EP3242910A1 - Matériau composite organique - Google Patents

Matériau composite organique

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Publication number
EP3242910A1
EP3242910A1 EP16701421.6A EP16701421A EP3242910A1 EP 3242910 A1 EP3242910 A1 EP 3242910A1 EP 16701421 A EP16701421 A EP 16701421A EP 3242910 A1 EP3242910 A1 EP 3242910A1
Authority
EP
European Patent Office
Prior art keywords
filler
compound according
weight
biomineral
plastic compound
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.)
Withdrawn
Application number
EP16701421.6A
Other languages
German (de)
English (en)
Inventor
Hans-Peter Meyerhoff
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.)
Individual
Original Assignee
Individual
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Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP3242910A1 publication Critical patent/EP3242910A1/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Withdrawn legal-status Critical Current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
    • C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
    • C08K11/005—Waste materials, e.g. treated or untreated sewage sludge
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/405—Compounds of aluminium containing combined silica, e.g. mica
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Definitions

  • the invention relates to plastics with biological Standstof ⁇ fen.
  • Biomaterials are plastics which are fully ⁇ or based on relevant proportions on renewable raw materials. In view of rising oil costs, the use of biomaterials is interesting not only for sustainability reasons but also for economic reasons.
  • biomaterials mostly oil-based plastics with a certain proportion of biologically produced fillers and / or fibers.
  • a relatively new area is the replacement of plastics by plastics from renewable raw materials or waste products, such.
  • plastics from renewable raw materials or waste products, such.
  • polypropylene or polyethylene from sugar cane fats or oils.
  • biological fillers based on wood are used.
  • thermostability A common problem of such biomaterials is the often inadequate thermostability.
  • the hydrophobic environment is also problematic in biological fillers with high inorganic content, especially if a highly filled plastic is to be produced.
  • biomaterials which overcome the disadvantages of the known bio-materials and in particular have a low uptake of water and swelling, and to the extent mög ⁇ Lich a high impact resistance and good chemical resistance.
  • previous fillers are often obtained from non-renewable ⁇ sources or come from fossil sources such as talc and chalk called as an example.
  • the object of the invention is to provide a plastic composition with a biological filler, which avoids the disadvantages of the prior art.
  • the plastics produced can also be highly filled plastics.
  • the object is achieved by a plastic compound with a biological component, wherein the plastic compound at least (a) min ⁇ least a biomineral filler, and (b) at least one polymer.
  • the biological filler can come from many different sources worldwide.
  • Biomineralische fillers are bi ⁇ yogurgi fillers with a high proportion of inorganic Be ⁇ constituents, in particular from renewable raw materials.
  • Particularly preferred are organic fillers having a Aschegeh ⁇ ago from about 5 percent by weight, preferably of more than 10 mass pro ⁇ percent (ash content 815 ° C according to DIN 51719). All information from Nor ⁇ men in the measurement of properties, eg. B. DIN 51719, refer to the latest version of the respective standard at the time of registration.
  • a high proportion of silicon dioxide and a concomitant lower proportion of bioorganic materials ensure that the water absorption of the compositions according to the invention is low. Preference is given to a water absorption of ⁇ 0.3% by mass, preferably ⁇ 0.2 (measured according to ISO 62). It may be necessary to dry the biomineral filler before use.
  • It is preferably a biological filler or biomineral filler which is obtained from an infinitely growing raw material.
  • the biological filler is preferably obtained from Reishül ⁇ sen, rice husks, sisal, hemp, cotton, pine, kenaf, bamboo, flax, pine wood and / or sugar cane.
  • the biomineral filler is preferably the ash obtained from rice hulls, rice husks, sisal, hemp, cotton, pine, kenaf, bamboo, flax, pine and / or sugar cane, more preferably ash from rice hulls and / or rice peas, most preferably the ash from rice hulls (RHA).
  • Rice hull ash has the particular advantage that it is available as a waste product in rice production in large quantities.
  • the structure of the rice causes the ashes to be very fine-grained. It can also be obtained in different quality levels.
  • the content can be from 80% by weight to 99% by weight, preferably from 80% by weight to 98% by weight. Particularly preferred at 90 wt .-% to 99 wt .-%.
  • ⁇ a color of black, anthracite, light gray to dark gray or white ⁇ have.
  • more than 50% by weight of the silica is amorphous silica, in particular more than 80% by weight, or more than 90% by weight.
  • the proportion of carbon is in the biomineral filler at from 0 to 10 wt .-%, preferably 0 to 6 wt .-%, particularly before Trains t ⁇ at 0 to 3 wt .-%.
  • rice hull ash has a high proportion of amor ⁇ PHEM silica.
  • the proportion of crystalline SiO 2 in particular of cristobalite, can be minimized, in particular to below 20% by weight, preferably below 10% by weight, very particularly preferably below 5% by weight.
  • the ash is mainly used as an additive for concretes or steel.
  • the heat generated during the production can be used to generate energy.
  • the biological filling material still comprises up to 30% by weight. ⁇ 6 other ingredients, preferably up to 20 wt .-%. Preference is given to further oxides of Fe, Al, Zr, Na, K, Mg, Mn, Ca, each with an ⁇ share of 0 to 10 wt .-%, preferably 0 to 5 wt .-%, particularly preferably with proportions of 0 to 3% by weight. In one embodiment of the invention, the others include
  • an oxide selected from the group of Fe, Al, Zr, Na, K, Mg, Mn, Ca in each case amounts of 0.1 to 10 wt .-%, preferably 0.1 to 5 wt .-%, particularly preferably with proportions of 0.1 to 3 wt .-%.
  • the oxide is selected from the group of Fe and Al. This does not rule out that other oxides occur in similar or lower proportions, the data always being 100% complementary with the content of the other constituents.
  • the biological filling material comprises at least the following components:
  • biomineral filler it is clearly a biomineral filler.
  • further constituents such as 0 to 10% by weight of carbon, preferably 0 to 5% by weight, particularly preferably 0 to 1% by weight, may always also be present.
  • impurities and small amounts of moisture may still be present.
  • the biological filling material comprises at least the following constituents:
  • the proportion of VOCs is preferably less than 1% by weight (105 ° C., 20 hours, weight 8 g).
  • the filler material to a temperature biomineralische ⁇ turstabiltician of at least 1000 ° C.
  • Fillers with a high content of so S1O 2 have not only a ge ⁇ rings water absorption capacity, they also allow for higher temperatures during processing. Therefore, such fillers can be incorporated into many thermoplastics. Thus, processing temperatures of over 150 ° C or over 450 ° C, especially well over 450 ° C, possible. This allows ⁇ example, the incorporation into polyamides such as polyamide-6, 6th
  • the biomineralische filler has a mean particle size of up to 500 ym on, preferably between 5 and 400 ym ym (measured with light scattering ⁇ ). This specification refers to the particle size in the finished composition.
  • the particles of the filler when added to the composition have a particle size of less than 400 ym (90% value measured with laser diffraction), particularly preferably additionally with a 50% value of less than 300 ym.
  • the biological filler has a 95% value of less than 600 ym, preferably zusharm ⁇ Lich a 50% value of less than 300 ym.
  • all particles measured in the filler by laser diffraction are smaller than 1.5 mm, preferably additionally with a 90% value of less than 400 ⁇ m and a 50% value of less than 300 ⁇ m.
  • the biomineral filler preferably has a specific gravity of between 0.08 and 3.2 g / cm 3 , preferably between 1.5 and 2.5 g / cm 3 .
  • the biological filling material has a density of up to 2.5 g / cm 3 , preferably up to 2.4 g / cm 3 , preferably up to 2.3 g / cm 3 .
  • a density of at least 1.8 g / cm 3 is preferred.
  • the density is therefore preferably in a range from 1.8 g / cm 3 to 2.5 g / cm 3 , in particular from 1.8 g / cm 3 to 2.3 g / cm 3 , very particularly from 1.8 to 2 , 2 g / cm 3 .
  • Preferred is a density of 2.0 to 2.4 g / cm 3 .
  • the density refers to the density of the material (specific gravity) not the bulk density.
  • the particles of the biological filler are preferably slightly porous. It preferably has a specific surface area of 15 to 30 m 2 / g (BET measurement with nitrogen).
  • rice hull ash has a low specific gravity of up to 2.3 g / cm 3 , in particular from 1.8 to 2.2 g / cm 3 .
  • the density can be influenced accordingly by the manufacturing process. Together with the high content of silicon dioxide, it is possible to produce similar highly filled composites, which in comparison to conventional fossil filling materials such as talc or chalk, mica, wollastonite, etc., have a lower density.
  • the biological filling material is present as a powder. Preferred with a bulk density of 200 to 800 kg / m 3 .
  • the filler may have a certain size distribution. This can be done by sieving
  • biomineral filler with a certain size distribution.
  • all particles having a size of more than 100 ⁇ m, preferably more than 80 ⁇ m, in particular more than 60 ⁇ m can be removed by a sieving step.
  • This sieved biomineral filler is particularly well suited.
  • suspensions of the biological filler in water have a pH of 4-7 in another embodiment of 6-8 (each measured as 5 wt% at room temperature).
  • At least 50% of the particles of the filler are spherical in number, preferably at least 60%, in particular at least 80% (determined by microscopy). This means that these particles can be ⁇ be written near ⁇ approximated by a sphere or an ellipsoid of revolution, wherein the aspect ratio of the axes is not greater than 3: 1, more preferably not greater than 1.5: 1.
  • the proportion of the biomineral filler is preferably at least 15% by weight, based on the compound, particularly preferably Trains t is at least 20 wt .-% preferably, more preferably from 15 wt% to 90 wt .-%, in particular 15 wt .-% to 80 wt .-%, Sonders be ⁇ a proportion of 10 parts by weight % to 40% by weight.
  • the biomineral filler also increases the content of renewable raw materials in the composite material. As a result, the most oil-based plastics can be saved.
  • ash-based fillers can be combined with other biological fillers.
  • the at least one further filler is preferably selected from rice husks, rice husks, wood, Si sal, hemp, cotton, pine, kenaf, bamboo, flax, Pi ⁇ nienholz and / or sugar cane.
  • ash from rice hulls or rice husks can be combined with other biological fillers.
  • the additional biological filler may also comprise fibers, for example wood fibers, sisal fibers, hemp fibers, jute fibers, cotton fibers.
  • the biological filler comprises at least 30 wt .-% organic filler ⁇ materials on the basis of the ash, preferably at least 50 wt .-%, more preferably at least 60 wt.%, Based on all used biological fillers.
  • the at least one polymer is preferably a thermoplastic or crosslinkable polymer, thermoset or a thermoplastic elastomer.
  • thermoplastic polymer or thermoplastic elastomer (b) are any thermoplastically deformable poly- understood that may be new or recyclate / regrind from old thermoplastic polymers.
  • Preference is given to thermoplastics having a viscosity corresponding to a melt index (MFI, 230 ° C./2.16 kg) of polypropylene (PP) of at least 20 g / 10 min.
  • MFI melt index
  • Preference is given to those whose viscosity corresponds to an MFI of PP of from 20 to 300 g / 10 min, more preferably from 50 g / 10 min to 200 g / 10 min corresponds.
  • polyolefins such as polyethylene, polypropylene, polybutylene, polyisobutylene and poly-4-methyl-1-pentene
  • polyolefin copolymers such as Luflexen® (Basel), Nordel® (Dow) and Engage® (DuPont) can be used.
  • Cycloolefincopolyme ⁇ re as Topas® (Celanese), polytetrafluoroethylene (PTFE), ethylene len / tetrafluoroethylene copolymers (ETFE), Polyvinylidendifluo- chloride (PVDF), polyvinyl chloride (PVC), polyvinylidene chloride, polyvinyl lyvinylalkohole, polyvinyl esters such as polyvinyl acetate, Vinyl ester copolymers, such as ethylene / vinyl acetate copolymers (EVA), polyvinylalkanals, such as polyvinyl acetal and polyvinyl butyral, (PVB), polyvinyl ketals, polyamides, such as Polyamed-6, polyamide-12, polyamide-6, 6, PA 6.66 triple 6 , or mixtures of PA 66 recyclate with PA 6 or other proportions of PA, polyamide-6, 10, polyimides, polystyrenes, poly
  • Polyphenylene sulfide such as polyoxymethylene (POM), polyaryls such as polyhenylene, polyarylenevinylenes, silicones, low-density polyethylene (LDPE), high density polyethylene (HDPE), ionomers, thermoplastic and thermosetting polyurethanes and mixtures thereof.
  • POM polyoxymethylene
  • polyaryls such as polyhenylene, polyarylenevinylenes, silicones, low-density polyethylene (LDPE), high density polyethylene (HDPE), ionomers, thermoplastic and thermosetting polyurethanes and mixtures thereof.
  • the polyamides can Triple 6.66 and PA 66 PA 6 with proportions, mixtures and ent ⁇ speaking copolymers are used, for example polyamide-6, polyamide-66.
  • the at least one thermoplastic may also be part of a blend, for example in blends of styrene polymers such as SAN with polymethacrylonitrile (PMI) or chlorinated polyethylene, or polyvinyl chloride with methyl acrylate-butadiene-styrene copolymer (MBS), ASA and / or ABS. It is important that the resulting mixture is still a thermoplastic.
  • styrene polymers such as SAN with polymethacrylonitrile (PMI) or chlorinated polyethylene, or polyvinyl chloride with methyl acrylate-butadiene-styrene copolymer (MBS), ASA and / or ABS.
  • At least one thermoplastic is a polyolefin, special ⁇ DERS preferably polypropylene (PP) or polyethylene (PE) and de- ren copolymers or copolymers such as EPDM
  • thermoset polymers comprising the aforementioned polymers, wel ⁇ che are additionally crosslinked with each other. This can be done by appropriate choice of monomers and / or addition of at least ei ⁇ nes crosslinker.
  • thermoset ⁇ resins such as diallyl phthalate resins (PDAP), epoxy resins (EP), amino noplaste (eg.
  • urea resins melamine resins, Dicyandiamidhar- ze), phenolic resins (eg., Phenol resins, for example phenol-formaldehyde resin), furfuryl alcohol formaldehyde resins (FF), Unge ⁇ saturated polyester resins (UP), polyurethane resins (PU), Reakti ⁇ onsspritzgegossene polyurethane resins (RIM-PU), furan resins, vinyl nylesterharze (VE VU), polyester-melamine Resins, blends of diallyl phthalate (PDAP) or diallyl isophthalate (PDAIP) resins, silicone resins.
  • Phenol resins for example phenol-formaldehyde resin
  • FF furfuryl alcohol formaldehyde resins
  • UP Unge ⁇ saturated polyester resins
  • PU polyurethane resins
  • RIM-PU Reakti ⁇ onsspritzgegossene polyurethane resins
  • plastics based on polylactate are also possible.
  • the polymers used must be processable at the temperatures used. It may be crystalline or amorphous polyolefin.
  • At least 50% by weight, 60% by weight, 70% by weight, 90% by weight, preferably 100% by weight of the polymer and / or elastomer used is at least one polyolefin.
  • the polyolefin is at least partly also made from renewable sources.
  • len, z. As sugarcane, fats or oils, won. Together with the biological filler, a composite material can thus be obtained which has been produced at more than 30% by weight, preferably more than 50% by weight, particularly preferably more than 65% by weight, from renewable sources.
  • sources are, for example, plants, such as sugar cane, but it can also be fats or oils, which are also produced as waste products.
  • the thermoplastic (b) has an average molecular weight M w in the range of 10,000 to 200,000 (measured by ultracentrifuge), preferably from 100,000 to 200,000.
  • polyethylene and polypropylene also include copolymers of ethylene or propylene with one or more ⁇ -olefins or styrene.
  • polyethylene copolymers comprised, the (wt least 50th ⁇ 6) in addition to ethylene as the principal monomer one or copolymerized more comonomers, preferably selected from styrene, vinyl acetate or ⁇ -olefins such as Example ⁇ , propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, n-aC 22 H 44 , n-aC 24 H 48 and NaC 2 oH 4 o.
  • polypropylene also includes copolymers containing, as the main monomer in addition to propylene (at least 50 wt .-%) containing one or more comonomers einpolymeri ⁇ Siert, preferably selected from styrene, ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, n- ⁇ -C22H 44 , n- ⁇ -C24H 48 and Na-C2oH 4 o.
  • the compound preferably comprises at least 5% by weight.
  • the compo ⁇ component (a) preferably from 5 wt .-% to 80 wt .-%.
  • the glass transition temperature (T G , determinable as inflection point in the DSC diagram) for the at least one thermoplastic is preferably below 150 ° C., preferably between 60 ° C. and 120 ° C.
  • At least one compatibilizing additive (c) may also be processed.
  • Such compatibilizers or coupler are preferably compounds based on maleic anhydride ⁇ , maleated polyethylene or maleated Polyp- ropylene, or copolymers acid from ethylene or propylene and acrylic, methacrylic acid, or trimellitic acid.
  • the content of such couplers is preferably between 0 and 8% by weight.
  • organosiloxanes can increase the compatibility.
  • Functional organosiloxanes eg.
  • organylorganyloxysilanes are in this context those silanes which carry at least one organic radical bound to the silicon atom via a carbon atom, which in turn may contain a functional group. The easier dispersion is likely to be due to be ⁇ worked through the silane waterproofing the surface of the biological filling material. Preference is therefore given to silanes which carry at least one hydrolyzable radical and at least one nonhydrolyzable radical.
  • silanes are used having at least one crosslinkable group
  • these groups may contain silanes with at least one ungesreli ⁇ saturated carbon bond, for example vinyl, Ac triacrylate or methacrylate groups.
  • crosslinkers if substances with crosslinkable groups are added.
  • the solvent may also be water, for example to hydrolyze added silanes.
  • the composition further comprises at least one additive (d).
  • additives are stabilizers, in particular light and UV stabilizers, for example sterically hindered amines (HALS), 2, 2, 6, 6-tetramethylmorpholine-N-oxides or 2, 2, 6, 6-tetramethylpiperidine-N-oxides (TEMPO) and other N-oxide derivatives such as NOR.
  • HALS sterically hindered amines
  • TEMPO 2, 2, 6, 6-tetramethylmorpholine-N-oxides
  • TEMPO 2, 2, 6, 6-tetramethylpiperidine-N-oxides
  • NOR N-oxide derivatives
  • suitable additives are UV absorbers such as benzophenone or benzotriazoles.
  • suitable additives are pigments, which can also cause a stabilization against UV light, such as titanium dioxide (for. Example, as a white pigment), or suitable substitute of white pigments, carbon black, iron oxide, other Me ⁇ -metal oxides and organic pigments, for example azo and phthalocyanine pigments.
  • suitable additives are biocides, in particular fungicides.
  • Further examples of suitable additives are spearurefän ⁇ ger, for example, alkaline earth metal hydroxides or alkaline earth metal oxides or fatty acid salts of metals, in particular metal stearates, be ⁇ Sonders preferably zinc stearate and calcium stearate, and further Chalk and hydrotalcite.
  • some fatty acid salts of metals, especially zinc stearate and calcium stearate also act as a lubricant in the processing.
  • Further examples of additives are antioxidants z.
  • phenols such as alkylated phenols, bisphenols, bicyclic phenols or antioxidants based on benzofuranones, organic sulfides and / or diphenylamines.
  • suitable additives are Weichma ⁇ cher, z.
  • esters of dicarboxylic acids such as phthalates, organic phosphates, polyesters and polyglycol derivatives.
  • Suitable additives are impact modifiers (for example polyamides, polybutylene terephthalates
  • PBT flame retardant
  • flame retardants in particular polycarbonate-based compositions are Ha ⁇ homologous compounds, containing in particular based on chlorine and bromine, and phosphorus compounds.
  • the compositions preferably contain phosphorus-containing flame retardants from the groups of the mono- and oligomeric phosphoric and phosphonic acid esters, phosphonatoamines and phosphazenes, it also being possible to use mixtures of a plurality of components selected from one or more of these groups as flame retardants.
  • Other phosphorus compounds not specifically mentioned herein may be used alone or in any combination with others
  • Flame retardants are used.
  • Other flame retardants may include organic halogen compounds such as Decabrombisphe- vinyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine minformaldehyd resins, inorganic hydroxide compounds, such as Mg, Al hydroxide, inorganic compounds such as antimony oxides, Ba ⁇ riummetaborat, hydroxoantimonate, zirconia , Zirconium hydroxide, Molybdenum oxide, ammonium, zinc borate, ammonium borate, Bari ⁇ ummetaborat, talc, silicate, silicon oxide and tin oxide, and Si be loxanriven.
  • organic halogen compounds such as Decabrombisphe- vinyl ether, tetrabromobisphenol
  • inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine minform
  • the flame retardants are often used in combination with so-called anti-drip agents, which reduce the tendency of the material for burning dripping in case of fire.
  • compounds of the substance classes of the fluorinated polyolefins, the silicones and aramid fibers may be mentioned here. These can also be used in the compositions according to the invention.
  • Fluorinated polyolefins are preferably used as antiperspirants.
  • additives are inorganic fillers which are present in particles and / or layer form, such as
  • Talc chalk, kaolin, mica, wollastonite, kaolin, Kieselkla ⁇ reindeer, magnesium carbonate, magnesium hydroxide, calcium carbonate, feldspar, barium sulfate, ferrite, iron oxide, metallic powder, oxides, chromates, glass beads, hollow glass beads, pigments, silica, hollow globular silicate fillers and / or phyllosilicates. These preferably have a particle size between 2 and 500 ym (measured with light scattering).
  • composition may also contain additional crosslinkers, which can lead to crosslinking of the thermoplastic or thermoset, for example by irradiation or heating.
  • chemical or physical blowing agent may be introduced in liquid or solid form in the Georgiaset ⁇ pollution, acid or sodium bicarbonate, for example, with Citronen Text- thermolabile carbamates.
  • This en ⁇ dotherme foaming agents are preferably used.
  • Another way, too to reach a foaming, is ren the use of Mikrosphot which are filled for example with gases or vaporizable liquid ⁇ speeds.
  • Suitable fillers are, in particular, alkanes, such as butane, pentane or hexane, but also their halogenated derivatives, such as, for example, dichloromethane or perfluoropentane.
  • foaming may also be achieved by adjustment of appropriate process parameters (extrusion temperature, full profile cooling rate) if the composition contains substances that become gaseous under the process conditions (e.g., water, hydrocarbons, etc.). Preferably, these are closed pores.
  • Mixtures of aggregates can also be used.
  • short glass fibers, carbon ⁇ fibers (carbon fibers, graphite fibers), boron fibers, aramid as further reinforcing materials as additives were in ⁇ way of example glass fibers, (p- or m-aramid fibers (eg Kevlar ® or Nomex ®, DuPont) or mixtures thereof), and basalt fibers called, wherein said reinforcing fibers can be used as long fibers or filaments with the usual ratios (length to diameter), also in the form of a mixture of different fibers.
  • thermoplastic fibers for example of PP, PA, PET, PP silicon fibers, etc., or vegetable fibers, natural fibers or fibers of natural polymers. Examples are jute, cotton, sisal and hemp fibers.
  • the compound produced comprises long glass fibers having a length of at least 0.5 mm and a diameter of 3 to 25 ⁇ m. In a further embodiment of the invention, the compound produced does not comprise long glass fibers with a length of at least 0.5 mm and a diameter of 3 to 25 ⁇ m.
  • the viscosity of Com pounds ⁇ after processing is not does not fall below a value corresponding to a MFI of PP of less than 10 g / 10 min.
  • the additives are preferably present in a content of 0 to 30 wt .-%, preferably, a content of 0 to 20 wt .-%.
  • the compounds of the invention can be used for the production of moldings of any kind. These can be produced by injection molding, extrusion and blow molding. Another form of processing is the production of moldings by deep drawing from previously prepared plates or films.
  • Another object of the present invention is a master terbatch comprising at least the components (a) and (b), with the difference that the masterbatch in particular has high levels of biomineralisches filler.
  • a proportion of biological filler of at least 30 wt .-%, preferably 30 to 90% wt .-%, preferably at least 50 wt .-%, in particular 50 wt .-% to 90 wt .-%.
  • constituents can 5 to 30 wt .-% component (b) and 0 to 6 wt .-% additives, preferably 0.5 wt .-% to 6 wt .-%, its hold ⁇ ent. All with the proviso that the proportions of the ingredients add up to 100% by weight.
  • the masterbatch is preferably prepared by the process according to the invention. It is also possible to produce cable compounds, in particular based on PVC. Due to the inorganic biological content, the proportion of non-biological additives for insulation and / or flame retardance can be reduced.
  • the object is also achieved by a method for producing a plastic with organic fraction, wherein Minim ⁇ least (a) min ⁇ least one polymer are processed into a compound at least one biomineralischer filler, and (b).
  • Minim ⁇ least (a) min ⁇ least one polymer are processed into a compound at least one biomineralischer filler, and (b).
  • the preferred embodiments correspond to those of the above-described plastic compound.
  • Method may also include other, not mentioned steps.
  • the compounding takes place in a mixing apparatus with high shear forces.
  • the mixing apparatus corresponds to an internal mixer ⁇ or a one- or multi-part / -well kneader.
  • Particularly preferred mixing apparatuses are kneterartige Re ⁇ actuators, one or more parts kneader, single- or multi-screw kneaders, mixers or mills. Very particular preference is single or multi-shaft kneaders.
  • the mixing apparatus is a screw kneader, such as a single-screw kneader (eg Ko-kneader, single-screw extruder with mixing and shearing parts), two-shaft Kneader (eg twin-screw extruder type ZSK or ZE, Kombiplast extruder, twin-screw kneading mixer MPC, two-stage mixer FCM, kneading screw extruder KEX, heavy-roller extruder).
  • kneaders with or without a punch, trough kneaders and banbury mixers Preference is given kneaders with a rotational and a translational (forward / backward) movement.
  • the mixing apparatus corresponds to a co-kneader, e.g. from Buss Compounding Systems AG (Pratteln, Switzerland).
  • the kneading time is usually 0.5 to 24 hours.
  • the temperatures in the mixing apparatus are generally from 20 ° C to 350 ° C, depending on the polymer used, preferably at 20 ° C to 230 ° C.
  • the temperature may change in the course of the mixing application, for example by one or more differently tempered zones.
  • the compound is obtained in the form of granules. This can be obtained by cutting the extrudate accordingly. As a result, for example, cylindrical granules can be obtained with a maximum extension of up to 20 mm, for example 1 mm to 5 mm. It can also discs or balls are obtained.
  • the manufacturing process may have other common
  • the invention also relates to the use of the invention shown SEN biomineral filler material according to the embodiments described above, particularly with a silica content of at least 60 wt .-%, preferably Minim ⁇ least 80 wt .-%, particularly preferably rice hull ash, especially prefers white rice hull ash, as filler in
  • Composite plastics in particular according to the inventive composition or the masterbatch.
  • Examples of the composite material according to the invention manufacturing asked shaped articles are films (as an anti-blocking agent), Professional ⁇ le, housing parts of all kinds, for example for the automobile interior such as instrument panels, household appliances, such as juice presses, coffee machines and mixers; for office machines such as monitors, printers, copiers; for panels, pipes, electrical installation ducts, windows, doors and profiles for the construction sector, interior work and exterior applications, such as building interior or exterior parts; in the field of electrical engineering as for switches and plugs.
  • films as an anti-blocking agent
  • Professional ⁇ le housing parts of all kinds, for example for the automobile interior such as instrument panels, household appliances, such as juice presses, coffee machines and mixers; for office machines such as monitors, printers, copiers; for panels, pipes, electrical installation ducts, windows, doors and profiles for the construction sector, interior work and exterior applications, such as building interior or exterior parts; in the field of electrical engineering as for switches and plugs.
  • Examples of building interior parts are railings, for example for stairs in the interior, and panels.
  • Examples of Gebudeau ⁇ golfier are roofs, facades, roof structures, window frames, porches, railings for external stairs, decking and cladding, for example, for buildings or parts of buildings.
  • Examples of profile parts are technical profiles, connecting hinges, moldings for interior applications such as moldings with complex geometries, multifunction profiles or packaging parts and decorative parts, furniture profiles and soil ⁇ profile.
  • composite materials according to the invention for Packaging suitable, for example, for boxes and boxes.
  • Another object of the present invention is the use of composite materials according to the invention as or for the production of furniture, such as tables, chairs, especially garden furniture and benches such as park ⁇ benches, for the production of profile parts and for the production of hollow bodies such as hollow sections for decking or window sills.
  • Inventive moldings show excellent Wittêtsbestän ⁇ speed, still excellent grip and very good mechanical properties and low water absorption, resulting in good weather dependence. Measurement results of the filler and the moldings produced are shown in the figures.
  • Fig. 2 Grain size distribution of filler II (ACS 901);
  • Fillers according to the invention were incorporated into different Ge ⁇ weight shares in polypropylene.
  • the properties of the samples are shown in Tables 1 and 2. Thereby be distinguished ⁇ A sample in which constituents> 60 ym were removed by a sieving method, while B shows the characteristics of samples with unscreened filler. Comparative samples containing 20% by weight of talc as filler show a higher density of 1.11 g / cm 3 . Comparative samples containing 30% by weight of talc as filler show a higher density of 1.15 g / cm 3 . Comparative samples with 40% by weight talc as filler show a higher density of 1.26 g / cm 3 .
  • PA 66 polyamide 6, 6
  • A denotes samples in which constituents> 60 ⁇ m are produced by a sieving process.
  • B show the properties of unsupported filler samples. Comparative samples containing 30% by weight tungstonite as filler show a density of 1.36 g / cm 3 and with 40% by weight wollastonite a density of 1.48 g / cm 3 . The excavation leads to a significant improvement in the properties.
  • the bending test was carried out according to DIN EN ISO 178 (ISO standard rods (80x10x4 in mm); Sample preparation: storage for 16 to 24 hours at 23 ° C in a closed vessel for temperature control, tester: Instron 4466, test speed: 2 mm / min; ⁇ width: 64mm, test temperature: 23 ° C, number of samples: 2 - 3).
  • the impact strength according to Charpy was measured according to DIN EN ISO 179/1 (test equipment: pendulum impact tester with replaceable pendulums (Zwick)) specimens: ISO standard rods (80x10x5mm 3 ); sample preparation: storage for 16 to 24 hours at 23 ° C in closed vessel for tempering; tester: pendulum impact tester 5J; test conditions: leu; specimen type 1; e ⁇ for schmalseiti ger shock; fürtemeratur: -30 ° C; number of samples: 5).
  • Tests according to DIN EN ISO 527-2 were carried out with tension rods according to DIN EN ISO 527-2 as test specimen.
  • the test specimens were 16 stored up to 24 hours at 23 ° C in a closed vessel for controlling the temperature (tester: Instron Universal 5900R; Test speed: 1 mm / min and 5 mm / min; exctempe ⁇ temperature: 80 ° C; number of samples: 4).
  • FIGS. 5 to 8 show tensile tests according to DIN EN ISO 527-2 for various samples.
  • TD20 stands for PP with 20% by weight of talc.
  • For the other samples is z.
  • FIGS. 7 and 8 show test specimens with a test body with 20% by weight filler and 20% by weight long glass fiber in PP in comparison with test specimens with PA6 with 30% by weight long glass fiber and PP with 40% by weight. -% long glass fiber.
  • Vb ACS 951 (95 wt% Si0 2 ) 90% 36.71 ym

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un composite de matière plastique pourvu d'un ingrédient biologique, (a) au moins une charge bio-minérale et (b) au moins un polymère étant traités pour former un composite. Selon l'invention, une charge bio-minérale régénérable est utilisée avec une teneur élevée en silice.
EP16701421.6A 2015-01-11 2016-01-11 Matériau composite organique Withdrawn EP3242910A1 (fr)

Applications Claiming Priority (3)

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EP15150716 2015-01-11
EP15188813 2015-10-07
PCT/EP2016/050403 WO2016110600A1 (fr) 2015-01-11 2016-01-11 Matériau composite organique

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AUPP819899A0 (en) * 1999-01-18 1999-02-11 Contract Research & Development (M) Sdn. Bhd. Conductive and flame retardant plastic fillers
RU2530130C2 (ru) * 2011-09-22 2014-10-10 Виктор Владимирович Виноградов Наполнитель резины
DE102014104869A1 (de) * 2014-04-04 2015-10-29 Hans-Peter Meyerhoff Biomaterialverbundwerkstoff

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