcol Impressor. Technical report, ASTM International, West Conshohocken, PA, 2013.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Reinforced Plastic Materials (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

La présente invention concerne de nouvelles résines de polyester insaturé à base de blocs de construction partiellement ou presque totalement dérivés de ressources renouvelables ou durables. Les résines présentées dans l'invention sont appropriées en vue de la fabrication de matériaux composites de polymère renforcé par des fibres (FRP) par différentes techniques de traitement, y compris des procédés de durcissement à froid et à chaud. Les résines durcies développées avec la présente invention présentent des propriétés mécaniques et thermophysiques qui correspondent aux performances de résines de polyester insaturé pétrochimiques classiques ou les dépassent.
PCT/PT2022/050019 2021-07-01 2022-06-07 Résines de polyester insaturé à hautes performances à base de ressources renouvelables WO2023277718A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PT117321A PT117321A (pt) 2021-07-01 2021-07-01 Resinas de poliéster insaturado de elevado desempenho baseadas em recursos renováveis
PT117321 2021-07-01

Publications (1)

Publication Number Publication Date
WO2023277718A1 true WO2023277718A1 (fr) 2023-01-05

Family

ID=83081535

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/PT2022/050019 WO2023277718A1 (fr) 2021-07-01 2022-06-07 Résines de polyester insaturé à hautes performances à base de ressources renouvelables

Country Status (2)

Country Link
PT (1) PT117321A (fr)
WO (1) WO2023277718A1 (fr)

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3760033A (en) * 1970-03-18 1973-09-18 Berger Jenson & Nicholson Ltd Polyester resin compositions
US5747597A (en) 1995-09-25 1998-05-05 Dainippon Ink And Chemicals, Inc. Curable resin composition and coating material composition
WO1999023122A1 (fr) 1997-11-04 1999-05-14 Composite Technology Group Llc Resines polyester et vinylester non styrenees
US20040092703A1 (en) 2002-11-13 2004-05-13 Germroth Ted Calvin Method for making isosorbide containing polyesters
US20040220340A1 (en) 2003-02-28 2004-11-04 Mcalvin John E. Styrene-free unsaturated polyester resin compositions for coating applications
US20090312485A1 (en) 2008-06-11 2009-12-17 E. I. Dupont De Nemours And Company Unsaturated polyester resin compositions comprising 1,3-propanediol
WO2010108962A1 (fr) * 2009-03-25 2010-09-30 Dsm Ip Assets B.V. Composition de résine de polyester insaturé
WO2011019557A1 (fr) * 2009-08-12 2011-02-17 Ashland Licensing And Intellectual Property Llc Formulations comprenant des résines de polyester insaturé modifié par isosorbide et additifs très faible retrait qui produisent des matrices à faible retrait
US7985826B2 (en) 2006-12-22 2011-07-26 Reichhold, Inc. Molding resins using renewable resource component
US9580542B2 (en) 2012-12-20 2017-02-28 Dow Global Technologies Llc FDCA-based polyesters made with isosorbide
US20170129994A1 (en) 2014-03-21 2017-05-11 Furanix Technologies B.V. Polyesters comprising 2,5-furandicarboxylate and saturated diol units having a high glass transition temperature
US20190031801A1 (en) 2011-08-10 2019-01-31 Drexel University Renewable Bio-Based (Meth)Acrylated Monomers as Vinyl Ester Cross-Linkers
US20190375890A1 (en) 2017-01-26 2019-12-12 Synvina C.V. 2, 5-furandicarboxylic acid-based polyesters
CN113754835A (zh) * 2021-08-11 2021-12-07 东莞市比翼新材料科技有限公司 油脂基改性不饱和聚酯树脂及其制备方法

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3760033A (en) * 1970-03-18 1973-09-18 Berger Jenson & Nicholson Ltd Polyester resin compositions
US5747597A (en) 1995-09-25 1998-05-05 Dainippon Ink And Chemicals, Inc. Curable resin composition and coating material composition
WO1999023122A1 (fr) 1997-11-04 1999-05-14 Composite Technology Group Llc Resines polyester et vinylester non styrenees
US20040092703A1 (en) 2002-11-13 2004-05-13 Germroth Ted Calvin Method for making isosorbide containing polyesters
US20040220340A1 (en) 2003-02-28 2004-11-04 Mcalvin John E. Styrene-free unsaturated polyester resin compositions for coating applications
US7985826B2 (en) 2006-12-22 2011-07-26 Reichhold, Inc. Molding resins using renewable resource component
US20090312485A1 (en) 2008-06-11 2009-12-17 E. I. Dupont De Nemours And Company Unsaturated polyester resin compositions comprising 1,3-propanediol
WO2010108962A1 (fr) * 2009-03-25 2010-09-30 Dsm Ip Assets B.V. Composition de résine de polyester insaturé
US20120157618A1 (en) 2009-03-25 2012-06-21 Marian Henryk Szkudlarek Unsaturated polyester resin
US8487041B2 (en) 2009-03-25 2013-07-16 Dsm Ip Assets B.V. Unsaturated polyester
WO2011019557A1 (fr) * 2009-08-12 2011-02-17 Ashland Licensing And Intellectual Property Llc Formulations comprenant des résines de polyester insaturé modifié par isosorbide et additifs très faible retrait qui produisent des matrices à faible retrait
US20190031801A1 (en) 2011-08-10 2019-01-31 Drexel University Renewable Bio-Based (Meth)Acrylated Monomers as Vinyl Ester Cross-Linkers
US9580542B2 (en) 2012-12-20 2017-02-28 Dow Global Technologies Llc FDCA-based polyesters made with isosorbide
US20170129994A1 (en) 2014-03-21 2017-05-11 Furanix Technologies B.V. Polyesters comprising 2,5-furandicarboxylate and saturated diol units having a high glass transition temperature
US20190375890A1 (en) 2017-01-26 2019-12-12 Synvina C.V. 2, 5-furandicarboxylic acid-based polyesters
CN113754835A (zh) * 2021-08-11 2021-12-07 东莞市比翼新材料科技有限公司 油脂基改性不饱和聚酯树脂及其制备方法

Non-Patent Citations (27)

* Cited by examiner, † Cited by third party
Title
"Gel permeation chromatography (GPC) - Part 1: Tetrahydrofuran (THF) as eluent", TECHNICAL REPORT, INTERNATIONAL ORGANIZATION FOR STANDARDIZATION, 2008
"Paints and varnishes - Determination of viscosity using rotatory viscometers-Part 2: Disc or ball viscometer operated at a specified speed", TECHNICAL REPORT, INTERNATIONAL ORGANIZATION FOR STANDARDIZATION, 2003
"Plastics - Determination of tensile properties — Part 2: Test conditions for moulding and extrusion plastics", TECHNICAL REPORT, INTERNATIONAL ORGANIZATION FOR STANDARDIZATION GENEVA, 2012
"Plastics (polyester resins) and paints and varnishes (binders) — Determination of partial acid value and total acid value", TECHNICAL REPORT, INTERNATIONAL ORGANIZATION FOR STANDARDIZATION, 2000
"Standard test method for assignment of the glass transition temperature by dynamic mechanical analysis", TECHNICAL REPORT, ASTM INTERNATIONAL, 2009
"Standard Test Method for Indentation Hardness of Rigid Plastics by Means of a Barcol Impressor", TECHNICAL REPORT, ASTM INTERNATIONAL, 2013
ALI HUSSAIN MOTAGAMWALAWANGYUN WONCANAN SENERDAVID MARTIN ALONSOCHRISTOS T. MARAVELIASJAMES A. DUMESIC: "Toward biomass-derived renewable plastics: Production of 2,5-furandicarboxylic acid from fructose", SCIENCE ADVANCES, vol. 4, no. 1, 2018
ANA C. FONSECAINES M. LOPESJORGE F.J. COELHOARMENIO C. SERRA: "Synthesis of unsaturated polyesters based on renewable monomers: Structure/properties relationship and crosslinking with 2-hydroxyethyl methacrylate", REACTIVE AND FUNCTIONAL POLYMERS, vol. 97, 2015, pages 1 - 11, XP029300473, DOI: 10.1016/j.reactfunctpolym.2015.10.002
DEBKUMAR BHATTACHARJEEKALYAN SEHANOBISH, FDCA-BASED POLYESTERS MADE WITH ISOSORBIDE, February 2017 (2017-02-01)
F.S. CARTAC.R. SOCCOLL.P. RAMOSJ.D. FONTANA: "Production of fumaric acid by fermentation of enzymatic hydrolysates derived from cassava bagasse. Bioresource Technology", BIOPROCESSING AND CHARACTERIZATION OF LIGNOCELLULOSICS, vol. 68, no. 1, 1999, pages 23 - 28
FENG GUOMIN WUZHONGXUE DAISHANGJIE ZHANGWENMING ZHANGWEILIANG DONGLIE ZHOUMIN JIANGFENGXUE XIN: "Current advances on biological production of fumaric acid", BIOCHEMICAL ENGINEERING JOURNAL, vol. 153, no. 107397, 2020
GIUSEPPE R. PALMESEJOHN JOSEPH LA SCALAJOSHUA MATTHEW SADLERANH- PHUONG THY LAM, RENEWABLE BIO-BASED (METH)ACRYLATED MONOMERS AS VINYL ESTER CROSS-LINKERS, January 2019 (2019-01-01)
HILDEBERTO NAVALIANZHOU CHEN, MOLDING RESINS USING RENEWABLE RESOURCE COMPONENT, July 2011 (2011-07-01)
JOHN MCALVINDANIEL OAKLEYPAUL HUTSONDAVID ZWISSLERTHOMAS FOLDA, STYRENE-FREE UNSATURATED POLYESTER RESIN COMPOSITIONS FOR COATING APPLICATIONS, November 2004 (2004-11-01)
KINGSLEY KEMA AJEKWENE: "Acrylate Polymers for Advanced Applications", 2020, article "Properties and Applications of Acrylates"
KUN LIANGMARCO DOSSIDAVIDE MOSCATELLIROBIN A. HUTCHINSON: "An Investigation of Free-Radical Copolymerization Propagation Kinetics of Styrene and 2-Hydroxyethyl Methacrylate", MACROMOLECULES, vol. 42, no. 20, 2009, pages 7736 - 7744
LASZLO SIPOSGERARDUS JOHANNES MARIA GRUTERJEFFREY JOHN KOLSTADGABRIEL DEGANDNICOLAS JACQUELRENE SAINT-LOUPMATHEUS ADRIANUS DAMJOSE, POLYESTERS COMPRISING 2,5-FURANDICARBOXYLATE AND SATURATED DIOL UNITS HAVING A HIGH GLASS TRANSITION TEMPERATURE, May 2017 (2017-05-01)
LINCHON B. MEHTAKUNAL K. WADGAONKARRAMANAND N. JAGTAP: "Synthesis and characterization of high bio-based content unsaturated polyester resin for wood coating from itaconic acid: Effect of various reactive diluents as an alternative to styrene", JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY, vol. 40, no. 5, 2019, pages 756 - 765
MARIAN HENRYK SZKUDLAREKJOHAN FRANZ GRADUS ANTONIUS JANSEN, UNSATURATED POLYESTER RESIN, July 2012 (2012-07-01)
MARIAN HENRYK SZKUDLAREKJOHAN FRANZ GRADUS ANTONIUS JANSENSTEFANUS JACOBUS DUYVESTIJN, UNSATURATED POLYESTER, July 2013 (2013-07-01)
MATTHEW ARTHUR PAGEHARI BABU SUNKARAJUDITH JOHANNA VAN GORP, UNSATURATED POLYESTER RESIN COMPOSITIONS COMPRISING 1,3-PROPANEDIOL, December 2009 (2009-12-01)
NICOLAS JACQUEL GABRIEL DEGANDRENE SAINT-LOUPMATHEUS ADRIANUS DAMBING WANG, 2,5-FURANDICARBOXYLIC ACID-BASED POLYESTERS, December 2019 (2019-12-01)
RICHARD M. ANDERSKENNETH R. ANDERSDALE K. BECKER, NONSTYRENATED POLYESTER AND VINYLESTER RESINS, May 1999 (1999-05-01)
SANG YUP LEEHYUN UK KIMTONG UN CHAEJAE SUNG CHOJE WOONG KIMJAE HO SHINDONG IN KIMYOO-SUNG KOWOO DAE JANGYU-SIN JANG: "A comprehensive metabolic map for production of bio-based chemicals", NATURE CATALYSTS, vol. 2, no. 1, 2019, pages 18 - 33
SURIANO RAFFAELLA ET AL: "Environmental Profile and Technological Validation of New High-Tg Unsaturated Polyesters from Fully Bio-Based Monomers and Reactive Diluents", JOURNAL OF POLYMERS AND THE ENVIRONMENT, vol. 29, no. 4, 20 February 2022 (2022-02-20), pages 1122 - 1133, XP037401849, ISSN: 1566-2543, DOI: 10.1007/S10924-020-01928-Z *
TED GERMROTHSAM TURNERLANNY TREECE, METHOD FOR MAKING ISOSORBIDE CONTAINING POLYESTERS, May 2004 (2004-05-01)
YUKIKO FUJITASHINYA UENOYOKO KAWASAKIKUMIKO FUKAKUSAHIDEFUMI MATSUYATOMOMASA MITANIAAKIRA KOMORIMIKA MATSUMURA, DURABLE RESIN COMPOSITION AND COATING MATERIAL COMPOSITION, May 1998 (1998-05-01)

Also Published As

Publication number Publication date
PT117321A (pt) 2023-01-02

Similar Documents

Publication Publication Date Title
Dai et al. Polyesters derived from itaconic acid for the properties and bio-based content enhancement of soybean oil-based thermosets
Liu et al. Development of biobased unsaturated polyester resin containing highly functionalized castor oil
US6121398A (en) High modulus polymers and composites from plant oils
Xia et al. Bio-based thermosetting polymers from vegetable oils
Xia et al. Vegetable oil-based polymeric materials: synthesis, properties, and applications
KR101394711B1 (ko) 겔 코트용 폴리에스테르 아크릴 수지의 저 ｖｏｃ 열경화성 조성물
Hofmann et al. Biobased thermosetting polyester resin for high-performance applications
Zhang Rosin-based chemicals and polymers
Bakare et al. Synthesis and characterization of bio‐based thermosetting resins from lactic acid and glycerol
Dai et al. Synthesis of eugenol-based multifunctional monomers via a thiol–ene reaction and preparation of UV curable resins together with soybean oil derivatives
Jahandideh et al. Synthesis, characterization and curing optimization of a biobased thermosetting resin from xylitol and lactic acid
EP2531539B1 (fr) Composition de résine comprenant un polymère saturé contenant d`isosorbide
Zhou et al. Two Strategies to precisely tune the mechanical properties of plant oil-derived epoxy resins
Jahandideh et al. Synthesis and characterization of novel star-shaped itaconic acid based thermosetting resins
Bamane et al. Replacement of traditional unsaturated acid by bio-based itaconic acid in the preparation of isophthalic acid-based unsaturated polyester resin
Dai et al. Reactive diluent derived from ferulic acid for the preparation of a fully biobased unsaturated polyester resin
MX2008016298A (es) Prepolimero de uretano-poliester no saturado y sus aplicaciones.
Hofmann et al. Development of high‐performance partially biobased thermoset polyester using renewable building blocks from isosorbide, 1, 3‐propanediol, and fumaric acid
JP6921744B2 (ja) メバロノラクトンから調製されるポリマーおよび誘導体
Ray et al. Thermosetting bioresins as matrix for biocomposites
WO2023277718A1 (fr) Résines de polyester insaturé à hautes performances à base de ressources renouvelables
Arvin et al. Effect of nature and extent of functional group modification on properties of thermosets from methacrylated epoxidized sucrose soyate
KR102032410B1 (ko) 다이머산 또는 이의 알킬 에스테르와 에폭시화 식물유를 포함하는 열가소성 폴리에스테르, 이의 제조방법 및 이를 포함하는 핫멜트 접착제
EP0441416A1 (fr) Composition de résine contenant des composés de masses moléculaires basses aptes à former un réseau hybride polyester-uréthane
Gaurangkumar Mistry Development Of Bio-Based Thermosetting Resins

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22760797

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE