Thermosetting bio-based casting material, molded body produced therefrom and method for producing such a molded body

Abstract

A thermosetting bio-based casting material comprises: (a) a mixture of several monofunctional acrylic monomers and / or methacrylic monomers, wherein one or more monomers are derived from recycled materials and one or more monomers are monomers of plant or animal origin, (b) one or more multifunctional acrylic bio-monomers and / or methacrylic bio-monomers of plant or animal origin, (c) one or more polymers or copolymers selected from polyacrylates, polymethacrylates, polyols, and polyesters derived from recycled materials or plant or animal origin, (d) inorganic filler particles of natural origin, wherein the proportion of the monofunctional acrylic monomers and / or methacrylic monomers and the multifunctional acrylic bio-monomers and / or methacrylic bio-monomers is 10-40wt%, the proportion of the polymers or copolymers is 1-16wt%, and the proportion of the inorganic filler particles is 44-89wt%.

Description

Technical Field

[0001] The invention relates to a thermosetting bio-based castable suitable for producing a molded body consisting of a polymer matrix formed by a polymeric castable in which filler particles are embedded. The invention also relates to a molded body produced from said castable, in the form of, for example, a kitchen sink, a washstand, a worktop, a bathtub or shower tray or a worktop, wherein the polymeric castable forms a biocomposite material, the composition of which is a polymer matrix in which filler particles are embedded.

[0002] The specific manufacturing method of the biocomposite material of the present invention or the molded body of the present invention is: first, the inorganic filler particles are dispersed in at least one bio(co)polymer and / or recycled (co)polymer solution in a mixture composed of recycled and bio-based monofunctional and multifunctional monomers to make the castable of the present invention, and then the castable is injected into the mold to fill the casting mold cavity, and the material is fixed according to the shape of the cavity by thermally induced polymerization of monofunctional biomonomers and multifunctional biomonomers with the help of heat. Background Art

[0003] It is known to manufacture kitchen sinks using, for example, polymeric casting compounds. Such kitchen sinks therefore have a polymer matrix in which filler particles are embedded in order to achieve the desired properties. The casting compound can be manufactured using suitable crosslinkable polymers, polymers of petrochemical origin, i.e. based on petroleum, being used. Kitchen sinks manufactured in this way have very good mechanical properties and are thermally stable over a wide temperature range. Nevertheless, the use of such polymers is disadvantageous, in particular for reasons of sustainability (environmental protection and conservation of resources). Summary of the invention

[0004] Therefore, based on the above problems, the present invention provides an improved casting material.

[0005] To solve the above problems, the present invention provides a thermosetting bio-based castable, comprising:

[0006] (a) a mixture of monofunctional acrylic and / or methacrylic monomers, one or more of which are made from recycled materials and one or more of which are of plant or animal origin,

[0007] (b) one or more polyfunctional acrylic bio-monomers and / or methacrylic bio-monomers of plant or animal origin,

[0008] (c) one or more polymers or copolymers selected from polyacrylates, polymethacrylates, polyols, polyesters derived from recycled materials or from vegetable or animal sources,

[0009] (d) inorganic filler particles of natural origin,

[0010] The ratio of the monofunctional acrylic monomer and / or methacrylic monomer and the multifunctional acrylic bio-monomer and / or methacrylic bio-monomer is 10-40 wt %, the ratio of the polymer or copolymer is 1-16 wt %, and the ratio of the inorganic filler particles is 44-89 wt %.

[0011] The casting material according to the invention is characterized in that, in particular with regard to the crosslinking substances used, the casting material consists predominantly of biomaterials or natural materials. According to the invention, a mixture of different monofunctional monomers is used. According to the invention, the mixture of monofunctional acrylic and methacrylic monomers used consists partly of recycled materials and partly of monomers of plant or animal origin, wherein at least one monomer originates from recycled materials and at least one monomer is bio-based, i.e. of plant or animal origin. That is, apart from the recycled components, polymers obtained in a petrochemical manner are hardly used in this context, but the recycled components also consist of recycled bio-based materials as appropriate. In any case, no new materials based on petrochemicals are used within the scope of the recycled monofunctional monomer components. Only monomers of plant or animal origin are used as polyfunctional monomers. Whenever monomers of plant or animal origin are used, whether monofunctional or polyfunctional, they can be referred to as "biomonomers", wherein biomonomers are monomers of biopolymers. The term "polyfunctional" includes difunctional, trifunctional and more highly functional biomonomers.

[0012] The polymer or copolymer used is preferably also of pure plant or animal origin, that is, these substances are not of petrochemical origin. However, as an alternative to the use of substances of plant / animal origin, polymers or copolymers composed of recycled materials can also be used in this article. Although most of these materials are of petrochemical origin, new materials are not used, but existing, recycled materials are reused, which is also beneficial from an environmental point of view. By using biomonomers and recycled materials, the petrochemical-based substances used so far are completely replaced with sustainable materials in the casting material of the present invention, even in the adhesive. Of course, it is preferred to use polymers or copolymers of pure plant or animal origin, so in this case, in addition to the recycled monofunctional monomer components, a casting material composed entirely of natural materials is obtained, because as mentioned above, the filler is also purely of natural origin. Therefore, the molded body made of the casting material of the present invention is a biological molded body, which is mainly composed of biological materials, i.e. natural materials. By producing biocomposites or biocomposites with filler particles and crosslinking materials from renewable resources, the consumption of materials produced by petrochemical means and thus of oil is reduced, thus having a positive impact on the environment.

[0013] In this document, the monofunctional acrylic biomonomer and / or methacrylic biomonomer of plant or animal origin, the multifunctional acrylic biomonomer and / or methacrylic biomonomer of plant or animal origin, and the biobased polymer or copolymer selected from polyacrylate, polymethacrylate, polyol, polyester of plant or animal origin refer to substances according to IUPAC Recommendations 2012, Pure Appl. Chem. Vol. 84, No. 2, pp. 377-410, 2012, "Terminology for biorelated polymers and applications (IUPAC Recommendations 2012)" (http: / / publications.iupac.org / pac / pdf / 2012 / pdf / 8402x0377.pdf), whereby, according to the definition on page 381, the term "biobased" is defined as "composed or derived in whole or in part of biological products issued from the biomass (including plant, animal, and marine or forestry The term "materials" refers to "materials" (composed entirely or partly of or derived from biological products produced from biomass (including plant, animal and marine or forest materials)), i.e. the use of bio-based (plant or animal) primary products or starting materials also enables the production of corresponding bio-based, i.e. plant or animal-derived monomers or polymers or copolymers.

[0014] Despite the use of predominantly natural materials for the production of castings or moldings, i.e., for example, kitchen sinks, these moldings surprisingly exhibit very good mechanical properties, which in some cases are even superior to known castings or moldings produced using cross-linked materials obtained in a petrochemical manner, in particular with regard to impact resistance or scratch resistance.

[0015] By using high-quality monofunctional and multifunctional bio-acrylate and bio-methacrylate monomers to produce biocomposite molded parts such as kitchen sinks, washstands, bathtubs, shower trays and worktops, it is possible to combine high technical performance requirements with a high Bio Renewable Carbon Content (BRC) in the product. A large number of different bio-based resources are available for the production of monofunctional and multifunctional bio-acrylate and bio-methacrylate monomers, such as vegetable oils, animal fats, wood. The BRC in the bio-monomers can reach up to 90%.

[0016] The molded body produced from the biocomposite material consists of a mixture of inorganic fillers which are embedded in a polymer matrix by a crosslinking polymerization process of the monofunctional and polyfunctional monomers and achieves a greater sustainability effect due to the use of renewable raw materials.

[0017] According to the present invention, the weight ratio of the monofunctional monomer to the polyfunctional monomer should be 2:1 to 80:1, preferably 4:1 to 70:1, and particularly 5:1 to 60:1.

[0018] The monofunctional monomers used may be in the form of recycled acrylates or bio-based acrylates from plant or animal sources. They may be selected from: n-butyl acrylate, methyl acrylate, ethyl acrylate, tert-butyl acrylate, isobutyl acrylate, isodecyl acrylate, dihydrodicyclopentadienyl acrylate, ethyl diethylene glycol acrylate, heptadecanyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, hydroxyethyl caprolactone acrylate, polycaprolactone acrylate, hydroxypropyl acrylate, dodecyl acrylate, octadecyl acrylate, tert-butyl acrylate, 2(2-ethoxy)ethyl acrylate, tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, ethoxylated 4-phenyl acrylate, trimethylcyclohexyl acrylate, octyldecyl acrylate, tridecyl acrylate, ethoxylated 4-nonylphenol acrylate, isobornyl acrylate, cyclotrimethylolpropane formal acrylate, ethoxylated 4-dodecyl acrylate, polyester acrylate, octadecyl acrylate, hyperbranched polyester acrylate, melamine acrylate, silicone acrylate, epoxy acrylate.

[0019] In addition, the monofunctional monomers used may be in the form of recycled methacrylates or bio-based methacrylates of plant or animal origin. They may be selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, behenyl methacrylate, vinyl polyethylene glycol methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, octadecyl polyethylene glycol methacrylate, isotridecyl methacrylate, ureido methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, 3,3,5-trimethylcyclohexanol methacrylate, isobornyl methacrylate, methoxypolyethylene glycol methacrylate, glycidyl methacrylate, hexylethyl methacrylate, glycerol formal methacrylate, dodecyltetradecyl methacrylate, C17,4-methacrylate.

[0020] The multifunctional biomonomers used may be in the form of bio-based acrylates, i.e. acrylates of plant or animal origin. They may be selected from: 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, polybutadiene diacrylate, 3-methyl-1,5-pentanediol diacrylate, ethoxylated bisphenol A-diacrylate, dipropylene glycol diacrylate, ethoxylated hexanediol diacrylate, 1,10-decanediol diacrylate, ester diol diacrylate, alkoxylated diacrylate, tricyclodecane dimethanol diacrylate, propoxylated neopentyl glycol diacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, dimethoxy ... - trimethylolpropane tetraacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, dipentaerythritol pentaacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated glyceryl triacrylate, aliphatic polyurethane diacrylate, aliphatic polyurethane hexaacrylate, aliphatic polyurethane triacrylate, aromatic polyurethane diacrylate, aromatic polyurethane triacrylate, aromatic polyurethane hexaacrylate, polyester hexaacrylate, epoxidized soybean oil diacrylate.

[0021] In addition, the multifunctional bio-monomers used can be in the form of bio-based methacrylates, i.e. methacrylates of plant or animal origin. They can be selected from: triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,10-decanediol dimethacrylate, 1,3-butanediol dimethacrylate, ethoxylated bisphenol A dimethacrylate, tricyclodecane dimethanol dimethacrylate, trimethylolpropane trimethacrylate.

[0022] According to the invention, the weight ratio of monofunctional or polyfunctional acrylate and / or methacrylate to polymer or copolymer, in particular selected from polyacrylates, polymethacrylates, polyols or polyesters, should be 90:10 to 60:40, preferably 85:15 to 70:30.

[0023] The inorganic filler particles are also of natural origin, i.e. biological origin, rather than synthetically produced. These inorganic filler particles can be selected from SiO2, Al2O3, TiO2, ZrO2, Fe2O3, ZnO, Cr2O5, carbon, metals or metal alloys, wherein a mixture of two or more different filler particle types can also be used. The mixing ratio can be arbitrary.

[0024] The inorganic filler particles should have a particle size of 0.010 to 8000 μm, preferably 0.05 to 3000 μm, and particularly 0.1 to 1300 μm. In addition, the inorganic filler particles should have an aspect ratio (length:width of a single particle) of 1.0 to 1000.

[0025] For ease of processing, the viscosity of the resulting casting compound should be adjusted in such a way that it can be injected into the mold under pressure by means of a suitable injection device in such a way that the cavity of the mold is completely filled.

[0026] In addition to the casting compound, the invention also relates to a molded body produced from the casting compound according to the invention. Since the casting compound contains biomonomers, biopolymers and biocopolymers, the molded body is a biocomposite body, ie, for example, a biocomposite kitchen sink or the like.

[0027] Different molded body types can be produced therein. Accordingly, the molded body can be a kitchen sink, a shower tray, a washstand, a bathtub, a worktop, or a floor panel, a wall panel or a ceiling panel, wherein this is not an exhaustive list.

[0028] As already mentioned, it has been shown that despite the use of bio-based starting materials (which constitute the casting compound), the obtained molded bodies still have very good properties, in particular mechanical properties. The polymeric biocomposite material of the molded body should have a molecular weight of 2 to 5 mJ / mm 2 Impact strength and thermal stability from -30 to 300°C.

[0029] One of the aforementioned advantages of the present invention is that by using one, two or more monofunctional bio-monomers, the thermal, mechanical and surface properties of the final product, i.e. the finished molded body, can be changed according to the product requirements. For example, the impact resistance can be improved by adding bio-dodecyl methacrylate monomer having good flexibility.

[0030] The concentration of bio-dodecyl methacrylate in the biocomposite is preferably about 0.5 to about 10 wt %, in particular 0.7 to 5.0 wt %. It has been found that small amounts of flexible bio-dodecyl methacrylate can improve impact resistance.

[0031] Another aforementioned advantage of the present invention is that the heat resistance of the finished molded body can be improved, for example, by adding bioisobornyl methacrylate monomers having a higher thermal stability.

[0032] The concentration of isobornyl biomethacrylate in the biocomposite is preferably about 1.0 to about 20 wt %, in particular 2.0 to 17.0 wt %. It has been found that small amounts of isobornyl biomethacrylate can improve scratch resistance.

[0033] Another advantage of the present invention is that, for example, by adding isobornyl bioacrylate monomers with improved weather resistance, aging resistance can be improved. The concentration of isobornyl bioacrylate in the biocomposite is preferably about 1.0 to about 10 wt%, especially 2.0 to 7.0 wt%. It has been found that small amounts of isobornyl bioacrylate can improve aging resistance.

[0034] Another advantage of the present invention is that chemical resistance is improved, for example, by adding a bio(1,10-decanediol diacrylate) bifunctional monomer. The concentration of bio(1,10-decanediol diacrylate) in the biocomposite is preferably about 0.15 to about 10 wt%, in particular 0.3 to 5.0 wt%. It has been found that small amounts of bio(1,10-decanediol diacrylate) can improve chemical resistance.

[0035] Another advantage of the present invention is that, for example, by adding the trifunctional monomer bio(propoxylated (3) glyceryl triacrylate), filler dispersion is improved due to excellent filler wetting. The concentration of bio(propoxylated (3) glyceryl triacrylate) in the biocomposite is preferably about 0.1 to about 5 wt %, in particular 0.3 to 2.0 wt %. It has been found that small amounts of bio(propoxylated (3) glyceryl triacrylate) can improve the distribution of fillers in the matrix and improve thermal and mechanical properties.

[0036] Another advantage of the present invention is that the wear resistance of the biocomposite of the shaped body can be improved, for example, by adding a biopolyethylene glycol dimethacrylate bifunctional monomer having a higher wear resistance. The concentration of the biopolyethylene glycol dimethacrylate in the biocomposite is preferably about 0.1 to about 10 wt %, in particular 0.3 to 5.0 wt %. It has been found that a small amount of biopolyethylene glycol dimethacrylate can improve the wear resistance.

[0037] Another advantage of the present invention is that the scratch resistance of the molded body can be improved by adding a bio-dipentaerythritol pentaacrylate multifunctional monomer having a higher scratch resistance. The concentration of the bio-dipentaerythritol pentaacrylate in the biocomposite is preferably about 0.1 to about 7 wt %, in particular 0.3 to 5.0 wt %. It has been found that a small amount of bio-dipentaerythritol pentaacrylate can improve the scratch resistance.

[0038] The inorganic fillers used can be in the form of: SiO2, specifically in the form of quartz particles, cristobalite particles, pyrolytic silica, aerated silica, silica fibers, silica filaments, silicate particles (such as layered silicates); Al2O3 particles, TiO2 particles, Fe2O3 particles, ZnO particles, Cr2O5 particles, carbon black particles, carbon nanotube particles, graphite particles or graphene particles.

[0039] To achieve an excellent stable dispersion of the inorganic filler in the polymer matrix, the monomer mixture may contain a combination of bio-based components of polymers and / or copolymers derived from recycled or bio-based resources in order to achieve a suitable viscosity.

[0040] The invention also relates to a method for producing a molded body of the aforementioned type, wherein a casting material of the type also mentioned above is used, which is introduced into a mold and polymerized in the mold at a temperature higher than room temperature, and the polymerized molded body is subsequently demolded and cooled.

[0041] The temperature during the polymerization should be between 60-140°C, preferably between 75-130°C, and in particular between 80-110°C.

[0042] Furthermore, the retention time of the casting compound in the mold for polymerization should be between 15-50 min, preferably between 20-45 min, in particular between 25-35 min.

[0043] The production of molded bodies from the thermosetting bio-based castable is a multi-stage process comprising the following stages:

[0044] - manufacturing a polymer matrix component;

[0045] - Dispersing the inorganic filler in the polymer matrix;

[0046] -Cross-linking polymerization of kitchen sinks, washbasins, bathtubs, countertops. DETAILED DESCRIPTION

[0047] Several test examples are given below to illustrate the casting material according to the invention, the molding according to the invention and the method according to the invention in detail.

[0048] Example 1:

[0049] Fabrication of polymer matrix components using different monofunctional monomers

[0050] Components used:

[0051] (a) Monofunctional monomers:

[0052] Monofunctional bio-based monomers:

[0053] Isobornyl methacrylate (IBOMA, Evonik Performance Materials GmbH), dodecyl methacrylate (LMA, Arkema France), isobornyl acrylate (IBOA; Miwon Specialty Chemical Co., Ltd), ethyl methacrylate (BCH Brühl Chemikalien Handel GmbH)

[0054] These components are derived from plant or animal sources, e.g. Terra IBOMA is made from pine resin.

[0055] Monofunctional recycled monomers:

[0056] Monofunctional recycled methacrylate monomer (rec.-MMA, Monómeros del Vallés, SL)

[0057] (b) Multifunctional monomers:

[0058] 1,10-(Decanediol diacrylate)(Arkema France)

[0059] (c) Polymer:

[0060] Acrylic glass fine grinding XP 85 (recycled PMMA, Kunststoff-und Farben-GmbH) and Aqualon EC-N100 0100 (bio-based ethylcellulose, Ashland Industrie Deutschland GmbH)

[0061] (d) Filling:

[0062] SiO2 [80% quartz, particle size 0.06–0.3 mm (Dorfner GmbH); 20% quartz powder, particle size 0.1–0.70 μm (Quarzwerke GmbH) and TiO2 particles (Crystal International BV)

[0063] (e) Additives:

[0064] Bio-based dispersing additive (0.1%) (BYK Chemie GmbH) and thixotropic additive (0.1%) (BYKChemie GmbH)

[0065] The composition for producing the polymer matrix was prepared by dissolving acrylic glass fine grind XP 85 (recycled PMMA, Kunststoff-und Farben-GmbH) and Aqualon EC-N100 0100 (bio-based ethylcellulose as biopolymer, Ashland Industrie Deutschland GmbH) in a mixture consisting of the monofunctional monomers in Table 1: isobornyl methacrylate (Evonik Performance Materials GmbH), dodecyl methacrylate (LMA, Arkema France), isobornyl acrylate (Miwon Specialty Chemical Co., Ltd), ethyl methacrylate (BCH Brühl Chemikalien Handel GmbH). The reaction mixture was heated to 40° C. to accelerate the dissolution for 100 min until a clear solution was obtained. For comparison of the matrix components, the compositions were prepared and summarized in Table 1:

[0066] Table 1:

[0067] Monofunctional monomer Sample 1 Sample 2 Sample 3 Recycled Methyl Methacrylate 62 50 35 Dodecyl Methacrylate 38 38 Isobornyl acrylate 28 Isobornyl Methacrylate 0 12 12 Ethyl Methacrylate 25

[0068] All samples in Table 1 were used as solvents with acrylic glass fine grind XP 85 and Aqualon EC-N100 011 (95:5) in a ratio of 80:20 to increase the viscosity of the reaction mass (from 120 to 155 cPs, Brookfield Viscometer DVI Prime), followed by the addition of 20 wt% of Bio(1,10-decanediol diacrylate) (Arkema France).

[0069] The clear solution in the mixture of acrylic glass fine grind XP85 and Aqualon EC-N100 011 with addition of bio (1,10-DDDA) in samples 1-3 was used to disperse an inorganic filler mixture (70 wt%), which contained 95 wt% SiO2 [80% quartz, particle size 0.06-0.3 mm (Dorfner GmbH), 20% quartz powder, particle size 0.1-0.70 μm (Quarzwerke GmbH)] and 5% TiO2 particles (Crystal International BV). In addition, a bio-based dispersing additive (0.1%) (BYK Chemie) and a thixotropic additive (0.1%) (BYK Chemie GmbH) were added. The castable produced in this way was stirred for 20 minutes (Dispermat AE-3M, VMA-Getzmann GmbH). The casting compound was used to produce a molded body in the form of a kitchen sink by injecting the casting compound into a mold and polymerizing it at 110° C. for 35 minutes.

[0070] Mechanical and thermal properties of kitchen sinks made from samples 1–3.

[0071] Table 2:

[0072] characteristic Sample 1 Sample 2 Sample 3 Compare Sinks <![CDATA[Impact resistance mJ / mm 2 > 3.2 2.7 2.9 2.3 Scratch resistance + + + + Taber wear, μg 10 15 14 12 Thermal resistance* + + + + Temperature resistance** + + + +

[0073] To measure the impact resistance, 12 test specimens with the dimensions 80 x 6 mm were cut from the water tank. The measurements were carried out on a ZwickRoell HIT P apparatus.

[0074] To measure the scratch resistance, a specimen (100 x 100 mm) was cut out and the surface topography before and after scratching was measured (Mitutoyo Surftest SJ 500P).

[0075] For the Taber abrasion test, a specimen (100 x 100 mm) was cut out and the abrasion test was carried out on an Elcometer 1720.

[0076] *The method is based on the test specification DIN EN 13310, in which the test object is placed in the center of the kitchen sink at a temperature of 180° C. for 20 minutes without leaving any visible changes on the surface of the sink.

[0077] **The method is based on the test specification DIN EN 13310, in which the sink is treated with 1000 cold-hot water cycles. Hot water (T=90°C) flows into the sink for 90 seconds, followed by a pause of 30 seconds, and then cold water (T=15°C) flows in for the next 90 seconds. This cycle is terminated by a pause of 30 seconds.

[0078] The composite material used for the comparison sink was produced according to patent application DE 38 32 351 A1 using organic compounds of petrochemical origin.

[0079] As shown in the table, the measured properties of all test examples are at least comparable to the properties of known comparative sinks composed of non-biobased components (regarding monomers and polymers), and in most cases even superior to the comparative sinks. For samples 1-3, in particular, the impact resistance is partially significantly improved.

[0080] Example 2:

[0081] Fabrication of polymer matrix components using different multifunctional monomers

[0082] Components used:

[0083] (a) Monofunctional monomers:

[0084] Recycled MMA and bio-based LMA, ratio 62:38 (recycled methacrylate monomer (rec.-MMA, Monómeros del Vallés, SL) and lauryl methacrylate (LMA, Arkema France) acting as bio-monomer)

[0085] (b) Multifunctional monomers:

[0086] 1,10-(Decanediol diacrylate), propoxylated (3) glycerol triacrylate (Arkema France), polyethylene glycol dimethacrylate (Arkema France) and epoxidized soybean oil diacrylate (Miwon Specialty Chemical Co., Ltd)

[0087] (c) Polymer:

[0088] Acrylic glass fine grinding XP 85 (recycled PMMA (Kunststoff- und Farben GmbH) and Aqualon EC-N100 0100 (ethyl cellulose, Ashland Industrie Deutschland GmbH)

[0089] (d) Filling:

[0090] SiO2 [80% quartz, particle size 0.06–0.3 mm (Dorfner GmbH); 20% quartz powder, particle size 0.1–0.70 μm (Quarzwerke GmbH) and TiO2 particles (Crystal International BV)

[0091] (e) Additives:

[0092] Bio-based dispersing additive (0.1%) (BYK Chemie GmbH) and thixotropic additive (0.1%) (BYKChemie GmbH)

[0093] The composition for producing the polymer matrix was prepared by dissolving acrylic glass fine grind XP 85 (recycled PMMA (Kunststoff- und Farben GmbH) and Aqualon EC-N100 0100 (ethyl cellulose, Ashland Industrie Deutschland GmbH) in a mixture of the monofunctional monomers of recycled MMA and LMA in a ratio of 62:38. The reaction mixture was heated to 40°C for 150 min to accelerate the dissolution, and then the multifunctional monomers: 1,10DDDA, propoxylated (3) glyceryl triacrylate (Arkema France), polyethylene glycol dimethacrylate (PEG-DMA, Arkema France), epoxidized soybean oil diacrylate (Miwon Specialty Chemical Co., Ltd) were added to obtain the composition for forming the polymer matrix. In order to compare the matrix components, compositions were prepared with different multifunctional monomers and are summarized in Table 3. The concentration of the multifunctional monomer is given in wt% relative to the amount of the monofunctional monomer:

[0094] Table 3:

[0095] Multifunctional Biomonomers Sample 4 Sample 5 Sample 6 1.10-Decanediol diacrylate 14 Propoxylated(3)glyceryl triacrylate 14 5 Polyethylene glycol dimethacrylate 10 10 Epoxidized soybean oil diacrylate 5

[0096] Mechanical and thermal properties of kitchen sinks made from samples 4–6

[0097] Table 4:

[0098] characteristic Sample 4 Sample 5 Sample 6 Compare Sinks <![CDATA[Impact resistance mJ / mm 2 > 3.1 3.5 2.8 2.3 Scratch resistance + + + + Taber wear, μg 15 11 18 12 Thermal resistance* + + + + Temperature resistance** + + + +

[0099] As shown by the measured values ​​in Table 4, in these test examples, the molded bodies also partially exhibit significantly improved mechanical properties, especially in terms of impact resistance and scratch resistance. That is, by using bio-based starting materials, not only beneficial improvements from an environmental point of view are achieved, but also improvements in the mechanical properties of the molded bodies in particular are achieved.

[0100] Example 3:

[0101] Fabrication of polymer matrix components using different recycled polymers or biopolymers

[0102] Components used:

[0103] (a) Monofunctional monomers:

[0104] Recycled MMA and bio-based LMA, ratio 62:38 (recycled methacrylate monomer (rec. MMA, Monómeros del Vallés, SL) and dodecyl methacrylate (LMA, Arkema France))

[0105] Multifunctional biomonomers:

[0106] Bio(1,10-decanediol diacrylate) (Arkema France) and propoxylated(3)glyceryl triacrylate (Arkema France), ratio 14:14.

[0107] (b) Polymer:

[0108] Recycled polymers and biopolymers and biocopolymers: recycled PMMA (Kunststoff-undFarben-GmbH), castor oil polymer (DOG Deutsche Oelfabrik Ges.f.chem.Erz.mbH&Co.KG)

[0109] (d) Filling:

[0110] SiO2 [80% quartz, particle size 0.06–0.3 mm (Dorfner GmbH); 20% quartz powder, particle size 0.1–0.70 μm (Quarzwerke GmbH) and TiO2 particles (Crystal International BV)

[0111] (e) Additives:

[0112] Bio-based dispersing additives (0.1%) (BYK Chemie) and thixotropic additives (0.1%) (BYK Chemie)

[0113] The composition for producing the polymer matrix was produced by dissolving recycled polymers and / or biopolymers and / or biocopolymers (recycled PMMA (Kunststoff-und Farben-GmbH), castor oil polymer (DOG Deutsche Oelfabrik Ges.f.chem.Erz.mbH & Co.KG)) in a mixture of the monofunctional monomers rec.MMA and LMA in a ratio of 68:32. The reaction mixture was heated to 40°C for 100 min to accelerate the dissolution, and then bio(1,10-decanediol diacrylate) (Arkema France) and propoxylated (3) glycerol triacrylate (Arkema France) were added in a ratio of 14:14 to obtain a composition for forming the polymer matrix. For comparison of the matrix components, compositions were produced with different recycled polymers and biopolymers and are summarized in Table 5. The concentration of the biopolymer is given in wt% relative to the amount of monofunctional monomers:

[0114] Table 5:

[0115] polymer Sample 7 Recycling PMMA 19 Castor Oil Polymer 5

[0116] A kitchen sink was manufactured as described in Example 1.

[0117] Mechanical and thermal properties of the kitchen sink made from Sample 7.

[0118] Table 6:

[0119]

[0120]

Claims

1. A thermosetting bio-based castable comprising: (a) a mixture of several monofunctional acrylic and / or methacrylic monomers, wherein one or more monomers are derived from recycled materials and one or more monomers are of plant or animal origin, (b) one or more multifunctional acrylic bio-monomers and / or methacrylic bio-monomers of plant or animal origin, (c) two or more polymers selected from polyacrylates, polymethacrylates, ethyl cellulose, castor oil polymers derived from recycled materials or plant or animal sources, (d) inorganic filler particles of natural origin, The ratio of the monofunctional acrylic monomer and / or methacrylic monomer and the multifunctional acrylic bio-monomer and / or methacrylic bio-monomer is 10-40 wt %, the ratio of the polymer is 1-16 wt %, and the ratio of the inorganic filler particles is 44-89 wt %. 2 . The casting material according to claim 1 , wherein the weight ratio of the monofunctional monomer to the multifunctional monomer is 2:1 to 80:

1. 3 . The casting material according to claim 1 , wherein the weight ratio of the monofunctional monomer to the multifunctional monomer is 4:1 to 70:

1. The casting material according to claim 1 , wherein the weight ratio of the monofunctional monomer to the multifunctional monomer is 5:1 to 60:

1.

5. The casting material according to any one of claims 1 to 4, wherein the monofunctional monomer is selected from recycled acrylates and acrylates of plant or animal origin, namely n-butyl acrylate, methyl acrylate, ethyl acrylate, tert-butyl acrylate, isobutyl acrylate, isodecyl acrylate, dihydrodicyclopentadienyl acrylate, ethyl diethylene glycol acrylate, heptadecanyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, hydroxyethyl caprolactone acrylate, hydroxypropyl acrylate, dodecyl acrylate, octadecyl acrylate, 2(2-ethoxy)ethyl acrylate, tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, ethoxylated 4-phenyl acrylate, trimethylcyclohexyl acrylate, octyldecyl acrylate, tridecyl acrylate, ethoxylated 4-nonylphenol acrylate, isobornyl acrylate, cyclotrimethylolpropane formal acrylate, ethoxylated 4-dodecyl acrylate, polyester acrylate, melamine acrylate , silicone acrylate, epoxy acrylate, and methacrylate selected from recycled methacrylates and methacrylates of plant or animal origin, namely methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, behenyl methacrylate, vinyl polyethylene glycol methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, octadecyl polyethylene glycol methacrylate, isotridecyl methacrylate, ureido methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, 3,3,5-trimethylcyclohexanol methacrylate, isobornyl methacrylate, methoxypolyethylene glycol methacrylate, glycidyl methacrylate, hexylethyl methacrylate, glyceryl formal methacrylate, tetradecyl methacrylate, C17,4-methacrylate.

6. The casting material according to claim 5, wherein the polyester acrylate comprises hyperbranched polyester acrylate and polycaprolactone acrylate.

7. The casting material according to any one of claims 1 to 4, wherein the multifunctional biomonomer is selected from acrylates of plant or animal origin, namely 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, polybutadiene diacrylate, 3-methyl-1,5-pentanediol diacrylate, dipropylene glycol diacrylate, 1,10-decanediol diacrylate, ester diol diacrylate, alkoxylated diacrylate, tricyclodecane dimethanol diacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, di-trimethylolpropane tetraacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, di-pentaerythritol pentaacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, The present invention relates to polyfunctional methacrylates of the present invention, such as pentaerythritol tetraacrylate, propoxylated glycerol triacrylate, aliphatic polyurethane diacrylate, aliphatic polyurethane hexaacrylate, aliphatic polyurethane triacrylate, aromatic polyurethane diacrylate, aromatic polyurethane triacrylate, aromatic polyurethane hexaacrylate, polyester hexaacrylate, epoxidized soybean oil diacrylate, and multifunctional methacrylates selected from plant or animal sources, namely triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,10-decanediol dimethacrylate, 1,3-butanediol dimethacrylate, ethoxylated bisphenol A-dimethacrylate, tricyclodecane dimethanol dimethacrylate, and trimethylolpropane trimethacrylate.

8. The casting material according to claim 7, wherein the alkoxylated diacrylate comprises ethoxylated bisphenol A-diacrylate, ethoxylated hexanediol diacrylate, propoxylated neopentyl glycol diacrylate.

9. The casting material according to any one of claims 1 to 4, wherein the weight ratio of the monofunctional and polyfunctional acrylates and / or methacrylates to the polymer is 90:10 to 60:

40.

10. The casting material according to any one of claims 1 to 4, wherein the weight ratio of the monofunctional and polyfunctional acrylates and / or methacrylates to the polymer is from 85:15 to 70:

30.

11. The castable according to any one of claims 1 to 4, wherein the inorganic filler particles are selected from SiO2, Al2O3, TiO2, ZrO2, Fe2O3, ZnO, Cr2O5, carbon, metal or metal alloy.

12. The casting material according to any one of claims 1 to 4, wherein the inorganic filler particles have a particle size of 0.010 to 8000 μm.

13. The casting material according to any one of claims 1 to 4, wherein the inorganic filler particles have a particle size of 0.05 to 3000 μm.

14. The casting material according to any one of claims 1 to 4, wherein the inorganic filler particles have a particle size of 0.1 to 1300 μm.

15. The castable according to any one of claims 1 to 4, wherein the inorganic filler particles have an aspect ratio of 1.0 to 1000, the aspect ratio being the length:width of a single particle.

16. The casting material according to any one of claims 1 to 4, wherein the casting material has a certain viscosity so as to be able to be injected into a mold.

17. A molded body produced using the casting compound according to any one of claims 1 to 16.

18. The molded body according to claim 17, wherein the molded body is a kitchen sink, a shower tray, a washstand, a bathtub, a countertop, or is a floor panel, a wall panel or a ceiling panel.

19. A method for producing a molded body as claimed in claim 17 or 18, wherein a casting material as claimed in any one of claims 1 to 14 is used, the casting material is introduced into a mold and polymerized in the mold at a temperature higher than room temperature, and the polymerized molded body is subsequently demolded and cooled.

20. The method of claim 19, wherein the temperature during the polymerization is between 60-140°C.

21. The method of claim 19, wherein the temperature during the polymerization is between 75-130°C.

22. The method of claim 19, wherein the temperature during the polymerization is between 80-110°C.

23. The method according to any one of claims 19 to 22, wherein the retention time of the castable in the mould for polymerisation to occur is between 15 - 50 min.

24. The method according to any one of claims 19 to 22, wherein the retention time of the castable in the mould for polymerisation to occur is between 20 - 45 min.

25. The method according to any one of claims 19 to 22, wherein the retention time of the castable in the mould for polymerisation to occur is between 25-35 min.

Images