WO2005040254A1 - Extrusionsverfahren zur herstellung von zähmodifizierten und schichtsilikatverstärkten thermoplastischen systemen - Google Patents
Extrusionsverfahren zur herstellung von zähmodifizierten und schichtsilikatverstärkten thermoplastischen systemen Download PDFInfo
- Publication number
- WO2005040254A1 WO2005040254A1 PCT/EP2004/052189 EP2004052189W WO2005040254A1 WO 2005040254 A1 WO2005040254 A1 WO 2005040254A1 EP 2004052189 W EP2004052189 W EP 2004052189W WO 2005040254 A1 WO2005040254 A1 WO 2005040254A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- process according
- extrusion process
- latex
- layered silicate
- water
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
- C08J3/2056—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase the polymer being pre-melted
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/29—Feeding the extrusion material to the extruder in liquid form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/76—Venting, drying means; Degassing means
- B29C48/765—Venting, drying means; Degassing means in the extruder apparatus
- B29C48/766—Venting, drying means; Degassing means in the extruder apparatus in screw extruders
- B29C48/767—Venting, drying means; Degassing means in the extruder apparatus in screw extruders through a degassing opening of a barrel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/297—Feeding the extrusion material to the extruder at several locations, e.g. using several hoppers or using a separate additive feeding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
Definitions
- the present invention relates to an extrusion process for the production of tough modified and layered silicate reinforced thermoplastic systems.
- Cross-sectoral lightweight materials are becoming increasingly important for the conservation of natural resources. It is crucial here that the weight advantages are combined with good and improved mechanical properties.
- One approach to realizing these requirements are nanocomposites, in which suitable materials are incorporated as nanoparticles in various matrices. The level of filling and the particle size are variable, it being crucial that the composite materials have a very fine and homogeneous particle distribution in the matrix.
- Natural and synthetic layered silicates are nanoparticles known from the prior art, which increase the stiffness of the material, but which are fine only with considerable effort, i.e. can be distributed as separate nanoparticles enveloped by the matrix. As larger macroparticles, they only increase the stiffness moderately and at the same time reduce the impact strength.
- An improvement in the properties of the above composites is provided by processes for the production of layered silicate-reinforced composites, such as the exfoliation and adsorption process, in which layered silicates and polymers are dispersed or dissolved in the same solvent, polymer and unfolded exfoliated layered silicates accumulating and after evaporation of the solvent form a multi-layer sandwich structure.
- Another method is intercalating polymerization in situ. In this process, the layered silicate is swollen in the liquid monomer or a solution of the monomer of the matrix material, and the formation of the polymer can thus take place between the intercalated sheets of the layered silicate.
- the polymerization can be initiated by an initiator substance or, for example, by radiation or heat treatment.
- the layered silicates are mixed with the polymer matrix in the molten state. Under these conditions, ideally matched layered silicates and polymers, the polymer can migrate into the spaces between the layered silicates and thus lead to the formation of either intercalated or exfoliated nanocomposites (Alexandre, M. and Dubois, P., Polymer-layered Silicate Nanocomposites: Preparation , Properties and Uses of a new Class of Materials, Materials Science and Engineering Reviews 28 (2000) 1 -36). No solvent is required with this method.
- nanocomposites In the context of the present invention, only composite materials with correspondingly finely distributed fillers are referred to as “nanocomposites” because the particles of at least one filler, which are individually surrounded by matrix material, have dimensions in the order of magnitude of nanometers in at least one dimension.
- melt intercalation can be carried out in an extruder.
- Liu et al. 1999 a nylon composite based on nylon and using montmorillonite (Liu, LM et al., Studies on Nylon-6 Clay Nanocomposites by Melt-Intercalation Process, J. Appl. Polym. Sci. 71 (1999) 1133-1138 ).
- montmorillonite Liu, LM et al., Studies on Nylon-6 Clay Nanocomposites by Melt-Intercalation Process, J. Appl. Polym. Sci. 71 (1999) 1133-1138 .
- the advantage of using an aqueous silicate solution is that the multilayer silicates swell strongly in water, and the widening of the layer spacing can be 40-50% and more. These enlarged gaps between the layers are therefore accessible to the respective polymer and the intercalation and exfoliation of the layered silicates is favored accordingly.
- the individual layers of the silicates with the particles of the toughness modifier can be combined to form elements that surprisingly improve toughness and strength (skeleton or card house structure).
- the at least partial and mostly extensive removal of the water from the compounding system leads to the mixture being optimally compounded.
- the water can e.g. assume the function of a physical propellant.
- part of the water introduced to remain bound chemically or in some other way in the compound.
- thermoplastic plastics for example polyethylene, polyester, polystyrene, polyvinyl chloride, polyamides
- elastomers for example polyurethane, styrene butadiene, ethylene propylene, polychloropen, etc.
- Silicone and natural rubber.
- Polyamides, linear polyesters (PET, PBT), polyoxymethylene and polyolefins (PE, PP) are particularly preferred.
- Layer silicates that can be used include all representatives of natural or synthetic swellable layer silicates. These include clayey stones and earths (e.g. bentonite and kaolinite), clay minerals (e.g.
- montmorillonite, beidellite, vermiculite, serpentine and synthetic layered silicates (e.g. MgO (Si0 2 ) s (AI 2 ⁇ 3 ) a (AB) (H 2 ⁇ ) x , where AB is an ion pair, such as NaF).
- natural rubber such as natural rubber (NR)
- synthetic rubber such as styrene butadiene (SBR), nitrile rubber (NBR), polychloropen (CR)
- SBR styrene butadiene
- NBR nitrile rubber
- CR polychloropen
- the layered silicates can be present in the polymer matrix as particles on a microscale, however, with suitable processing, the aim is for the layered silicates to be present in an intercalated form or in the exfoliated state, ie as individual layers which are embedded in the polymer matrix (nanoscale).
- dispersion comprises a system of several phases, one of which is continuous and at least one further is finely divided, such as, for example, in the case of an emulsion, suspension or molecular dispersion.
- the dispersions of toughness modifier and layered silicate are introduced into the compounding system separately in terms of time and / or space.
- the advantage of this procedure is that the dispersions are easier to handle separately, and no undesired interactions between the toughness modifier and the silicate layers can take place at this stage.
- toughness modifier and layered silicate are introduced together into the compounding system. It is advantageous here that only one common process step has to be carried out. This is tantamount to a lower system outlay.
- Another preferred embodiment of the present invention is characterized in that the water is removed from the compounding system during the extrusion by evaporation.
- the removal of the water from the compounding system by evaporation is recommended because the temperature in the mixture has already increased due to the extrusion and mixing of the solutions and possibly also by introducing the melt and the evaporation of water with little or no additional energy expenditure is possible.
- Dried rubber can be easily dispersed in water.
- An aqueous dispersion of rubber is also called latex. Therefore, in a preferred embodiment of the present invention, toughness modifiers comprising natural and synthetic rubber and mixtures thereof are used by being in aqueous dispersion, i.e. be used as latex.
- the use of all water-dispersible toughness modifiers according to the present invention is conceivable. When suspending the rubber, make sure that the rubber particles are dispersed as finely as possible. The particle size should be in the range ⁇ 10 ⁇ m.
- the toughness modifiers used include latex and latex mixtures of natural rubbers (such as Example natural rubber (NR)) or synthetic rubber (such as styrene butadiene (SBR), nitrile rubber (NBR), polychloropen (CR).
- natural rubbers such as Example natural rubber (NR)
- synthetic rubber such as styrene butadiene (SBR), nitrile rubber (NBR), polychloropen (CR).
- SBR styrene butadiene
- NBR nitrile rubber
- CR polychloropen
- the latex or the latex mixture or the rubber or the rubber mixture is pre-vulcanized.
- Pre-vulcanization with e.g. Sulfur or high energy radiation is advantageous to maintain the original particle size of the toughness modifier. Otherwise, the particle size could change under the compounding conditions depending on the compatibility with the matrix. Pre-vulcanization is therefore an important measure to control particle size and distribution in a targeted manner.
- the toughness modifier used has a particle size of 0.1-10 ⁇ m.
- the particle size and the distance between the particles are very important for the formation of microcracks around the particles in the polymer matrix. Matrix molecules can grow into these microcracks and form microfibrils, which result in extremely high toughness of the resulting composite material.
- a very good toughness is achieved, for example, by particle diameters of approximately 0.5 ⁇ m and distances between these particles of 1-10 ⁇ m, particularly preferably approximately 2 ⁇ m.
- the toughness modifier is characterized in that the structure of the particles of the toughness modifier consists of core and shell.
- Particles with a structure of core (e.g. polystyrene) and shell (e.g. polyacrylate) have the advantage that the difference in stiffness (modulus of elasticity) between the rubber phase and the matrix can be varied by modifying the shell. This changes the stress concentration on the particles, which determines the extent to which cavities of the matrix form in the vicinity of the particles. This in turn is a crucial factor in increasing toughness.
- the particles of the toughness modifier have reactive groups on their surface. Via these reactive groups, these particles can interact with the functional groups of the respective matrix polymer and thereby create a chemical bond.
- reactive groups include hydroxyl, carboxyl and epoxy groups.
- the toughness modifier used is contained in the compounded product of the process in a proportion of 1-40% by weight, preferably in a proportion of 5-25% by weight. These concentrations provide a product with optimal toughness.
- the layered silicate used comprises natural and synthetic layered silicates, such as, for example, bentonite and fluorine heteroite, which are swellable in water. While natural layered silicates are available particularly cheaply, it is advantageous in the case of synthetic layered silicates that they are particularly pure, which is of great advantage, for example, in view of the thermal and thermooxidative stability.
- Another preferred embodiment of the present invention is characterized in that the layered silicate is contained in the compounded product of the process in a proportion of 1-10% by weight.
- the layered silicate is preferably contained in the compounded product of the process in a proportion of 4-8% by weight. This concentration is optimal for the formation of individual layers and for the homogeneous distribution of these individual layers in the matrix.
- the method according to the present invention provides, compared to the methods previously known in the prior art, a product which has optimal characteristics with regard to toughness and rigidity.
- chemical pretreatment is generally required to introduce layered silicates in order to obtain a product with the desired properties.
- the layered silicates are "organophilically equipped" by cation exchange in order to ensure that the originally very polar layered silicates are compatible with the matrix. This process step is usually very complex and expensive and, according to the present invention, is advantageously not necessary.
- the layer-silicate is exfoliated or intercalated in the compound that is in the extruder.
- a sufficiently long residence time of the mixture in the extruder is essential and the process according to the invention provides a further advantage, consisting in that this time is saved in that the layered silicate is introduced into the extruder already in the swollen state and can be exfoliated there more quickly.
- the essentially aqueous dispersion additionally contains up to a total of 50% by volume of polar, water-soluble organic compounds.
- polar, water-soluble organic compounds include, among others, holes and glycols, but also water-soluble polymers, such as polyvinyl alcohol, which can be advantageous as a thickener.
- cationic surfactants are optionally added to the dispersion in order to stabilize the latex.
- FIGS. 1 and 2 The individual shows:
- FIG. 1 shows a flowchart of an extrusion process according to the invention for the production of tough modified and layered silicate reinforced thermoplastic systems
- FIG. 2 shows a schematic representation of a cross section through an extrusion device for the inventive production of tough modified and layered silicate reinforced thermoplastic systems.
- FIG. 1 shows the sequence of compounding the individual starting materials in a production process according to the invention for the production of tough modified and layered silicate reinforced thermoplastic systems in a flow chart.
- the raw material of the polymer matrix (for example a granulate of the polymer matrix material) is first melted in a melting device 1.
- a melting device 1 for example a granulate of the polymer matrix material
- the layered silicate in aqueous dispersion is first added to the melt of the polymer matrix in the admixing stage 2a via the admixing device 3a.
- the resulting mixture is composed of the polymer matrix, the layered silicate and water and is homogenized in the mixing device 4a.
- water can optionally be removed from the system in a drainage step 5a via the drainage device 6a.
- latex is added via the admixing device 8a, and so the resulting mixture is composed of the polymer matrix, the layered silicate, the latex and water, which is homogenized again in the mixing device 9a.
- dewatering step 10a water is removed from the compounding system via the dewatering device 11a and the resulting compound essentially comprises the polymer matrix with the layered silicate and latex and is optionally further homogenized by the dispensing device 12a and the product is finally dispensed.
- latex and layered silicate dispersions are added to the polymer matrix melt in reverse order.
- Such an embodiment is shown in the middle branch of the flow chart in FIG. 1.
- latex is first added to the polymer matrix melt in the admixing stage 2b via the admixing device 3b in a first step.
- the resulting mixture is composed of the polymer matrix, the latex and water and is homogenized in the mixing device 4b.
- water can optionally be removed from the system in a dewatering step 5b via the dewatering device 6b.
- the subsequent admixing stage 7b is followed by the addition of layered silicate in aqueous dispersion via the admixing device 8b, and so the resulting mixture of the polymer matrix, the layered silicate, the latex and water is composed, which again in the mixing device 9b is homogenized.
- dewatering step 10b water is discharged from the compounding system via the dewatering device 11b and the resulting compound essentially comprises the polymer matrix with the layered silicate and latex and is optionally further homogenized by the dispensing device 12b and the product is finally dispensed.
- a third embodiment of the present invention is shown in the bottom branch of the flow chart of FIG. 1.
- the latex and layered silicate dispersion are added together in a mixing stage 2c via the mixing device 3c.
- the resulting mixture is composed of the polymer matrix, the layered silicate, latex and water and is homogenized in the mixing device 4c.
- a compound is obtained which essentially consists of polymer matrix, layered silicate and latex.
- FIG. 2 shows a top view of a lateral cross section through an extrusion device 21 for the production according to the invention of tough modified and layered silicate reinforced thermoplastic systems.
- This device is essentially formed by an elongated cylindrical tube 22, in the interior 23 of which there is a screw 24 which extends substantially continuously over almost the entire length of the cylindrical tube 22, but the cross section of the tube also extends over its length can vary in order to be able to provide higher or lower pressures.
- the screw is expediently moved from left to right.
- the sealing element 29 prevents the backflow of melt against the transport direction of the screw 24.
- the sealing element 29 is generally a steel disk, the outer circumference of which is slightly less than the inner circumference of the cylindrical tube and through the opening of which the melt can still flow, the reflux of the melt against the direction of transport of the screw being significantly reduced.
- Another possibility of separating the areas 27 and 30 by the delimitation area 28 is a special screw configuration with the formation of a compression onsseg ents.
- the compounding area 30 in the embodiment shown here, there is a filling device 31 for introducing phyllosilicate in aqueous dispersion 32.
- An evaporation area 35 is optionally conceivable after this area, in which excess gas 34 can be removed via the evaporation device 33. If such an evaporation area 35 is realized, a further delimitation area 37 would be advantageous in which a sealing element 36 (analogous to the sealing element 29) is provided.
- a further filling device 39 for introducing latex 40 into the compounding system in the compounding area 38.
- the mixture of polymer matrix, layered silicate dispersion and latex is mixed and homogenized in the compounding area 38 by the movement of the screw 24.
- the compound mixture is transported from left to right through the extrusion device 21.
- the evaporation area 41 in which excess gases 43, essentially water vapor, can be removed via the evaporation device 42.
- the evaporated compound 45 is conveyed out of the extrusion device 21 by the transport movement of the screw 24 through the outlet nozzle 44.
- Nanocomposites based on polyamide 6 were produced on a twin-screw extruder (ZSE from Werner & Pfleiderer, Germany).
- a natural Na bentonite (EXM 757, Süd-Chemie, Germany, abbreviated: B) was used as layered silicate.
- An NBR latex (Perbunan N Latex 1120 from Polymerlatex GmbH, Germany) was used for the toughness modification and the solids content was 45% by weight. The rubber content was adjusted to 5% by weight and the proportion of the layered silicate in the finished compound to 1% by weight by metering the latex or the aqueous dispersion of the layered silicate separately.
- Nanocomposites were produced analogously to Example 1 on a twin-screw extruder (ZSE from Werner & Pfleiderer, Germany), a synthetic Na-fluorohectorite (Somasif ME-100 from Co-op Chemicals, Japan, abbreviated: F) being chosen as the layered silicate.
- the rubber content here was adjusted to 35% by weight and the proportion of the layered silicate in the finished compound to 10% by weight by separate metering in of the latex or the aqueous dispersion of the layered silicate.
- Process control, evaporation, screw configuration and residence time were also chosen as in Example 1.
- the product thus produced via the "latex route” was granulated and then injection molded (B2).
- Nanocomposites based on polybutylene terephthalate (Ultradur B4520, BASF AG, Germany, abbreviated: PBT) were produced as described in Example 1, an acrylic latex (Plextol X 4324, Polymerlatex GmbH, Germany, abbreviated: ACR) for the toughening in this case. served with 60 wt .-% solids.
- the layered silicate (bentonite, B) was dispersed in the latex before it was added to PBT.
- Example 4 was carried out analogously to Example 3, with a polymer dispersion (average particle size: 0.5 ⁇ m) with particles of a core (polystyrene) / shell (polyacrylate) structure (abbreviated: AC-KS) for the toughening in this case. served.
- the polystyrene / polyacrylate ratio was 65/35% by weight.
- the layered silicate (bentonite, B) was dispersed here in the polymer dispersion before it was added to PBT (B4).
- the rubbers which were obtained by precipitation (coagulation) from the same dispersion as in B4 were used for comparison purposes (V4).
- the mechanical properties were determined as in Example 1 - but without conditioning the test specimens - and are summarized in Table 4. Table 4
- a polyoxymethylene of the injection molding type (Hostaform C9021, Ticona GmbH, Germany, abbreviated: POM) was produced analogously to Example 1 and here by the addition of Na fluorhectorite (F) and polyester urethane latex (Impranil DLP-R, Bayer AG, Germany, Rubber content: 50% by weight, abbreviated: PUR) refined.
- the same compound was produced via the "melting route” (V5).
- the PUR was obtained from the latex by freeze drying. The results are shown in Table 5.
- a nanocomposite was produced analogously to Example 1, an isotactic polypropylene homopolymer (Hostalen PPH 2150 from Basell, Germany, abbreviated: PP) with a high-ammonium-containing natural rubber latex (Rubber Research Institute, India, abbreviated: NR) and Na- Bentonite was refined.
- the NR content of the latex was 60% by weight.
- the melt-compounded mixture which was produced using solid NR (SMR-CV) and powder dosing of B, was used for comparison purposes (V7). The results are listed in Table 7.
- the melt-compounded mixture which was prepared using solid NR (SMR-CV) and powder dosing of B, was used for comparison purposes (V8). The results are listed in Table 8.
- a nanocomposite was produced analogously to Example 8, the latex here being pre-vulcanized (NR-P).
- NR-P pre-vulcanized
- zinc diethyl dithiocarbamate and sulfur in aqueous dispersion were added to the latex, in each case in 1 part by weight per 100 parts by weight of dry NR and then the temperature was raised to 70.degree. After 4 hours of storage, the latex was cooled to room temperature and the previous ammonium content was restored.
- the melt-compounded mixture which was prepared using solid NR (SMR-CV) and powder dosing of B, was used for comparison purposes (V9).
- PP was refined both without pre-vulcanization (NR) and with pre-vulcanization (NR-P).
- the mixture 50/40/10 had the property profile of a thermoplastic elastomer and was therefore characterized differently than before.
- the results are listed in Table 10, it being noted that a DVR value of 100% corresponds to an ideal thermoplastic and a DVR value of 0% corresponds to an ideal rubber.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- 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)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04766801A EP1678241A1 (de) | 2003-10-20 | 2004-09-15 | Extrusionsverfahren zur herstellung von zähmodifizierten und schichtsilikatverstärkten thermoplastischen systemen |
JP2006534736A JP2007508961A (ja) | 2003-10-20 | 2004-09-15 | 靱性を改良化し層状ケイ酸塩で教化した熱可塑系を調製するための押出し方法 |
US10/576,404 US20060264553A1 (en) | 2003-10-20 | 2004-09-15 | Extrusion method for the production f strength-modified and phyllosilicate reinforced thermoplastic systems |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10348548.1 | 2003-10-20 | ||
DE10348548A DE10348548A1 (de) | 2003-10-20 | 2003-10-20 | Extrusionsverfahren zur Herstellung von zähmodifizierten und schichtsilikatverstärkten thermoplastischen Systemen |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005040254A1 true WO2005040254A1 (de) | 2005-05-06 |
Family
ID=34442110
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2004/052189 WO2005040254A1 (de) | 2003-10-20 | 2004-09-15 | Extrusionsverfahren zur herstellung von zähmodifizierten und schichtsilikatverstärkten thermoplastischen systemen |
Country Status (6)
Country | Link |
---|---|
US (1) | US20060264553A1 (de) |
EP (1) | EP1678241A1 (de) |
JP (1) | JP2007508961A (de) |
CN (1) | CN1871282A (de) |
DE (1) | DE10348548A1 (de) |
WO (1) | WO2005040254A1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010511740A (ja) * | 2006-11-30 | 2010-04-15 | ザ テキサス エー アンド エム ユニバーシティ システム | ナノコンポジットポリマーの製造に有用な挿入剤非含有組成物 |
EP2305447A1 (de) * | 2009-10-05 | 2011-04-06 | Basf Se | Verfahren zur Herstellung von Bauteilen aus einer thermoplastischen Formmasse, sowie Bauteile aus einer thermoplastischen Formmasse |
WO2011038990A1 (de) * | 2009-09-29 | 2011-04-07 | Evonik Röhm Gmbh | Verfahren und anlage zur einfärbung von kunststoffformmassen |
WO2012100936A1 (de) * | 2011-01-26 | 2012-08-02 | Gneuss Kunststofftechnik Gmbh | Verfahren und vorrichtung zum herstellen von mit nanopartikein versehenen kunststoffschmelzen |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8877250B2 (en) | 2005-12-20 | 2014-11-04 | Bridgestone Corporation | Hollow nano-particles and method thereof |
DE102006029572A1 (de) | 2006-06-22 | 2007-12-27 | Siemens Ag | Verfahren zum Erzeugen eines Bauteils mit einer nanostrukturierten Beschichtung sowie Verfahren zur Herstellung eines Granulats beziehungsweise einer Polymerfolie, geeignet für das Verfahren zum Beschichten |
DE102008038667A1 (de) * | 2008-08-12 | 2010-02-25 | K+S Ag | Herstellungsverfahren von thermoplastischen Polymeren enthaltend grobskalige und/oder nanoskalige, gecoatete, desagglomerierte Magnesiumhydroxidpartikel und eine Vorrichtung hierzu |
EP2370349B1 (de) | 2008-12-31 | 2014-10-29 | Bridgestone Corporation | Herstellungsverfahren für core-first-nanopartikel, nanopartikel und zusammensetzung |
US9062144B2 (en) | 2009-04-03 | 2015-06-23 | Bridgestone Corporation | Hairy polymeric nanoparticles with first and second shell block polymer arms |
US8377337B2 (en) * | 2010-05-04 | 2013-02-19 | Sabic Innovative Plastics Ip B.V. | Method of incorporating an additive into a polyamide-poly(arylene ether) composition, composition prepared thereby, and article comprising the composition |
US9428604B1 (en) | 2011-12-30 | 2016-08-30 | Bridgestone Corporation | Nanoparticle fillers and methods of mixing into elastomers |
TWI454515B (zh) | 2012-07-20 | 2014-10-01 | Mitsubishi Gas Chemical Co | And a method for producing a resin composition containing active particles |
CN110229501B (zh) * | 2018-03-06 | 2021-02-05 | 中国科学院化学研究所 | 一种尼龙弹性体纳米复合材料及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1384652A (fr) * | 1962-10-12 | 1965-01-08 | Ici Ltd | Procédé de malaxage d'additifs dans des matières thermoplastiques |
EP0125483A2 (de) * | 1983-04-16 | 1984-11-21 | BASF Aktiengesellschaft | Schlagzähe thermoplastische Formmassen und Verfahren zu ihrer Herstellung |
DE19854170A1 (de) * | 1998-11-24 | 2000-05-25 | Basf Ag | Thermoplastische Nanocomposites |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4305901A (en) * | 1973-07-23 | 1981-12-15 | National Gypsum Company | Wet extrusion of reinforced thermoplastic |
DE3806548C2 (de) * | 1987-03-04 | 1996-10-02 | Toyoda Chuo Kenkyusho Kk | Verbundmaterial und Verfahren zu dessen Herstellung |
DE19913661A1 (de) * | 1999-03-25 | 2000-09-28 | Basf Ag | Verfahren zum Einarbeiten mindestens eines Feststoffpulvers A in die Schmelze mindestens eines thermoplastischen Polymeren B |
JP4100850B2 (ja) * | 2000-01-14 | 2008-06-11 | 株式会社カネカ | ポリスチレン系樹脂押出発泡体及びその製造方法 |
JP2004517980A (ja) * | 2000-09-21 | 2004-06-17 | ローム アンド ハース カンパニー | 極性モノマーと多価カチオンとに関わる方法および組成物 |
EP2253448B1 (de) * | 2001-01-22 | 2012-12-26 | Kuraray Co., Ltd. | Verfahren zur Herstellung einer EVOH-Zusammensetzung |
-
2003
- 2003-10-20 DE DE10348548A patent/DE10348548A1/de not_active Withdrawn
-
2004
- 2004-09-15 CN CNA2004800307885A patent/CN1871282A/zh active Pending
- 2004-09-15 EP EP04766801A patent/EP1678241A1/de not_active Withdrawn
- 2004-09-15 JP JP2006534736A patent/JP2007508961A/ja not_active Withdrawn
- 2004-09-15 WO PCT/EP2004/052189 patent/WO2005040254A1/de active Application Filing
- 2004-09-15 US US10/576,404 patent/US20060264553A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1384652A (fr) * | 1962-10-12 | 1965-01-08 | Ici Ltd | Procédé de malaxage d'additifs dans des matières thermoplastiques |
EP0125483A2 (de) * | 1983-04-16 | 1984-11-21 | BASF Aktiengesellschaft | Schlagzähe thermoplastische Formmassen und Verfahren zu ihrer Herstellung |
DE19854170A1 (de) * | 1998-11-24 | 2000-05-25 | Basf Ag | Thermoplastische Nanocomposites |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010511740A (ja) * | 2006-11-30 | 2010-04-15 | ザ テキサス エー アンド エム ユニバーシティ システム | ナノコンポジットポリマーの製造に有用な挿入剤非含有組成物 |
WO2011038990A1 (de) * | 2009-09-29 | 2011-04-07 | Evonik Röhm Gmbh | Verfahren und anlage zur einfärbung von kunststoffformmassen |
US9427889B2 (en) | 2009-09-29 | 2016-08-30 | Evonik Roehm Gmbh | Process and system for colouring plastics moulding compositions |
EP2305447A1 (de) * | 2009-10-05 | 2011-04-06 | Basf Se | Verfahren zur Herstellung von Bauteilen aus einer thermoplastischen Formmasse, sowie Bauteile aus einer thermoplastischen Formmasse |
WO2012100936A1 (de) * | 2011-01-26 | 2012-08-02 | Gneuss Kunststofftechnik Gmbh | Verfahren und vorrichtung zum herstellen von mit nanopartikein versehenen kunststoffschmelzen |
Also Published As
Publication number | Publication date |
---|---|
EP1678241A1 (de) | 2006-07-12 |
US20060264553A1 (en) | 2006-11-23 |
JP2007508961A (ja) | 2007-04-12 |
DE10348548A1 (de) | 2005-05-19 |
CN1871282A (zh) | 2006-11-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1678241A1 (de) | Extrusionsverfahren zur herstellung von zähmodifizierten und schichtsilikatverstärkten thermoplastischen systemen | |
DE102017214080B4 (de) | Zusammensetzung von Verbindungen als Innenausstattungsmaterial für Fahrzeuge durch Verwendung von Naturfasern | |
EP0085778A1 (de) | Glasfaserverstärkte Polyvinylchlorid-Zusammensetzung | |
EP1627014B1 (de) | Gummimehl-enthaltende elastomerlegierungen | |
DE10164335A1 (de) | Harzverbundmaterial | |
DE19882437B4 (de) | Verfahren zur Herstellung eines ein Polymer umfassenden Verbundmaterials | |
EP2154177B1 (de) | Herstellungsverfahren von thermoplastischen Polymeren enthaltend grobskalige und/oder nanoskalige, gecoatete, dessagglomerierte Magnesiumhydroxidpartikel und eine Vorrichtung hierzu | |
EP2516514B1 (de) | Verfahren zur herstellung eines flächenförmigen gummibelags und flächenförmiger gummibelag | |
DE2746181A1 (de) | Verfahren zur herstellung thermoplastischer massen mit erhoehter gasundurchlaessigkeit | |
EP1780241A1 (de) | Verwendung von Polyamid-Formmassen zur Herstellung von Formteilen mit reduzierter Oberflächenverkohlung | |
EP2389820A1 (de) | Handschuh | |
EP1229075B2 (de) | Verfahren zur Herstellung eines thermoplastischen Polymerkomposits auf Stärkebasis mit integrierten nanoskopischen Teilchen | |
DE69924849T2 (de) | Thermoplastische harzzusammensetzung, verfahren zu deren herstellung und biaxial orientierter film der die zusammensetzung enthält | |
WO2000023512A1 (de) | Polymerer, teilkristalliner thermoplastischer werkstoff mit nanoskaligem nukleierungsmittel und daraus hergestellte hochtransparente formteile | |
DE1544706C3 (de) | Formmassen aus Polyolefinen und Polyamiden | |
WO2012069564A1 (de) | Polymer-nanocomposite mit schichtmineralien und verfahren zu ihrer herstellung | |
Reinsch et al. | Continuous electric sorting in the recycling process of plastics | |
DE102012014871B4 (de) | Mehrschichtiges Fahrzeuginnenverkleidungsteil sowie Verfahren zum Herstellen eines mehrschichtigen Fahrzeuginnenverkleidungsteils | |
DE102018119427A1 (de) | Verbundwerkstoff, extrudat und extrusionsverfahren | |
WO2014036578A1 (de) | Formkörper, enthaltend ein elastomer sowie cellulosische partikel | |
DE102004023900A1 (de) | Verfahren zur Herstellung von polymeren Verbundmaterialien sowie die nach diesem Verfahren enthaltenen Verbundmaterialien | |
DE102007048995B4 (de) | Verfahren zur Vereinzelung von Silikat-Plättchen aus Schichtsilikaten | |
DE102017106505A1 (de) | Verträglichkeitsvermittler zur Verträglichmachung von Polyolefin-Gemischen, Verfahren zu dessen Herstellung, sowie Verfahren zur Herstellung von Formteilen aus Polyolefin-Gemischen | |
DE102016000028B4 (de) | Transparenter thermoplastischer Werkstoff mit Nanoblasenstruktur sowie daraus hergestellte transparente Halbzeuge und Formteile | |
DE102022122136A1 (de) | Verfahren zur Herstellung eines Barriereschichtlaminats, Barriereschichtlaminat und aus dem Barriereschichtlaminat hergestellter Behälter |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200480030788.5 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2004766801 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2006534736 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 978/KOLNP/2006 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2006264553 Country of ref document: US Ref document number: 10576404 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 2004766801 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 10576404 Country of ref document: US |