EP2222915B1 - Linoléum thermoplastique - Google Patents

Linoléum thermoplastique Download PDF

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Publication number
EP2222915B1
EP2222915B1 EP08859529A EP08859529A EP2222915B1 EP 2222915 B1 EP2222915 B1 EP 2222915B1 EP 08859529 A EP08859529 A EP 08859529A EP 08859529 A EP08859529 A EP 08859529A EP 2222915 B1 EP2222915 B1 EP 2222915B1
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EP
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Prior art keywords
component
thermoplastic
molding composition
present
vegetable oil
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EP08859529A
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German (de)
English (en)
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EP2222915A1 (fr
Inventor
Konrad Knoll
Michel Pepers
Peter Wolf
Piyada Charoensirisomboon
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BASF SE
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BASF SE
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N1/00—Linoleum, e.g. linoxyn, polymerised or oxidised resin

Definitions

  • the present invention relates to a thermoplastic molding composition
  • a thermoplastic molding composition comprising particles of at least one oxidatively crosslinked vegetable oil as core, which is enveloped by at least one thermoplastic, at least one other thermoplastic, at least one resin, at least one filler and optionally further additives, a process for preparing such a molding composition and a material containing a carrier layer and such a thermoplastic molding composition.
  • Linoleum is a flooring developed by Frederick Walton in 1863, which consists mainly of oxidatively polymerized linseed oil, rosin, cork and wood flour, titanium oxide, dyes and a jute fabric. Advantages of linoleum are above all the resistance to oils, fats and tar. Linoleum is antistatic and slightly fungicidal and bacteriostatic against various microorganisms. The cause of this effect is the permanent emission of small amounts of various aldehydes, such as hexanal, acrolein, acetaldehyde, etc., which come from the virtually never-ending Leinöloxidation in the air or are residues of the oxidation reaction in the manufacturing process.
  • various aldehydes such as hexanal, acrolein, acetaldehyde, etc.
  • linoleum Disadvantages of linoleum, for example, that this typical linoleum odor in sensitive people can be shown to trigger irritation of the mucous membranes and allergies. Furthermore, linoleum is not very puncture resistant and not suitable for use in damp rooms. In addition, linoleum is very sensitive to alkalis and is chemically degraded by them.
  • thermoplastic molding compositions prepared from renewable raw materials should have at least 50% ingredients from natural sources.
  • the cost of such new molding compounds should be comparable to those for synthetic molding compositions.
  • the new thermoplastic molding compounds should comply with the regulations and requirements for plastics used in connection with foodstuffs.
  • JP 03-241083 Tinima Inc. discloses a floor covering and a method of making the same.
  • This floor covering is obtained by adding a polymerizable vegetable oil such as linseed oil, a thermoplastic elastomer such as a styrene elastomer or styrene-butadiene block copolymer, a curing agent such as trimethylolpropane trimethacrylate and a filler such as cork powder or wood chips are mixed, are brought into the desired shape and then irradiated with high-energy radiation, for example with UV radiation.
  • a polymerizable vegetable oil such as linseed oil
  • a thermoplastic elastomer such as a styrene elastomer or styrene-butadiene block copolymer
  • a curing agent such as trimethylolpropane trimethacrylate
  • a filler such as cork powder or wood chips
  • the object of the present invention is to provide a thermoplastic molding composition which consists to a major part of substances which are of natural origin, which has a stiffness which is comparable to that of impact-resistant polystyrene (HIPS), which can be produced inexpensively, and which comply with the regulations regarding the use in the food sector.
  • HIPS impact-resistant polystyrene
  • the object according to the invention is achieved by a method for producing such a molding compound, by a material comprising a carrier layer and a thermoplastic molding compound, a floor covering containing such a material and by the use of the thermoplastic molding composition according to the invention in materials.
  • thermoplastic molding composition according to the present invention will be described in detail below.
  • Component A is a compound having Component A:
  • thermoplastic molding composition of the invention as component A are (A) particles of at least one oxidatively crosslinked vegetable oil as a core, which is surrounded by at least one thermoplastic, containing.
  • Suitable vegetable oils which are oxidatively crosslinked according to the invention, and in this oxidatively crosslinked form in which particles according to component A are present in the thermoplastic molding composition, are mentioned in US Pat Drying oils and related products, 2005, published by Wiley-VCH, Weinheim, pages 1 to 16 ,
  • Examples of preferred vegetable oils are linseed oil, perilla oil, tung oil, oiticica oil, fish oils, safflower oil, sunflower oil, soybean oil, cottonseed oil and mixtures thereof. Flaxseed oil is preferably used.
  • oils can be obtained on an industrial scale by cold or hot pressing of the respective seeds.
  • a purification of the oils obtained by distillation is optionally performed.
  • crosslinking of the vegetable oil present in component A of the thermoplastic molding composition according to the invention is effected by oxidation, see also Drying oils and retarded products, 2005, published by Wiley-VCH, Weinheim, pages 1 to 16 ,
  • the first step of the crosslinking reaction by oxidation is the formation of hydroperoxides in the allylic position with the double bonds.
  • a radical is formed by dehydrogenation which is converted to hydroperoxide by addition of oxygen.
  • an isomerization of the double bonds remaining in the molecule can take place.
  • the next step in the crosslinking of said vegetable oils is the formation of a peroxy radical by degradation of the hydroperoxide.
  • a free radical chain formation process is started, and oxygen bonds or carbon-carbon bonds are formed. Termination reactions in this process step is the recombination of radicals.
  • hydroperoxides are not the first reaction step, but cyclic peroxides are formed by the direct attack of oxygen on the conjugated bond system. Reaction of these peroxides with allylic methylene groups or dissociation yields radicals that form carbon-oxygen and carbon-carbon bonds in a radical chain mechanism. This reaction can also be terminated by recombination of the radicals or disproportionation.
  • the crosslinking of said vegetable oils by oxidation can be catalyzed by suitable catalysts.
  • Suitable catalysts are all metals which can be present in different oxidation states and which can undergo redox reactions.
  • Suitable metals for cross-linking vegetable oils are selected from the group consisting of cobalt, iron, manganese, cerium, lead, zirconium and mixtures of these metals.
  • the oxidatively crosslinked vegetable oils, which are present in the core of the particles, can also by passing air at a temperature of generally 80 to 140 ° C, preferably 90 to 120 ° C are obtained.
  • hydroperoxides are formed, which decompose into free radicals and thus increase the molecular weight by radical chain transfer reaction.
  • the degree of crosslinking of the oxidatively crosslinked vegetable oils can be determined by rheological methods or by measuring the degree of swelling. These methods are known to the person skilled in the art.
  • thermoplastic molding composition according to the invention, the particles which are used as component A, are enveloped by at least one thermoplastic.
  • thermoplastic all polymers, i. Homopolymers and copolymers, referred to, which can be reversibly deformed in a certain temperature range, reversibly means that this process can be repeated as often as desired by cooling and reheating to the molten state, as long as not using thermal decomposition of the material by overheating ,
  • thermoplastic molding composition As shell of the particles, which are present as component A in the thermoplastic molding composition according to the invention, it is generally possible to use all thermoplastics known to the person skilled in the art.
  • the thermoplastics include e.g. Polyamides (PA), polyetheretherketones (PEEK), polyesters such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyvinyl chloride (PVC), polyurethane (PU), polyoxymethylene (POM), polyethersulfone (PES), poly-n-butylmethacrylate (PBMA) , Polymethyl methacrylate (PMMA), polyimides or styrene acrylonitrile (SAN).
  • PA Polyamides
  • PEEK polyetheretherketones
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PVC polyvinyl chloride
  • PU polyurethane
  • POM polyoxymethylene
  • PES polyethersulfone
  • PBMA poly-n-butylmethacrylate
  • PMMA Polymethyl methacrylate
  • SAN Polyimides or styrene acryl
  • thermoplastics selected from the group consisting of homopolymers and copolymers composed of vinylic, aromatic monomers, ethylenically unsaturated monomers and / or dienes.
  • Suitable vinylic, aromatic monomers correspond to the general formula (I) in which R 1 to R 8 independently of one another may denote hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 5 -C 20 -aryl, where the alkyl, alkenyl and alkynyl Radicals may be linear or branched and may optionally be substituted by functional groups selected from the group consisting of amine, imine, ether, hydroxy, aldehyde, keto, carboxylic acid, carboxylic anhydride, nitrile group.
  • R 1 to R 3 are independently hydrogen or C 1 -C 20 -alkyl, more preferably hydrogen, methyl, ethyl or propyl, and R 4 to R 8 are independently hydrogen, methyl or ethyl. Most preferably, R 1 is hydrogen or methyl, and R 2 to R 8 are hydrogen.
  • styrene, ⁇ -methylstyrene, para-methylstyrene, 1,1-diphenylethylene, para-tert-butylstyrene or mixtures are used as vinylic, aromatic monomers.
  • Suitable ethylenically unsaturated monomers are generally selected from the group consisting of ⁇ , ⁇ -unsaturated mono- and dicarboxylic acids, their esters, anhydrides and nitriles.
  • Preferred ⁇ , ⁇ -unsaturated monocarboxylic acids are acrylic acid and methacrylic acid.
  • esters of these ⁇ , ⁇ -unsaturated monocarboxylic acids are reaction products of said monocarboxylic acid with compounds bearing at least one OH function, i. with monohydric or polyhydric alcohols.
  • Preferred methacrylic esters are C 1 -C 8 -alkyl esters of methacrylic acid, for example methyl methacrylate (MMA), ethyl methacrylate, n-, i-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, Octyl methacrylate or 2-ethylhexyl methacrylate.
  • MMA methyl methacrylate
  • ethyl methacrylate ethyl methacrylate
  • n- i-propyl methacrylate
  • n-butyl methacrylate isobutyl methacrylate
  • sec-butyl methacrylate tert-butyl methacrylate
  • Preferred acrylic acid esters are C 1 -C 8 -alkyl esters of acrylic acid, for example methyl acrylate, ethyl acrylate, n-, i-propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate or 2 ethylhexyl acrylate.
  • Suitable nitriles of ⁇ , ⁇ -unsaturated monocarboxylic acids are acrylonitrile and methacrylonitrile, with acrylonitrile being preferred.
  • Suitable ⁇ , ⁇ -unsaturated dicarboxylic acids or ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides are, for example, maleic acid or maleic anhydride.
  • all homo- or copolymerizable dienes may be present in the thermoplastic forming the shell of the particle in component A.
  • 1,3-dienes particularly preferably 1,3-butadiene, 2,3-dimethylbutadiene, piperylene and / or isoprene.
  • polystyrene is used as the shell of the particle present as component A.
  • Polystyrene can be prepared by all methods known to those skilled in the art, for example cationic, anionic or free-radical initiated polymerization in emulsions, solutions or substance.
  • the polystyrene which is present as a shell in the particle has a weight-average molecular weight of 80,000 to 300,000 g / mol, for example 100,000 to 200,000 g / mol.
  • SAN copolymer In a further particularly preferred embodiment, a copolymer of styrene and acrylonitrile is used as the shell of the particle present as component A.
  • This so-called SAN copolymer generally has a weight-average molecular weight of 80,000 to 300,000 g / mol, for example 100,000 to 200,000 g / mol. Methods of making a suitable SAN copolymer are known to those skilled in the art.
  • the binding of the at least one thermoplastic to the oxidatively crosslinked vegetable oil, which is present in the core can take place by interactions or by covalent bonds, in each case between the molecules of the thermoplastic and the molecules of the crosslinked vegetable oil in the core.
  • a block or graft rubber is present in the particle used as component A.
  • a block or graft rubber is present in the particle used as component A.
  • ABS copolymers are copolymers composed of acrylic acid, butadiene and styrene. Methods of making ABS copolymers are known to those skilled in the art.
  • SBS copolymers are block copolymers made up of styrene and butadiene. SBS copolymers and methods for their preparation are described, for example, in WO 97/40079 , These block polymers are prepared by anionic polymerization in a non-polar solvent, wherein the initiation takes place by means of organometallic compounds. Preference is given to compounds of the alkali metals, especially of lithium. Examples of initiators are methyllithium, ethyllithium, propyllithium, n-butyllithium, sec. Butyllithium and tert. Butyl lithium. The organometallic compound is added as a solution in a chemically inert hydrocarbon.
  • the dosage depends on the desired molecular weight of the polymer, but is usually in the range of 0.002 to 5 mol%, based on the monomers.
  • the solvents used are preferably aliphatic hydrocarbons such as cyclohexane or methylcyclohexane.
  • the random blocks of the block copolymers which simultaneously contain styrene and diene are prepared by adding a soluble potassium salt, in particular a potassium alkoxide, in particular tertiary alkoxides having at least 7 carbon atoms.
  • a soluble potassium salt in particular a potassium alkoxide, in particular tertiary alkoxides having at least 7 carbon atoms.
  • Typical corresponding alcohols are e.g. 3-ethyl-3-pentanol and 2,3-dimethyl-3-pentanol. Tetrahydrolinalool (3,7-dimethyl-3-octanol) proved to be particularly suitable.
  • other potassium salts which are inert to metal alkyls are also suitable in principle. These include dialkylpotassium amides, alkylated diarylpotassium amides, alkylthiolates and alkylated arylthiolates.
  • the polymerization temperature can be between 0 and 130
  • component A particles which contain flaxseed oil as vegetable oil, a SBS block copolymer as rubber and are coated with polystyrene.
  • the particles used as component A contain linseed oil as vegetable oil, a graft rubber based on styrene and / or butadiene and a shell of a styrene-acrylonitrile copolymer.
  • the particles which are present in the thermoplastic molding composition according to the invention as component A generally have a diameter of 1 to 100 .mu.m, preferably 1 to 10 .mu.m.
  • the shell of the particle present as component A generally has a layer thickness of 10 to 30 nm.
  • the oxidatively crosslinked vegetable oil is present in an amount of from 10 to 60% by weight, preferably from 20 to 50% by weight, particularly preferably from 25 to 45% by weight, based in each case on the entire thermoplastic molding composition ,
  • Component A is generally present in the thermoplastic molding composition in an amount of from 10 to 70% by weight, preferably from 40 to 60% by weight, in each case based on the total thermoplastic molding composition.
  • Component B is a compound having Component B:
  • thermoplastic molding composition according to the invention contains as component B at least one further thermoplastic which is compatible with the at least one thermoplastic present in the shell of component A.
  • component B at least one further thermoplastic which is compatible with the at least one thermoplastic present in the shell of component A.
  • Thermoplastics suitable as component B are selected from the group consisting of copolymers of at least one vinylic, aromatic monomer and optionally at least one ⁇ , ⁇ -unsaturated monocarboxylic acid or the corresponding nitrile, for example polystyrene (PS) or styrene acrylonitrile (SAN).
  • PS polystyrene
  • SAN styrene acrylonitrile
  • thermoplastics are selected from the group consisting of polycarbonates (PC), polyurethanes (PU), polyamides (PA), polyesters such as polyethylene terephthalates (PET) or polybutylene terephthalates (PBT), polyetheretherketones (PEEK), polyvinyl chlorides (PVC), polyurethanes (PU ), Polyoxymethylenes (POM), polyethersulfones (PES), poly-n-butylmethacrylates (PBMA), polymethyl methacrylates (PMMA), polyimides and biodegradable homo- and copolymers, for example polylactides or polybutyrate.
  • PC polycarbonates
  • PU polyurethanes
  • PA polyamides
  • PET polyethylene terephthalates
  • PBT polybutylene terephthalates
  • PEEK polyetheretherketones
  • PVC polyvinyl chlorides
  • PVC polyurethanes
  • POM Polyoxymethylenes
  • PES polyethersul
  • the at least one further thermoplastic material used as component B is selected from the group consisting of polystyrenes, polyesters, styrene-acrylonitrile copolymers, polycarbonates, polyurethanes and biodegradable polymers, for example polylactides or polybutyrate.
  • Polycarbonates are polymers that can be formally obtained by reaction of carbonic acid and compounds having at least two hydroxy functions. They are accessible, for example, by reacting the corresponding alcohols with phosgene or carbonic diesters in polycondensation and transesterification reactions.
  • Suitable polyesters for the thermoplastic molding composition according to the invention are preferably selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate and blends thereof. Polyesters can be obtained by reaction of diols with dicarboxylic acids or hydroxycarboxylic acids.
  • Polyurethanes are copolymers obtained by polyaddition of compounds having at least two hydroxy functions and compounds having at least two isocyanate groups.
  • Examples of polyurethanes to be used according to the invention are those prepared from polyester and / or polyether diols and z. B. from 2,4- or 2,6-toluene diisocyanate, 4,4'-methylene di (phenyl isocyanate) and hexamethylene diisocyanate. It can be used linear or branched polyurethanes.
  • a biodegradable polymer is used in the thermoplastic molding composition according to the invention in a preferred embodiment.
  • biodegradable polymers are polylactides or polybutyrate.
  • Polylactides also called polylactic acids, occur in the optically active D or L form due to the asymmetric carbon atom.
  • Polylactides which can be used according to the invention can be prepared by all processes known to the person skilled in the art.
  • Polylactides are accessible, for example, by the ionic polymerization of lactide, an annular combination of two lactic acid molecules. At temperatures between 140 and 180 ° C and the action of catalytically active tin compounds such as tin oxide, the formation of polylactide takes place in a ring-opening polymerization. Lactide itself can be produced by fermentation of molasses or by fermentation of glucose with the help of various bacteria. In addition, high molecular weight and pure polylactides can be produced by polycondensation directly from lactic acid.
  • Component B may also be a mixture of said thermoplastics with each other or a mixture of said thermoplastics with each other with so-called “toughness boosters" as an additive, which are preferably selected from the group consisting of SBS copolymers, for example under the trade name Styroflex® or under the trade name Ecoflex®.
  • Ecoflex® is a blend of aromatic and aliphatic esters based on poly-epsiloncaprolactone and 1,4-butanediol.
  • SBS copolymers the above applies.
  • component B if the shell of the particle contains polystyrene, polystyrene is also used, optionally in admixture with an SBS copolymer.
  • the component B if the shell of the particle includes styrene acrylonitrile, also styrene acrylonitrile, polyester, polyurethane or polylactide used, optionally in admixture with Ecoflex ®.
  • thermoplastic material used as component B is in the thermoplastic molding composition of the present invention in an amount of 20 to 80 wt .-%, preferably 30 to 70 wt .-%, particularly preferably 40 to 60 wt .-%, each based on the Total mass of the thermoplastic molding compound, before.
  • thermoplastic molding composition according to the present invention contains as component C at least one resin which is compatible with the at least one thermoplastic present in the shell of component A.
  • both synthetically prepared resins and naturally occurring resins can be used.
  • thermoplastic molding composition A selection of natural resins that can be used in the thermoplastic molding composition according to the present invention is in: Natural Resins, Wiley-VCH Verlag, Weinheim, 2005, pages 1 to 19 , disclosed.
  • Particularly preferred natural resins are selected from the group consisting of acaroid resin, amber, asphaltite, balsam of Peru, toru balsam, benzoin, Canada balm, Chinese or Japanese varnish, copal, damar, dragon's blood resin, elemi, frankincense (Olibanum), galbanum , Labdanum, Mastic, Myrrh, Sandarak, Schellak, Styrax, Utah resin, Venice turpentine, rosin and mixtures thereof. Particular preference is given to using rosin.
  • resins occur in nature and can be obtained or isolated by methods known to those skilled in the art, for example by scoring the bark of the corresponding tree and collecting the resin or extracting the wood of the corresponding tree with suitable solvents, for example naphtha.
  • Suitable synthetically produced resins are generally copolymers, for example low molecular weight thermoplastic materials such as low molecular weight polyesters. These are known to the person skilled in the art.
  • Component C is in the thermoplastic molding composition according to the invention generally in an amount of 1 to 30 wt .-%, preferably 5 to 20 wt .-%, particularly preferably 8 to 15 wt .-%, each based on the total mass of the thermoplastic molding composition according to the invention , in front.
  • the thermoplastic molding composition according to the invention contains as component D at least one filler.
  • component D all fillers known to those skilled in the art can be used, which are suitable for use in polymeric materials.
  • suitable fillers are mineral fillers, salts, for example carbonates of the alkali and alkaline earth metals, such as calcium carbonate, or compounds such as titanium dioxide, zirconium dioxide and mixtures thereof.
  • suitable fillers are selected from the group consisting of cork flour, such as recycled bottle corks, wood flour, such as sawdust.
  • the suitable particle size of the filler used as component D is known to the person skilled in the art.
  • Component D is generally present in an amount of up to 50% by weight, preferably 20 to 30% by weight.
  • additives may be present as component E in the thermoplastic molding composition according to the invention.
  • Suitable further additives are, for example, dyes, UV stabilizers, bleaches, deodorants, antioxidants and mixtures thereof.
  • component E is generally present in an amount of from 0.1 to 2% by weight, preferably from 1 to 2% by weight, based in each case on the entire thermoplastic molding composition.
  • thermoplastic molding composition according to the invention The sum of the amounts of components A, B, C, D present in the thermoplastic molding composition according to the invention and optionally E is 100% by weight.
  • Step (1) of the method according to the invention comprises preparing a solution or a dispersion of at least one thermoplastic in the at least one vegetable oil.
  • step (1) a solution or dispersion of the at least one thermoplastic in the at least one vegetable oil is prepared, depending on how soluble the at least one thermoplastic is in the at least one vegetable oil.
  • a solution is prepared.
  • the amount of at least one thermoplastic in the at least one vegetable oil is generally the amount which should also be present in the later component (A).
  • thermoplastic molding composition according to the invention applies.
  • the preparation of the solution or of the dispersion can be carried out by all methods known to the person skilled in the art.
  • the at least one vegetable oil is heated before the at least one thermoplastic is added.
  • the temperature of the heated vegetable oil when adding the at least one thermoplastic is 50 to 150 ° C, preferably 60 to 140 ° C.
  • the preparation of the solution or the dispersion in step (1) of the process according to the invention is generally carried out at atmospheric pressure, however, the inventive method can also be carried out at a pressure below atmospheric pressure or a pressure above atmospheric pressure.
  • Step (2) of the process of the invention comprises oxidizing the at least one vegetable oil in the solution or dispersion of step (1) to obtain particles comprising the at least one oxidatively crosslinked vegetable oil as the core and the at least one thermoplastic as the shell.
  • oxidation can be carried out by all methods known to the person skilled in the art.
  • Suitable oxidizing agents are selected from the group consisting of oxidizing gases such as oxygen, halogens, hydrogen peroxide, inorganic peroxides, organic peroxides, air, liquid or dissolved or dispersed oxidizing agents and mixtures of these oxidizing agents.
  • the oxidation in step (2) of the process according to the invention takes place by flowing the solution or dispersion from step (1) with air.
  • the temperature in step (2) of the process according to the invention is generally more than 110.degree. C., preferably 115 to 150.degree.
  • step (2) of the process according to the invention is carried out in the presence of a catalyst.
  • Suitable catalysts are metals and metal compounds which can be present in different oxidation states and can undergo redox reactions. Examples of metals that can be used as oxidation catalysts are selected from the group consisting of cobalt, iron, manganese, cerium, lead, zirconium and mixtures thereof.
  • the oxidation in step (2) of the process according to the invention is preferably carried out in the presence of a manganese catalyst.
  • Suitable compounds of the catalytically active compounds are organic and inorganic salts and complex compounds.
  • Exemplary manganese oleate is called.
  • the catalytically active metals are used in step (2) of the inventive method in an amount of 0.001 to 2 wt .-%.
  • at least one further salt is used which serves for the regeneration of the catalytically active compound, for example a zinc salt, preferably a zinc alkoxide.
  • This additional compound is used in the same amount as the catalytically active compound or in a 2-, 3- 4- or 5-fold excess with respect to the catalytically active compound.
  • the catalytically active metal compound is already admixed in step (1).
  • the catalytically active metal is not removed after completion of the process according to the invention, so that the resulting thermoplastic molding composition contains the corresponding amount of metal salt in addition to the components A to D and optionally E.
  • the oxidation is generally carried out until the degree of crosslinking of the vegetable oil to be oxidatively crosslinked has reached the desired value. This can be determined by an increase in the viscosity of the solution or dispersion during the oxidation.
  • the reaction time is generally between 0.1 and 8 hours, preferably between 0.5 and 6 hours, more preferably between 1 and 4 Hours.
  • the reaction time for the oxidation step (2) depends on the vegetable oil used, the thermoplastic present, the oxidizing agent used, the catalyst used, and the concentration of the thermoplastic in the vegetable oil, and can be easily determined by those skilled in the art by observing the increase in viscosity be determined.
  • thermoplastic molding composition After the oxidation has ended, particles have formed in the solution or dispersion, in the core of which at least one vegetable oil is present in oxidatively crosslinked form.
  • the mechanism or the individual reaction steps have already been explained above with respect to the thermoplastic molding composition.
  • the at least one thermoplastic is present in the shell of the particle produced in step (2), the molecular chains of this thermoplastic being covalently or coordinatively bound to the oxidatively crosslinked vegetable oil.
  • thermoplastic molding composition according to the invention applies.
  • Step (3) of the process of the invention comprises mixing the particles of step (2) with components (B), (C), (D) and optionally (E) to obtain the molding material.
  • step (3) is carried out at a suitable temperature at which the individual components are miscible, for example 50 to 200 ° C.
  • thermoplastic molding composition according to the invention is produced by the process according to the invention.
  • the present invention also relates to a material comprising a carrier layer or fibers and a thermoplastic molding composition according to the present invention.
  • fabrics of synthetically produced or naturally available fibers can be used.
  • natural fibers are cotton, jute or linen.
  • synthetically produced fibers are fibers of homo- and copolymers selected from the group consisting of polyesters, polyamides, polyolefins and blends of the aforementioned polymers. It can according to the invention also Glass fibers, preferably in conventional dimensions, are used, these according to the invention do not form tissue.
  • the material according to the invention is obtained by applying the thermoplastic molding composition prepared according to the invention as a melt or in solution or dispersion to the carrier layer or mixing it with the glass fibers.
  • the material produced according to the invention can be used as a floor covering, wall covering, for covering furniture, in the automotive sector, in wet rooms such as in the bathroom and toilet area, in housings or in components.
  • the present invention also relates to a floor covering, wall covering, furniture, car parts, housings or components containing the material according to the invention.
  • the present invention also relates to the use of the thermoplastic molding composition according to the present invention in materials.

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Claims (12)

  1. Matériau de moulage thermoplastique contenant
    (A) des particules d'au moins une huile végétale réticulée par oxydation en tant que noyau, qui est enveloppé par au moins un thermoplastique, en tant que composant A,
    (B) au moins un thermoplastique supplémentaire, qui est compatible avec le ou les thermoplastiques présents dans l'enveloppe du composant A, en tant que composant B,
    (C) au moins une résine, qui est compatible avec le ou les thermoplastiques présents dans l'enveloppe du composant A, en tant que composant C,
    (D) au moins une charge en tant que composant D et
    (E) éventuellement des additifs supplémentaires en tant que composant E,
    un caoutchouc séquencé ou greffé étant également présent dans les particules utilisées en tant que composant A.
  2. Matériau de moulage selon la revendication 1, caractérisé en ce que le thermoplastique contenu dans l'enveloppe du composant A est choisi parmi les homo-et copolymères formés à partir de monomères vinyliques, aromatiques, de monomères éthyléniquement insaturés et/ou de diènes.
  3. Matériau de moulage selon la revendication 1 ou 2, caractérisé en ce que le thermoplastique utilisé en tant que composant B est choisi parmi les homo- et copolymères formés à partir de monomères vinyliques, aromatiques, de monomères éthyléniquement insaturés et/ou de diènes.
  4. Matériau de moulage selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la résine utilisée en tant que composant C est choisie dans le groupe constitué par la résine acaroïde, l'ambre, l'asphaltite, le baume du Pérou, le baume de Toru, la benzoïne, le baume du Canada, la laque chinoise ou japonaise, le copal, le dammar, la résine de sang de dragon, l'élémi, l'encens (olibanum), le galbanum, le labdanum, le mastic, la myrrhe, la sandaraque, la gomme laque, le styrax, la résine d'Utah, la térébenthine de Venise, la colophane et leurs mélanges.
  5. Matériau de moulage selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la charge utilisée en tant que composant C est le carbonate de calcium.
  6. Procédé de fabrication d'un matériau de moulage thermoplastique contenant des particules d'au moins une huile végétale réticulée par oxydation en tant que noyau, qui est enveloppé par au moins un thermoplastique, en tant que composant A, au moins un thermoplastique supplémentaire, qui est compatible avec le ou les thermoplastiques présents dans l'enveloppe du composant A, en tant que composant B, au moins une résine, qui est compatible avec le ou les thermoplastiques présents dans l'enveloppe du composant A, en tant que composant C, au moins une charge en tant que composant D et éventuellement des additifs supplémentaires en tant que composant E, un caoutchouc séquencé ou greffé étant également présent dans les particules utilisées en tant que composant A, comprenant les étapes suivantes :
    (1) la fabrication d'une solution ou dispersion d'au moins un thermoplastique dans au moins une huile végétale,
    (2) l'oxydation de la ou des huiles végétales dans la solution ou dispersion de l'étape (1) pour obtenir des particules qui contiennent la ou les huiles végétales réticulées par oxydation en tant que noyau et qui sont enveloppées par au moins un thermoplastique, et
    (3) le mélange des particules de l'étape (2) avec les composants (B), (C), (D) et éventuellement (E) pour obtenir le matériau de moulage thermoplastique.
  7. Procédé selon la revendication 6, caractérisé en ce que l'oxydation à l'étape (2) est réalisée en présence d'un catalyseur à base de manganèse.
  8. Procédé selon la revendication 6 ou 7, caractérisé en ce que l'oxydation est réalisée à une température supérieure à 115 °C.
  9. Matériau, contenant une couche support ou des fibres et un matériau de moulage thermoplastique selon l'une quelconque des revendications 1 à 5.
  10. Matériau selon la revendication 9, caractérisé en ce que la couche support est un tissu de jute.
  11. Revêtement de sol, revêtement de mur, meubles, parties d'automobiles, boîtiers ou éléments de construction contenant un matériau selon la revendication 9 ou 10.
  12. Utilisation du matériau de moulage thermoplastique selon l'une quelconque des revendications 1 à 5 dans des matériaux.
EP08859529A 2007-12-13 2008-12-11 Linoléum thermoplastique Not-in-force EP2222915B1 (fr)

Priority Applications (1)

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EP08859529A EP2222915B1 (fr) 2007-12-13 2008-12-11 Linoléum thermoplastique

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EP07123091 2007-12-13
PCT/EP2008/067316 WO2009074645A1 (fr) 2007-12-13 2008-12-11 Linoléum thermoplastique
EP08859529A EP2222915B1 (fr) 2007-12-13 2008-12-11 Linoléum thermoplastique

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EP2222915B1 true EP2222915B1 (fr) 2011-04-20

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EP (1) EP2222915B1 (fr)
JP (2) JP2011506664A (fr)
AT (1) ATE506484T1 (fr)
DE (1) DE502008003320D1 (fr)
WO (1) WO2009074645A1 (fr)

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JP5624464B2 (ja) 2007-07-10 2014-11-12 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 難燃性を有する弾性共重合体
ATE499411T1 (de) 2007-07-10 2011-03-15 Basf Se Flammwidrige thermoplastische formmassen
EP2609246A1 (fr) * 2010-08-25 2013-07-03 Basf Se Matière à mouler thermoplastique, procédé pour sa fabrication et son utilisation
US8697795B2 (en) 2010-08-25 2014-04-15 Konrad Knoll Thermoplastic linoleum
US20240270987A1 (en) * 2023-02-13 2024-08-15 3D Systems, Inc. Compositions comprising an asphaltite additive for additive manufacturing

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NL8600266A (nl) * 1985-12-07 1987-07-01 Dsm Resins Bv Harssamenstelling en werkwijze voor de bereiding van deze harssamenstelling.
DE3843482A1 (de) * 1988-12-23 1990-06-28 Huels Troisdorf Verfahren zur herstellung von flaechengebilden wie boden- oder wandbelaegen, insbesondere aus naturoelen
NL8900009A (nl) * 1989-01-04 1990-08-01 Stamicarbon Harssamenstelling en werkwijze voor de bereiding van deze harssamenstelling.
JPH0680235B2 (ja) * 1990-02-19 1994-10-12 株式会社タジマ 床材およびその製造方法
JP3241083B2 (ja) 1992-03-25 2001-12-25 積水化学工業株式会社 管継手
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EP2222915A1 (fr) 2010-09-01
JP2015129301A (ja) 2015-07-16
US8466215B2 (en) 2013-06-18
WO2009074645A1 (fr) 2009-06-18
JP2011506664A (ja) 2011-03-03
DE502008003320D1 (en) 2011-06-01
ATE506484T1 (de) 2011-05-15
US20100261824A1 (en) 2010-10-14

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