EP2609246A1 - Matière à mouler thermoplastique, procédé pour sa fabrication et son utilisation - Google Patents

Matière à mouler thermoplastique, procédé pour sa fabrication et son utilisation

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Publication number
EP2609246A1
EP2609246A1 EP11746262.2A EP11746262A EP2609246A1 EP 2609246 A1 EP2609246 A1 EP 2609246A1 EP 11746262 A EP11746262 A EP 11746262A EP 2609246 A1 EP2609246 A1 EP 2609246A1
Authority
EP
European Patent Office
Prior art keywords
vegetable oil
component
oil
ethylenically unsaturated
molding composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP11746262.2A
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German (de)
English (en)
Inventor
Konrad Knoll
Michel Pepers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ineos Styrolution Europe GmbH
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP11746262.2A priority Critical patent/EP2609246A1/fr
Publication of EP2609246A1 publication Critical patent/EP2609246A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent

Definitions

  • the present invention relates to a thermoplastic molding composition, at least comprising particles of non-oxidatively polymerized vegetable oil, which is crosslinked via functional groups, as component (A), at least one thermoplastic polymer as component (B), optionally at least one resin as component (C ), optionally at least one filler as component (D) and optionally further additives, a process for their preparation and their use.
  • 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 has a mild fungicidal and bacteriostatic effect 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 are, for example, that the typical linoleum odor in susceptible persons can demonstrably cause mucous membrane irritation 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 of Tajima Inc. discloses a floor covering and a method for its production.
  • This flooring is obtained by mixing 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 into the desired shape are brought and then irradiated with high-energy rays, for example, with UV radiation.
  • the material thus obtained contains no particles but consists of a more or less homogeneous, hardened mass, which is then no longer thermoplastically processable.
  • 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, depending on the mixing ratio of the components, has a stiffness which is comparable to that of impact-resistant polystyrene (Hl PS), or is elastic, and which can be produced inexpensively. Furthermore, the thermoplastic molding composition is said to have improved mechanical properties, for example with regard to scratch resistance, compared with materials of the prior art and show a favorable combination of stiffness / surface hardness with impact resistance and resistance to aging and weathering.
  • thermoplastic molding composition according to the invention comprising at least
  • thermoplastic polymer at least one thermoplastic polymer as component (B),
  • thermoplastic molding composition according to the present invention will be described in detail below.
  • thermoplastic molding composition according to the invention are as component A particles of non-oxidatively polymerized vegetable oil, which is crosslinked via functional groups included.
  • Suitable vegetable oils which are non-oxidatively polymerized according to the invention, and are present in this polymerized form in the particle as component A in the thermoplastic molding composition are, for example, in Drying oils and related products, 2005, published by Wiley-VCH, Weinheim, pages 1 to 16 , called.
  • Examples of preferred vegetable oils are selected from the group consisting of linseed oil, perilla oil, tung oil, oiticica oil, fish oils, safflower oil, sunflower oil, soybean oil, cottonseed oil and mixtures thereof.
  • linseed oil, soybean oil or a mixture thereof is used.
  • the present invention relates, in a preferred embodiment, to the thermoplastic molding composition of the invention, wherein the vegetable oil is selected from the group consisting of linseed oil, perilla oil, tung oil, oiticica oil, fish oils, safflower oil, sunflower oil, soybean oil, cottonseed oil and mixtures thereof.
  • the vegetable oil is selected from the group consisting of linseed oil, perilla oil, tung oil, oiticica oil, fish oils, safflower oil, sunflower oil, soybean oil, cottonseed oil and mixtures thereof.
  • 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.
  • the polymerization of the vegetable oil present in component A of the thermoplastic molding composition according to the invention is effected by a non-oxidative polymerization.
  • the first step of the polymerization reaction according to the invention is preferably an isomerization of the non-conjugated double bonds into conjugated double bonds.
  • isomerization is not necessary for the formation of conjugated double bonds.
  • the non-oxidative polymerization of the at least one vegetable oil preferably takes place in a Diels-Alder reaction, particularly preferably in an intermolecular Diels-Alder reaction.
  • the at least one non-oxidatively polymerized vegetable oil present in component A of the thermoplastic molding composition according to the invention is the product of an intermolecular Diels-Alder reaction of the at least one vegetable oil. It is also possible according to the invention for additional products of the intramolecular Diels-Alder reaction of the at least one vegetable oil to be present in component A. However, since the intramolecular reaction prevents an increase in the molecular weight of the polymer, it is not preferred.
  • the particles present as component A comprise a copolymer of at least one vegetable oil and at least one ethylenically unsaturated monomer.
  • the present invention therefore also relates to the molding composition according to the invention, wherein the particles (component A) comprise a vegetable oil polymer and / or a copolymer of vegetable oil with at least one ethylenically unsaturated monomer.
  • the non-oxidative polymerization of the at least one vegetable oil is carried out in the presence of ethylenically unsaturated and thus polymerizable compounds.
  • ethylenically unsaturated compounds are all monomers known to those skilled in the art, which can polymerize under thermal conditions and / or in the presence of radical initiators with the compounds present in the reaction mixture, preferably free-radically.
  • suitable ethylenically unsaturated monomers are, for example, monomers of the general form
  • R 7 , R 8 independently of one another can denote hydrogen, C 1 -C 20 -alkyl, C 2 -C 2 o-alkenyl, C 2 -C 20 -alkynyl, C 5 -C 20 -aryl, where the alkyl, alkenyl and alkynyl radicals may be linear or branched and optionally with functional len groups selected from the group consisting of amine, imine, ether, hydroxy, aldehyde, keto, carboxylic acid, carboxylic anhydride, nitrile group, may be substituted.
  • R 1 to R 3 independently of one another are hydrogen or C 1 -C 20 -alkyl, more preferably hydrogen, methyl, ethyl or propyl, and R 4 to R 8 are each 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, para-tert-butylstyrene, vinyltoluene or mixtures are used as ethylenically unsaturated aromatic monomers.
  • Other ethylenically unsaturated monomers suitable for preparing the vegetable oil-monomer copolymer according to the invention are, for example, ⁇ , ⁇ -unsaturated monocarboxylic acids or derivatives thereof, for example acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, acrylonitrile, methacrylonitrile and mixtures thereof, more preferably acrylonitrile.
  • the particle present as component (A) contains a vegetable oil-monomer copolymer which, in addition to the at least one vegetable oil, contains at least one monomer selected from the group consisting of styrene, ⁇ -methylstyrene, vinyltoluene, acrylonitrile and mixtures thereof.
  • the polymeric material present in component A thus preferably contains, after the non-oxidative polymerization, in the presence of the monomers mentioned, polymeric molecules in which vegetable oil units and the stated monomers are preferably uniformly distributed.
  • the said ethylenically unsaturated monomers polymerize with the vegetable oil present and / or the non-oxidatively polymerized vegetable oil preferably by thermally induced radical formation.
  • the monomer is added slowly to the vegetable oil initially introduced.
  • to 1 mole of pure linseed oil at 250 ° C 3 moles of styrene are added within 20 hours and heated for another 10 hours.
  • the reaction solution is then preferably completely styrene-free and contains, for example, only 0.6% of polystyrene (based on styrene used).
  • the polymeric material contained in the particle present as component A based on at least one vegetable oil and optionally at least one of the abovementioned ethylenically unsaturated monomers, is used before or after the preferred Diels-Alder reaction for the formation of intermolecular carbon-carbon Single and double bonds according to the invention provided with functional groups.
  • the functional groups into the particles present as component A for example, the vegetable oil present before the non-oxidative polymerization or the Diels-Alder reaction carried out according to the preferred one, if appropriate in the presence of the abovementioned ethylenically unsaturated monomers with at least one further ethylenic unsaturated compound obtained functionalized with suitable, for example at least two hydroxyl-functional compounds in a transesterification reaction.
  • suitable for example at least two hydroxyl-functional compounds in a transesterification reaction.
  • Corresponding compounds are known per se to the person skilled in the art.
  • the at least one vegetable oil used according to the invention contains triple esters of the corresponding fatty acids with glycerol. By reacting these triple esters with compounds which have at least two hydroxyl functions, depending on the molar ratio of vegetable oil and compound which has at least two hydroxyl functions, corresponding esters which have at least one free hydroxyl function are formed.
  • compounds having at least two hydroxyl functions are preferably used, selected from the group consisting of ethylene glycol, 1, 2-propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, Neopentyl glycol, glycerol, trimethylolpropane, pentaerythritol, sugar-alcohols derived from sugars such as sorbitol, etc., triethanolamine and mixtures thereof.
  • compounds which, in addition to at least one hydroxyl function have at least one amino function, for example ethanolamine, diethanolamine or mixtures thereof.
  • the at least one vegetable oil or the polymeric product obtained by the preferred Diels-Alder reaction is based on at least one vegetable oil and optionally at least one ethylenic unsaturation. saturated functionalized by reaction with a suitable compound in the ene reaction known in the art. If conjugated double bonds are still present in the product obtained, these will, at least in part, react with maleic anhydride in a Diels-Alder reaction.
  • any compound which appears suitable for an ene reaction to the person skilled in the art can generally be used, preferably selected from the group consisting of maleic anhydride, maleimide and mixtures thereof.
  • the present invention relates in particular to the thermoplastic molding composition according to the invention, wherein the functional groups present in the particle are selected from carboxylic acid anhydride group or hydroxy group.
  • the mechanism of the ene reaction is known to those of skill in the art and is described, for example, in U.S. Poth, Drying Oils and Related Products, Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2002, page 12 and in JO Metzger, U. Biermann, Products of the thermal ene reaction of unsaturated fatty compounds and maleic anhydride, Fat Sei. Technol. No. 96 (1994) pages 321 to 323.
  • Functionalization of the at least one vegetable oil or of the polymer formed by the non-oxidative polymerization, which optionally contains ethylenically unsaturated monomers, makes functional groups, preferably carboxylic acid groups or carboxylic anhydride groups, particularly preferred
  • the functional groups introduced into the at least one vegetable oil or the abovementioned polymer can be reacted with appropriate reagents in order to achieve crosslinking via these functional groups.
  • reagents are used which have at least two functional groups which can react with the functional group present in the vegetable oil or the polymer, the functionalized polymer is crosslinked by reaction with these reagents.
  • Suitable reagents for crosslinking are, for example, compounds selected from the group consisting of compounds containing at least two OH, NH 2 , NHR, isocyanate functions and / or carboxylic acid function.
  • diols such as ethylene glycol, propylene glycol 1, 4-butanediol, hydroquinone, resorcinol or pyrocatechol, polyols such as glycerol, pentaerythritol or sugar alcohols, diamines such as ethylenediamine, hexamethylenediamine, decamethylenediamine, phenylenediamines, Amino alcohols such as ethanolamine, diethanolamine or triethanolamine, and mixtures thereof are particularly preferred.
  • diisocyanates such as hexamethylene diisocyanate, tolylene diisocyanate or isophorone isocyanate or oligoisocyanates are particularly preferred.
  • di- and oligoanhydrides such as oligomers of maleic anhydride with other vinylic monomers such as styrene, or the maleination products of di- and oligoenes such as unsaturated fats.
  • the reagent used is a compound which contains at least two hydroxyl functions
  • ester functions are formed in the polymeric material having the carboxylic acid functions which are preferably present.
  • amide functions are formed in the polymeric material with the preferably present carboxylic acid functions.
  • the reagent used is a compound which contains at least one hydroxyl function and at least one amine function, ester and amide functions are formed in the polymeric material having the carboxylic acid functions which are preferably present.
  • a diisocyanate is used as the crosslinking reagent, urethane groups are formed with hydroxyl functions present in the polymer.
  • the particles present in the thermoplastic molding composition as component A have a shell.
  • This particle shell preferably contains at least one thermoplastic polymer.
  • the thermoplastic polymer present in the shell is the same, which is also present as a matrix material (component (B)) in the molding composition according to the invention.
  • thermoplastic polymers are all polymers, ie homopolymers and copolymers, which can be reversibly deformed within a certain temperature range, whereby reversibly means that this process is carried out by cooling. tion and reheating until the molten state can be repeated as often as long as it does not start to overheat a thermal decomposition of the material.
  • thermoplastic polymers are generally suitable which have a glass transition temperature above room temperature, ie> 25 ° C.
  • a preferred range for the glass transition temperature is 50 to 200 ° C, more preferably 70 to 150 ° C.
  • the present invention also relates to the molding composition according to the invention, wherein the particles (component A) have a shell which is obtained either by grafting the non-oxidatively polymerized vegetable oil or by blending with at least one thermoplastic polymer.
  • thermoplastic polymers having a glass transition temperature of> 25 ° C. selected from the group consisting of homopolymers and copolymers composed of vinylic, aromatic monomers, ethylenically unsaturated monomers and / or dienes.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 independently of one another have the following meanings: R 5 , R 6 ,
  • R 7, R 8 are independently hydrogen, CrC 2 -alkyl, C 2 -C 2 -alkenyl, C 2 -C 20 - alkynyl, can 5 -C 20 aryl C, wherein the alkyl, alkenyl and alkynyl Radicals can be linear or branched and optionally with functional groups selected from the group consisting of amine, imine,
  • Ether hydroxy, aldehyde, keto, carboxylic acid, carboxylic anhydride, nitrile group, may be substituted.
  • R 1 to R 3 independently of one another are hydrogen or C 1 -C 20 -alkyl, particularly preferably hydrogen, methyl, ethyl or propyl, and R 4 to R 8 are each independently hydrogen, methyl or ethyl.
  • R 1 is hydrogen or methyl
  • R 2 to R 8 are hydrogen.
  • the shell comprises at least one thermoplastic polymer having a glass transition temperature of> 25 ° C., composed of monomers selected from the group consisting of styrene, ⁇ -methylstyrene, para-methylstyrene, 1,1-diphenylethylene, para tert-butylstyrene, vinyltoluene and mixtures thereof.
  • Ethylenically unsaturated monomers from which the thermoplastic polymers can be built up in the shell of the particles present as component (A) are selected from the group consisting of esters and nitriles of ⁇ , ⁇ -unsaturated mono- and dicarboxylic acids.
  • Preferred esters of these ⁇ , ⁇ -unsaturated monocarboxylic acids are reaction products of said monocarboxylic acid with compounds which carry at least one OH function, ie with monohydric or polyhydric alcohols.
  • Preferred methacrylic acid esters are C 1 -C 8 -alkyl esters of methacrylic acid, provided the glass transition temperature is> 25 ° C., for example methyl methacrylate (MMA), ethyl methacrylate, n-, i-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate. Butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octylmethyl acrylate or 2-ethylhexyl methacrylate.
  • MMA methyl methacrylate
  • Preferred acrylic acid esters are C 1 -C 8 -alkyl esters of acrylic acid, provided the glass transition temperature is> 25 ° C., 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. It is also possible to use mixtures of two or more acrylates and / or methacrylates.
  • 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 can be present in the thermoplastic polymer which forms the shell of the particle present as component (A), provided that the glass transition temperature of the thermoplastic polymer is> 25 ° C.
  • 1,3-dienes particularly preferably 1,3-butadiene, 2,3-dimethylbutadiene, 1,3-pentadiene (piperylene) and / or isoprene. Since the glass transition temperature should be> 25 ° C, these monomers can be used only in small amounts, for example less than 25 wt .-%, preferably less than 15 wt .-%.
  • the shell of the particles present as component (A) comprises at least one thermoplastic polymer selected from the group consisting of polymethylmethacrylate (PMMA), poly-n-butylmethacrylate (PBMA), polystyrene, styrene-acrylonitrile (SAN), homopolymers and copolymers from vinylic, aromatic monomers, ethylenically unsaturated monomers and optionally small amounts of dienes and mixtures thereof.
  • PMMA polymethylmethacrylate
  • PBMA poly-n-butylmethacrylate
  • SAN styrene-acrylonitrile
  • Particularly preferred monomer combinations in copolymers are styrene / acrylonitrile, alpha-methylstyrene / acrylonitrile, alpha-methylstyrene / styrene / acrylonitrile, styrene / methyl methacrylate, styrene /
  • polystyrene or copolymers containing styrene are 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 preferably 5000 to 500 000 g / mol, more preferably 10000 to 200000 g / mol.
  • the polymer preferably used according to the invention can be introduced in the form of a block copolymer in combination with a diene block.
  • the mass ratio of B to S in the range 35/65 to 90/10, more preferably 40/60 to 80/20.
  • These block polymers are preferably prepared by anionic polymerization.
  • B-based diene rubbers are radically grafted with type S monomers.
  • 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 5,000 to 300,000 g / mol, particularly preferably 10,000 to 200,000 g / mol. Methods of making a suitable SAN copolymer are known to those skilled in the art.
  • the bonding of the at least one thermoplastic material present in the shell to the polymerized vegetable oil or copolymer built up from vegetable oil and at least one ethylenically unsaturated monomer which is present in the particle can occur by intermolecular interactions or by covalent bonds, in each case between the molecules of the thermoplastic material and the molecules of the polymerized vegetable oil or of the copolymer composed of vegetable oil and at least one ethylenically unsaturated monomer in the core.
  • the shell of the particle prefferably bound to the polymerized vegetable oil present in the particle by polymerization of the monomers which are suitable for the shell or to the copolymer composed of vegetable oil and at least one ethylenically unsaturated monomer.
  • At least one block or grafted rubber to which the thermoplastic polymer can be attached by grafting is present in the shell of the particle present as component A, optionally in addition to the said thermoplastic polymers.
  • ABS copolymers in uncrosslinked form, butadiene-styrene copolymers or block copolymers which have at least one hard block composed of at least one styrenic monomer or a derivative thereof and at least one soft block made of a styrene monomer and at least one diene, for example SBS Copolymers, used in component A.
  • SBS Copolymers SBS Copolymers
  • rubbers are used according to the invention, they are added in non-agglomerated, non-crosslinked form.
  • ABS copolymers are copolymers composed of acrylic acid, butadiene and styrene. Methods of making ABS copolymers are known to those skilled in the art. According to the invention, uncrosslinked ABS copolymers are used.
  • SBS copolymers are block copolymers made up of styrene and butadiene. SBS copolymers and processes 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, in particular 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 preferably 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, for. For example, 3-ethyl-3-pentanol and 2,3-dimethyl-3-pentanol. Particularly suitable is tetrahydrolinalool (3,7-dimethyl-3-octanol).
  • other potassium salts which are inert to metal alkyls are also suitable in principle.
  • the polymerization temperature can be between 0 and 130 ° C.
  • Further additives suitable for the preparation of the random styrene and diene-containing blocks according to the invention are ethers, for example tetrahydrofuran, and tertiary amines, for example tetramethylethylenediamine (TMEDA). By these additives, the proportion of more reactive vinylic side groups is increased, which contributes according to the invention to bind the styrene diene blocks to the vegetable oil polymer.
  • 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.
  • Vegetable oil-based polymers each functionalized preferably with maleic anhydride and the crosslinking is preferably carried out by reagents having at least two hydroxyl functions.
  • the production of the cross-linked plant peoples and the selection of the graft shell are independent of one another, wherein an adjustment of the polarity of the polymeric vegetable oil with the rubber blocks or the rubber graft base is preferably carried out.
  • pure vegetable oil in particular linseed oil
  • 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 ⁇ , preferably 1 to 10 ⁇ on.
  • the shell of the particle present as component A generally has a layer thickness of 10 to 100 nm.
  • 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.
  • Another possibility according to the invention consists in grafting polymer chains, for example polystyrene, SAN, PMMA, onto the polypvegetable oil at different times. This can already happen at the stage of the pure oil, where the monomer is introduced together with the oil and then polymerized at temperatures which lead to the desired molar mass, for example between 100 and 250.degree. The oil is then partially grafted, but hardly polymerized. It is preferred to use the polypvegetable oil instead.
  • Another possibility is to first crosslink the polypvegetable oil, then to swell the crosslinked particles with monomer and possibly radical starter and then to polymerize the dispersion. This procedure gives a particularly reliable connection of the thermoplastic chains to the polymer oil.
  • the matrix can be polymerized.
  • the polymerized vegetable oil is reacted with maleic anhydride (MSA) for functionalization.
  • MSA maleic anhydride
  • this functionalized polymer is reacted with a small amount, preferably markedly substoichiometric with respect to MSA, of monomers containing at least one double bond and at least one hydroxyl function, for example hydroxymethyl methacrylate (HEMA) or allyl alcohol, so that double bonds are present on the particle surface.
  • HEMA hydroxymethyl methacrylate
  • allyl alcohol hydroxymethyl methacrylate
  • the polymerized vegetable oil is functionalized with hydroxy functions.
  • this functionalized polymer with a small amount, preferably clearly substoichiometric based on the introduced hydroxy functions, monomers containing at least one double bond and at least one carboxylic acid function, for example reactive (meth) acrylic acids, MSA, chlorides or anhydrides of unsaturated carboxylic acids or unsaturated isocyanates , Reacted so that double bonds are obtained at the particle surface, since the carboxylic acid functions react with the on-surface hydroxy functions. These can then be reacted with the monomers that make up the polymer of the matrix.
  • Component B is a compound having Component B:
  • thermoplastic molding composition according to the invention contains at least one thermoplastic polymer as component (B). This thermoplastic polymer forms the so-called "matrix" of the thermoplastic molding composition.
  • thermoplastic polymers known to the person skilled in the art can be used as component (B) in the thermoplastic molding composition according to the invention.
  • At least one thermoplastic polymer which is compatible with the at least one thermoplastic polymer which is present in the optionally present shell of the particles is preferably used as component (B).
  • compatible means that a good interfacial adhesion is achieved in order to ensure the mechanical binding of the vegetable oil particles and, furthermore, that no incompatibility reactions between the two thermoplastics occur, for example decomposition, segregation, chemical reactions, discolorations or negative effects on the mechanical properties of the thermoplastic molding composition according to the present invention.
  • Thermoplastic polymers suitable as component B are preferably selected from the group consisting of copolymers of at least one vinylic aromatic monomer and optionally at least one ⁇ , ⁇ -unsaturated mono- carboxylic acid or the corresponding nitrile, for example polystyrene (PS) or styrene-acrylonitrile (SAN).
  • PS polystyrene
  • SAN styrene-acrylonitrile
  • thermoplastic polymers are selected from the group consisting of polycarbonates (PC), polyurethanes (PU), polyesters such as polyethylene terephthalates (PET) or polybutylene terephthalates (PBT), polyvinyl chlorides (PVC), polyurethanes (PU), polyoxymethylenes (POM), Polymethyl methacrylates (PMMA), and biodegradable homo- and copolymers, such as polylactides or polybutyrate.
  • PC polycarbonates
  • PU polyurethanes
  • PET polyethylene terephthalates
  • PBT polybutylene terephthalates
  • PVC polyvinyl chlorides
  • PU polyurethanes
  • POM polyoxymethylenes
  • PMMA Polymethyl methacrylates
  • biodegradable homo- and copolymers such as polylactides or polybutyrate.
  • the at least one thermoplastic polymer 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 containing 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-resp. 2,6-toluene diisocyanate, 4,4'-methylene di (phenyl isocyanate) and hexamethylene diisocyanate. It can be used linear or branched polyurethanes.
  • thermoplastic molding composition in a preferred embodiment, at least one biodegradable polymer is used as component B.
  • biodegradable polymers are known to the person skilled in the art, for example polylactides or polybutyrate.
  • 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 for biodegradable polymers from a mixture of aromatic and aliphatic esters based on poly-epsilon-caprolactone and 1, 4-butanediol With regard to the styrene polymers (and also of the other polymers), block copolymers of the type SBS, SEBS, SIS and SEPS can be used.
  • component B if the shell of the particle (component A) contains polystyrene, polystyrene is also used, optionally in admixture with a styrene-butadiene block copolymer.
  • component B if the shell of the particle (component A) contains styrene-acrylonitrile, likewise styrene / acrylonitrile, polymethyl methacrylate, styrene / MMA, polyester, polyurethane or polylactide are used, optionally in admixture with the abovementioned styrene butadiene block copolymers.
  • thermoplastic polymer used as component B is in the thermoplastic molding composition according to the invention generally 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 composition, before.
  • Component C is in the thermoplastic molding composition according to the invention generally 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 composition, before.
  • thermoplastic molding composition according to the present invention optionally contains as component C at least one resin as component (C).
  • both synthetically prepared resins and naturally occurring resins can be used.
  • thermoplastic molding composition of the present invention A selection of natural resins that can be used in the thermoplastic molding composition of the present invention is disclosed in: Natural Resins, Wiley-VCH Verlag, Weinheim, 2005, pages 1-19.
  • 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.
  • 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.
  • the at least one resin (component C) is present in the particles (component A).
  • the present invention therefore preferably relates to the molding composition according to the invention, wherein at least one resin (component C) is present in the particles (component A).
  • component C is present in the thermoplastic molding composition according to the invention, it is generally present in an amount of from 1 to 30% by weight, preferably from 5 to 30% by weight, particularly preferably from 10 to 30% by weight, in each case based on the total mass of the thermoplastic molding composition according to the invention. These resins increase the glass transition temperature of component A and make the product stiffer.
  • Component D is generally present in an amount of from 1 to 30% by weight, preferably from 5 to 30% by weight, particularly preferably from 10 to 30% by weight, in each case based on the total mass of the thermoplastic molding composition according to the invention.
  • thermoplastic molding composition according to the invention contains at least one filler as component D.
  • 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, for example, recycled bottle corks and wood flour, preferably having a particle size of less than 0.5 mm, more preferably less than 0.2 mm.
  • the proportion of wood flour may be above 50 wt .-%, preferably above 70 wt .-%, wherein the maximum amount is 90 wt .-%.
  • the wood flour is added to the melt of the finished thermoplastic.
  • WPCs wood-plastic composites
  • polymers containing acid anhydride groups for example, prepared by copolymerization with 1 to 10 wt .-% maleic anhydride wherein the anhydride groups react with the wood components.
  • fatty acid-based waxes such as stearylamide or erucic acid amide are preferably added in amounts of up to 5% by weight.
  • Another particularly preferred filler is calcium carbonate.
  • the suitable particle size of the filler used as component D is known to the person skilled in the art. If component D is present in the thermoplastic molding composition according to the invention, this is generally present for mineral fillers in an amount of up to 50% by weight, preferably 20 to 30% by weight.
  • component E in the thermoplastic molding composition according to the invention.
  • Suitable further additives are generally known to the person skilled in the art, 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 , The sum of the amounts of components A and B present in the thermoplastic molding composition according to the invention and optionally C, D and / or E is in each case 100% by weight.
  • the present invention also relates to a process for the preparation of the thermoplastic molding composition according to the invention, comprising at least the steps: non-oxidative polymerization of at least one vegetable oil, optionally in the presence of at least one ethylenically unsaturated monomer, to a polymerized vegetable oil or a copolymer of vegetable oil and at least one ethylenically unsaturated monomer, and
  • step (1) Introducing functional groups into the polymerized vegetable oil or into the copolymer of vegetable oil and at least one ethylenically unsaturated monomer from step (1) in order to obtain a functionalized polymerized vegetable oil or copolymer of vegetable oil and at least one ethylenically unsaturated monomer,
  • step (3) introducing functional groups into at least one vegetable oil to obtain a functionalized vegetable oil; and non-oxidatively polymerizing the functionalized vegetable oil of step (3) optionally in the presence of at least one ethylenically unsaturated monomer to form a functionalized polymerized vegetable oil or To obtain a copolymer of vegetable oil and at least one ethylenically unsaturated monomer,
  • thermoplastic polymer (component B) Adding the at least one thermoplastic polymer (component B) to the functionalized polymerized vegetable oil or copolymer Vegetable oil and at least one ethylenically unsaturated monomer from step (2) or (4) to obtain a mixture, and
  • sequence (1), (2), (5) and (6) preference is given to the sequence (1), (2), (5) and (6). More preferred is the order (3), (4), (5) and (6).
  • sequence (5), (1), (2) and (6) or (5), (3), (4) and (6) is also possible according to the invention.
  • Step (1) The individual steps of the method according to the invention are described in detail below: Step (1):
  • Step (1) of the process according to the invention comprises the non-oxidative polymerization of at least one vegetable oil, optionally in the presence of at least one ethylenically unsaturated monomer, to obtain a polymerized vegetable oil or a copolymer of vegetable oil and at least one ethylenically unsaturated monomer.
  • the at least one vegetable oil optionally in the presence of at least one ethylenically unsaturated monomer, can be treated with all non-oxidative processes known to those skilled in the art which result in at least partial polymerization of the at least one vegetable oil and / or with the optionally present one
  • non-oxidative means that in step (1) of the process according to the invention, no substances which have an oxidizing effect on the at least one vegetable oil are present.
  • the polymerization of the vegetable oil in step (1) is carried out by a Diels-Alder reaction, for example intermolecularly and / or intramolecularly, more preferably by an intermolecular Diels-Alder reaction.
  • the present invention therefore preferably relates to the process according to the invention, wherein the polymerization in step (1) is effected by a Diels-Alder reaction.
  • the polymerization in step (1) is effected by a Diels-Alder reaction.
  • this is reacted in step (1) under conditions which result in a polymerization of the at least one vegetable oil in a Diels-Alder reaction, preferably in an intermolecular diene. Alder reaction, lead.
  • the Diels-Alder reaction is known to those skilled in the art and described, for example, in J. March, Advanced Organic Chemistry, Third Edition, Wiley-Interscience 1985, pages 745-768. A schematic representation is shown above with respect to component A of the thermoplastic molding composition.
  • step (1) If at least one vegetable oil which does not have conjugated double bonds is used in the process according to the invention, in a preferred embodiment in step (1) these nonconjugated double bonds are first isomerized to form conjugated double bonds. In a preferred embodiment, this isomerization takes place under the same conditions as the Diels-Alder reaction, so that molecules with unconjugated double bonds are preferably isomerized in situ to molecules having conjugated double bonds.
  • Step (1) of the process according to the invention can be carried out in the presence or absence of a solvent.
  • Suitable solvents are known per se to the person skilled in the art, preferably these do not contain any groups reactive under the prevailing conditions.
  • step (1) is carried out in the absence of a solvent, i. the at least one vegetable oil is reacted in substance.
  • step (1) of the process according to the invention is carried out non-oxidatively, step (1) is carried out in the absence of an oxidizing substance.
  • the polymerization in step (1) is preferably carried out with exclusion of air, for example by superposition / rinsing with protective gas such as nitrogen, argon or carbon dioxide.
  • the non-oxidative polymerization of the at least one vegetable oil in step (1) by a Diels-Alder reaction, preferably an intermolecular Diels-Alder reaction, optionally combined with prior isomerization of unconjugated double bonds into conjugated double bonds, is generally carried out at a temperature. which ensures a sufficient reaction rate, in a preferred embodiment, step (1) of the method according to the invention in a Temperature of 200 to 400 ° C, more preferably 250 to 350 ° C, for example, 280 to 300 ° C performed.
  • Step (1) of the method according to the invention can be carried out at any pressure, for example at atmospheric pressure.
  • the reaction time in step (1) of the process according to the invention is generally chosen so that a sufficiently high conversion, i. a sufficiently high degree of polymerization of at least one vegetable oil is ensured.
  • the reaction time is, for example, 30 to 60 hours, preferably 38 to 50 hours.
  • Step (1) of the process according to the invention can be carried out in any suitable reactor for such a reaction, for example, stirred tank for batch processes, segregated stirred tank, pointed bottom reactor, ROSSkes- cascade, tower reactor or tubular reactor for continuous processes.
  • any suitable reactor for such a reaction for example, stirred tank for batch processes, segregated stirred tank, pointed bottom reactor, ROSSkes- cascade, tower reactor or tubular reactor for continuous processes.
  • step (1) of the process according to the invention comprises the non-oxidative polymerization of at least one vegetable oil in the presence of at least one ethylenically unsaturated monomer to obtain a polymerized vegetable oil or a copolymer of vegetable oil and at least one ethylenically unsaturated monomer.
  • a corresponding method is described in the above-cited Hamann et al. called.
  • Suitable and preferred ethylenically unsaturated monomers which can be used in step (1) of the process according to the invention have already been mentioned above with regard to component (A) of the process according to the invention.
  • step (1) of the process according to the invention is a mixture of at least one vegetable oil and at least one ethylenically unsaturated monomer selected from the group consisting of styrene, ⁇ -methylstyrene, para-methylstyrene, 1,1-diphenylethylene, para-tert-butylstyrene, vinyltoluene, acrylic acid esters, methacrylic acid esters, acrylonitrile, methacrylonitrile and mixtures thereof.
  • a copolymer of the at least one vegetable oil and the at least one ethylenically unsaturated monomer is formed.
  • the at least one vegetable oil preferably polymerizes in the Diels-Alder reaction described above.
  • the present at least one ethylenically unsaturated monomer polymerizes with itself, with the least amount of at least one vegetable oil and / or already formed Diels-Alder products, preferably in a free-radical polymerization.
  • the present invention also relates to the process according to the invention, wherein the polymerization of the vegetable oil or of the vegetable oil polymer and of the ethylenically unsaturated monomer in step (1) or (4) is a thermally induced polymerization.
  • radicals necessary for this purpose do not enter the reaction mixture by free-radical initiators known to the person skilled in the art but to be added from the outside, but that these radicals are prepared from the present monomers under the temperatures according to the invention, ie. H. thermally, be formed.
  • the at least one ethylenically unsaturated monomer is added for this purpose to the at least one vegetable oil, generally in an amount in which it is also to be present in the polymeric material forming the particle.
  • 5 to 60% by weight, preferably 15 to 50% by weight, of at least one ethylenically unsaturated monomer are added in order to polymerize together with the at least one vegetable oil under the conditions prevailing in step (1) of the process according to the invention.
  • the polymeric material obtained in step (1) of the process according to the invention based on at least one vegetable oil and optionally at least one ethylenically unsaturated monomer, is present in a preferred embodiment as a viscous, pale yellow oil or as a rubber.
  • the at least one thermoplastic polymer or ethylenically unsaturated monomer constituting the thermoplastic polymer, optionally present in the shell of the particles is added in step (1) so that the particles contain forming polymeric material based on at least one vegetable oil as the core and a shell of at least one thermoplastic polymer in step (1).
  • thermoplastic polymer or ethylenically unsaturated monomer constituting the thermoplastic polymer is added in step (1) so that the particles contain forming polymeric material based on at least one vegetable oil as the core and a shell of at least one thermoplastic polymer in step (1).
  • thermoplastic polymer (s) present in the shell of the particles what has been said above with respect to the thermoplastic molding composition of the invention applies.
  • thermoplastic polymer or the corresponding monomers present in the shell of the particles is present in an amount of, for example, 3 to 50% by weight, preferably 5 to 20% by weight. %, in each case based on the sum of the starting materials in step (1) added.
  • Step (2) of the method according to the invention comprises introducing functional groups into the polymerized vegetable oil or into the copolymer of vegetable oil and at least one ethylenically unsaturated monomer from step (1) to form a functionalized polymerized vegetable oil or copolymer of vegetable oil and at least one ethylenic to obtain unsaturated monomers.
  • the polymeric material obtained in step (1) it is reacted with at least one functionalizing compound.
  • Suitable functionalizing compounds and their amounts are mentioned above with respect to the thermoplastic molding composition.
  • the compounds used for the functionalization, in particular maleic anhydride are generally in an amount of 0.1 to 20 wt .-%, preferably 1 to 10 wt .-%, particularly preferably 3 to 9 wt .-%, each based on the polymeric Material used.
  • the functional groups introduced particularly preferably according to the invention are anhydride group and hydroxy group.
  • step (2) of the process according to the invention the polymeric material from step (1) is preferably reacted in an ene reaction with the at least one functionalizing compound, in particular maleic anhydride.
  • the at least one functionalizing compound in particular maleic anhydride.
  • maleic anhydride This is known to those skilled in Ullmann's & U. Poth, Drying Oils and Related Products Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2002, page 12 and in JO Metzger, U. Biermann, Products of Thermal Ene-Reaction of Unsaturated Fats and Maleic Anhydride, Fat Sei. Technol. 96, Vol. 9 (1994) pages 321 to 323.
  • the functionalization of the vegetable oil-based polymer with maleic anhydride can also be carried out simultaneously by a Diels-Alder reaction.
  • step (2) of the process according to the invention are generally carried out at a suitable reaction temperature, for example 100 to 350.degree. C., preferably 150 to 300.degree. C., particularly preferably 160 to 280.degree.
  • the polymeric material obtained in step (1) of the process according to the invention by compounds which have at least two hydroxyl functions. Details and preferred, usable compounds are mentioned above.
  • the triglycerides present in the vegetable oil are converted into compounds having at least one free hydroxyl function in a transesterification reaction by the action of compounds having at least two hydroxyl functions.
  • This transesterification reaction takes place according to the invention preferably under the action of a basic compound, for example an aqueous sodium and / or potassium hydroxide solution or other transesterification catalysts.
  • This transesterification reaction can be carried out, for example, at 100 to 350.degree. C., preferably 150 to 300.degree. C., particularly preferably 160 to 280.degree.
  • a polymeric material which contains functional groups, preferably carboxylic acid and / or hydroxyl groups, more preferably succinic groups and / or hydroxy groups.
  • all steps are carried out in the absence of a solvent, i. H. in substance.
  • steps (1) and (2) of the method according to the invention belong to a first embodiment, in which initially a polymeric material is formed, which is subsequently functionalized.
  • a second embodiment of the method according to the invention includes the steps (3) and (4), wherein first a vegetable oil is functionalized, and this functionalized vegetable oil is optionally reacted in the presence of further ethylenically unsaturated monomers in a polymeric material. Step 3):
  • Step (3) of the method of the invention comprises introducing functional groups into at least one vegetable oil to obtain a functionalized vegetable oil.
  • the functionalization in step (3) is analogous to the functionalization according to step (2) of the method according to the invention with the difference that in step (3) no polymers, but monomers are functionalized.
  • step (3) For the functionalization of the at least one vegetable oil according to step (3), this is reacted with at least one functionalizing compound.
  • Suitable functionalizing compounds and their amounts are mentioned above with respect to the thermoplastic molding composition. Particular preference is given to using ⁇ , ⁇ -unsaturated mono-, dicarboxylic acids, esters, anhydrides or nitriles thereof or compounds having at least two hydroxyl functions thereof for functionalization. Very particularly preferred examples are maleic acid and / or maleic anhydride, in particular maleic anhydride.
  • the compounds used for functionalization, especially maleic anhydride are generally in an amount of 0, 1 to 20 wt .-%, preferably 1 to 10 wt .-%, particularly preferably 3 to 9 wt .-%, each based on the at least one vegetable oil used.
  • the at least one vegetable oil is preferably reacted in an ene reaction with the at least one functionalizing compound, in particular maleic anhydride.
  • the at least one functionalizing compound in particular maleic anhydride.
  • step (3) of the process according to the invention are generally carried out at a suitable reaction temperature, for example 100 to 350 ° C, preferably 150 to 300 ° C, particularly preferably 160 to 280 ° C.
  • step (3) of the process according to the invention it is also possible in step (3) of the process according to the invention to functionalize at least one vegetable oil by means of compounds which have at least two hydroxyl functions. Details and preferred, usable compounds are mentioned above.
  • the triglycerides present in the vegetable oil are converted by the action of compounds having at least two hydroxyl functions to compounds having at least one free hydroxyl function.
  • This transesterification reaction is carried out according to the invention preferably under the action of a basic compound, for example an aqueous sodium and / or potassium hydroxide solution or other transesterification catalysts.
  • This transesterification reaction can be carried out, for example, at 100 to 350.degree. C., preferably 150 to 300.degree. C., particularly preferably 160 to 280.degree.
  • a monomeric material which is based on at least one vegetable oil and contains functional groups, preferably carboxylic acid and / or hydroxyl groups, more preferably succinic groups and / or hydroxy groups.
  • Step (4) of the process of the invention comprises the non-oxidative polymerization of the functionalized vegetable oil of step (3), optionally in the presence of at least one ethylenically unsaturated monomer, to obtain a functionalized polymerized vegetable oil or copolymer of vegetable oil and at least one ethylenically unsaturated monomer ,
  • step (4) of the process according to the invention corresponds to the polymerization described with respect to step (1), with the difference that in step (4) already functionalized vegetable oil molecules are used, whereas in step (1) (still) unfunctionalized vegetable oil molecules be used.
  • Step (4) of the process according to the invention comprises the non-oxidative polymerization of at least one functionalized vegetable oil, optionally in the presence of at least one ethylenically unsaturated monomer, to obtain a polymerized, functionalized vegetable oil or a functionalized copolymer of vegetable oil and at least one ethylenically unsaturated monomer ,
  • the at least one functionalized vegetable oil if appropriate in the presence of at least one ethylenically unsaturated monomer, can be treated with all non-oxidative processes known to the person skilled in the art which result in at least partial polymerization of the at least one vegetable oil and / or with the optionally present at least one an ethylenically unsaturated monomer.
  • Non-oxidative in the sense of the present invention means that in step (4) of the process according to the invention, no substances which have an oxidizing effect on the at least one functionalized vegetable oil are present.
  • the polymerization in step (4) is carried out by a Diels-Alder reaction, for example intermolecularly and / or intramolecularly, more preferably by an intermolecular Diels-Alder reaction.
  • step (4) in which only at least one functionalized vegetable oil is used, this is reacted in step (4) under conditions which result in a polymerization of the at least one functionalized vegetable oil in a Diels-Alder reaction, preferably in an intermolecule - laren Diels-Alder reaction.
  • Diels-Alder reaction is known to those skilled in the art. and described, for example, in J. March, Advanced Organic Chemistry, Third Edition, Wiley-Interscience 1985, pages 745-768. A schematic representation is shown above with respect to component A of the thermoplastic molding composition.
  • step (4) are first isomerized to form conjugated double bonds.
  • this isomerization takes place under the same conditions as the Diels-Alder reaction, so that molecules having unconjugated double bonds are preferably isomerized in situ to molecules having conjugated double bonds.
  • Step (4) of the process according to the invention can be carried out in the presence or absence of a solvent.
  • Suitable solvents are known per se to those skilled in the art, preferably they do not contain any reactive groups under the prevailing conditions.
  • step (4) is carried out in the absence of a solvent, i. H. the at least one functionalized vegetable oil is reacted in substance.
  • step (4) is carried out in the absence of an oxidizing substance.
  • step (4) is preferably carried out with exclusion of air, for example by superposition / rinsing with protective gas such as nitrogen, argon or carbon dioxide.
  • the non-oxidative polymerization of the at least one functionalized vegetable oil in step (4) by a Diels-Alder reaction, preferably an intermolecular Diels-Alder reaction, optionally combined with prior isomerization of non-conjugated double bonds into conjugated double bonds, is generally carried out at one temperature , which ensures a sufficient reaction rate, in a preferred embodiment, step (4) of the inventive method at a temperature of 200 to 400 ° C, more preferably 250 to 350 ° C, for example 280 to 300 ° C.
  • Step (4) of the process according to the invention can be carried out at any pressure, for example at atmospheric pressure.
  • the reaction time in step (4) of the process according to the invention is generally chosen so that a sufficiently high conversion, ie a sufficiently high degree of polymerization of the at least one vegetable oil is ensured.
  • the reaction time is, for example, 30 to 60 hours, preferably 38 to 50 hours.
  • Step (4) of the process according to the invention can be carried out in any reactor which appears suitable for such a reaction, for example stirred tanks for batch processes, segregated stirred tank, pointed bottom reactor, stirred tank cascade, tower reactor or tubular reactor for continuous processes.
  • any reactor which appears suitable for such a reaction, for example stirred tanks for batch processes, segregated stirred tank, pointed bottom reactor, stirred tank cascade, tower reactor or tubular reactor for continuous processes.
  • step (4) of the process according to the invention comprises the non-oxidative polymerization of at least one functionalized vegetable oil in the presence of at least one ethylenically unsaturated monomer to form a polymerized vegetable oil or a copolymer of functionalized vegetable oil and at least one to obtain ethylenically unsaturated monomers.
  • a suitable method is described, for example, in the above mentioned document Hamann et al. called.
  • Suitable and preferred ethylenically unsaturated monomers which can be used in step (4) of the process according to the invention have already been mentioned above with respect to step (1) of the process according to the invention.
  • step (4) of the process according to the invention is a mixture of at least one functionalized vegetable oil and at least one ethylenically unsaturated monomer selected from the group consisting of styrene, ⁇ -methylstyrene, para-methylstyrene, 1, 1-diphenylethylene , para-tert-butylstyrene, vinyltoluene, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, acrylonitrile, methacrylonitrile and mixtures thereof.
  • a copolymer of the at least one vegetable oil and the at least one ethylenically unsaturated monomer is formed.
  • the at least one functionalized vegetable oil preferably polymerizes in the above-described Diels-Alder reaction.
  • the present at least one ethylenically unsaturated monomer polymerizes with itself, with the at least one vegetable oil and / or with already formed Diels-Alder products, preferably in a free-radical polymerization.
  • radicals necessary for this purpose are not known to the person skilled in the art and to be added from the outside to the radical initiator Reaction mixture, but that these radicals from the present monomers under the present invention temperatures, ie thermally formed.
  • the at least one ethylenically unsaturated monomer is added for this purpose to the at least one functionalized vegetable oil, generally in an amount in which it is also to be present in the particulate-forming polymeric material.
  • 5 to 60% by weight, preferably 15 to 50% by weight, of at least one ethylenically unsaturated monomer is added in order to polymerize together with the at least one functionalized vegetable oil under the conditions prevailing in step (4) of the process according to the invention.
  • the polymeric material obtained in step (4) of the process according to the invention based on at least one functionalized vegetable oil and optionally at least one ethylenically unsaturated monomer is present in a preferred embodiment as a viscous oil.
  • the at least one thermoplastic polymer or ethylenically unsaturated monomer constituting the thermoplastic polymer, optionally present in the shell of the particles is added in step (4), such that the particles contain a polymeric Form material based on at least one functionalized vegetable oil as a core and a shell of at least one thermoplastic polymer in step (4).
  • thermoplastic polymer or the corresponding monomers which are or are present in the shell of the particles what has been said above with respect to the thermoplastic molding composition according to the invention applies.
  • thermoplastic polymer or the corresponding monomers present in the shell of the particles is present in an amount of, for example, 3 to 50% by weight, preferably 5 to 20% by weight. %, in each case based on the sum of the starting materials in step (4) added.
  • Step (5) of the process of the invention comprises adding the at least one thermoplastic polymer (component B) to the functionalized polymerized vegetable oil or copolymer of vegetable oil and at least one ethylenically unsaturated monomer from step (2) or (4) to form a mixture receive.
  • step (5) can be carried out completely or partially before step (1) or (3), depending on the embodiment. However, step (5) is preferably carried out after step (2) or step (4).
  • Step (5) of the process according to the invention comprises the addition of the matrix material present in the inventive thermoplastic molding material to the functionalized polymers obtained from steps (2) or (4).
  • thermoplastic polymers which are added in step (5) have already been mentioned above with respect to component (B).
  • thermoplastic polymer which is added in step (5) according to the invention forms the so-called "matrix" of the thermoplastic molding composition
  • thermoplastic polymers known to those skilled in the art can be admixed.
  • step (5) preference is given to using at least one thermoplastic polymer which is compatible with the at least one thermoplastic polymer which is present in the optionally present shell of the particles.
  • compatible means that a good interfacial adhesion is achieved in order to ensure the mechanical binding of the vegetable oil particles and, furthermore, that no incompatibility reactions between the two thermoplastics occur, for example decomposition, segregation, chemical reactions, discoloration or negative influences the mechanical properties of the thermoplastic molding composition according to the present invention.
  • Suitable thermoplastic polymers are preferably 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
  • thermoplastic polymers are selected from the group consisting of polycarbonates (PC), polyurethanes (PU), polyamides (PA), polyesters such as polyethylene terephthalates (PET) or polybutylene terephthalates (PBT), polyether ether ketones (PEEK), polyvinyl chlorides (PVC), polyurethanes (PU), polyoxymethylenes (POM), polyethersulfones (PES), poly-n-butylmethacrylates (PBMA), polymethylmethacrylates (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 polyether ether ketones
  • PVC polyvinyl chlorides
  • POM polyurethanes
  • POM polyoxymethylenes
  • PES polyethersul
  • the at least one thermoplastic polymer admixed in step (5) is 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
  • thermoplastic polymers are selected from the group consisting of polycarbonates (PC), polyurethanes (PU), polyesters such as polyethylene terephthalates (PET) or polybutylene terephthalates (PBT), polyvinyl chlorides (PVC), polyurethanes (PU), polyoxymethylenes (POM), polymethyl methacrylates ( PMMA), and biodegradable homo- and copolymers, for example polylactides or polybutyrate.
  • PC polycarbonates
  • PU polyurethanes
  • PET polyethylene terephthalates
  • PBT polybutylene terephthalates
  • PVC polyvinyl chlorides
  • PU polyurethanes
  • POM polyoxymethylenes
  • PMMA polymethyl methacrylates
  • biodegradable homo- and copolymers 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 process 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, for example, from 2,4-resp. 2,6-toluene diisocyanate, 4,4'- Methylene di (phenyl isocyanate) and hexamethylene diisocyanate. It can be used linear or branched polyurethanes.
  • thermoplastic molding composition according to the invention at least one biodegradable polymer is used in step (5).
  • biodegradable polymers are known to the person skilled in the art, for example polylactides or polybutyrate.
  • Polylactides which are 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.
  • step (5) may also be a mixture of said thermoplastics with each other with so-called tougheners, which are preferably selected from the group consisting of SBS copolymers, preferably used for styrene polymers, and for styrene copolymers and polyesters, for example, a mixture of aromatic and aliphatic esters Base poly-epsilon-caprolactone and 1,4-butanediol.
  • tougheners are preferably selected from the group consisting of SBS copolymers, preferably used for styrene polymers, and for styrene copolymers and polyesters, for example, a mixture of aromatic and aliphatic esters Base poly-epsilon-caprolactone and 1,4-butanediol.
  • step (5) if the shell of the particle (component A) contains polystyrene, polystyrene is also used, optionally in admixture with an SBS copolymer. In a further preferred embodiment, in step (5), if the shell of the particle (component A) contains styrene-acrylonitrile, likewise styrene-acrylonitrile, polyester, polyurethane or polylactide is used, optionally mixed with the abovementioned SBS copolymers, soft polyurethanes or polyesters. In step (5), the at least one thermoplastic polymer is added in an amount of 20 to 80% by weight.
  • thermoplastic component in each case based on the total mass of the thermoplastic molding composition, admixed.
  • step (5) of the process according to the invention can be carried out by all methods known to the person skilled in the art, for example in an extruder, kneader, LIST reactor or static melt mixer.
  • Step (5) of the process according to the invention can be carried out at any temperature that appears appropriate to the person skilled in the art, preferably at a temperature at which both the functionalized polymer from step (2) or (4) and the matrix material can be mixed, for example from 120 to 320 ° C, preferably 180 to 280 ° C.
  • step (5) takes place until sufficient mixing of the individual components has been achieved, for example a few minutes.
  • Step (6) of the process of the invention comprises crosslinking the mixture of step (5) by adding at least one reagent which reacts with the functional groups introduced in step (2) or (3) to obtain the thermoplastic molding composition.
  • the functional groups introduced into the at least one vegetable oil or the abovementioned polymer in particular hydroxyl, carboxylic acid, carboxylic ester and / or carboxylic anhydride groups, can be reacted with appropriate reagents in order to achieve crosslinking via these functional groups. Since, in a preferred embodiment, reagents are used which have at least two functional groups which can react with the functional group present in the vegetable oil or the polymer, the functionalized polymer is crosslinked by reaction with these reagents.
  • suitable reagents for crosslinking are, for example, compounds selected from the group consisting of compounds containing at least two OH, NH 2 , NHR functions, particularly preferred are diols such as Glycol or 1,4-butanediol, polyols such as glycerol and pentaerythritol, diamines such as hexamethylenediamine, amino alcohols such as ethanolamine or N-methylethanolamine, and mixtures thereof.
  • suitable reagents for crosslinking are, for example, compounds selected from the group consisting of compounds containing at least two isocyanate functions, epoxy functions, carboxylic anhydride functions and / or carboxylic acid function, particularly preferred are hexamethylene diisocyanate , Tolylene diisocyanate, methylenedicyclohexyl diisocyanate, isophorone diisocyanate, the product class of glycidyl ethers (Araldite), products from the double addition of maleic anhydride to olefins and the single and / or double MSA addition per double bond to dienes or oligoenes, and mixtures thereof.
  • suitable reagents for crosslinking are, for example, compounds selected from the group consisting of compounds containing at least two isocyanate functions, epoxy functions, carboxylic anhydride functions and / or carboxylic acid function, particularly preferred are hexamethylene diisocyanate , Tolylene diisocyanate, methylenedi
  • the reagent used is a compound which contains at least two hydroxyl functions
  • ester functions are formed in the polymeric material having the carboxylic acid functions which are preferably present.
  • amide functions are formed in the polymeric material with the preferably present carboxylic acid functions.
  • the reagent used is a compound which contains at least one hydroxyl function and at least one amine function, ester and amide functions are formed in the polymeric material having the carboxylic acid functions which are preferably present.
  • the degree of crosslinking of the crosslinked vegetable oil-based polymers can be determined by rheological methods or by measuring the degree of swelling. These methods are known to the person skilled in the art.
  • step (6) the polymeric material obtained in step (5) is reacted in known reactions with reagents having at least two functional groups which react with the functional group present in the polymer, preferably a carboxylic acid function can be to achieve a crosslinking of the functionalized polymeric material.
  • reagents having at least two functional groups which react with the functional group present in the polymer, preferably a carboxylic acid function can be to achieve a crosslinking of the functionalized polymeric material.
  • Suitable reagents are mentioned above. These are added in step (6) in an amount of generally about 100 mol% based on the functional groups contained in the vegetable oil (co) polymer.
  • Crosslinking is preferably carried out by transesterification, transamidation, esterification, urethanization and / or amidation reactions. Suitable procedural Conditions with respect to temperature, pressure, reactors, catalysts, etc. are known in the art.
  • step (6) of the process according to the invention the cross-linking is carried out in a preferred embodiment under the action of a high shear.
  • Methods or devices for causing a high shear energy to act on a reaction mixture are known to the person skilled in the art, for example kneaders such as two-shaft and multi-shaft kneaders, extruders or LIST reactors.
  • thermoplastic molding composition is obtained, which is crosslinked.
  • the optional components are preferably added at certain points of the process.
  • Component (C), if present, is preferably added prior to cross-linking and / or before or after the addition of the thermoplastic.
  • Component (D) if mineral, if present, is preferably added before or after the addition of the thermoplastic, in the preferred case of wood or cork flour, if present, after crosslinking.
  • thermoplastic molding composition has particularly advantageous mechanical properties, for example high rigidity, high toughness, high scratch resistance, advantageous tribological properties, for example low frictional resistance, low abrasion, and high durability. Therefore, the thermoplastic molding composition according to the invention can be used in all applications in which these particularly advantageous mechanical properties are required, for example in building materials such as floor coverings, films, window frames, insulation and packaging materials, for housings of apparatus, for housing parts, in the automotive sector, for outdoor applications , as unpainted plastic surfaces.
  • the present invention also relates to the use of the thermoplastic molding composition according to the invention in building materials, floor coverings, external cladding of houses, roofing, foils, window frames, insulation and packaging materials, for housing of apparatuses, eg. B. in the electrical or electronics sector, for housing parts, z.
  • apparatuses eg. B. in the electrical or electronics sector
  • housing parts e.g. B.
  • the present invention also relates to building materials, films, window frames, insulating and packaging materials, housings of apparatus, housing parts, sports equipment, toys, bicycles and motorized bicycles, unpainted plastic surfaces containing a thermoplastic molding composition according to the invention.
  • the articles mentioned consist of the thermoplastic molding composition according to the invention.
  • Crosslinking The crosslinker is calculated at 65% conversion of the maleination.
  • BUNA-SAN BUNA 565 SIC with Grafted Styrene (76) / Acry I n itri I (24).
  • the grafted rubber contains about 30 wt .-% free SAN copolymer, which is attributed to the matrix.
  • the speed of the list reactor refers to the gearbox and amounts to a maximum of 3000 rpm. Converted to the cleaning shaft this corresponds to a speed of 332 U / min and for the stirrer shaft of 83 U / min.
  • the addition of the appropriate compatibilizer (shell) and maleic anhydride takes place uniformly over the 4 filler neck.
  • the list reactor is closed with the couplings and purged with nitrogen. Before heating, the nitrogen and exhaust pipes are closed so that sublimated MSA is not expelled.
  • the painting is operated for 12 hours at 210 ° C and a speed of 300 rev / min (engine speed), a pressure build-up is not observed. Unreacted MSA is expelled at 220 ° C by means of nitrogen transmission.
  • the corresponding matrix polymer is filled evenly at 120 to 150 ° C with nitrogen countercurrent in the Listreaktor.
  • Camlock couplings with nitrogen and exhaust gas connection can be flexibly changed at the 4 filler neck.
  • the compounding is carried out for 0.5 hours at 240 ° C and a speed of 300 rev / min.
  • the direction of rotation of the two opposing shafts is changed regularly to counteract the existing conveying effect.
  • the corresponding crosslinker is added at 240 ° C via the 4 filler neck and the reactor is heated to 280 ° C.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

La présente invention concerne une matière à mouler thermoplastique, contenant au moins des particules d'huile végétale non-oxydante polymérisée, qui est réticulée par des groupes fonctionnels, comme composant (A), au moins un polymère thermoplastique, comme composant (B), le cas échéant au moins une résine, comme composant (C), le cas échéant au moins une charge, comme composant (D) et le cas échéant d'autres additifs. L'invention concerne également un procédé pour produire ladite matière à mouler thermoplastique ainsi que son utilisation.
EP11746262.2A 2010-08-25 2011-08-24 Matière à mouler thermoplastique, procédé pour sa fabrication et son utilisation Withdrawn EP2609246A1 (fr)

Priority Applications (1)

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EP11746262.2A EP2609246A1 (fr) 2010-08-25 2011-08-24 Matière à mouler thermoplastique, procédé pour sa fabrication et son utilisation

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10173970 2010-08-25
EP11746262.2A EP2609246A1 (fr) 2010-08-25 2011-08-24 Matière à mouler thermoplastique, procédé pour sa fabrication et son utilisation
PCT/EP2011/064514 WO2012025554A1 (fr) 2010-08-25 2011-08-24 Matière à mouler thermoplastique, procédé pour sa fabrication et son utilisation

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EP2609246A1 true EP2609246A1 (fr) 2013-07-03

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US8697795B2 (en) 2010-08-25 2014-04-15 Konrad Knoll Thermoplastic linoleum

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GB452944A (en) * 1934-06-30 1936-09-02 Congoleum Nairn Inc Improvements in or relating to mouldable compositions and the manufacture of linoleum or the like
DE3843482A1 (de) * 1988-12-23 1990-06-28 Huels Troisdorf Verfahren zur herstellung von flaechengebilden wie boden- oder wandbelaegen, insbesondere aus naturoelen
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
DE19615533A1 (de) 1996-04-19 1997-10-23 Basf Ag Thermoplastische Formmasse
DE19906832C2 (de) * 1999-02-18 2003-06-26 Dlw Ag Kontinuierliches Verfahren zur Herstellung eines vernetzten Bindemittels auf Basis ungesättigter Fettsäuren und/oder Fettsäureester, das Bindemittel sowie seine Verwendung
WO2000060013A1 (fr) * 1999-04-02 2000-10-12 Sanyo Chemical Industries, Ltd. Materiau pour resine destinee a la coupe, produit en resine moule comme matiere premiere pour modele et procede de fabrication de modele
ATE506484T1 (de) * 2007-12-13 2011-05-15 Basf Se Thermoplastisches linoleum
DE102008052116A1 (de) 2008-10-20 2010-04-22 Lanxess Deutschland Gmbh Kautschukmischungen mit funktionalisierten Dienkautschuken und Mikrogelen, ein Verfahren zur Herstellung und deren Verwendung

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CN103154357A (zh) 2013-06-12
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