EP2057218A1 - Composite contenant du sulfate de baryum - Google Patents

Composite contenant du sulfate de baryum

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Publication number
EP2057218A1
EP2057218A1 EP07802931A EP07802931A EP2057218A1 EP 2057218 A1 EP2057218 A1 EP 2057218A1 EP 07802931 A EP07802931 A EP 07802931A EP 07802931 A EP07802931 A EP 07802931A EP 2057218 A1 EP2057218 A1 EP 2057218A1
Authority
EP
European Patent Office
Prior art keywords
barium sulfate
rubber
composite
composite according
phr
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Withdrawn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
EP07802931A
Other languages
German (de)
English (en)
Inventor
Sonja Grothe
Petra Fritzen
Jochen Winkler
Bernd Rohe
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.)
Venator Germany GmbH
Original Assignee
Sachtleben Chemie GmbH
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 Sachtleben Chemie GmbH filed Critical Sachtleben Chemie GmbH
Publication of EP2057218A1 publication Critical patent/EP2057218A1/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Withdrawn legal-status Critical Current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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates

Definitions

  • the invention relates to a barium sulfate-containing composite, a process for its preparation and the use of this composite.
  • US-B-6 667 360 discloses polymeric composites containing from 1 to 50% by weight of nanoparticles having particle sizes of from 1 to 100 nm.
  • metal oxides metal sulfides, metal nitrides, metal carbides, metal fluorides and metal chlorides are proposed, wherein the surface of these particles is unmodified.
  • the polymeric matrix there are mentioned epoxides, polycarbonates, silicones, polyesters, polyethers, polyolefins, synthetic rubber, polyurethanes, polyamide, polystyrenes, polyphenylenes oxides, polyketones and copolymers, and mixtures thereof.
  • the patent application DE 102005025719 A1 discloses a method for incorporating disagglomerated barium sulfate having an average particle size of less than 0.5 ⁇ m, which is coated with a dispersant, in precursors of plastics, for example in polyols.
  • a plastic is prepared which comprises a dispersant and a crystallization inhibitor-containing deagglomerated barium sulfate.
  • WO 2007-039625 A1 describes the use of barium sulfate or calcium carbonate particles which contain at least one organic component in transparent polymers.
  • a general disadvantage of using the organically coated, deagglomerated barium sulfate particles is that the organic components are not universally applicable.
  • a further disadvantage of the deagglomerated barium sulfate particles described in the applications DE 102005025719 A1 and WO 2007-039625 A1 is the particle size distribution of the secondary particles, which has an average particle diameter of less than 2 ⁇ m, preferably ⁇ 250 nm, particularly preferably ⁇ 200 nm, very particularly preferably ⁇ 130 nm, even more preferably ⁇ 100 nm, particularly preferably ⁇ 50 nm.
  • Such fine secondary particle distributions lead to a strong tendency to dust which, for reasons of safety at work, must be avoided, in particular in the case of nanoscale particles.
  • the object of the present invention is to overcome the disadvantages of the prior art.
  • the object of the invention is to provide a composite which, compared with composites of the prior art, has significantly improved flexural moduli, flexural strengths, tensile moduli, tensile strengths, fracture toughness, fracture toughness, impact toughness and wear rates.
  • the mechanical and tribological properties of polymer composites were already greatly improved when using precipitated, barium-modified barium sulfate having crystallite sizes d 50 of less than 350 nm (measured by the Debye-Scherrer method). This is all the more surprising as the non-surface-modified barium sulfate particles can not build up a bond between the particle and the matrix.
  • the advantage of the subsequent surface modification lies in the high flexibility that is possible with it.
  • This procedure makes it possible, on the one hand, for particle formation to be carried out in the customary manner during the precipitation of barium sulfate, that is to say particle formation is not adversely affected by co-precipitates. On the other hand, it is easier to control the particle size and morphology of the barium sulfate particles.
  • the precipitation of the barium sulfate to be used according to the invention can be carried out by all methods known from the prior art. According to the invention, preference is given to using barium sulfate which has been prepared in a precipitation reactor for precipitating nanoscale particles, in particular a reaction cell for ultrafast mixing of several reactants, for example aqueous solutions of barium hydroxide or barium sulphide or barium chloride and sodium sulphate or sulfuric acid. According to the invention, the barium sulfate is present after precipitation in the form of a precipitation suspension.
  • the barium sulfate used according to the invention is washed and concentrated, so that the wastewater produced is not organically contaminated.
  • the barium sulfate is now in the form of a concentrated barium sulfate suspension.
  • the drying of the concentrated barium sulfate suspension can be carried out by means of spray drying, freeze drying and / or mill drying. Depending on the drying process, subsequent grinding of the dried powders may be necessary. The grinding can be carried out by methods known per se.
  • spray-dried barium sulfate powders are used to prepare the composites of the present invention. These have the advantage that the relatively coarse spray dryer agglomerates form a low-dust and very readily flowable powder, which is also surprisingly well dispersible.
  • the composite according to the invention contains a polymeric matrix with 0.1 to 60% by weight of precipitated barium sulfate particles having average crystallite sizes d 50 of less than 350 nm (measured by the Debye-Scherrer method).
  • the crystallite size d 50 is preferably less than 200 nm, particularly preferably from 3 to 50 nm.
  • the barium sulfate particles may be both surface-modified and not surface-modified.
  • the composites of the invention may contain constituents known per se to the person skilled in the art, for example mineral fillers, glass fibers, stabilizers, process additives (also called protective systems), for example dispersing aids, release agents, antioxidants, antiozonants, inter alia), pigments, flameproofing agents (e.g. Aluminum hydroxide, antimony trioxide, magnesium hydroxide, etc.), vulcanization accelerators, vulcanization retarders, zinc oxide, stearic acid, sulfur, peroxide and / or plasticizers.
  • constituents known per se to the person skilled in the art for example mineral fillers, glass fibers, stabilizers, process additives (also called protective systems), for example dispersing aids, release agents, antioxidants, antiozonants, inter alia), pigments, flameproofing agents (e.g. Aluminum hydroxide, antimony trioxide, magnesium hydroxide, etc.), vulcanization accelerators, vulcanization retarders, zinc oxide, stearic acid, sulfur, peroxide and
  • a composite of the invention may, for example, additionally up to 80 wt .-%, preferably 10 to 80 wt .-%, mineral fillers and / or glass fibers, up to 10 wt .-%, preferably 0.05 to 10 wt .-% stabilizers and Process additives (eg dispersing aids, release agents, antioxidants, etc.), up to 10% by weight of pigment and up to 40% by weight of flameproofing agents (eg aluminum hydroxide, antimony trioxide, magnesium hydroxide, etc.).
  • Process additives eg dispersing aids, release agents, antioxidants, etc.
  • flameproofing agents eg aluminum hydroxide, antimony trioxide, magnesium hydroxide, etc.
  • a composite according to the invention in which the composite contains 100 phr of elastomer, 0.1 to 300 phr of barium sulfate, 0 to 10 phr of vulcanization accelerator, 0 to 10 phr of vulcanization retarder, 0 to 20 phr of zinc oxide, 0 to 10 phr of stearic acid, 0 to 20 may be mentioned by way of example phr sulfur and / or peroxide, 0 to 300 phr mineral filler, 0 to 200 phr plasticizer, 0 to 30 phr protective system containing preferably antioxidants and antiozonants; contains.
  • the polymeric matrix according to the invention can consist of an elastomer or a duromer.
  • the elastomer may be, for example, natural rubber (NR), isoprene rubber (IR), butyl rubber (CUR, BIIR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber ( NBR), bromobutyl rubber (BIIR), styrene-butadiene-isoprene rubber (SBIR), chloroprene rubber (CR), chlorosulfonated polyethylene rubber (CSM), hydrogenated NBR rubber (HNBR), polymethylsiloxane-vinyl rubber (VMQ), acrylate-ethylene rubber (AEM), acrylate rubber (ACM), fluoro rubber (FKM), fluorosilicone rubber (FVMQ), thermoplastic elastomers (TPE), thermoplastic elastomers (TPE) based on polyamide (TPA
  • thermosets for example, unsaturated polyester resins (UP), phenolic resins, melamine resins, formaldehyde molding compounds, vinyl ester resins, diallyl phthalate resins, silicone resins or urea resins are suitable. Particularly suitable of the duromers are UP resins.
  • ultrafine barium sulfate particles without surface modification can be used.
  • the barium sulfate particles in a particular embodiment, may have an inorganic and / or an organic surface modification.
  • the inorganic surface modification of the ultrafine barium sulfate is typically at least one inorganic compound selected from aluminum, antimony, barium, calcium, cerium, chlorine, cobalt, iron, phosphorus, carbon, manganese , Oxygen, sulfur, silicon, nitrogen, strontium, vanadium, zinc, tin and / or zirconium compounds or salts.
  • inorganic compound selected from aluminum, antimony, barium, calcium, cerium, chlorine, cobalt, iron, phosphorus, carbon, manganese , Oxygen, sulfur, silicon, nitrogen, strontium, vanadium, zinc, tin and / or zirconium compounds or salts.
  • examples include sodium silicate, sodium aluminate and aluminum sulfate.
  • the inorganic surface treatment of ultrafine BaSO 4 takes place in aqueous slurry.
  • the reaction temperature should preferably not exceed 50 0 C.
  • the pH of the suspension is, for example, using NaOH adjusted to pH values greater than 9.
  • the after-treatment chemicals inorganic compounds
  • water-soluble inorganic compounds such as, for example, aluminum, antimony, barium, calcium, cerium, chlorine, cobalt, iron, phosphorus, carbon, manganese, , Oxygen, sulfur, silicon, nitrogen, strontium, vanadium, zinc, tin and / or zirconium compounds or salts.
  • the pH and the amounts of aftertreatment chemicals are chosen according to the invention such that the latter are completely dissolved in water.
  • the suspension is stirred vigorously, so that the aftertreatment chemicals are distributed homogeneously in the suspension, preferably for at least 5 minutes.
  • the pH of the suspension is lowered. It has proven to be advantageous to lower the pH slowly and with vigorous stirring. Particularly advantageously, the pH is lowered within 10 to 90 minutes to values of 5 to 8.
  • a maturation time preferably a maturation time of about one hour, follows according to the invention.
  • the temperatures should preferably not exceed 50 0 C.
  • the aqueous suspension is then washed and dried. For drying ultrafine, surface-modified BaSO 4 , spray drying, freeze drying and / or mill drying, for example, are suitable. Depending on the drying process, subsequent grinding of the dried powders may be necessary. The grinding can be carried out by methods known per se.
  • an aqueous BaSO 4 suspension of already inorganically surface-modified BaSO 4 particles is additionally modified with at least one silane.
  • silanes it is preferred to use alkoxyalkylsilanes, more preferably the alkoxyalkylsilanes are selected from octyltriethoxysilane, gamma-methacrylpropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-isocynatopropyltriethoxysilane,
  • Vinyltrimethoxysilane and / or hydrolyzed silanes such as gamma-aminopropylsilsesquioxane (GE).
  • GE gamma-aminopropylsilsesquioxane
  • a BaSO 4 suspension of inorganic surface-modified BaSO 4 particles under vigorous stirring or with dispersion with an alkoxyalkylsilane. It joins according to the invention a maturation time, preferably a maturation time of 10 to 60 minutes, preferably at temperatures of at most 40 ° C. Then proceed as described above.
  • the alkoxyalkylsilane may also be applied after drying to the inorganically modified particles by mixing.
  • Suitable organic surface modifiers are the following compounds: polyethers, silanes, polysiloxanes, polycarboxylic acids, fatty acids, polyethylene glycols, polyesters, polyamides, polyalcohols, organic phosphonic acids, titanates, zirconates, alkyl and / or arylsulfonates, alkyl and / or aryl sulfates, alkyl and / or aryl phosphoric acid esters.
  • the production of organically surface-modified barium sulfate can be carried out by methods known per se.
  • the barium sulfate suspension is mixed with a barium component, so that a barium excess is formed.
  • the barium component used may be any water-soluble barium compound, for example barium sulphide, barium chloride and / or barium hydroxide.
  • the barium ions adsorb on the surfaces of the barium sulfate particles.
  • organic compounds are added to this suspension with vigorous stirring and / or during dispersion.
  • the organic compounds should be selected so that they form a sparingly soluble compound with barium ions.
  • the organic compounds precipitate with the excess barium ions on the surface of the barium sulfate.
  • Suitable organic compounds are compounds selected from the group of alkyl and / or arylsulfonates, alkyl and / or aryl sulfates, alkyl and / or aryl phosphoric esters or mixtures of at least two of these compounds, where the alkyl or aryl radicals are substituted by functional groups can.
  • the organic compounds may be fatty acids, which may be functional Own groups. It is also possible to use mixtures of at least two such compounds.
  • alkylsulfonic acid salt sodium polyvinyl sulfonate
  • sodium polyvinyl sulfonate sodium polyvinyl sulfonate
  • the organically modified barium sulfate can be used either directly in the form of the present aqueous paste or dried before use.
  • the drying can be carried out according to known methods.
  • the use of convection dryers, spray dryers, grind dryers, freeze dryers and / or pulsation dryers is suitable for drying.
  • other dryers are likewise usable according to the invention.
  • subsequent grinding of the dried powders may be necessary.
  • the grinding can be carried out by methods known per se.
  • the organically modified barium sulfate may be further post-treated after functional modification with functional silane derivatives or functional siloxanes.
  • functional silane derivatives or functional siloxanes used are: octyltriethoxysilane, Methyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -glycidyloxypropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, vinyltrimethoxysilane.
  • the organically surface-modified barium sulfate particles optionally have one or more functional groups, for example one or more hydroxyl, amino, carboxyl, epoxy, vinyl, methacrylate, and / or isocyanate groups, thiols, alkylthiocarboxylates, di- and / or or polysulfidic groups.
  • one or more functional groups for example one or more hydroxyl, amino, carboxyl, epoxy, vinyl, methacrylate, and / or isocyanate groups, thiols, alkylthiocarboxylates, di- and / or or polysulfidic groups.
  • the surface modifiers may be chemically and / or physically attached to the particle surface.
  • the chemical bond can be covalent or ionic.
  • As a physical bond dipole-dipole or van der Waals bonds are possible.
  • the attachment of the surface modifiers via covalent bonds or via physical dipole-dipole bonds is preferred.
  • the surface-modified barium sulfate particles have the ability to partially or completely enter into a chemical and / or physical bond to the polymeric matrix via the surface modifiers.
  • Covalent and ionic bonds are suitable as chemical bond types.
  • physical bond types dipole-dipole and van der Waals bonds are suitable.
  • a masterbatch can be prepared which preferably contains 5-80% by weight of barium sulfate.
  • This masterbatch can then be either diluted only with the crude polymer or mixed with the other ingredients of the recipe and optionally redispersed.
  • a method can also be chosen in which the barium sulfate is first incorporated and dispersed in organic substances, in particular in amines, polyols, styrenes, formaldehydes and its molding compositions, vinyl ester resins, polyester resins or silicone resins. These barium sulfate-added organic substances can then be used as starting material for composite production.
  • organic substances in particular in amines, polyols, styrenes, formaldehydes and its molding compositions, vinyl ester resins, polyester resins or silicone resins.
  • These barium sulfate-added organic substances can then be used as starting material for composite production.
  • To disperse the barium sulfate in the masterbatch or in an organic substance it is possible to use customary dispersion methods, in particular using melt extruders, dissolvers, three-rollers, ball mills, bead mills, dip mills, ultrasound or kneaders. Particularly advantageous is the
  • the composite according to the invention surprisingly has outstanding mechanical and tribological properties.
  • the composite according to the invention has significantly improved flexural moduli, flexural strengths, tensile moduli, tensile strengths, fracture toughness, fracture toughness, impact toughness and wear rates.
  • the applications include, for example, bumpers or interior panels in trains but also aircraft made of thermoset molding compounds. High tensile strengths must be realized especially with adhesives.
  • Applications for elastomeric plastics, based for example on polymers such as styrene-butadiene rubber (SBR), are u. a. Seals and vibration absorbers.
  • Barium sulfate composites the duromer being at least one unsaturated polyester resin (UP), a phenolic resin, a melamine resin, a formaldehyde molding composition, a vinyl ester resin, a diallyl phthalate resin, a silicone resin and / or a urea resin, preferably an UP resin;
  • UP unsaturated polyester resin
  • elastomer at least one elastomer is selected from: natural rubber (NR), isoprene rubber (IR), butyl rubber (CUR, BIIR), butadiene rubber (BR), styrene-butadiene rubber (SBR ), Acrylonitrile
  • NBR butadiene rubber
  • BIIR bromobutyl rubber
  • SBIR styrene-butadiene-isoprene rubber
  • CSM chloroprene rubber
  • HNBR hydrogenated NBR rubber
  • VMQ polymethylsiloxane Vinyl rubber
  • AEM acrylate-ethylene rubber
  • ACM acrylate rubber
  • FKM fluoro rubber
  • FVMQ fluorosilicone rubber
  • TPE thermoplastic elastomers
  • TPE thermoplastic elastomers
  • TPE thermoplastic elastomers
  • TPE thermoplastic elastomers
  • TPE thermoplastic elastomers
  • TPE thermoplastic elastomers
  • TPE thermoplastic elastomers
  • TPE thermoplastic elastomers
  • TPE thermoplastic elastomers
  • TPE thermoplastic elastomers
  • TPE thermoplastic elastomers
  • TPE thermoplastic elastomers
  • TPE thermoplastic elast
  • Barium sulfate composites wherein the composite 20 to 99.8 wt .-% duromer, 0.1 to 60 wt .-% barium sulfate, 0 to 80 wt .-% mineral filler and / or glass fiber, 0.05 to 10 wt % Process additives, 0 to 10 wt% pigment, and 0 to 40 wt% aluminum hydroxide;
  • Barium sulfate composites wherein the composite comprises 100 phr of elastomer, 0.1 to 300 phr of barium sulfate, 0 to 10 phr of vulcanization accelerator, 0 to 10 phr of vulcanization retarder, 0 to 20 phr of zinc oxide, 0 to 10 phr of stearic acid, 0 to 20 phr of sulfur and or peroxide, 0 to 300 phr mineral filler, 0 to 200 phr plasticizer, 0 to 30 phr protective system, preferably containing antioxidants and antiozonants; contains
  • Barium sulfate composites wherein the proportion of barium sulfate in the composite 0.1 to 60 wt .-%, preferably 0.5 to 30 wt .-%, particularly preferably 1, 0 to 20 wt .-%, is; - Process for the preparation of the barium sulfate composite;
  • the barium sulfate composite wherein the barium sulfate is first incorporated and dispersed in organic substances, in particular in amines, polyols, styrenes, formaldehydes and its molding compositions, vinyl ester resins, polyester resins or silicone resins, the barium sulfate both inorganic or organic surface-modified also can not be surface-modified;
  • Barium sulfate composite which has improved mechanical properties and improved tribological properties
  • Barium sulfate composite in which the improvement in strength and toughness can be observed in a bending test or a tensile test;
  • Barium sulfate composite having improved impact strengths and / or impact strengths
  • Barium sulfate composite which has improved wear resistance
  • Barium sulfate composite the improved stress cracking resistance.
  • barium sulfate composite for components for the automotive, aerospace or space sector, in particular for weight saving, for example in the form of bumpers or interior trim - Use of the barium sulfate composite in particular in the form of seals or vibration dampers.
  • the starting material used is a precipitated, unmodified barium sulfate having a crystallite size d 50 of 26 nm.
  • the non-surface-modified barium sulfate is dispersed with a bead mill to 25 wt .-% in the UP resin Palapreg P17-02 until the Hegmann wedge is a fineness smaller than 5 microns.
  • This dispersion is according to material weight according to Table 1 with the other resin Palapreg H814-01 and the additives in the dissolver (dissolver disc: diameter 30 mm) at 1500 rpm, stirred in a 180 ml plastic cup and slowly added with increasing speed the required weight of fillers. After completion of the filler addition is for 3 minutes at 6500 revolutions / min, dispersed. To the raw mass of the required amount of glass fibers is added, which are underlined with the help of a spatula. In the kneader, this mixture is homogenized for a further 3 minutes at 50 U / min.
  • the resulting mass is carefully smoothed out into a mold impregnated with release agent with 12 recesses of 80 mm x 15 mm x 4 mm.
  • a lower pressure plate of the tool is a Teflon plate
  • the upper pressure plate a polished, chromed metal plate.
  • the heated to 150 0 C press the plates together with paper protection for one minute at 150 0 C tempered (with normal closing of the press), then the plates are pressed at a pressure of 100 bar at 150 0 C. After pressing, the plates are allowed to cool and the specimens are pushed out of the mold.
  • test specimens are tested in 3-point bending tests according to DIN EN ISO 178 and in
  • the composites of the invention show greatly improved compared to the pure resin
  • the starting material used is a surface-modified barium sulfate having a crystallite size d 50 of 26 nm.
  • the barium sulfate surface is aftertreated inorganically and silanized.
  • the inorganic surface modification consists of a silicon-aluminum-oxygen compound.
  • silanization the 3-methacryloxy-propyltrimethoxy-silane was used.
  • the inorganic surface-modified barium sulfate can be prepared, for example, by the following process:
  • the suspension is homogenized for a further 10 minutes with vigorous stirring. Subsequently, the pH is adjusted slowly, preferably within 60 minutes, by adding a 5% sulfuric acid to a pH of 7.5. It follows a maturation period of 10 minutes at a temperature of 40 0 C at.
  • the suspension is then washed to a conductivity of less than 100 ⁇ S / cm and then spray dried. The washed suspension is adjusted to a solids content of 20% by weight with demineralized water and dispersed by dissolver for 15 minutes. 15 g of the 3-methacryloxy-propyltrimethoxy-silane are slowly added to the suspension with dissolution dispersion. The suspension is then dispersed for a further 20 minutes with the dissolver and then dried in a freeze dryer.
  • the surface-modified barium sulfate is dispersed with a bead mill to 25 wt .-% in the UP resin Palapreg P17-02 until the Hegmann wedge is a fineness smaller than 5 microns.
  • This dispersion is according to material weight according to Table 3 with the other resin Palapreg H814-01 and the additives in the dissolver (dissolver disc: diameter 30 mm) at 1500 rev / min, stirred in a 180 ml plastic cup and slowly with increasing speed added the required weight of fillers. After completion of the filler addition is for 3 minutes at 6500 revolutions / min, dispersed. To the raw mass of the required amount of glass fibers is added, which are underlined with the help of a spatula. In the kneader, this mixture is homogenized for a further 3 minutes at 50 U / min.
  • the resulting mass is carefully smoothed out into a mold impregnated with release agent with 12 recesses of 80 mm x 15 mm x 4 mm.
  • a lower pressure plate of the tool is a Teflon plate
  • the upper pressure plate a polished, chromed metal plate.
  • the heated to 150 ° C press the plates including paper protection for one minute at 150 0 C tempered (with normal closing of the press), then the plates are pressed at a pressure of 100 bar at 150 ° C. After pressing, the plates are allowed to cool and the specimens are pushed out of the mold.
  • test specimens are tested in 3-point bending tests according to DIN EN ISO 178 and in impact tests according to DIN EN ISO 179. The results are shown in Table 4.
  • the composites of the invention show greatly improved properties compared to the pure resin.
  • the starting material used is an organically surface-modified barium sulfate having a crystallite size d 50 of 20 nm.
  • an organic surface modification an acrylate-functional oleyl cetyl alcohol sulfate Na salt was used.
  • the organic surface-modified barium sulfate can be prepared, for example, by the following process:
  • the organically surface-modified barium sulfate is dispersed with a bead mill at 25% by weight into the UP resin Palapreg P17-02 until a fineness of less than 5 ⁇ m is present on the Hegmann wedge.
  • This dispersion is according to material weight in Table 1 with the other resin Palapreg H814-01 and the additives in the dissolver (dissolver disc: diameter 30 mm) at 1500 rev / min. Stirred in a 180 ml plastic cup and slowly added with increasing speed the required weight of fillers. After completion of the filler addition is for 3 minutes at 6500 revolutions / min, dispersed. To the raw mass of the required amount of glass fibers is added, which are underlined with the help of a spatula. In the kneader, this mixture is homogenized for a further 3 minutes at 50 U / min.
  • the resulting mass is carefully smoothed out into a mold impregnated with release agent with 12 recesses of 80 mm x 15 mm x 4 mm.
  • a lower pressure plate of the tool is a Teflon plate
  • the upper pressure plate a polished, chromed metal plate.
  • the plates In the heated to 150 0 C press the plates together with paper protection for one minute at 150 0 C tempered (with normal closing of the press), then the plates are pressed at a pressure of 100 bar at 150 0 C. After pressing, the plates are allowed to cool and the specimens are pushed out of the mold.
  • the test specimens are tested in 3-point bending tests according to DIN EN ISO 178 and in impact tests according to DIN EN ISO 179. The results are shown in Table 6.
  • the composites of the invention show greatly improved properties compared to the pure resin.

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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)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Compounds Of Unknown Constitution (AREA)

Abstract

L'invention concerne des composites contenant du sulfate de baryum, des procédés de fabrication de ceux-ci et leur utilisation.
EP07802931A 2006-08-25 2007-08-27 Composite contenant du sulfate de baryum Withdrawn EP2057218A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006039855 2006-08-25
PCT/EP2007/058893 WO2008023075A1 (fr) 2006-08-25 2007-08-27 Composite contenant du sulfate de baryum

Publications (1)

Publication Number Publication Date
EP2057218A1 true EP2057218A1 (fr) 2009-05-13

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EP07802930.3A Not-in-force EP2057217B1 (fr) 2006-08-25 2007-08-27 Composite contenant du sulfate de baryum
EP07802931A Withdrawn EP2057218A1 (fr) 2006-08-25 2007-08-27 Composite contenant du sulfate de baryum

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EP07802930.3A Not-in-force EP2057217B1 (fr) 2006-08-25 2007-08-27 Composite contenant du sulfate de baryum

Country Status (10)

Country Link
US (2) US20090326114A1 (fr)
EP (2) EP2057217B1 (fr)
JP (2) JP2010501709A (fr)
CN (2) CN101583658A (fr)
BR (2) BRPI0717172A2 (fr)
CA (2) CA2661526A1 (fr)
MX (2) MX2009001984A (fr)
NO (1) NO20090880L (fr)
TW (2) TW200909500A (fr)
WO (2) WO2008023074A1 (fr)

Families Citing this family (57)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005029309A1 (de) * 2005-06-04 2006-12-07 Solvay Infra Bad Hönningen GmbH Dispersion von desagglomeriertem Bariumsulfat in halogenierten Lösungsmitteln, Ethern oder Estern
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US20090318594A1 (en) 2009-12-24
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EP2057217B1 (fr) 2017-02-22
MX2009001984A (es) 2009-03-06
WO2008023074A1 (fr) 2008-02-28
EP2057217A1 (fr) 2009-05-13
WO2008023075A1 (fr) 2008-02-28
BRPI0717172A2 (pt) 2013-10-15
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CA2661509A1 (fr) 2008-02-28
BRPI0716575A2 (pt) 2013-11-05

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