US20060155018A1 - Master batches based on pre-exfoliated nanoclays and the use of the same - Google Patents
Master batches based on pre-exfoliated nanoclays and the use of the same Download PDFInfo
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- US20060155018A1 US20060155018A1 US10/541,625 US54162504A US2006155018A1 US 20060155018 A1 US20060155018 A1 US 20060155018A1 US 54162504 A US54162504 A US 54162504A US 2006155018 A1 US2006155018 A1 US 2006155018A1
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
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- 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
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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- 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
- C08K3/346—Clay
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- 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
- C09C1/42—Clays
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- 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
- C08K2201/011—Nanostructured additives
Definitions
- Ground nanoclay in which the average particle size has been lowered below the particle size of the nanoclays available commercially is highly advantageous particularly when the result is preparation of a masterbatch which serves together with halogen-free fillers for use as a flame retardant in polymer compositions.
- the nanoclays have then been reduced to an average particle size at which it would per se have to be assumed that they have become incapable of achieving any desired action, it is nevertheless found that use of this type of masterbatch markedly improves not only the mechanical properties of the polymer composition but also its processing properties.
- the fatty acid derivatives encompass hydrogenated derivatives, alcohol derivatives, amine derivatives, and mixtures of these.
- the average molecular weight of EPM and/or of EPDM is preferably less than 20 000.
- the ethylene:propylene ratio in EPM and/or EPDM may be from 40:60 to 60:40.
- polymer powders such as polyethylene-ethylene-vinyl acetate copolymers (EVA), ethylene-ethyl acrylate copolymers (EEA), ethylene-methyl acrylate copolymers (EMA), ethylene-butyl acrylate copolymers (EBA), their maleic-anhydride-(MAH)-modified derivatives, ionomers, styrene-elastomer systems, ether-ester block copolymers, polyether-polyamide block copolymers (PEBA), mixtures of thermoplastic polymers, thermoplastic polyurethane elastomers, thermoplastic silicone rubber, or mixtures of the polymers mentioned. Examples which may be mentioned of these mixtures are EVA/SAN, EVA/PA11, EVA/PS, and also PVDF/EVA. The latter is commercially available as ALCRYN from DuPont.
- the resultant powder masterbatch is a free-flowing, almost dust-free powder with very good metering capability, its UTBD being 0.65 kg/l.
- the very good metering capability makes this powder masterbatch very suitable for continuous compounding assemblies.
- EVA powder can also generally be used instead of the polyolefin powder.
- the resultant powder masterbatch is a free-flowing, almost dust-free powder with very good metering capability, its UTBD being 0.81 kg/l.
- the very good metering capability makes this powder masterbatch very suitable for continuous compounding assemblies.
- the polymer masterbatch as in Inventive Example 16 is obtained as stated in Inventive Example 15, but the powder masterbatch obtained as in Inventive Example 2a is used here instead of the powder masterbatch of Inventive Example 2.
- the polymer masterbatch as in Inventive Example 17 is obtained as stated in Inventive Example 15, but the powder masterbatch obtained as in Inventive Example 3 is used here instead of the powder masterbatch of Inventive Example 2.
Abstract
The invention relates to a composition, in particular to a pulverulent masterbatch, which comprises a nanoclay composed of a swellable inorganic layered material which has been modified by a pre-exfoliating additive or by an additive mixture. The additive or the additive mixture has been selected from the group of the ethylene-propylene copolymers (EPM), the ethylene-propylene terpolymers (EPDM), the thermoplastic elastomers, the coupling agents, the crosslinking agents, or their mixtures. The pulverulent masterbatch or the composition can give a homogeneous mixture with a polymer powder and can be used in that form. It is also possible to prepare a polymer masterbatch via compounding of the pulverulent masterbatch with a carrier polymer. The powder masterbatch or the polymer masterbatch may be used as a filler or in filler systems in a very wide variety of polymer compositions.
Description
- The invention relates to compositions, in particular masterbatches based on organically intercalated nanoclay, to inventive uses of these compositions/masterbatches, and to a process for their preparation.
- It has been known for a relatively long time that the properties of plastics or of polymeric materials in general can be improved by means of nanoclays as fillers. A significant source of these nanoclays here is water-swellable naturally occurring or synthetic phyllosilicates. Swelling in water releases nano-lamellae, thus producing genuine networks. Polymers or long-chain ions in general, or other charged particles, can penetrate into the intermediate layers, this process being termed intercalation.
- To permit the resultant intercalated nanoclays to be used industrially, they have to be exfoliated with use of further swelling agents. The initial close-range order within the phyllosilicates is lost in this exfoliation process. Completely exfoliated smectites, e.g. montmorillonite as an example of this type of phyllosilicate, can form particle sizes with a very high aspect ratio of up to 1000, obtained via layers with diameter of about 1 nm, width of about 100 nm, and length of from 500 to 1000 nm.
- For the purposes of this application, the term nanoclay is always understood to mean organically intercalated phyllosilicates. This corresponds to the interpretation generally used in this sector. These nanoclays are commercially available. The name “Nanofil” is used by Südchemie AG to market a montmorillonite-based nanoclay. Examples are “Nanofil 15” and “Nanofil 5”, these having been organically intercalated with distearoyldimethylammonium chloride. A product from the US company Elementis Corp. with the name “EA 108” is based on hectorite.
- A chemical problem in the use of these nanoclays in the plastics-processing industry is that the naturally occurring or synthetic phyllosilicates first have to be rendered organophilic so that they can be processed with the hydrophobic plastics. Cation exchange has achieved importance as a significant process for this organophilic modification of the phyllosilicates. Cation exchange is carried out in the aqueous phase with cationic surfactants based on ammonium surfactants, or on phosphonium surfactants, or on sulfonium surfactants. Another known process is acid activation. This uses hydrochloric acid, for example.
- Nanoclays have achieved importance as additives in halogen-free flame retardants. For example, DE-A-199 21 472 discloses a flame-retardant polymer composition which comprises a thermoplastic or crosslinkable polymer, magnesium hydroxide, calcium hydroxide, zinc hydroxide, and/or aluminum hydroxide and/or double hydroxides of these as halogen-free filler, and also an organically intercalated phyllosilicate based on swellable smectites.
- Nanoclays are preferred for use as additives in halogen-free flame retardants because they promote formation of a stable crust layer during combustion of the polymer. Formation of this crust layer inhibits further ignition of the polymer, or collapse of, or fall of material from, the burning polymer, these being processes which could promote fire spread.
- The nanoclay fillers have to be exfoliated within the polymer into which they are to be introduced if they are to develop their activity. However, complete exfoliation is seen to be a problem in the prior art. The presence of swelling agents during the compounding process is problematic for reasons of process technology especially when organic solvents are used. It has hitherto also been impossible to use conventional coupling agents, such as functionalized silanes.
- In the finished polymer, an unfavorable factor observed hitherto is that the use of nanoclay fillers considerably impairs mechanical properties and extrudability of polymer compositions. Nanoclay fillers pose problems during incorporation into the respective polymer composition. Because their exfoliation is difficult, it has also been difficult hitherto to disperse them uniformly through the entire polymer composition. This and their high cost to date have limited their field of application. Additional problems arise in the electrical sector. In particular in brine, immersion tests using 300 V over two or more days led to failure of the polymer via arcing.
- Against this background, an object underlying the present invention was to provide nanoclay fillers which can be uniformly dispersed in various polymeric materials, while improving their properties, particularly with respect to pre-exfoliation and, respectively, complete delamination/exfoliation after incorporation into the desired polymer, and to introduce the use of nanoclay fillers into new application sectors, while reducing the costs which have to be incurred for their use, and with this increasing their cost-effectiveness.
- This object is achieved via a composition as claimed in claim 1, in particular a pulverulent (powder) masterbatch which comprises a nanoclay composed of a swellable inorganic layered material which has been modified by a pre-exfoliating additive or by an additive mixture.
- The term masterbatch is known per se in chemistry and is the name for a premix which is first prepared and then used in a production process or process sequence. For the purposes of the present invention, it has been found that disadvantages known from the prior art can be eliminated if the pulverulent masterbatch is first prepared and is used in the form of a previously prepared unit in a polymer or in a polymer composition, where this can also be a plastic, as a filler for modification of properties.
- The average particle size of the nanoclay present in the masterbatch is from 0.1 to 1000 μm, preferably from 0.1 to 100 μm, particularly preferably from 1 to 15 μm, and very particularly preferably from 2 to 10 μm.
- The nanoclay may comprise ground nanoclay or may have been completely ground. Grinding per se is a known process which permits high throughput and therefore provides high yields of ground nanoclay. No particular requirements have to be placed upon the grinding process itself. It can take place by means of a jet mill or ball mill, but in particular via a vibratory mill, roll mill, impact mill, attrition mill, or pinned disk mill.
- Ground nanoclay in which the average particle size has been lowered below the particle size of the nanoclays available commercially is highly advantageous particularly when the result is preparation of a masterbatch which serves together with halogen-free fillers for use as a flame retardant in polymer compositions. Very surprisingly, although the nanoclays have then been reduced to an average particle size at which it would per se have to be assumed that they have become incapable of achieving any desired action, it is nevertheless found that use of this type of masterbatch markedly improves not only the mechanical properties of the polymer composition but also its processing properties.
- This improvement of mechanical and of processing properties permits higher loading of the polymer composition with flame-retardant, preferably halogen-free filler, for the same mechanical properties and the same processing quality.
- On the other hand, however, lower loading with the flame-retardant filler may be preferred in order thus to improve mechanical properties and processing quality further without bringing about any simultaneous impairment of the flame-retardant properties of the polymer compositions. Further details will be given at a later stage below of the inventive use of the pulverulent masterbatch for providing flame retardancy to polymers or to polymer compositions.
- The inorganic layered material has preferably been selected from naturally occurring or synthetic phyllosilicates (layered silicates). Phyllosilicates of this type which may particularly be mentioned are the smectites, among which are montmorillonite, hectorite, saponite, and beidellite. Bentonite can also be used.
- The inventive composition or inventive masterbatch may also comprise at least one additive selected from the group of the saturated and unsaturated fatty acids and their salts, the fatty acid derivatives, the polymer fatty acids, the siloxane derivatives, or their mixtures.
- All of the additives or additive mixtures mentioned here serve to improve the exfoliation of the nanoclay, and the fatty acids and fatty acid derivatives mentioned have the particular advantage here that they have the best chemical compatibility with respect to the intercalating agents usually used but are nevertheless inexpensive.
- Surprisingly, it has been found that the best product properties are achieved if a dry, pulverulent nanoclay is used as starting material for the preparation of the inventive composition/of the masterbatch, the nanoclay then being modified in a dry process by the pre-exfoliating additive or by the additive mixture. In this process, the nanoclay is coated by the dry additive or by the additive mixture, and use may be made here of conventional dry mixers, in particular those with high rotation rate. “Dry” here means the opposite of a non-pulverulent or pasty (extrudable) mass, or of a slurry or suspension. The inventive modification of the nanoclay is therefore preferably a surface modification process or a surface coating process.
- A particular advantage of the inventive additives or additive mixtures is obtained in combination with ground nanoclay, because this is a finely divided powder which can form a fine dust and therefore poses a potential source of explosion risk. Use of one of the additives mentioned or of any desired mixture of the additives mentioned can markedly mitigate or eliminate this problem.
- The fatty acids or fatty acid derivatives are preferably those selected from fatty acids having from 10 to 13 carbon atoms. Mention may be made here particularly of lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, caproic acid, and castor oil.
- The fatty acids, in particular the members mentioned of this group, have the advantage of ready availability in large quantities together with low cost, and are also safe to handle on a large industrial scale.
- The fatty acid derivatives encompass hydrogenated derivatives, alcohol derivatives, amine derivatives, and mixtures of these.
- They may also have been selected from the group of the polymeric fatty acids, of the keto fatty acids, of the fatty acid alkyloxazolines and fatty acid alkylbisoxazolines, or their mixtures.
- Among the unsaturated fatty acids, mention may particularly be made of the mono- or polyunsaturated hydroxy fatty acids.
- If a siloxane derivative is used as additive, this is preferably an oligomeric or polymeric siloxane or, respectively, siloxane derivative, in particular an oligoalkylsiloxane, polydialkylsiloxane, polyalkylarylsiloxane, polydiarylsiloxane, or a mixture thereof, and the siloxane derivatives mentioned here have particularly preferably been functionalized by at least one reactive group.
- As an alternative to the additives mentioned, additives selected from the group of the ethylene-propylene copolymers (EPM), the ethylene-propylene terpolymers (EPDM), the thermoplastic elastomers, the coupling agents, the crosslinking agents, or their mixtures may also be present.
- The functionalized silanes may be mentioned as a coupling agent to be used.
- The average molecular weight of EPM and/or of EPDM is preferably less than 20 000. The ethylene:propylene ratio in EPM and/or EPDM may be from 40:60 to 60:40.
- In one of its inventive embodiments, the pulverulent masterbatch in the form of the substantially homogeneous mixture of the pre-exfoliated nanoclay may have been mixed substantially homogeneously with a polymer powder. The polymer powder is intended primarily to inhibit caking of the powder masterbatch when, by way of example, this is stored at an elevated temperature. It contributes decisively to the improvement of the free-flowability of the finished powder masterbatch. A suitable selection criterion for the respective polymer powder to be used is in essence compatibility with the intended further use of the powder masterbatch. Examples which should be mentioned are suitable polymer powders such as polyethylene-ethylene-vinyl acetate copolymers (EVA), ethylene-ethyl acrylate copolymers (EEA), ethylene-methyl acrylate copolymers (EMA), ethylene-butyl acrylate copolymers (EBA), their maleic-anhydride-(MAH)-modified derivatives, ionomers, styrene-elastomer systems, ether-ester block copolymers, polyether-polyamide block copolymers (PEBA), mixtures of thermoplastic polymers, thermoplastic polyurethane elastomers, thermoplastic silicone rubber, or mixtures of the polymers mentioned. Examples which may be mentioned of these mixtures are EVA/SAN, EVA/PA11, EVA/PS, and also PVDF/EVA. The latter is commercially available as ALCRYN from DuPont.
- The inventive object is likewise achieved via a polymer masterbatch which has been obtained via compounding of the pulverulent masterbatch in one of its inventive embodiments together with a predetermined carrier polymer.
- Carrier polymers suitable for this purpose encompass polyethylene-ethylene-vinyl acetate copolymers (EVA), ethylene-ethyl acrylate copolymers (EEA), ethylene-methyl acrylate copolymers (EMA), ethylene-butyl acrylate copolymers (EBA), their maleic-anhydride-(MAH)-modified derivatives, ionomers, styrene-elastomer systems, ether-ester block copolymers, polyether-polyamide block copolymers (PEBA), mixtures of thermoplastic polymers, thermoplastic polyurethane elastomers, thermoplastic silicone rubber, or mixtures of the polymers mentioned. Examples which may be mentioned of these mixtures are EVA/SAN, EVA/PA11, EVA/PS, and also PVDF/EVA. The latter is commercially available as ALCRYN from DuPont.
- A fact which is advantageous and which simplifies industrial application is that substantially the same starting materials are suitable as polymer powder for formation of the substantially homogeneous mixture with the powder masterbatch and as carrier polymer for formation of the polymer masterbatch. The result is not only simpler industrial handling but also avoidance of compatibility problems.
- The proportion of the carrier polymer in the polymer masterbatch is from 10 to 90% by weight, preferably from 40 to 70% by weight. For use of the polymer masterbatch is has proven advantageous for it to be in pellet form.
- The inventive powder masterbatches or polymer masterbatches, if appropriate in one of the embodiments mentioned, may be introduced into a wide variety of uses as nanofiller in polymers, in polymer compositions, or generally in plastics. This also includes their additional use in previously known filler systems in order to reduce the content of previously conventional filler and generally to improve the property profile of the resultant polymers or polymer compositions.
- An important sector here is use in halogen-free flame retardants. Halogen-free fillers substantially used in flame retardants are aluminum hydroxide, aluminum oxide hydrate (boehmite), magnesium hydroxide, magnesium oxide, brucite, magnesium carbonate, hydromagnesite, huntite, bauxite, calcium carbonate, talc, glass powder, melamine isocyanurates, their derivatives and preparations, borates, stannates, and hydroxystannates, phosphates, or any desired mixtures thereof. To ensure compatibility between the halogen-free filler used and the polymer or the polymer composition into which these fillers are to be incorporated in order to generate the halogen-free flame retardant, the prior art previously required that the halogen-free fillers, and in particular mention may be made here of aluminum hydroxides and magnesium hydroxides, had been surface-modified. That was the only way of obtaining a desirable level of mechanical and/or electrical properties. Surprisingly and advantageously, it has now been found that the previously conventional surface-modification of the halogen-free fillers is not needed if the halogen-free fillers mentioned are used together with the inventive masterbatch.
- Additional information which should be given in relation to the halogen-free fillers mentioned is that use is particularly made here of aluminum hydroxide (alumina trihydrate (termed ATH) of the general formula Al2O3×3H2O) and magnesium hydroxide in their various forms, and for both of these groups it is not only their effectiveness in flame retardants that is worthy of mention, but also their particular effectiveness in the field of reduction of smoke generation, and their use in halogenated, in particular brominated and chlorinated, polymers, also inter alia in PVC. Use in combination with the inventive powder masterbatch or with the inventive polymer masterbatch can reduce the proportion of halogen-free filler without any adverse effect on property profile.
- In the case of the magnesium hydroxides, either the synthetic form or the naturally occurring material brucite can equally be used. These fillers are preferably ground to average particle sizes of from 1 to 12 μm, preferably from 2 to 8 μm. When the fillers are used in combination with the inventive masterbatch and the processing temperature is above 180° C., or the service temperature of the finished polymers or plastics is above 150° C. for a prolonged period, particularly good results are achieved when the average particle size of the fillers is from 2 to 8 μm.
- One particularly surprising use of the inventive masterbatch, either in its powder masterbatch form or in its polymer masterbatch form, is as a filler in unblended polyolefins or else in their mixtures (also termed “alloys”), in engineering plastics, such as polyamide and polyesters, and also in their mixtures, in polystyrenes, and in thermosets, such as unsaturated polyester (UP) systems and epoxy resin systems.
- It has been found that the powder masterbatches or polymer masterbatches used as fillers in these polyolefin systems achieve ideal, i.e. exfoliated dispersion in the polymer matrix, hitherto impossible with non-polar polymers. Previously there were considerable problems in achieving uniform dispersion of even very small proportions, e.g. from 0.1 to 15% by weight, of conventionally obtainable nanoclays in this type of polymer matrix, and the result was considerable impairment of mechanical properties and moreover unpredictable, variable performance in the combustibility test.
- A particular overall advantage found with the inventive powder masterbatches and inventive polymer masterbatches is that they can be used as compatibilizers and also as crust-formers and therefore also as effective constituents of flame retardants. The polymer composition may also comprise stabilizers known per se to the person skilled in the art.
- Another broad field of application for the powder masterbatches or polymer masterbatches is their use as filler in elastomers and in thermosets.
- The advantages of the powder masterbatches or polymer masterbatches in their use in the wide variety of polymer systems mentioned may be summarized in very general terms as follows: use of the powder masterbatches or polymer masterbatches achieves improved surface properties of the polymer composition, e.g. surface smoothness or uniformity, absence of greasy surface appearance, and excellent performance in printing and copying processes. Alongside this, there is an improvement in abrasion resistance and a favorable effect on permeability properties, and also on friction properties. A particularly advantageous feature which may be mentioned for industrial utilization is the absence of permeability for various gaseous substances. Processing quality, e.g. in the injection-molding process, can be markedly improved via increased plasticity and moldability. Other advantageous properties which should be mentioned are reduced shrinkage, improved processability in extruders generally, and reduced haze. In blow molding, good processability and an overall effect of stabilizing the blown material were observed. Fire tests, such as B1 and UL 94, revealed less dropping of the material even at very low loading with the nanoclay filler in the form of the powder masterbatch or polymer masterbatch.
- Preparation of a polymer composition comprising one of the embodiments of the inventive powder masterbatch can be carried out in a simple manner, as illustrated by way of example for a flame-retardant polymer composition.
- First, a nanoclay is selected, pre-exfoliated, and optionally finely ground to give a desired particle size. This gives the pulverulent masterbatch which can also be processed with a polymer powder to give a substantially homogeneous mixture. There are two different possible procedures for introducing this masterbatch with the flame-retardant, preferably also halogen-free filler into the polymer to form the flame-retardant polymer composition. Firstly, the pulverulent masterbatch can be mixed with the filler and then compounded with the polymer to give the flame-retardant polymer composition. In a second variant, the pulverulent masterbatch and the filler, separately from one another, are metered into the stream of the molten polymer, and thus embedded therein, thus forming the flame-retardant polymer composition.
- A polymer masterbatch can also be used as the basis for preparation of this type of flame-retardant polymer composition. The polymer desired for the polymer composition is then compounded with one of the inventive embodiments of a polymer masterbatch by first again selecting and pre-exfoliating the nanoclay, and optionally finely grinding it to a desired particle size. This gives a pulverulent masterbatch, if appropriate in a homogeneous mixture with a polymer powder. The resultant powder masterbatch is compounded with a carrier polymer which has been matched to the polymer powder or is the same as the polymer powder used, thus forming a polymer masterbatch, further processing then giving the finished flame-retardant polymer composition. Here again, two alternative procedures are possible. In the first alternative, the polymer masterbatch is mechanically mixed with the polymer in which it is to be incorporated, and is then compounded with the flame-retardant, preferably halogen-free, filler to give the finished flame-retardant polymer composition. In the second variant, the polymer masterbatch is introduced together with the polymer which is to be rendered flame-retardant into a first inlet of the compounding machine, and the flame-retardant filler is added at a later juncture (“downstream”) to the molten polymer composition, or is metered in by what is known as the “split-feed” process, thus forming the finished flame-retardant polymer composition.
- The process described for the powder masterbatch and for the polymer masterbatch cannot only be used to prepare flame-retardant polymeric compositions but can in principle also be utilized for a wide variety of other applications of the powder masterbatch and of the polymer masterbatch, e.g. in the compounding of polyolefins. The excellent results during compounding are attributable to the fact that via the powder masterbatch, which is also the starting point for the polymer masterbatch, the nanoclay used has by this stage been treated in such a way as to prepare and promote the exfoliation of the layers of the nanoclay used, before the actual compounding step takes place. Consequently, the compounding process is more effective, and the energy cost and time cost for exfoliating the nanoclay within the desired polymer become lower. The result is a very substantial advantage for compounding when use is made of the prepared masterbatches, because the residence time of the polymer is thus reduced, and the heat history of the polymer is minimized, this being a precautionary measure and counter-measure with respect to thermal degradation. On the other hand, the color strength and the mechanical properties of the finished polymer composition, or of the compounded material, are markedly improved, throughput is increased, and the costs for the compounding process are noticeably reduced. Another substantial advantage which may be mentioned for the use of one of the inventive masterbatches is that the total loading of the polymer or of the polymer composition with the nanoclay can be reduced, indeed preferably to a proportion of 2% by weight, and particularly preferably to a proportion below 1% by weight, without, for example, impairing the flame-retardant properties in the case of use for preparation of a flame retardant. By way of comparison here, the total loading required in the case of conventional loading of the polymer composition with the nanoclay is from 5 to 10% by weight.
- These marked improvements during the compounding process itself, and also with respect to the property profile of the compounded polymers or polymer compositions may be explained by the fact that the process of preparing the nanoclays in the form of the masterbatch, serving to promote exfoliation even before the compounding process begins, helps to make mixing of the nanoclay with the polymer and with other halogen-free fillers and/or polymers also used if appropriate more effective than the mixing during the actual compounding step.
- By way of example, in the case of a polymer or of a polymer composition based on polypropylene with a total filler loading of 65% by weight, a tensile strain at break of more than 200% (corresponding to 2 m/m) and preferably 500% (corresponding to 5 m/m) or more could be demonstrated after the compounding process, compared with 10% (corresponding to 0.1 m/m) without use of the inventive masterbatches.
- The abovementioned processes for preparation of the flame-retardant polymer composition are supplemented via downstream processing steps, such as extrusion of the resultant polymer composition in order to produce cables or wires. Further processes which may follow are injection-molding of the polymer composition, film-blowing, and rotational molding, to mention just a few ways of processing the resultant polymer composition to give a finished product.
- The polymers or polymer compositions obtained by using polymeric or pulverulent masterbatches may advantageously be used in the flame retardancy sector as synergists for crust formation and as compatibilizers, but also generally as a means of improving a wide variety of properties in polymer compositions, and as barrier-layer-forming compositions. Elastomers and thermosets are also among these polymer compositions whose properties can be noticeably improved.
- Selected inventive examples will be used below for more detailed illustration of the invention.
- The polymer compositions obtained in the inventive examples and in the comparative examples were subjected to the standard tests and standard measurements mentioned below:
- melt index (MFI) to DIN 53 735,
- tensile strength to DIN 53 455,
- tensile strain at break to DIN 53 455,
- impact resistance test (an) to DIN 53 454,
- combustion performance by the UL 94 test, Underwriters Laboratories standard.
- UTBD (untamped bulk density) is the term used for uncompacted bulk density in kg/l.
- The high-speed mixer used was always a 60/2500 from M.T.I.
- I. Preparation of a Powder Masterbatch
- A commercially available high-speed mixer, which has to have explosion protection, is used as follows:
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- 100 kg of “Nanofil 15” nanoclay from Südchemie AG, Germany, are heated to a temperature of about 45° C. at 1360 rpm (revolutions per minute), and at this temperature
- 34 kg of “Pripol 1004” polymer fatty acid from Unichema International, Emmerich, Germany, are metered in as additive over a period of about 30 s.
- The reaction mixture is heated to the discharge temperature of 100° C. at the stated rotation rate, and is then cooled to a final temperature of about 30° C. in a cooling mixer.
- 40 kg of a polyolefin powder are mixed homogeneously with the reaction mixture obtained above, in order to inhibit caking, e.g. on storage at a relatively high temperature, and the material is drawn off and packed into sacks having a barrier layer.
- The resultant powder masterbatch is a free-flowing, almost dust-free powder with very good metering capability, its UTBD being 0.65 kg/l. The very good metering capability makes this powder masterbatch very suitable for continuous compounding assemblies. By way of example, EVA powder can also generally be used instead of the polyolefin powder.
- A commercially available high-speed mixer, which has to have explosion protection, is used as follows:
-
- 100 kg of “Nanofil 15” nanoclay from Südchemie AG, Germany, are heated to a temperature of about 45° C. at 1360 rpm (revolutions per minute), and at this temperature
- 24 kg of “Lithsolvent KU” polymer fatty acid, and
- 4.4 kg of “Lithsolvent PL” polydiethylsiloxane, both from KeBo, Düsseldorf, Germany, are metered in in the stated sequence as additive.
- The reaction mixture is heated to the discharge temperature of 90° C. at the stated rotation rate, and is then cooled to a final temperature of about 30° C. in a cooling mixer.
- 20 kg of a polyolefin powder are mixed homogeneously with the reaction mixture obtained above, in order to inhibit caking, e.g. on storage at a relatively high temperature, and the material is drawn off and packed into sacks having a barrier layer.
- The resultant powder masterbatch is a free-flowing, almost dust-free powder with very good metering capability, its UTBD being 0.82 kg/l. The very good metering capability makes this powder masterbatch very suitable for continuous compounding assemblies.
- A commercially available high-speed mixer, which has to have explosion protection, is used as follows:
-
- 100 kg of “Nanofil 5” nanoclay from Südchemie AG, Germany, are heated to a temperature of about 45° C. at 1360 rpm (revolutions per minute), and at this temperature
- 24 kg of “Lithsolvent KU” polymer fatty acid, and
- 4.4 kg of “Lithsolvent PL” polydiethylsiloxane, both from KeBo, Düsseldorf, Germany, are metered in in the stated sequence as additive over a period of about 30 s.
- The reaction mixture is heated to the discharge temperature of 90° C. at the stated rotation rate, and is then cooled to a final temperature of about 30° C. in a cooling mixer.
- The resultant powder masterbatch is a free-flowing, almost dust-free powder with very good metering capability, its UTBD being 0.69 kg/l. The very good metering capability makes this powder masterbatch very suitable for continuous compounding assemblies.
- A commercially available high-speed mixer, which has to have explosion protection, is used as follows:
-
- 100 kg of “Nanofil 5” nanoclay from Südchemie AG, Germany, are heated to a temperature of about 45° C. at 1360 rpm (revolutions per minute), and at this temperature
- 4.4 kg of “Lithsolvent PK” polydimethylsiloxane, and
- 24.4 kg of “Lithsolvent STT” polydecanoic acid, both from KeBo, Düsseldorf, Germany, are metered in in the stated sequence as additive over a period of about 30 s.
- The reaction mixture is heated to the discharge temperature of 130° C. at the stated rotation rate, and is then cooled to a final temperature of about 30° C. in a cooling mixer.
- The resultant powder masterbatch is a free-flowing, almost dust-free powder with very good metering capability, its UTBD being 0.65 kg/l. The very good metering capability makes this powder masterbatch very suitable for continuous compounding assemblies.
- A commercially available high-speed mixer, which has to have explosion protection, is used as follows:
-
- 100 kg of “Nanofil 948” nanoclay from Südchemie AG, Germany, are heated to a temperature of about 45° C. at 1360 rpm (revolutions per minute), and at this temperature
- 24.4 kg of “Lithsolvent KU” polymer fatty acid, and
- 4.4 kg of “Lithsolvent PL” polydiethylpolysiloxane, both from KeBo, Düsseldorf, Germany, are metered in in the stated sequence as additive over a period of about 30 s.
- The reaction mixture is heated to the discharge temperature of 110° C. at the stated rotation rate, and is then cooled to a final temperature of about 30° C. in a cooling mixer.
- 80 kg of a polyolefin powder are mixed homogeneously with the reaction mixture obtained above, in order to inhibit caking, e.g. on storage at a relatively high temperature, and the material is drawn off and packed into sacks having a barrier layer.
- The resultant powder masterbatch is a free-flowing, almost dust-free powder with very good metering capability, its UTBD being 0.73 kg/l. The very good metering capability makes this powder masterbatch very suitable for continuous compounding assemblies.
- A commercially available high-speed mixer, which has to have explosion protection, is used as follows:
-
- 100 kg of “Nanofil 5” nanoclay from Südchemie AG, Germany, are heated to a temperature of about 45° C. at 1360 rpm (revolutions per minute), and at this temperature
- 24.4 kg of “Lithsolvent KTB” polylauric acid, and
- 4.4 kg of “Lithsolvent PK” polydimethylpolysiloxane, both from KeBo, Düsseldorf, Germany, are metered in in the stated sequence as additive over a period of about 30 s.
- The reaction mixture is heated to the discharge temperature of 85° C. at the stated rotation rate, and is then cooled to a final temperature of about 30° C. in a cooling mixer.
- 40 kg of a polyolefin powder are mixed homogeneously with the reaction mixture obtained above, in order to inhibit caking, e.g. on storage at a relatively high temperature, and the material is drawn off and packed into sacks having a barrier layer.
- The resultant powder masterbatch is a free-flowing, almost dust-free powder with very good metering capability, its UTBD being 0.67 kg/l. The very good metering capability makes this powder masterbatch very suitable for continuous compounding assemblies.
- A commercially available high-speed mixer, which has to have explosion protection, is used as follows:
-
- 100 kg of “Elementis EA 108” nanoclay from Elementis USA, are heated to a temperature of about 45° C. at 1360 rpm (revolutions per minute), and at this temperature
- 24.4 kg of “Lithsolvent KU” polymer fatty acid, and
- 4.4 kg of “Lithsolvent PL” polydiethylpolysiloxane, both from KeBo, Düsseldorf, Germany, are metered in in the stated sequence as additive over a period of about 30 s.
- The reaction mixture is heated to the discharge temperature of 100° C. at the stated rotation rate, and is then cooled to a final temperature of about 30° C. in a cooling mixer.
- 80 kg of a polyolefin powder are mixed homogeneously with the reaction mixture obtained above, in order to inhibit caking, e.g. on storage at a relatively high temperature, and the material is drawn off and packed into sacks having a barrier layer.
- The resultant powder masterbatch is a free-flowing, almost dust-free powder with very good metering capability, its UTBD being 0.81 kg/l. The very good metering capability makes this powder masterbatch very suitable for continuous compounding assemblies.
- A commercially available high-speed mixer, which has to have explosion protection, is used as follows:
-
- 100 kg of “SCP 30 B” nanoclay from Southern Clay Products, Gonzales, Tex., USA, are heated to a temperature of about 45° C. at 1360 rpm (revolutions per minute), and at this temperature
- 24.4 kg of “Lithsolvent KU” polymer fatty acid, and
- 4.4 kg of “Lithsolvent PL” polydiethylpolysiloxane, both from KeBo, Düsseldorf, Germany, are metered in in the stated sequence as additive over a period of about 30 s.
- The reaction mixture is heated to the discharge temperature of 100° C. at the stated rotation rate, and is then cooled to a final temperature of about 30° C. in a cooling mixer.
- 80 kg of a polyolefin powder are mixed homogeneously with the reaction mixture obtained above, in order to inhibit caking, e.g. on storage at a relatively high temperature, and the material is drawn off and packed into sacks having a barrier layer.
- The resultant powder masterbatch is a free-flowing, almost dust-free powder with very good metering capability, its UTBD being 0.61 kg/l. The very good metering capability makes this powder masterbatch very suitable for continuous compounding assemblies.
- A commercially available high-speed mixer, which has to have explosion protection, is used as follows:
-
- 100 kg of “Nanofil 5” nanoclay from Südchemie AG, Germany, are heated to a temperature of about 60° C. at 1360 rpm (revolutions per minute), and at this temperature
- 24.4 kg of “Lithsolvent OF” isostearyl titanate, and
- 4.4 kg of “Lithsolvent PL” polydiethylpolysiloxane, both from KeBo, Düsseldorf, Germany, are metered in in the stated sequence as additive over a period of about 30 s.
- The reaction mixture is heated to the discharge temperature of 65° C. at the stated rotation rate, and is then cooled to a final temperature of about 30° C. in a cooling mixer.
- The resultant powder masterbatch is a free-flowing, almost dust-free powder with very good metering capability, its UTBD being 0.56 kg/l. The very good metering capability makes this powder masterbatch very suitable for continuous compounding assemblies.
- A commercially available high-speed mixer, which has to have explosion protection, is used as follows:
-
- 100 kg of “Nanofil 15” nanoclay from Südchemie AG, Germany, are heated to a temperature of about 45° C. at 1360 rpm (revolutions per minute), and at this temperature
- 12.2 kg of “Pristerene 4912” stearic acid from Unichema International, Emmerich, Germany are metered in as additive over a period of about 30 s.
- The reaction mixture is heated to the discharge temperature of 78° C. at the stated rotation rate, and is then cooled to a final temperature of about 30° C. in a cooling mixer.
- The resultant powder masterbatch is a free-flowing, almost dust-free powder with very good metering capability, its UTBD being 0.74 kg/l. The very good metering capability makes this powder masterbatch very suitable for continuous compounding assemblies.
- A commercially available high-speed mixer, which has to have explosion protection, is used as follows:
-
- 100 kg of “Nanofil 15” nanoclay from Südchemie AG, Germany, are heated to a temperature of about 45° C. at 1360 rpm (revolutions per minute), and at this temperature
- 14 kg of “Pristerene 4934” palmitic acid from Unichema International, Emmerich, Germany, and
- 6 kg of “Lithsolvent KU-A” polymer fatty acid from KeBo, Düsseldorf, Germany, are metered in as additive in in the stated sequence over a period of about 30 s.
- The reaction mixture is heated to the discharge temperature of 120° C. at the stated rotation rate, and is then cooled to a final temperature of about 30° C. in a cooling mixer.
- 50 kg of a polyolefin powder are mixed homogeneously with the reaction mixture obtained above, in order to inhibit caking, e.g. on storage at a relatively high temperature, and the material is drawn off and packed into sacks having a barrier layer.
- The resultant powder masterbatch is a free-flowing, almost dust-free powder with very good metering capability, its UTBD being 0.80 kg/l. The very good metering capability makes this powder masterbatch very suitable for continuous compounding assemblies.
- A commercially available high-speed mixer, which has to have explosion protection, is used as follows:
-
- 100 kg of “Nanofil 5” nanoclay from Südchemie AG, Germany, are heated to a temperature of about 45° C. at 1360 rpm (revolutions per minute), and at this temperature
- 34 kg of “EPIKOTE 1004” polymer from Schell are metered in as additive over a period of about 30 s.
- The reaction mixture is heated to the discharge temperature of 120° C. at the stated rotation rate, and is then cooled to a final temperature of about 30° C. in a cooling mixer.
- 50 kg of a polyolefin powder are mixed homogeneously with the reaction mixture obtained above, in order to inhibit caking, e.g. on storage at a relatively high temperature, and the material is drawn off and packed into sacks having a barrier layer.
- The resultant powder masterbatch is a free-flowing, almost dust-free powder with very good metering capability, its UTBD being 0.63 kg/l. The very good metering capability makes this powder masterbatch very suitable for continuous compounding assemblies.
- A commercially available high-speed mixer, which has to have explosion protection, is used as follows:
-
- 100 kg of “Nanofil 15” nanoclay from Südchemie AG, Germany, are heated to a temperature of about 45° C. at 1360 rpm (revolutions per minute), and at this temperature
- 42 kg of “Edinor C 12/98-100” lauric acid from Henkel KG, Germany, are metered in as additive over a period of about 30 s.
- The reaction mixture is heated to the discharge temperature of 80° C. at the stated rotation rate, and is then cooled to a final temperature of about 30° C. in a cooling mixer.
- The resultant powder masterbatch is a free-flowing, almost dust-free powder with very good metering capability, its UTBD being 0.49 kg/l. The very good metering capability makes this powder masterbatch very suitable for continuous compounding assemblies.
- A commercially available high-speed mixer, which has to have explosion protection, is used as follows:
-
- 100 kg of “Nanofil 5” nanoclay from Südchemie AG, Germany, are heated to a temperature of about 45° C. at 1360 rpm (revolutions per minute), and at this temperature
- 33 kg of “Trilene 66” liquid elastomer from Uniroyal, USA, were used as initial charge in the mixer, and then heated to 100° C. at the stated rotation rate. At this temperature,
- 7 kg of “Lithsolvent OF” isostearyl tetratitanate from KeBo, Düsseldorf, Germany, were then metered in over a period of about 30 s.
- The reaction mixture is heated to the discharge temperature of 120° C. at the stated rotation rate, and is then cooled to a final temperature of about 30° C. in a cooling mixer.
- 50 kg of a polyolefin powder are mixed homogeneously with the reaction mixture obtained above, in order to inhibit caking, e.g. on storage at a relatively high temperature, and the material is drawn off and packed into sacks having a barrier layer.
- The resultant powder masterbatch is a free-flowing, almost dust-free powder with very good metering capability, its UTBD being 0.89 kg/l. The very good metering capability makes this powder masterbatch very suitable for continuous compounding assemblies.
- A commercially available high-speed mixer, which has to have explosion protection, is used as follows:
-
- 100 kg of “Nanofil 32” nanoclay from Südchemie AG, Germany, are heated to a temperature of about 45° C. at 1360 rpm (revolutions per minute), and at this temperature
- 24.4 kg of “Lithsolvent OF” isostearyl tetratitanate and
- 4.4 kg of “Lithsolvent PL” polydiethylsiloxane, both from KeBo, Düsseldorf, Germany, are then metered in in the stated sequence as additive over a period of about 30 s.
- The reaction mixture is heated to the discharge temperature of 100° C. at the stated rotation rate, and is then cooled to a final temperature of about 30° C. in a cooling mixer.
- 40 kg of a polyolefin powder are mixed homogeneously with the reaction mixture obtained above, in order to inhibit caking, e.g. on storage at a relatively high temperature, and the material is drawn off and packed into sacks having a barrier layer.
- The resultant powder masterbatch is a free-flowing, almost dust-free powder with very good metering capability, its UTBD being 0.86 kg/l. The very good metering capability makes this powder masterbatch very suitable for continuous compounding assemblies.
- II. Preparation of a Polymer Masterbatch
- In principle, any of the processing machines used in the compounding industry for preparation of highly filled systems may be used for preparation of a polymer masterbatch, examples being a two-roll mill, internal mixer, FCM, single-screw extruder, twin-screw extruder, Buss co-kneader, or a comparable processing machine. If a Buss co-kneader is used, its process length should correspond to at least 11 L/D.
- The powder masterbatch obtained from Inventive Example 2 and the carrier polymer selected with respect to the desired finished polymer or the polymer composition are introduced into a Buss co-kneader or into a comparative suitable processing machine.
- In the inventive example, 60% by weight of the powder masterbatch obtained as in Example 2 and 40% by weight of the carrier polymer are used. For the purposes of this inventive example, the carrier polymer used comprises EVA, as is obtainable commercially with the name “Escorene Ultra UL 00119” from Exxon-Mobil.
- Zones 1 and 2 of the Buss co-kneader, and also its pelletizing screw (PS) are heated to about 135° C., and the die is heated to about 145° C., and the carrier polymer is continuously metered into the main intake of the Buss co-kneader. The corresponding amount of the selected powder masterbatch is added in the ratio by weight stated above, e.g. by means of a gravimetric feed system, into the main intake of the Buss co-kneader. In the barrel, the powder masterbatch is mixed with the carrier polymer, and the resultant polymer masterbatch is then processed to give pellets, cooled, and drawn off.
- The polymer masterbatch is obtained in the form of cylindrical or lenticular pellets.
- The polymer masterbatch as in Inventive Example 16 is obtained as stated in Inventive Example 15, but the powder masterbatch obtained as in Inventive Example 2a is used here instead of the powder masterbatch of Inventive Example 2.
- The polymer masterbatch as in Inventive Example 17 is obtained as stated in Inventive Example 15, but the powder masterbatch obtained as in Inventive Example 3 is used here instead of the powder masterbatch of Inventive Example 2.
- The polymer masterbatch as in Inventive Example 18 is obtained as stated in Inventive Example 15, but the powder masterbatch obtained as in Inventive Example 8 is used here instead of the powder masterbatch of Inventive Example 2.
- The powder masterbatch obtained from Inventive Example 2 and the carrier polymer selected with respect to the desired finished polymer or the polymer composition are introduced into a Buss co-kneader or into a comparative suitable processing machine.
- In the inventive example, 60% by weight of the powder masterbatch obtained as in Example 2 and 40% by weight of the carrier polymer are used. The carrier polymer used for the purposes of this inventive example comprised an EP-g-MAH, as is available commercially with the name “FUSABOND” from DuPont, USA.
- Zones 1 and 2 of the Buss co-kneader, and also its PS are heated to about 165° C., and the die is heated to about 170° C., and the carrier polymer is continuously metered into the main intake of the Buss co-kneader. The corresponding amount of the selected powder masterbatch is added in the ratio by weight stated above, e.g. by means of a gravimetric feed system, into the main intake of the Buss co-kneader. In the barrel, the powder masterbatch is mixed with the carrier polymer, and the resultant polymer masterbatch is then processed to give pellets, cooled, and drawn off.
- The polymer masterbatch is obtained in the form of cylindrical or lenticular pellets.
- The powder masterbatch obtained from Inventive Example 2 and the carrier polymer selected with respect to the desired finished polymer or the polymer composition are introduced into a Buss co-kneader or into a comparative suitable processing machine.
- In the inventive example, 60% by weight of the powder masterbatch obtained as in Example 2 and 40% by weight of the carrier polymer are used. The carrier polymer used for the purposes of this inventive example comprised a PP-g-MAH as available commercially with the name “EXXELOR PO 1050” from Exxon-Mobil.
- Zones 1 and 2 of the Buss co-kneader, and also its PS are heated to about 165° C., and the die is heated to about 175° C., and the carrier polymer is continuously metered into the main intake of the Buss co-kneader. The corresponding amount of the selected powder masterbatch is added in the ratio by weight stated above, e.g. by means of a gravimetric feed system, into the main intake of the Buss co-kneader. In the barrel, the powder masterbatch is mixed with the carrier polymer, and the resultant polymer masterbatch is then processed to give pellets, cooled, and drawn off.
- The polymer masterbatch is obtained in the form of cylindrical or lenticular pellets.
- The powder masterbatch obtained from Inventive Example 8 and the carrier polymer selected with respect to the desired finished polymer or the polymer composition are introduced into a Buss co-kneader or into a comparative suitable processing machine.
- In the inventive example, 60% by weight of the powder masterbatch obtained as in Example 2 and 40% by weight of the carrier polymer are used. The carrier polymer used for the purposes of this inventive example comprised EEA as is available commercially with the name “Escor 5000” from Exxon-Mobil.
- Zones 1 and 2 of the Buss co-kneader, and also its PS are heated to about 125° C., and the die is heated to about 135° C., and the carrier polymer is continuously metered into the main intake of the Buss co-kneader. The corresponding amount of the selected powder masterbatch is added in the ratio by weight stated above, e.g. by means of a gravimetric feed system, into the main intake of the Buss co-kneader. In the barrel, the powder masterbatch is mixed with the carrier polymer, and the resultant polymer masterbatch is then processed to give pellets, cooled, and drawn off.
- The polymer masterbatch is obtained in the form of cylindrical or lenticular pellets.
- The powder masterbatch obtained from Inventive Example 3 and the carrier polymer selected with respect to the desired finished polymer or the polymer composition are introduced into a Buss co-kneader or into a comparative suitable processing machine.
- In the inventive example, 60% by weight of the powder masterbatch obtained as in Example 3 and 40% by weight of the carrier polymer are used. The carrier polymer used for the purposes of this inventive example comprised a calcium ionomer as is available commercially with the name “ACLYN AC 201 A” from Allied Signal, USA.
- Zones 1 and 2 of the Buss co-kneader, and also its PS are heated to about 125° C., and the die is heated to about 135° C., and the carrier polymer is continuously metered into the main intake of the Buss co-kneader. The corresponding amount of the selected powder masterbatch is added in the ratio by weight stated above, e.g. by means of a gravimetric feed system, into the main intake of the Buss co-kneader. In the barrel, the powder masterbatch is mixed with the carrier polymer, and the resultant polymer masterbatch is then processed to give pellets, cooled, and drawn off. The polymer masterbatch is obtained in the form of cylindrical or lenticular pellets.
- The powder masterbatch obtained from Inventive Example 8 and the carrier polymer selected with respect to the desired finished polymer or the polymer composition are introduced into a Buss co-kneader or into a comparative suitable processing machine.
- In the inventive example, 60% by weight of the powder masterbatch obtained as in Example 3 and 40% by weight of the carrier polymer are used. The carrier polymer used for the purposes of this inventive example comprised an EAAZ polymer as is obtainable commercially with the name “Iotek 7010” from Exxon-Mobil, USA.
- Zones 1 and 2 of the Buss co-kneader, and also its PS are heated to about 110° C., and the die is heated to about 125° C., and the carrier polymer is continuously metered into the main intake of the Buss co-kneader. The corresponding amount of the selected powder masterbatch is added in the ratio by weight stated above, e.g. by means of a gravimetric feed system, into the main intake of the Buss co-kneader. In the barrel, the powder masterbatch is mixed with the carrier polymer, and the resultant polymer masterbatch is then processed to give pellets, cooled, and drawn off. The polymer masterbatch is obtained in the form of cylindrical or lenticular pellets.
- The powder masterbatch obtained from Inventive Example 3 and the carrier polymer selected with respect to the desired finished polymer or the polymer composition are introduced into a Buss co-kneader or into a comparative suitable processing machine.
- In the inventive example, 60% by weight of the powder masterbatch obtained as in Example 3 and 40% by weight of the carrier polymer are used. The carrier polymer used for the purposes of this inventive example comprised a maleic anhydride-(MAH)-modified polypropylene, as is available commercially with the name “EXXELOR PO 1015” from Exxon-Mobil, USA, which had been blended with 10% by weight of Escorene Ultra 00328, likewise from Exxon-Mobil.
- Zones 1 and 2 of the Buss co-kneader, and also its PS are heated to about 185° C., and the die is heated to about 200° C., and the carrier polymer is continuously metered into the main intake of the Buss co-kneader. The corresponding amount of the selected powder masterbatch is added in the ratio by weight stated above, e.g. by means of a gravimetric feed system, into the main intake of the Buss co-kneader. In the barrel, the powder masterbatch is mixed with the carrier polymer, and the resultant polymer masterbatch is then processed to give pellets, cooled, and drawn off. The polymer masterbatch is obtained in the form of cylindrical or lenticular pellets.
- The powder masterbatch obtained from Inventive Example 5 and the carrier polymer selected with respect to the desired finished polymer or the polymer composition are introduced into a Buss co-kneader or into a comparative suitable processing machine.
- In the inventive example, 60% by weight of the powder masterbatch obtained as in Example 3 and 40% by weight of the carrier polymer are used. The carrier polymer used for the purposes of this inventive example comprised polycaprolactam, as is available commercially with the name “Grilamid 20 LM” from EMS-Chemie, Switzerland.
- Zones 1 and 2 of the Buss co-kneader, and also its PS are heated to about 200° C., and the die is heated to about 220° C., and the carrier polymer is continuously metered into the main intake of the Buss co-kneader. The corresponding amount of the selected powder masterbatch is added in the ratio by weight stated above, e.g. by means of a gravimetric feed system, into the main intake of the Buss co-kneader. In the barrel, the powder masterbatch is mixed with the carrier polymer, and the resultant polymer masterbatch is then processed to give pellets, cooled, and drawn off. The polymer masterbatch is obtained in the form of cylindrical or lenticular pellets.
- III. Powder Masterbatch and Polymer Masterbatch in Selected Polymer Compositions
- All of the percentages in the tables below are based on percent by weight unless otherwise stated.
- The following abbreviations are used in the tables:
-
- ATH=alumina trihydrate of the general formula Al2O3×3H2O
- PUMB=powder masterbatch
- POMB=polymer masterbatch
TABLE 1 Inventive Example P1 P2 P3 P4 [%] [%] [%] [%] Escorene Ultra 00119 40 40 40 40 ATH 4 m2/g 54 54 54 54 PUMB of Inv. Ex. 3 6 PUMB of Inv. Ex. 6 6 PUMB of Inv. Ex. 7 6 PUMB of Inv. Ex. 9 6 Melt index g/10 min 7 3 2 3.2 190/10 Tensile strength N/mm2 10.5 9.5 11 8.2 Tensile strain at 6.2 4.2 2.4 6.6 break m/m - The results obtained as in Table 1 show, when compared with the values obtained in the comparative example as in Table 3, that use of the inventive powder masterbatch gave substantially improved tensile strain at break with the same and sometimes even better tensile strengths, while flame retardancy properties were at least the same.
TABLE 2 Inventive Example P5 P6 P7 P8 [%] [%] [%] [%] Escorene Ultra 00119 36 36 36 36 ATH 4 m2/g 54 54 54 54 POMB of Inv. Ex. 23 10 POMB of Inv. Ex. 17 10 POMB of Inv. Ex. 19 10 POMB of Inv. Ex. 18 10 Melt index g/10 min 5 7 4 6 190/10 Tensile strength N/mm2 8 10 11 9.4 Tensile strain at 6.1 4.5 3.6 7 break m/m - Table 2 states results obtained using inventive polymer masterbatches. When comparison is made with the tensile strain at break values obtained in Table 1 using powder masterbatches, the values are seen, with one exception, to be further improved.
- With respect to comparison with the values obtained in Table 3, the statements previously made in relation to Table 1 are in principle again applicable.
TABLE 3 C1 C2 C3 C4 Comparative Example [%] [%] [%] [%] Escorene Ultra 00119 40 40 40 40 ATH 4 m2/g 60 54 54 Mg(OH)2 - FR 20 60 Nanofil 15 6 Nanofil 5 6 Melt index g/10 min 1 1 1.5 0.75 190/10 Tensile strength N/mm2 9.7 10.8 10 9.3 Tensile strain at 1.4 1.2 1.5 4 break m/m - FR 20 is the name used by the producer, Dead Sea Bromine, Israel, for the grade of magnesium hydroxide used here.
- The values obtained in the comparative example for melt index and tensile strain at break are themselves borderline with respect to processability. The values obtained in C1, C2, and C4 for tensile strain at break are below the standard of 1.5.
TABLE 4 Inventive Example P9 P10 P11 P12 [%] [%] [%] [%] PP-Eltex KL 104 30 30 30 30 Mg(OH)2 FR 20 60 60 60 60 POMB of Inv. Ex. 16 10 POMB of Inv. Ex. 18 10 POMB of Inv. Ex. 19 10 POMB of Inv. Ex. 23 10 Melt index g/10 min 5.7 8.0 6.3 12 230/5 Tensile strength N/mm2 13.8 16 14.5 11 Tensile strain at 1.8 1.9 2.4 3.1 break m/m Impact resistance 50 no no no fracture fracture fracture (60) (58) (40) - The values stated in brackets with respect to impact resistance indicate the impact energy determined in each case when the material exhibited no fracture.
- Fracture of the material was found only for Inventive Example P9. However, a good value for impact resistance was nevertheless achieved and was far above the values for the comparative examples as in Table 5, and which still provides good processability, including in construction of casings.
TABLE 5 Comparative Example C5 C6 C7 C8 [%] [%] [%] [%] PP-Eltex KL 104 35 35 35 35 Mg(OH)2 FR 20 65 59 59 59 Nanofil 948 6 Elementis EA 108 6 Cloisite 30 B 6 Melt index g/10 min 0.1 1.0 1.0 1.0 230/5 Tensile strength N/mm2 15 13 14 13.5 Tensile strain at 0.01 0.09 0.1 0.08 break m/m Impact resistance 8 10 12 9 - The impact resistance achieved in these comparative examples is far below the values required, for example, in construction of casings. An impact resistance of 8, as was determined for Comparative Example C5, indicates a very brittle, hard material, and is unsuitable for construction of casings. Impact resistances required here are at least 30.
- Because all of the materials of Comparative Examples C5 to C8 exhibited fracture of the material, there was no need to state fracture energy here.
TABLE 6 Inventive Example P13 P14 P15 P16 [%] [%] [%] [%] PA Ultramid B3L 45 45 45 45 Mg(OH)2 FR 20 45 45 45 45 POMB of Inv. Ex. 22 10 POMB of Inv. Ex. 24 10 POMB of Inv. Ex. 25 10 POMB of Inv. Ex. 20 10 Melt index g/10 min 275/10 Tensile strength N/mm2 37 43 46 50 Tensile strain at 0.02 0.08 0.05 0.08 break m/m Impact resistance 16 25 14 30 - Tensile strain at break is a problematic property which may be mentioned for engineering polyamides, for example with the PA6 Ultramid B3L used here. It is normally not above 0.02 for engineering polyamides, as clearly shown by Table 7 with the Comparative Experiments C9-C12. Only C10 exhibits a value improved by one order of magnitude, because AMEO was also used in that example. The conventionally poor values for tensile strain at break are seen in brittle fracture of conventional engineering polyamides.
TABLE 7 Comparative Example C9 C10 C11 C12 [%] [%] [%] [%] PA6 Ultramid B3L 45 45 45 45 Mg(OH)2 FR 20 55 49 49 FR 20 (+1% AMEO) 55 Cloisite 25 A 6 Cloisite 30 B 6 Melt index g/10 min 275/10 Tensile strength N/mm2 50 60 35 40 Tensile strain at 0.02 0.03 0.01 0.01 break m/m Impact resistance 20 32 13 12 - As previously apparent from the comments on Table 6, tensile strain at break is exceptionally important for the type of engineering polyamides used here for the polymer composition. As is seen here, each of the inventively prepared polymer compositions with the exception of P13 has a tensile strain at break which is at least three orders of magnitude above the values ever conventionally achieved in the prior art for tensile strain at break.
TABLE 8 with polar (starting) polymer: Inventive Example/ Comparative C13 P17 P18 P19 P20 C14 P21 P22 Example [%] [%] [%] [%] [%] [%] [%] [%] PE-EVA 100 95 80 80 95 80 90 90 00119 Nanofil 5 5 20 PUMB 2 20 PUMB 2a 20 PUMB 6 5 PUMB 1 10 PUMB 5 10 Melt index 6 12 16 15 14 6 15 17 g/10 min 190/10 Tensile 26 22 20 29 15 13 23 25 strength N/mm2 Tensil 17 14 12 17 11 8.5 15 16 strain at break m/m - The polymer compositions prepared inventively with polar (starting) polymer, which hitherto were regarded as impossible to realize in the prior art, exhibit an excellent property profile. A particularly advantageous feature found is that no burrs are produced during the extrusion process, and that the material is in all respects capable of very good extrusion. Shrinkage during the mold-casting process is smaller and the surface is markedly better.
- The trials are also designed to contradict a prejudice widespread among persons skilled in the art, according to which the property profile of the polymer compositions or of the compounded polymer materials can be improved linearly with a higher proportion of filler.
- As Table 8 shows, the experimental pair P21-P22 has the most balanced property profile, with high test values or balanced intermediate values for the properties studied.
TABLE 9 with non-polar (starting) polymer: Inventive Example/ Comparative C15 C16 P23 P24 P25 P26 P27 Example [%] [%] [%] [%] [%] [%] [%] Riblene FL 100 80 80 80 95 90 90 30 Nanofil 5 20 PUMB from 20 5 Inv. Ex. 1 PUMB from 20 Inv. Ex. 3 POMB from 10 Inv. Ex. 17 POMB from 10 Inv. Ex. 21 Melt 4 20 45 46 42 47 40 index g/10 min 190/10 Tensile 13.5 10 12 11 11.5 12.5 11.5 strength N/mm2 Ultimate tensile strength N/mm2 Tensile 9.0 0.2 1.3 1.1 6.2 3.6 2.5 strain at break m/m - This example of a polymer composition or of a compounded polymer material relates to a film grade for blown-film production. The non-linearity previously mentioned for the polymer/filler masterbatch compositions with respect to the percentage proportions of the masterbatch, which fundamentally also represents a filler, is again clearly seen here. Experiment P25 achieved a very good overall profile of properties with balanced test results, the profile being, when compared, even better than, for example, in Experiments P23 and P24 with 20% of masterbatch.
- However, P23 and P24 also show markedly better values when compared with the Comparative Experiment C16. Film stability is not ensured with the material of the comparative experiment mentioned, with only 0.2 for tensile strain at break.
TABLE 10 with non-polar (starting) polymer: C17 C18 P28 P29 P30 P31 P32 P33 Example [%] [%] [%] [%] [%] [%] [%] [%] Eltex KL 100 95 95 95 95 80 90 90 104 Nanofil 5 5 PUMB, 5 20 Inv. Ex. 5 PUMB, 5 Inv. Ex. 8 PUMB, 5 Inv. Ex. 11 POMB, 10 Inv. Ex. 18 POMB, 10 Inv. Ex. 20 Melt 2 18 25 25 22 33 30 28 index g/10 min 190/10 Tensile 31 23 24 31.5 26 21 25 30 strength N/mm2 Tensil 16 10 12 15 14 1.0 3.5 2.0 strain at break m/m - Eltex KL 104 in Table 10 designates a polypropylene used for injection molding and extrusion. The most balanced property profile can again be achieved with the inventive polymer compositions or inventive compounded polymer materials with compositions of Experiments P28-P30. The non-linearity can therefore also be observed here.
- In contrast, P30 achieves an excellent value for melt index, whereas here the tensile strain at break obtained is less favorable. However, this is not decisive for the processing method mentioned. Tensile strain at break for polypropylene is fundamentally set by way of the extrusion process itself.
- Fundamentally, it can be stated that the polymers, polymer compositions and, respectively, compounded materials prepared with use of powder masterbatches or of polymer masterbatches have substantial advantages over the polymers, polymer compositions and, respectively, compounded materials known hitherto in the prior art and prepared only with nanoclays as fillers. They are capable of more effective processing, are substantially dust-free, and exhibit relatively high bulk density (uncompacted).
Claims (31)
1. A pulverulent masterbatch composition, comprising a nanoclay, which comprises an organically intercalated swellable inorganic layered material, which has been surface coated in a dry process with a pre-exfoliating additive or additive mixture.
2. The composition as claimed in claim 1 , characterized in that the average particle size of the nanoclay is from 0.1 to 1000 μm.
3. The composition as claimed in claim 1 , characterized in that the nanoclay comprises a ground nanoclay.
4. The composition as claimed in claim 1 , characterized in that the inorganic layered material is selected from naturally occurring or synthetic phyllosilicates.
5. The composition as claimed in claim 1 , characterized in that the additive or the additive mixture has been selected from the group consisting of saturated or unsaturated fatty acids and their salts, fatty acid derivatives, polymer fatty acids, siloxane derivatives, and their mixtures.
6. The composition as claimed in claim 5 , characterized in that the fatty acid or fatty acid derivatives have been selected from fatty acids having from 10 to 30 carbon atoms.
7. The composition as claimed in claim 5 , characterized in that the fatty acid derivatives have been selected from the group consisting of hydrogenated derivatives, alcohol derivatives, amine derivatives, and their mixtures.
8. The composition as claimed in claim 5 , characterized in that the unsaturated fatty acids comprise mono- or polyunsaturated hydroxy fatty acids.
9. The composition as claimed in claim 5 , characterized in that the fatty acid derivatives have been selected from the group consisting of polymeric fatty acids, keto fatty acids, fatty acid alkyloxazolines, fatty acid alkylbisoxazolines, and their mixtures.
10. The composition as claimed in claim 5 , characterized in that the siloxane derivatives have been selected from the group consisting of oligoalkyl-siloxanes, polydialkylsiloxanes, polyalkylaryl-siloxanes, polydiarylsiloxanes, and their mixtures.
11. The composition as claimed in claim 10 , characterized in that the siloxane derivatives are functionalized with at least one reactive group.
12. The composition as claimed in claim 1 , characterized in that the additive or the additive mixture has been selected from the group consisting of ethylene-propylene terpolymers (EPM), ethylene-propylene copolymers (EPDM), thermoplastic elastomers, coupling agents, crosslinking agents, and their mixtures.
13. The composition as claimed in claim 12 , wherein the average molecular weight of the EPM and EPDM is less than 20 000.
14. The composition as claimed in claim 12 , characterized by an ethylene:propylene ratio of the EPM and the EPDM from 40:60 to 60:40.
15. A substantially homogeneous mixture comprising the composition of claim 1 with a polymer powder.
16. (canceled)
17. (canceled)
18. (canceled)
19. (canceled)
20. A filler for use in polymers or polymer compositions comprising the composition of claim 1 .
21. (canceled)
22. A combination product comprising the filler as claimed in claim 20 in combination with a flame-retardant filler.
23. The combination product of claim 22 wherein the flame-retardant filler comprises a halogen-free filler.
24. The combination product of claim 23 , characterized in that the halogen-free flame-retardant filler has been selected from aluminum hydroxide, aluminum oxide hydrate (boehmite), magnesium hydroxide, magnesium oxide, brucite, magnesium carbonate, hydromagnesite, huntite, bauxite, calcium carbonate, talc, glass powder, melamine isocyanurates, their derivatives and preparations, borates, stannates, and hydroxystannates, phosphates, and their mixtures.
25. A filler for use in polyolefins and their mixtures, in engineering plastics and their mixtures, and alloys comprising the composition of claim 1 .
26. (canceled)
27. A product mixture comprising an elastomer or thermoset and the composition of claim 1 .
28. A process for the preparation of a polymer or polymer composition comprising the steps of:
a) providing a carrier polymer or polymer composition,
b) providing the pulverulent masterbatch composition as claimed in claim 1 , and
c) compounding the pulverulent masterbatch composition with the carrier polymer or polymer composition.
29. The process as claimed in claim 28 , wherein the pulverulent masterbatch composition is homogenously mixed with a polymer powder before compounding with the carrier polymer or polymer composition.
30. The process as claimed in claim 28 , comprising the further step of compounding a flame-retardant filler with the carrier polymer or polymer composition.
31. A process for the preparation of the pulverulent masterbatch composition as claimed in claim 1 comprising the steps of
a) providing an organically intercalated swellable inorganic layered material, and
b) surface-coating the organically intercalated swellable inorganic layered material in a dry process with the pre-exfoliating additive or additive mixture of claim 1.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
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GB0300374.6 | 2003-01-08 | ||
GB0300374A GB0300374D0 (en) | 2003-01-08 | 2003-01-08 | Organoclay compositions |
DE10326977 | 2003-06-12 | ||
DE10326977.0 | 2003-06-12 | ||
PCT/EP2004/000071 WO2004063264A1 (en) | 2003-01-08 | 2004-01-08 | Master batches based on pre-exfoliated nanoclays and the use of the same |
Publications (1)
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US20060155018A1 true US20060155018A1 (en) | 2006-07-13 |
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US10/541,496 Expired - Fee Related US7528191B2 (en) | 2003-01-08 | 2004-01-08 | Composition based on pre-exfoliated nanoclay and use thereof |
US10/541,625 Abandoned US20060155018A1 (en) | 2003-01-08 | 2004-01-08 | Master batches based on pre-exfoliated nanoclays and the use of the same |
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US10/541,496 Expired - Fee Related US7528191B2 (en) | 2003-01-08 | 2004-01-08 | Composition based on pre-exfoliated nanoclay and use thereof |
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US (2) | US7528191B2 (en) |
EP (2) | EP1581587B1 (en) |
JP (2) | JP2006517597A (en) |
KR (2) | KR20050097501A (en) |
AT (2) | ATE355328T1 (en) |
DE (2) | DE502004003032D1 (en) |
DK (1) | DK1581588T3 (en) |
ES (2) | ES2279338T3 (en) |
PT (1) | PT1581588E (en) |
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US20060155035A1 (en) * | 2003-01-08 | 2006-07-13 | Heinz-Dieter Metzemacher | Composition based on pre-exfoliated nanoclay and use thereof |
US7528191B2 (en) | 2003-01-08 | 2009-05-05 | Rockwood Clay Additives, Gmbh | Composition based on pre-exfoliated nanoclay and use thereof |
US7867614B2 (en) * | 2003-06-12 | 2011-01-11 | Rockwood Clay Additives, Gmbh | Method for producing nanocomposite additives with improved delamination in polymers |
US20070072980A1 (en) * | 2003-06-12 | 2007-03-29 | Sud-Chemie Ag | Method for producing nanocomposite additives with improved delamination in polymers |
US20080004381A1 (en) * | 2004-08-13 | 2008-01-03 | Peter Putsch | Polmer Blend of Non-Compatible Polymers |
US7947774B2 (en) | 2006-10-20 | 2011-05-24 | Cornell Research Foundation, Inc. | Ethylene-vinyl acetate copolymer of increased mechanical properties |
US20080211139A1 (en) * | 2006-10-20 | 2008-09-04 | Sogah Dotsevi Y | Ethylene-vinyl acetate copolymer of increased mechanical properties |
US10414900B2 (en) | 2013-12-17 | 2019-09-17 | Byk Usa Inc. | Pre-exfoliated layered material |
US10131753B2 (en) | 2014-01-31 | 2018-11-20 | Kimberly-Clark Worldwide, Inc. | Nanocomposite packaging film |
US11058791B2 (en) | 2014-01-31 | 2021-07-13 | Kimberly-Clark Worldwide, Inc. | Thin nanocomposite film for use in an absorbent article |
CN105482320A (en) * | 2016-01-28 | 2016-04-13 | 西安科技大学 | Polyvinyl chloride toughening and strengthening master batch and preparation method and application thereof |
FR3058418A1 (en) * | 2016-11-10 | 2018-05-11 | Centre National De La Recherche Scientifique - Cnrs - | NANOCOMPOSITES NANOMATERIAU / COLLOIDAL POLYMOLECULAR SYSTEM, AND METHODS OF PREPARATION |
WO2018087484A1 (en) * | 2016-11-10 | 2018-05-17 | Centre National De La Recherche Scientifique | Colloidal nanomaterial/polymolecular system nanocomposites, and preparation methods |
Also Published As
Publication number | Publication date |
---|---|
SI1581588T1 (en) | 2007-08-31 |
DE502004003032D1 (en) | 2007-04-12 |
ES2279338T3 (en) | 2007-08-16 |
US7528191B2 (en) | 2009-05-05 |
WO2004063264A1 (en) | 2004-07-29 |
WO2004063260A2 (en) | 2004-07-29 |
DK1581588T3 (en) | 2007-04-02 |
EP1581587B1 (en) | 2007-04-11 |
JP2006517597A (en) | 2006-07-27 |
ATE359321T1 (en) | 2007-05-15 |
KR20050097502A (en) | 2005-10-07 |
DE502004003464D1 (en) | 2007-05-24 |
EP1581588B1 (en) | 2007-02-28 |
ATE355328T1 (en) | 2006-03-15 |
US20060155035A1 (en) | 2006-07-13 |
KR20050097501A (en) | 2005-10-07 |
EP1581588A2 (en) | 2005-10-05 |
JP2006515896A (en) | 2006-06-08 |
PT1581588E (en) | 2007-05-31 |
ES2281776T3 (en) | 2007-10-01 |
WO2004063260A3 (en) | 2004-09-23 |
EP1581587A1 (en) | 2005-10-05 |
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