WO2024200021A1 - Formulation de résine pour la production d'une matière plastique thermodurcissable, matière plastique thermodurcissable et matériau composite correspondants - Google Patents

Formulation de résine pour la production d'une matière plastique thermodurcissable, matière plastique thermodurcissable et matériau composite correspondants Download PDF

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Publication number
WO2024200021A1
WO2024200021A1 PCT/EP2024/056777 EP2024056777W WO2024200021A1 WO 2024200021 A1 WO2024200021 A1 WO 2024200021A1 EP 2024056777 W EP2024056777 W EP 2024056777W WO 2024200021 A1 WO2024200021 A1 WO 2024200021A1
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Prior art keywords
resin
resin formulation
thermosetting plastic
itaconic acid
group
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PCT/EP2024/056777
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German (de)
English (en)
Inventor
Laura Boskamp
Katharina KOSCHEK
Gideon ABELS
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Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
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Priority to EP24712201.3A priority Critical patent/EP4688907A1/fr
Publication of WO2024200021A1 publication Critical patent/WO2024200021A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/061—Polyesters; Polycarbonates
    • 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
    • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/16—Biodegradable polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2397/00—Characterised by the use of lignin-containing materials
    • C08J2397/02—Lignocellulosic material, e.g. wood, straw or bagasse

Definitions

  • Resin formulation for producing a thermosetting plastic, corresponding thermosetting plastic and composite material Resin formulation for producing a thermosetting plastic, corresponding thermosetting plastic and composite material
  • the present invention relates to a resin formulation for producing a thermosetting plastic.
  • the invention further relates to a thermosetting plastic.
  • the invention also relates to the use of a resin formulation according to the invention and/or a thermosetting plastic according to the invention.
  • the invention also relates to a composite material comprising a thermosetting plastic according to the invention as a polymer matrix.
  • FRP Fiber-reinforced plastics
  • the weight reduction has made it possible, among other things, to significantly reduce fuel consumption.
  • Many polymers for FRP are currently obtained from fossil raw materials. Not only are these a limited resource, their processing also requires large amounts of energy and leads to high CO2 emissions.
  • cross-linked polymer systems are mainly used for FRP production. These materials, which are made up of reactive systems, are extremely stable and durable, but make recycling or a simple way of decomposing or composting these polymers and thus also the FRPs made from them almost impossible. For this reason, FRPs with petroleum-based polymers have a poor ecological balance.
  • UP resins unsaturated polyester resins
  • thermal or chemical treatments or the respective monomers can be recovered.
  • UP resins are widely used in combination with glass fibers in certain areas such as automobile and shipbuilding due to their good price/performance ratio.
  • thermosets cross-linked polymers
  • the literature describes bio-based UP resins based on itaconic acid, isosorbides and vegetable oils, some of which are slightly biodegradable.
  • this biodegradability usually requires long-term storage in industrial compost.
  • thermoplastics which are characterized by other processing and recycling options compared to cross-linked systems, bio-based alternatives are increasingly being considered.
  • PLA polylactide
  • PLA-based polymers are bio-based and, under certain conditions, simultaneously biodegradable (for example, microbially degradable at a temperature of 52 °C (thermophilic) or 37 °C (mesophilic)) or compostable (for example through industrial composting).
  • biodegradable for example, microbially degradable at a temperature of 52 °C (thermophilic) or 37 °C (mesophilic)
  • compostable for example through industrial composting.
  • a major challenge is the provision of resin formulations for the production of thermosets which
  • (iii) preferably also have good and easy processability (particularly in their handling for use as a polymer matrix for FRPs).
  • thermosetting systems that can be produced from them often each have disadvantages in at least one of the three properties mentioned above.
  • resin compositions disclosed in the document US 2008/0004369 A1 and the thermosets that can be produced from them have significant disadvantages in terms of their processability and mechanical properties according to our own investigations, which are explained in more detail below.
  • Other resin formulations such as the itaconic acid-based polyester resin STRUKTOL® VP3830 from Schill and Seilacher Struktol GmbH, are not biodegradable or compostable.
  • the primary object of the present invention was to provide a resin formulation for producing a duromer which meets the above-mentioned criteria; i.e. has advantageous mechanical properties of a duromer system, which in particular enable its use for FRPs, but at the same time is biodegradable or compostable and is preferably also characterized by easy processability.
  • a further object of the present invention was to provide a corresponding thermosetting plastic with the above-mentioned advantageous combination of properties.
  • the present invention should also make it possible to provide the resin formulation and/or the thermosetting plastic to be specified for typical applications, such as as an adhesive or as a matrix resin for a composite material (e.g. in the automotive industry).
  • a further task was to specify a composite material comprising the specified thermosetting plastic as a polymer matrix.
  • the primary object of the present invention can be achieved by a resin formulation for producing a thermosetting plastic, a) comprising or consisting of
  • At least one resin obtainable by reaction (modification) of a biodegradable and/or compostable polymer with one or more modifiers wherein the one or more modifiers are selected from the group consisting of alcohols, ketones, aldehydes, imines, acrylonitriles, peroxides, thiocarboxylic acids, sulfonic acids, thioaldehydes, thioketones, azides, thiocyanates, furans, itaconic acid and derivatives of itaconic acid, and
  • Young's modulus of 1700 Pa or more preferably 2,000 MPa or more, particularly preferably 3,000 MPa or more;
  • the stated primary object is achieved by the aforementioned resin formulation, wherein the biodegradable and/or compostable polymer is selected from the group consisting of polylactides (PLA), polycaprolactones (PCL), chitin, chitosan, polyhydroxy fatty acids (PHF, also referred to as polyhydroxyalkanoates or PHA), polyhydroxyacetic acid, starch, cellulose, lignin and derivatives thereof, and the one or more modifiers are selected from the group consisting of itaconic acid, hydroxymethylfurfural (HMF) and derivatives thereof.
  • PLA polylactides
  • PCL polycaprolactones
  • PHF polyhydroxy fatty acids
  • PHA polyhydroxyacetic acid
  • HMF hydroxymethylfurfural
  • thermosetting plastics which have the desired mechanical properties such as high rigidity and high tensile strength and at the same time are also biodegradable. are biodegradable or compostable.
  • the corresponding resin formulations can be processed under mild reaction conditions - such as comparatively low temperatures - which enable easy handling of the resin formulations.
  • plastics that can be produced from resin formulations according to the invention thus combine the material properties of a classic duromer and are characterized by durability and thermal and chemical stability over the course of their life cycle, but at the same time also enable recycling due to their ability to be biodegradable or compostable.
  • the resin formulations according to the invention are resin formulations that are not yet cured or at least not yet fully cured.
  • the final curing, which leads to the formation of a thermosetting plastic, can take place in the case of resin formulations according to the invention with or without the addition of thermal energy (i.e. with or without heating).
  • the resin formulations according to the invention can therefore be hot-curing and/or cold-curing.
  • biodegradable polymer refers to polymers which can be decomposed by microorganisms such as bacteria (i.e. are biodegradable).
  • a polymer is "compostable" in the sense of the present invention if the polymer can be noticeably, preferably completely, decomposed under composting conditions within a specified foreseeable period of time.
  • these are preferably compostable polymers which are decomposable within 45 days using composting conditions in accordance with DIN EN ISO 20200:2015, preferably (using composting conditions in accordance with DIN EN ISO 20200:2015) are completely decomposable within 45 days, particularly preferably (using composting conditions in accordance with DIN EN ISO 20200:2015) are completely decomposable within 10 days.
  • the term "decomposable” means causing a noticeable, visually perceptible separation of individual parts from a polymer or thermosetting plastic.
  • a polymer or thermosetting plastic is considered to be "completely” decomposed if the degree of decomposition of the polymer or thermosetting plastic determined in accordance with DIN EN ISO 20200:2015 is 100% (i.e. if no plastic material remains in the sieve even when sieving with a 2 mm sieve).
  • the at least one resin of a resin formulation according to the invention is obtainable by reacting or modifying a biodegradable and/or compostable polymer with one or more of the modifiers mentioned.
  • the at least one resin of a resin formulation according to the invention therefore differs from those resins for the production of which a modifier is only added to the starting material or the monomer component for the production of the resin before production/polymerization of the resin.
  • reaction or modification of the biodegradable and/or compostable pen with one or more of the modifiers mentioned represents an essential aspect for achieving the advantageous properties of the thermosetting plastic that can be produced from the resin formulation according to the invention, since the reaction or modification contributes significantly to the thermosetting plastic that can be produced from the resin formulation according to the invention not only having the ability to be biodegradable or compostable but also having the advantageous mechanical properties explained above.
  • the ultimate functionality of the resin which enables curing, can either be introduced into the compound by the modifier (for example in the case of choosing polylactide as the biodegradable and compostable polymer and itaconic acid as the modifier) or can already be present in the selected biodegradable and/or compostable polymer to be modified and can simply be retained as part of the reaction with the modifier.
  • polymer is to be understood broadly in the sense of the present invention and includes both polymers with low and high degrees of polymerization, as long as they are biodegradable and/or compostable. Oligomers are understood as polymers in the sense of the present invention and are accordingly included in the term "polymer” in the sense of the present invention.
  • resin classes preferred in the context of the present invention are polyester resins, preferably saturated or unsaturated polyester resins, epoxy resins, furan resins, phenolic resins and vinyl esters.
  • the selection of the at least one hardener and/or - in the case of saturated or unsaturated polyester resin as the at least one resin - the at least one copolymerizable monomer is determined by the choice of the resin or resins for the respective resin formulation and the suitability of the hardener/copolymerizable monomer for hardening the resin or resins; and vice versa.
  • all hardeners or copolymerizable monomers suitable for hardening the respective resin are suitable.
  • the respective resins and hardeners or copolymerizable monomers can each have more than one type of functional group, which means that certain hardeners can also be suitable for hardening different types of resins.
  • a resin formulation according to the invention can comprise more than one resin as well as more than one hardener or more than one copolymerizable monomer.
  • thermosetting plastics with particularly advantageous properties with regard to biodegradability or compostability and at the same time high mechanical strength.
  • the modifiers for producing the resins for the resin formulations can of course also have more than one type of functional group.
  • the at least one resin of the resin formulation according to the invention is a polylactide modified with itaconic acid and/or itaconic acid derivatives
  • the selective choice of the at least one copolymerizable monomer or reactive diluent from the copolymerizable monomers specified above and in the claims has proven to be essential in order to achieve the desired advantageous properties.
  • the choice of a suitable copolymerizable monomer is by no means trivial.
  • thermosetting plastics can be obtained from polylactide modified with itaconic acid and/or itaconic acid derivatives using styrene as a copolymerizable monomer or reactive diluent, which has excellent biodegradability and compostability.
  • thermosetting plastic that is not biodegradable or compostable or that is only poorly biodegradable, if at all, when using styrene as a copolymerizable monomer or reactive diluent, the skilled person would have deliberately refrained from using styrene in particular and would not have considered its use in the search for a solution to the problem at hand.
  • thermosetting plastic in particular for use as a polymer matrix in FRPs
  • a resin formulation which, as stated above and in the claims, is suitable for producing a thermosetting plastic that can be decomposed within 45 days using composting conditions in accordance with DIN EN ISO 20200:2015 and at the same time has an elastic modulus of 1700 Pa or more and/or a tensile strength of 20 MPa or more and/or an elongation at break of 1.5% or more.
  • the E-modulus also called elastic modulus
  • thermosetting plastic which meets the requirements for certification according to one or more of the following standards:
  • a resin formulation according to the invention wherein the resin formulation is produced partially or completely from renewable raw materials (ie is bio-based).
  • renewable raw materials ie is bio-based
  • a or several of the components of the resin formulation according to the invention are to be selected from compounds made from renewable raw materials.
  • polylactide modified with itaconic acid also referred to as PLA-ITA
  • PLA-ITA polylactide modified with itaconic acid
  • dimethyl itaconate can be used as the copolymerizable monomer.
  • a resin formulation according to the invention is preferably suitable for producing a thermosetting plastic which (in addition to or as an alternative to its biodegradability or grainability) can be split into its reactants and/or monomeric components.
  • Splitting the thermosetting plastic into its reactants or monomeric components has the advantage that the corresponding reactants or monomeric components are immediately available again as starting materials for the production of further resins, resin formulations or other valuable chemical materials after splitting has taken place and the thermosetting plastic is thus accessible to chemical recycling.
  • a resin formulation according to the invention is preferred, wherein the modifier is itaconic acid.
  • a resin formulation according to the invention is preferred, wherein the at least one resin is a saturated or unsaturated polyester resin (UP resin) and/or an epoxy resin, preferably an unsaturated polyester resin.
  • UP resin saturated or unsaturated polyester resin
  • epoxy resin preferably an unsaturated polyester resin.
  • a resin formulation according to the invention wherein the chain length of the at least one resin is in the range from 500 g/mol to 50,000 g/mol, preferably in the range from 500 g/mol to 800 g/mol.
  • a resin formulation according to the invention wherein the proportion of hardeners and/or copolymerizable monomers (reactive diluents) in the resin formulation is 1 wt.% to 99 wt.%, preferably 10 wt.% to 50 wt.%, particularly preferably 10 wt.% to 30 wt.%, based on the total mass of the resin formulation, and/or the ratio of the total mass of hardeners and/or copolymerizable monomers (reactive diluents) to the total mass of resins in the resin formulation is 2:1.
  • thermosetting plastics In principle, a higher proportion of hardeners and/or copolymerizable monomers (reactive thinners) results in stronger cross-linking. By reducing the proportion of hardeners and/or copolymerizable monomers (reactive thinners), the brittleness of the thermosetting plastic produced from the resin formulation can generally be reduced. In addition, a higher proportion of resin has a generally positive effect on the biodegradability or compostability of the thermosetting plastic produced from the resin formulation. The preferred ratios mentioned above make it possible to produce thermosetting plastics that have both particularly advantageous biodegradability or compostability and sufficiently high mechanical strength.
  • a resin formulation according to the invention is preferred, wherein the at least one resin is a polylactide modified with itaconic acid and/or itaconic acid derivatives and/or the at least one copolymerizable monomer is styrene.
  • a resin formulation according to the invention wherein the at least one resin is a polylactide modified with itaconic acid and/or itaconic acid derivatives and the at least one copolymerizable monomer is styrene.
  • thermosetting plastics with particularly outstanding properties in terms of biodegradability or compostability and mechanical strength
  • their further advantage is the large-scale availability of these components or the starting materials for their production. For example, around 15,000 tons of itaconic acid are produced from molasses and 210,000 tons of polylactide from corn starch are produced annually.
  • a resin formulation according to the invention additionally comprising one or more catalysts or catalyst systems, preferably selected from the group consisting of tin(II)-2-ethylhexanoate, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and citric acid, and/or one or more initiators, preferably thermal initiators, particularly preferably selected from the group consisting of methyl ethyl ketone peroxide (MEKP), N,N-azobisisobutyronitrile (AIBN) and dibenzoyl peroxide (BPO), and/or one or more accelerators, preferably selected from the group consisting of cobalt compounds and amine compounds, and/or one or more inhibitors, preferably selected from the group consisting of phenols, quinones and their derivatives, and/or one or more plasticizers, preferably selected from the group consisting of glycerin, epoxidized soybean oil, acetyltributyl cit
  • initiators
  • the catalysts mentioned above as preferred are used, for example, to produce the biodegradable and/or compostable polymer and are therefore often also included in the subsequent resin formulation.
  • the addition of initiators and/or accelerators and/or inhibitors serves, among other things, to influence the pot life of the resin formulation, with long pot lives being preferred.
  • the pot life of the resin formulation can be influenced both by the choice of the type as well as the choice of the amount of initiators, accelerators or inhibitors.
  • one or more of the additional components catalysts or catalyst systems, initiators, accelerators, inhibitors, plasticizers and impact modifiers are made from renewable raw materials (i.e. bio-based).
  • a resin formulation according to the invention is preferred, wherein the resin formulation is one-component or multi-component, preferably two-component, wherein resins and hardeners or copolymerizable monomers are preferably present separately from one another in different components.
  • the presence of resins and hardeners or copolymerizable monomers in different components is particularly preferred for cold-curing resin formulations.
  • the individual components can be mixed for use of the resin formulations, for example, by hand or with commercially available mixing equipment.
  • the individual components are preferably mixed together shortly before the thermosetting plastic is produced. In some cases, the production of the thermosetting plastic is already initiated by mixing the individual components of the multi-component resin formulation.
  • a resin formulation according to the invention wherein the resin formulation is present as a (viscous) liquid at room temperature (25 °C) and normal pressure (1.013 25 bar) and/or has a pot life of more than 10 minutes, preferably more than 30 minutes, particularly preferably more than 60 minutes.
  • the aim of the present invention is to achieve a resin formulation which is preferably characterized by easy processability. Easy processability is achieved in particular by the presence of the resin formulation in liquid or low-viscosity form at room temperature and normal pressure.
  • the resin formulations according to the invention differ in this respect of resin formulations known from the prior art that it is easily possible to obtain a resin formulation that is liquid (low viscosity) at room temperature.
  • the resin formulation is present as a (viscous) liquid at room temperature, it can be processed using methods commonly used in the FRP sector, such as hand lamination or pressing. Furthermore, if the resin formulation is present as a (viscous) liquid at room temperature, the energy or heat input that would otherwise be required to liquefy the resin formulation before processing can be avoided.
  • the above-mentioned preferably long pot lives can usually be achieved for resin formulations according to the invention in comparison to resin formulations known from the prior art, whereby a significantly larger time window for processing is usually available for resin formulations according to the invention in comparison to resin formulations known from the prior art.
  • thermodefination a resin formulation according to the invention, wherein the temperature required for mixing the at least one resin with the at least one hardener and/or the at least one copolymerizable monomer is less than 100 °C, preferably less than 90 °C, particularly preferably a maximum of 80 °C.
  • temperature necessary for mixing pot means that the viscosity of at least one of the components to be mixed is too high below this temperature for homogeneous mixing of resin and hardener or copolymerizable monomer to be possible.
  • the possibility of using the lowest possible temperature for mixing resin and hardener or copolymerizable monomer is therefore advantageous because this reduces evaporation of the component with a higher vapor pressure or lower boiling point, thus enabling a more precise setting of a desired ratio between the components and reducing the occurrence of any harmful vapors.
  • a resin formulation according to the invention is also preferred, wherein the viscosity required for mixing the at least one resin with the at least one hardener and/or the at least one copolymerizable monomer is 1 Pa*s.
  • the viscosity is determined using a rheological test. This can be isothermal or temperature-dependent. Usually, the temperature-dependent course is tested first and then isothermal.
  • thermosetting plastic a) obtainable by curing, preferably thermal curing, of a resin formulation according to the invention or preferably according to the invention (as defined above and in the claims) and/or b) wherein the thermosetting plastic is decomposable within 45 days using composting conditions according to DIN EN ISO 20200:2015, preferably is completely decomposable within 45 days, particularly preferably is completely decomposable within 10 days and has one or more of the following mechanical properties, determined according to DIN EN ISO 527-4:
  • Young's modulus of 1700 MPa or more preferably 2000 MPa or more, particularly preferably 3000 MPa or more;
  • thermosetting plastic according to the invention or preferably according to the invention
  • the invention also relates to the use of a resin formulation according to the invention or preferably according to the invention (as defined above and in the claims) and/or a thermosetting plastic according to the invention (as defined above and in the claims), as a plastic and/or as an adhesive and/or as a matrix resin for a composite material, preferably for a fiber-reinforced plastic and/or in one or more of the following areas:
  • thermosetting plastics according to the invention are suitable for the production of pipes and/or tanks for the transport and storage of molecular hydrogen (H2).
  • resin formulations according to the invention or thermosetting plastics according to the invention are particularly suitable for products that are only used once and yet have to withstand high mechanical loads during their service life.
  • the invention also relates to a composite material, preferably fiber-reinforced plastic, comprising as polymer matrix a thermosetting plastic according to the invention (as defined above and in the claims).
  • a composite material preferably fiber-reinforced plastic
  • thermosetting plastics according to the invention are particularly suitable and interesting as a polymer matrix for corresponding composite materials due to their exceptional material properties.
  • Fig. 1 to Fig. 3 Comparison of the modulus of elasticity of the tensile strength and the elongation at break of a non-inventive fiber composite plastic produced using the commercially available UP resin VP3830 from Schill and Seilacher Struktol GmbH (designated with the sample number "1") and a fiber composite plastic according to the invention produced using a resin formulation according to the invention comprising itaconic acid-modified polylactide as resin and styrene as copolymerizable monomer (designated with the sample number "3").
  • thermosetting plastics obtained by curing resin formulations comprising either (i) itaconic acid modified polylactide as resin (referred to as “PLA-ITA” in Fig. 4) or (ii) the commercially available UP resin VP3830 from Schill and Seilacher Struktol GmbH (referred to as “Struktol” in Fig. 4) and a mixture of styrene and dimethyl itaconate as copolymerizable monomers.
  • PLA-ITA itaconic acid modified polylactide as resin
  • Struktol the commercially available UP resin VP3830 from Schill and Seilacher Struktol GmbH
  • thermosetting plastic produced from a (non-inventive) resin formulation comprising the commercially available UP resin VP3830 from Schill and Seilacher Struktol GmbH as resin and styrene as copolymerizable monomer (designated with the sample number "1"); a thermosetting plastic, produced from a (inventive) resin formulation comprising polylactide modified with itaconic acid as resin and styrene as copolymerizable monomer (designated with the sample number "3"); and a thermosetting plastic, made from a resin formulation (not according to the invention) comprising a resin obtained from the polymerization of L-lactic acid and itaconic acid and styrene as a copolymerizable monomer (designated with the sample number "5"). Materials used:
  • Example 1 Preparation of a resin formulation comprising itaconic acid modified polylactide as resin and styrene as copolymerizable monomer (according to the invention) 240 g of lactide were melted at about 100°C and 42.23 g of propylene glycol were added while stirring. Once a homogeneous liquid was obtained, 1.2 g of tin(II)-2-ethylhexanoate were slowly added dropwise while stirring vigorously. The reaction solution was then stirred for 1 h at 120 °C and then for 3 h at 150 °C. 280 g of the resulting polylactide (PLA) were dried at 80 °C while stirring in an oil pump vacuum.
  • PLA polylactide
  • the vacuum was then replaced by a protective gas atmosphere and 193 mL of toluene, 107.58 g of itaconic acid, 193.2 mg of p-methoxyphenol and 1.94 g of p-toluenesulfonic acid were added one after the other.
  • the temperature of the reaction mixture was gradually increased from 80 °C to 180 °C within one hour and this temperature was maintained for a further 20 hours.
  • the water formed was distilled off and collected in a suitable apparatus; it served as an indicator of the progress of the reaction. As soon as no more new water was formed, the reaction was complete.
  • the toluene was then removed on a rotary evaporator at 80 °C.
  • the product was dried at 80 °C for 18 hours in a vacuum oven and then for a further 2 hours with stirring using a KPG stirrer in an oil pump vacuum. A protective gas atmosphere was then introduced and the heat source was removed. A proportion of 33% (based on the total mass) of styrene was gradually added to the bio-based resin thus obtained as a copolymerizable monomer or reactive diluent and the mixture was stirred with the KPG stirrer until a homogeneous liquid was obtained. After cooling to room temperature, the mixture was filled into UV-protected storage containers.
  • the resin formulation prepared in Example 1 was mixed with 2 wt.% of the thermal initiator methyl ethyl ketone peroxide.
  • the textile semi-finished product was then impregnated with the resin formulation by hand lamination.
  • the fiber volume content was 30%.
  • the semi-finished product impregnated with the resin formulation was first heated to 180 °C in a mold with a pressure of 90 kN at a heating rate of 10 K/min and then held at this temperature for 30 min.
  • the mold was then cooled to 30 °C and the fiber composite plastic, comprising the hardening of the resin formulation as a polymer matrix.
  • the fiber composite plastic obtained was then post-cured outside the press for 2 hours at 180°C. plastic from a commercially available
  • a fiber composite plastic was produced from the flax fiber semi-finished product used in Example 2 and the commercially available UP resin VP3830 from Schill and Seilacher Struktol GmbH.
  • the system with the product name VP3830 from Schill and Seilacher Struktol GmbH is a bio-based UP resin based on itaconic acid, which - unlike the resin produced in Example 1 - does not contain any PLA.
  • a proportion of 30% (based on the total mass) of styrene as a copolymerizable monomer or reactive diluent was gradually added to the UP resin VP3830, the mixture was stirred with a KPG stirrer until a homogeneous liquid was obtained and then cooled to room temperature.
  • the fiber-reinforced plastic was produced from the resin formulation thus prepared and the flax fiber semi-finished product in a manner analogous to the production method described in Example 2, whereby the resin formulation was cured for 2 hours at 80 °C and then for a further 2 hours at 120 °C.
  • the changed curing conditions for resin formulations according to the invention and not according to the invention are due to the fact that the advantageously short curing times for the resin formulation prepared in Example 1 cannot be used for the commercial UP resin, but instead longer curing times at lower temperatures are required for the curing of the commercial UP resin.
  • the resin formulation according to the invention according to Example 1 has significantly lower shrinkage during curing compared to the non-inventive resin formulation according to Example 2.
  • the reduced shrinkage together with the shorter curing time of resin formulations according to the invention represents a significant advantage in the industrial manufacturing process.
  • Example 4 mechanical properties of the fiber-reinforced plastics produced in Examples 2 and 3 Samples were cut from the fiber-reinforced plastics manufactured according to examples 2 and 3 to determine the modulus of elasticity, tensile strength and elongation at break. The cut sample pieces were first dried for 15 hours at 30 °C to remove any humidity absorbed during cutting and then tested in an air-conditioned test laboratory (52% humidity, 23 °C). The determination of modulus of elasticity, tensile strength and elongation at break was carried out in accordance with DIN EN ISO 527-4.
  • the results of the investigations are shown in Fig. 1 to Fig. 3.
  • the results show that the mechanical properties of the fiber-reinforced plastic produced using the resin formulation according to the invention comprising itaconic acid-modified polylactide as resin and styrene as copolymerizable monomer (designated in the figures with sample number 3) and the fiber-reinforced plastic produced using the commercially available UP resin VP3830 (designated in the figures with sample number 1) are in a similar range of values, with the fiber-reinforced plastic according to the invention having a higher tensile strength and a higher elongation at break in comparison.
  • Example 5 Investigation of the biodegradability and compostability of the fiber-reinforced plastics produced in Examples 2 and 3
  • thermosetting plastics were cured at 80 °C for 4 hours and for a further 2 hours at 120 °C in a mold with a pressure of 90 kN and the modulus of elasticity, tensile strength and elongation at break of the resulting thermosetting plastics were determined in accordance with DIN EN ISO 527-4.
  • a non-inventive resin formulation according to Example 3 was also produced, for which a mixture of styrene and dimethyl itaconate was also used as copolymerizable monomers or reactive diluents.
  • the comparison sample was cured at 80 °C for 2 h and for a further 2 h at 120 °C in a mold with a pressure of 90 kN and the modulus of elasticity, tensile strength and elongation at break of the thermosetting plastic obtained from this resin formulation were determined in accordance with DIN EN ISO 527-4.
  • a resin was first produced by polymerizing a mixture comprising L-lactic acid and itaconic acid.
  • a glass apparatus consisting of a distillation bridge and two glass flasks connected to a diaphragm pump was used as the reactor. The heating rates were adjusted using a hotplate and a thermocouple. Water was formed as a byproduct of the esterification. This was permanently removed during the reaction using vacuum distillation.
  • Example 9 of US 2008/0004369 A1 The test procedure according to Example 9 of US 2008/0004369 A1 was only deviated from insofar as the pressure specified in Example 1 of US 2008/0004369 A1 was used for the test (since Example 9 could not otherwise be reproduced).
  • the pressure was applied to a diaphragm pump according to Example 1 of US 2008/0004369 A1.
  • the resin obtained differs in particular from the at least one resin used in resin formulations according to the invention in that the resin obtained here Resin was not obtained by reaction (modification) of a biodegradable and/or compostable polymer with one or more modifiers, but the modifier (itaconic acid) was added to the monomer (L-lactic acid) for the production of the polymer before the start of polymerization and the polymerization of the monomer took place directly in the presence of the modifier.
  • Processing the resin proved to be cumbersome, as mixing the resin with methacrylic anhydride or styrene required heating the resin to at least 130 °C. Below 130 °C, the resin was not sufficiently fluid for processing and demixing was observed when attempting to mix it with copolymerizable monomer.
  • thermosetting plastic from the resin and methacrylic anhydride was only possible by adding the methacrylic anhydride directly together with the initiator methyl ethyl ketone peroxide (MEKP, 2 wt. %) to the resin after heating it to a temperature of 130 °C.
  • MEKP initiator methyl ethyl ketone peroxide
  • the pot life for the resin formulation in this case was less than 2 minutes, which made processing even more difficult.
  • the resin formulation was immediately filled into a mold and cured for 3 hours at 160 °C.
  • the resin was first heated to 130 °C and then mixed homogeneously with 30 wt.% styrene (based on the total mass). The resulting mixture was then cooled to room temperature, leaving a viscous mixture.
  • the necessary heating of the resin to 130 °C for mixing with styrene made processing extremely complicated, as styrene has a high vapor pressure and a boiling point of 145 °C, and therefore a large amount of styrene evaporated when the resin and styrene were mixed (for comparison: to mix the polylactide modified with itaconic acid with styrene according to Example 1 above, a temperature of only 80 °C is required).
  • methyl ethyl ketone peroxide (MEKP, 2% by weight) was also added to the mixture of resin and styrene as an initiator and the mixture was then cured at 120 °C for 30 minutes.
  • Example 8 Investigation of the mechanical properties and biodegradability or compostability of thermosetting plastics according to the invention and not according to the invention
  • thermosetting plastics The mechanical properties as well as the biodegradability or compostability of the following “pure” (i.e. not containing any reinforcing fibers) thermosetting plastics were investigated:
  • thermosetting plastic according to the invention prepared from the resin formulation described in Example 1 above (according to the invention) comprising itaconic acid modified polylactide as resin and styrene as copolymerizable monomer using the curing conditions explained in Example 2 above;
  • thermosetting plastic prepared from the resin formulation described in Example 3 above (non-inventive) comprising the commercially available UP resin VP3830 from Schill and Seilacher Struktol GmbH as resin and styrene as copolymerizable monomer using the curing conditions explained in Example 3 above;
  • thermosetting plastic not according to the invention prepared in Example 7 using styrene as copolymerizable monomer.
  • the mechanical properties were investigated by determining the modulus of elasticity, tensile strength and elongation at break according to DIN EN ISO 527-4, as explained in more detail in Example 4 above.
  • the biodegradability and compostability were investigated based on decomposition studies under simulated composting conditions according to DIN EN ISO 20200:2015, as explained in more detail in Example 5 above.
  • thermosetting plastic produced in Example 7 using methacrylic anhydride as the copolymerizable monomer no defect-free, standard-compliant test specimens could be produced due to the short pot life.
  • a determination of the E-modulus, tensile strength and elongation at break according to DIN EN ISO 527-4 was therefore not possible for this plastic.
  • the values for the E-modulus, tensile strength and elongation at break for the other thermosetting plastics examined are shown in Fig. 5 to Fig. 7. In Fig. 5 to Fig.
  • thermosetting plastic produced from the resin formulation comprising the commercially available UP resin VP3830 as the resin and styrene as the copolymerizable monomer is designated with the sample number "1"; the thermosetting plastic produced from the resin formulation comprising itaconic acid-modified polylactide as the resin and styrene as the copolymerizable monomer is designated with the sample number "3"; and the thermosetting plastic prepared in Example 7 using styrene as a copolymerizable monomer is designated with the sample number “5”.
  • thermosetting plastic according to the invention produced from the resin formulation comprising itaconic acid-modified polylactide as resin and styrene as copolymerizable monomer, has excellent mechanical properties and, in comparison to the other materials tested, has a significantly higher modulus of elasticity and a significantly higher tensile strength, and its elongation at break is comparable to that of the thermosetting plastic produced in Example 7 using styrene as copolymerizable monomer.
  • thermosetting plastic according to the invention produced from the resin formulation comprising itaconic acid-modified polylactide as resin and styrene as copolymerizable monomer, decomposes completely within 10 days, so that residual pieces of it can no longer be found in the compost. Complete decomposition within 10 days can also be observed for the thermosetting plastic not according to the invention produced in Example 7 using methacrylic anhydride as copolymerizable monomer.
  • thermosetting plastic produced from the resin formulation comprising the commercially available UP resin VP3830 as resin and styrene as copolymerizable monomer, as well as for the non-inventive thermosetting plastic produced in Example 7 using styrene as copolymerizable monomer, no perceptible decomposition can be detected even after 40 days under composting conditions.
  • thermosetting plastics and fiber-reinforced plastics be obtained that are characterized by both high mechanical strength and good biodegradability and grain postability.
  • the resin formulation according to the invention shows good biodegradability and grain postability despite the use of styrene as a copolymerizable monomer.
  • the resin formulation according to the invention is also characterized by short curing times and easy processing at low temperatures.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une formulation de résine pour la fabrication d'une matière plastique thermodurcissable. L'invention concerne également une matière plastique thermodurcissable. L'invention concerne en outre l'utilisation d'une formulation de résine selon l'invention et/ou d'une matière plastique thermodurcissable selon l'invention. L'invention concerne en outre un matériau composite comprenant une matière plastique thermodurcissable selon l'invention en tant que matrice polymère.
PCT/EP2024/056777 2023-03-30 2024-03-14 Formulation de résine pour la production d'une matière plastique thermodurcissable, matière plastique thermodurcissable et matériau composite correspondants Ceased WO2024200021A1 (fr)

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EP24712201.3A EP4688907A1 (fr) 2023-03-30 2024-03-14 Formulation de résine pour la production d'une matière plastique thermodurcissable, matière plastique thermodurcissable et matériau composite correspondants

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DE102023108198.5A DE102023108198A1 (de) 2023-03-30 2023-03-30 Harzformulierung zur Herstellung eines duromeren Kunststoffes, entsprechender duromerer Kunststoff und Verbundwerkstoff
DE102023108198.5 2023-03-30

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080004369A1 (en) 2004-11-17 2008-01-03 Jukka Seppala Crosslinkable Biopolymer

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080004369A1 (en) 2004-11-17 2008-01-03 Jukka Seppala Crosslinkable Biopolymer

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
NIMA ESMAEILI: "Synthesis and characterization of methacrylated star-shaped poly(lactic acid) employing core molecules with different hydroxyl groups", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 134, no. 39, 15 October 2017 (2017-10-15), US, XP093162301, ISSN: 0021-8995, Retrieved from the Internet <URL:https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fapp.45341> [retrieved on 20240514], DOI: 10.1002/app.45341 *
SHAOKUN CHANG ET AL: "Synthesis of polylactide-based thermoset resin and its curing kinetics", POLYMER INTERNATIONAL, vol. 61, no. 10, 10 October 2012 (2012-10-10), GB, pages 1492 - 1502, XP055349137, ISSN: 0959-8103, DOI: 10.1002/pi.4233 *
ZENGHUI DAI: "Fully Biobased Composites of an Itaconic Acid Derived Unsaturated Polyester Reinforced with Cotton Fabrics", ACS SUSTAINABLE CHEMISTRY & ENGINEERING, vol. 6, no. 11, 26 September 2018 (2018-09-26), US, pages 15056 - 15063, XP093162303, ISSN: 2168-0485, DOI: 10.1021/acssuschemeng.8b03539 *

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