WO2013053598A1

WO2013053598A1 - Method for producing polymer nanoparticle compounds using a nanoparticle dispersion

Info

Publication number: WO2013053598A1
Application number: PCT/EP2012/068934
Authority: WO
Inventors: Franz-Erich Baumann; Klaus-Dieter SCHÜBEL; Harald HÄGER; Beate HESSLING; Juergen Kreutz; Emine KAHRAMAN; Stephanie MÖRTH
Original assignee: Evonik Degussa Gmbh
Priority date: 2011-10-11
Filing date: 2012-09-26
Publication date: 2013-04-18
Also published as: EP2766411A1; DE102011084269A1

Abstract

A nanoparticle-containing molding compound is produced using a method which has the following steps: a) a thermoplastic molding compound in the form of compact particles is provided; b) a dispersion of nanoparticles in a dispersing agent is applied onto the surface of the molding compound particles; c) the dispersion is allowed to be drawn into the edge zone of the molding compound particles; and d) the dispersing agent is removed at a temperature of at least 50 °C. Using said method, the nanoparticles are introduced into the edge zone of the molding compound particles so as to adhere to said edge zone. The nanoparticles are homogeneously distributed in the thus produced molded bodies.

Description

Process for the preparation of polymer nanoparticle compounds by means of a

Nanoparticle dispersion

The invention relates to a method for producing a polymer nanoparticle compound by so-called "tumbling" of a nanoparticle dispersion onto a thermoplastic polymer.

The modification of thermoplastic materials with nanoparticles, sometimes also referred to as nanoscale particles, provides access to novel materials with application-related interesting features

Property combinations, such as a difficult flammability, improved UV stability or increased scratch resistance. The incorporation of photoactive nanoparticles, for example, metal oxides or lanthanum hexaboride also allows corresponding moldings by means of laser marking,

Laser engraving, three-dimensional (3D) laser engraving or laser structuring to edit or to connect by laser welding (WO 2005084955;

WO 2005084956; WO 2006094881), without the other material properties, such as transparency, toughness or color, are adversely affected, especially since the desired effects already with very low

Reached additive amounts. In many cases, even additive concentrations of much less than 0.1 percent by weight are sufficient.

However, these small amounts of additive involve a number of process engineering problems. On the one hand, there are considerable concerns recently about the use of isolated nanoparticles, since in these cases they are harmful to health

Effects in particular on the respiratory organs due to the fine dust-like consistency are feared. On the other hand, there are considerable dosing problems. The introduction of larger quantities (typically more than 5

Weight percent) of inorganic or organic fillers, additives, dyes, pigments, etc. in thermoplastic polymers is carried out according to the prior art via a powder metering in a single or Mehrschneckencompounder. However, when only small amounts (less than 5 weight percent and typically less than about 2 weight percent) to small amounts (typically less than about 0.5 weight percent) of additives in the form of nanoparticles are compounded into thermoplastic polymers, the problematic ones are encountered Safety aspects of the nanoparticles also adds to the difficulties with the low dosage.

It is therefore the object of a thermoplastic molding composition so

compound that small to minute amounts of nanoparticles can be incorporated without releasing nanoparticles as dust into the environment.

According to the invention, it has been found that the use of nanoparticles dispersed in a suitable fluid, the release of such

Nanoparticle dusts is not to be feared. In addition, very small amounts of nanoparticles can be reliably metered in this way.

The invention thus relates to a process for the preparation of a

nanoparticle-containing molding composition which comprises the following steps: a) a thermoplastic molding composition in the form of compact particles is provided; b) a dispersion of nanoparticles in a dispersant is applied to the

Surface applied to the molding material particles;

c) it is waited until the dispersion is drawn into the edge zone of the molding material particles;

d) the dispersant is removed at a temperature of at least 50 ° C.

With the help of this method, the nanoparticles are firmly adhering introduced into the edge zone of the molding material particles.

In step b), the molding material particles may be at a temperature level of, for example, 0 ° C to 160 ° C. Usually they are at a temperature level of 20 ° C to a maximum of 80 ° C. The dispersion may be poured, dropped, sprayed or applied in any other suitable manner. It is advantageous if the molding material particles are moved mechanically.

In step c), the temperature of the mixture may be, for example, 20 ° C to 180 ° C and preferably 60 ° C to 150 ° C. In individual cases, caking the It can also be advantageous here to avoid molding compound particles if the molding compound particles are mechanically moved.

In step d), the temperature is preferably in the range of 80 ° C to 170 ° C, and more preferably in the range of 100 ° C to 160 ° C. Removing the

Dispersant can be accelerated by means of an inert purge gas and / or by applying vacuum. Alternatively, the dispersant may also be removed by reflow in a conveying aggregate such as an extruder and applying a vacuum. The useful temperature range is limited here by the melting or softening range of the molding composition and upwards by the temperature at which the molding material begins to decompose.

If step d) is carried out without melting the molding material particles, the product, which now consists of molding material particles with nanoparticles embedded in the edge zone, can be converted into a homogeneous composition with nanoparticles in granular form or directly by conventional shaping methods such as injection molding, extrusion through a further compounding step or blow molds are converted into moldings or semi-finished products. Likewise, when step d) has been carried out with melting in a conveying aggregate and applying a vacuum, the product

then in a homogeneously interspersed with nanoparticles molding compound in

Granule form or directly by conventional shaping processes in moldings or semi-finished be reworked.

The invention thus also relates to the modified molding compound particles which are obtained when step d) is carried out without melting the molding compound particles; These molding compound particles differ from conventionally produced nanoparticle - containing molding material particles in that

essentially the total nanoparticle content in the peripheral zone of the

Embedded molding compound particles.

The invention further provides a method for producing a molded part or semifinished product, in which 1) modified molding compound particles are used, which are obtained when the step d) is carried out without melting the molding material particles, and

2) these particles directly without intergranulation by a

Shaping process via the melt such as injection molding, extrusion or blow molding are processed to form part or semi-finished.

With this method, when sufficient mixing takes place in the melt, homogeneous moldings are obtained. In the context of the invention, the term "molding composition" means that the composition can be shaped by conventional molding processes over the melt.The molding composition can be a pure polymer, but it can also be a polymer containing customary additives. Conventional additives are, for example, dyes , Pigments, flame retardants, stabilizers, fillers, fibrous

Reinforcing agents, processing aids, impact modifiers, plasticizers or antistatic agents. It is of course within the scope of the invention that such additives can also be subsequently compounded, ie after step d), via the melt. For the thermoplastic molding composition which is provided in step a), in principle all meltable polymers can be used. Preferably, the molding composition contains 50 to 100 wt .-% of one or more such polymers, based on the total molding composition. Examples of suitable polymers are polyamides, polyalkyl (meth) acrylates, polycarbonate, thermoplastic polyesters, polyester carbonate, polyimides, polyetherimides, polymethacrylimides, polysulfone,

Styrene polymers, polyolefins, especially those with cyclic building blocks, olefin-maleimide copolymers, polyvinylcyclohexane, polyaryleneetherketone and

Polyvinyl chloride, however, the invention is not limited to these exemplified polymers.

The polyamide may be a partially crystalline polyamide such as PA6, PA66, PA610, PA612, PA10, PA810, PA106, PA1010, PA1 1, PA101 1, PA1012, PA1210; PA1212, PA814, PA1014, PA618, PA512, PA613, PA813, PA914, PA1015, PA1 1, PA12 or a partially aromatic polyamide, a so-called polyphthalamide (PPA). (The marking of the polyamides complies with international standards, with the first digit (s) indicate the C atomic number of the starting diamine and the last digit (s) indicate the C atomic number of the dicarboxylic acid. If only one number is mentioned, this means that it has been assumed that an α, ω-aminocarboxylic acid or the lactam derived therefrom; see also H. Domininghaus, The plastics and their properties, pages 272 et seq., VDI-Verlag, 1976.) Suitable PPAs are, for example, PA66 / 6T, PA6 / 6T, PA6T / MPMDT (MPMD stands for 2-methylpentamethylenediamine) , PA9T, PA10T, PA1 1T, PA12T, PA14T as well

Copolycondensates of these last types with an aliphatic diamine and an aliphatic dicarboxylic acid or with a ω-aminocarboxylic acid or a

Lactam. Other suitable polyamides are poly (etheresteramide) or

Poly (ether amides); Such products are z. B. in DE-OSS 25 23 991, 27 12 987 and 30 06 961 described. Semicrystalline polyamides have a melting enthalpy of more than 25 J / g, measured by the DSC method according to ISO 1 1357 at the 2nd heating and integration of the melt peak.

The polyamide may also be a semi-crystalline polyamide. Semicrystalline polyamides have a melting enthalpy of 4 to 25 J / g, measured by the DSC method according to ISO 1 1357 at the 2nd heating and integration of the melt peak. Examples of suitable semi-crystalline polyamides are

The polyamide from 1, 10-decanedioic acid or 1, 12-dodecanedioic acid and 4,4'-diaminodicyclohexylmethane (PA PACM10 and PA PACM12), starting from a 4,4'-diaminodicyclohexylmethane with a trans, trans isomer content of 35 to 65 %;

- Copolymers based on the above-mentioned semi-crystalline polyamides; such as

Blends of the above-mentioned semi-crystalline polyamides and an amorphous polyamide compatible therewith.

Semi-crystalline polyamides are usually transparent.

The polyamide may also be an amorphous polyamide. Amorphous polyamides have a melting enthalpy of less than 4 J / g as measured by the DSC method according to ISO 1 1357 during the 2nd heating and integration of the melting peak. Examples of amorphous polyamides are:

the polyamide of terephthalic acid and / or isophthalic acid and the

Isomer mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the polyamide of isophthalic acid and 1,6-hexamethylenediamine,

the copolyamide from a mixture of terephthalic acid / isophthalic acid and

1, 6-hexamethylenediamine, optionally mixed with 4,4'-diaminodicyclohexylmethane,

the copolyamide of terephthalic acid and / or isophthalic acid, 3.3'-dimethyl-

4,4'-diaminodicyclohexylmethane and laurolactam or caprolactam,

the (co) polyamide from 1 .12-dodecanedioic acid or sebacic acid, 3.3'-dimethyl

4,4'-diaminodicyclohexylmethane and optionally laurolactam or

caprolactam,

the copolyamide of isophthalic acid, 4,4'-diaminodicyclohexylmethane and laurolactam or caprolactam,

the polyamide of 1, 12-dodecanedioic acid and 4,4'-diaminodicyclohexylmethane (at low trans, trans isomeric content),

the (co) polyamide of terephthalic acid and / or isophthalic acid and an alkyl-substituted bis (4-aminocyclohexyl) methane homolog, optionally mixed with hexamethylenediamine,

the copolyamide of bis (4-amino-3-methyl-5-ethylcyclohexyl) methane, optionally together with a further diamine, and isophthalic acid, optionally together with a further dicarboxylic acid,

the copolyamide of a mixture of m-xylylenediamine and another

Diamine, z. For example, hexamethylenediamine, and isophthalic acid, optionally together with another dicarboxylic acid such as. As terephthalic acid and / or

2,6-

the copolyamide from a mixture of bis (4-amino-cyclohexyl) methane and bis (4-amino-3-methyl-cyclohexyl) methane and aliphatic dicarboxylic acids having 8 to 14 carbon atoms, and

Polyamides or copolyamides from a mixture containing 1, 14-tetradecanedioic acid and an aromatic, arylaliphatic or cycloaliphatic diamine.

These examples can be obtained by adding additional components (eg

Caprolactam, laurolactam or diamine / dicarboxylic acid combinations) or by partial or complete replacement of starting components by other components are varied as much as possible.

As the polyalkyl (meth) acrylate, polyalkyl (meth) acrylates having 1 to 6 carbon atoms in the carbon chain of the alkyl group are suitable, with the methyl group being preferred as the alkyl group. As examples, u. a. Polymethyl methacrylate and polybutyl methacrylate called. However, it is also possible to use copolymers of the polyalkyl (meth) acrylates. Thus, up to 50 wt .-%, preferably up to 30 wt .-% and particularly preferably up to 20 wt .-% of the alkyl (meth) acrylate by other monomers such. As (meth) acrylic acid, styrene, acrylonitrile, acrylamide or the like. be replaced. Also suitable are copolymers of methyl methacrylate and

Dicyclopentylmethacrylat. The molding composition can be adjusted to impact strength, for example by adding a core / shell rubber customary for such molding compositions. In addition, at less than 50 wt .-%, preferably at most 40 wt .-%, more preferably at most 30 wt .-% and particularly preferably at most 20 wt .-% other thermoplastics such as SAN (styrene / acrylonitrile Copolymer) and / or polycarbonate.

Polycarbonates suitable according to the invention contain units which

Carbonic acid diesters of diphenols are. Such diphenols may be, for example, the following: hydroquinone, resorcinol, dihydroxybiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, a, a'-bis (hydroxyphenyl) diisopropylbenzenes and their ring-alkylated or ring-halogenated derivatives or else a, co-bis (hydroxyphenyl) -polysiloxanes , A particularly preferred diphenol is bisphenol A.

The polycarbonates used in this invention are known

Process produced, for example by the phase boundary process or after the melt transesterification process.

The polycarbonate molding composition can, for example, to less than 50 wt .-%, preferably less than 40 wt .-%, more preferably less than 30% by weight and particularly preferably less than 20 wt .-%, based on the total Polymer base, other polymers such as polyethylene terephthalate, polybutylene terephthalate, polyesters of cyclohexanedimethanol,

Ethylene glycol and terephthalic acid, polyesters of cyclohexanedimethanol and cyclohexanedicarboxylic acid, polyalkyl (meth) acrylates, SAN, styrene- (meth) acrylate copolymers, polystyrene (amorphous or syndiotactic), polyetherimides, polyimides, polysulfones and / or polyarylates (eg based on of bisphenol A and

Isophthalic / terephthalic acid).

Thermoplastic polyesters are obtained by polycondensation of diols

Dicarboxylic acids or their polyester-forming derivatives, such as dimethyl esters produced. Suitable diols have the formula HO-R-OH, where R is a divalent, branched or unbranched aliphatic and / or cycloaliphatic radical having 2 to 40, preferably 2 to 12, carbon atoms. Suitable dicarboxylic acids have the formula HOOC-R'-COOH, where R 'is a divalent aromatic radical having 6 to 20, preferably 6 to 12, carbon atoms.

Examples of diols include ethylene glycol, trimethylene glycol, tetramethylene glycol, 2-butenediol-1, 4, hexamethylene glycol, neopentyl glycol, cyclohexanedimethanol and C ₃₆ -diol dimerdiol. The diols can be used alone or as a diol mixture.

As aromatic dicarboxylic acids come z. As terephthalic acid, isophthalic acid, 1, 4, 1, 5, 2,6 or 2,7-naphthalenedicarboxylic acid, biphenyl-4,4'-dicarboxylic acid and diphenyl ether-4,4'-dicarboxylic acid in question. Up to 30 mol% of these dicarboxylic acids can by aliphatic or cycloaliphatic dicarboxylic acids having 3 to 50 carbon atoms, and preferably having 6 to 40 carbon atoms, such as. As succinic acid, adipic acid, sebacic acid, dodecanedioic acid or cyclohexane-1, 4-dicarboxylic acid, be replaced.

Examples of suitable polyesters are polyethylene terephthalate,

Polypropylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polypropylene-2,6-naphthalate, polybutylene-2,6-naphthalate, the polyester

Terephthalic acid and 1, 4-cyclohexanedimethanol and copolyester

Terephthalic acid, 1,4-cyclohexanedimethanol and ethylene glycol.

Polyestercarbonates are composed of at least one diphenol, of at least one aromatic dicarboxylic acid and of carbonic acid. As diphenols are the same as suitable for polycarbonate. The amount derived from aromatic dicarboxylic acids, based on the sum of the parts derived from aromatic dicarboxylic acids and from carbonic acid, is at most 99.9 mol%, at most 95 mol%, at most 90 mol%, at most 85 mol%, at most 80 Mol% or at most 75 mol%, while their minimum proportion is 0.1 mol%, 5 mol%, 10 mol%, 15 mol%, 20 mol% or 25 mol%. Suitable aromatic dicarboxylic acids are

for example, orthophthalic acid, terephthalic acid, isophthalic acid, tert-butylisophthalic acid, 3,3'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 3,4'-benzophenonedicarboxylic acid, 2,2-bis (4-carboxyphenyl) -propane and trimethyl-3-phenylindane-4,5-dicarboxylic acid. Of these, terephthalic acid and / or isophthalic acid are preferably used.

Polyarylates are derived from diphenols and aromatic dicarboxylic acids. As diphenols are the same as for polycarbonate, while as

Dicarboxylic acid are the same as suitable for polyester carbonate.

Polyimides are prepared in known manner from tetracarboxylic acids or their

Anhydrides and diamines. When the tetracarboxylic acid and / or the diamine contains an ether group, a polyetherimide results. A particularly suitable ether-containing tetracarboxylic acid is the compound I; from it are obtained together with aromatic diamines amorphous polyetherimides, which are commercially available.

Other suitable polyimides are polymethacrylimides, sometimes as

Polyacrylimide or polyglutarimides called. These are products starting from polyalkyl acrylates or polyalkyl methacrylates, in which two adjacent carboxylate groups have been converted to a cyclic acid imide. The imide formation is preferably with ammonia or primary amines, such as. As methylamine performed. The products and their preparation are known (Hans R. Kricheldorf, Handbook of Polymer Synthesis, Part A, published by Marcel Dekker Inc. New York-Basel-Hong Kong, p. 223 f., HG Elias, macromolecules, Hüthig and Wepf Verlag Basel-Heidelberg-New York; US 2,146,209 A; US 4,246,374).

Suitable polysulfones are usually by polycondensation of a

Diphenol / Dihalogendiarylsulfon mixture in an aprotic solvent in the presence of a base such. B. sodium carbonate. As diphenol, for example, those which are also used for the production of

Polycarbonates are suitable, but in particular bisphenol A, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenyl and hydroquinone, although mixtures of different diphenols can be used. The

Dihalogen compound is in most cases 4,4'-dichlorodiphenylsulfone; however, it is also possible to use any other dihalogen compound in which the halogen is activated by a para-positional sulfone group. As a halogen, fluorine is also suitable in addition to chlorine. The term "polysulfone" also includes the polymers commonly referred to as "polyethersulfone" or "polyphenylsulfone." Suitable types are commercially available.

Suitable styrenic polymers are, for example, homopolystyrene or copolymers of styrene with up to 50 mol%, based on the monomer mixture, of others

Monomers such. For example, methyl methacrylate, maleic anhydride, acrylonitrile or

Maleimides. Styrene-maleimide copolymers are also accessible, for example, by reacting styrene-maleic anhydride copolymers with ammonia or primary amines such as methylamine or aniline. As the polyolefin, for example, polyethylene or polypropylene can be used. Polyolefins with cyclic building blocks can be prepared by copolymerization of at least one cyclic or polycyclic olefin, for example norbornene or tetracyclododecene, with at least one acyclic olefin, for example ethene (WO 00/20496, US Pat. No. 5,635,573, EP-A-0 729 983, EP -A- 0 719 803). This substance class is called COC. Another suitable class of compounds, commonly referred to as COP, are optionally hydrogenated products of the ring-opening metathetic polymerization of

polycyclic olefins, for example norbornene, dicyclopentadiene, substituted derivatives or Diels-Alder adducts thereof (EP-A-0 784 066, WO 01/14446, EP-A-0 313 838, US Pat. No. 3,676,390, WO 96/20235). Olefin-maleimide copolymers are known, for example, from US Pat. No. 7,018,697.

Vinylcyclohexane-based polymers can be prepared either by polymerization or copolymerization of vinylcyclohexane or by catalytic hydrogenation of styrenic polymers (WO 94/21694, WO 00/49057, WO 01/30858, FS Bates et al., PCHE-Based Pentablock Copolymers: Evolution of a New Plastic, AIChE Journal Vol. 47, No. 4, pp. 762-765).

Polyarylene ether ketone contains units of the formulas

(-Ar-X-) and (-Ar'-Y-), wherein Ar and Ar 'represent a bivalent aromatic radical, preferably 1, 4-phenylene, 4,4'-biphenylene and 1, 4, 1, 5 - or 2,6-naphthylene. X is an electron-withdrawing group, preferably carbonyl or sulfonyl, while Y represents another group such as O, S, CH ₂ , isopropylidene or the like. Here, at least 50%, preferably at least 70% and particularly preferably at least 80% of the groups X represent a carbonyl group, while at least 50%, preferably at least 70% and particularly preferably at least 80% of the groups Y consist of oxygen.

In the preferred embodiment, 100% of the X groups are made up

Carbonyl groups and 100% of the groups Y from oxygen. In this

Embodiment may, for example, the polyarylene ether ketone

Polyetheretherketone (PEEK, Formula I), a polyetherketone (PEK, Formula II)

Polyether ketone ketone (PEKK; Formula III) or a polyetheretherketone ketone (PEEKK, Formula IV), but of course other arrangements of the carbonyl and oxygen groups are possible.

The polyarylene ether ketone is partially crystalline, which manifests itself, for example, in the DSC analysis by finding a crystallite melting point T _m , the

in the majority of cases is around 300 ° C or above.

Polyvinyl chloride (PVC) is well known to those skilled in the art, so further characterization is unnecessary here.

The molding material is in the form of compact particles. Under compact

According to the invention, particles are understood to mean non-porous three-dimensional structures of every possible shape, which are produced by solidification of a melt and optionally subsequent comminution. For example, they may be spherical, rod-shaped, barrel-shaped or irregularly shaped. Common particles are granules, shot or powder. In contrast, in the

WO2007032663 taught to impregnate porous materials with a dispersion of nanoparticles; There, the pores act as transport channels while

According to the invention, the dispersion is diffused into the polymer matrix with swelling.

Nanoparticles which can be used according to the invention are all nanoscale particles which are insoluble in a dispersant and can be dispersed therein. "Nanoscale" means that their diameter is in the range up to 1000 nm The nanoparticles generally have a mean diameter d ₅₀ of less than 400 nm, preferably from 20 to 250 nm, particularly preferably from 30 to 170 nm, particularly preferably from The average diameter d ₅₀ is measured by means of photon correlation spectroscopy in accordance with ISO 13321. Photon correlation spectroscopy, also referred to as dynamic light scattering, is an optical measuring method for determining the size distribution of particles in liquids. The method exploits the scattering of laser light through the particles.The measuring principle is based on the Brownian molecular motion of the particles.The smaller they are, the faster they move at the same temperature.The light of a laser radiates through the sample to be examined, thereby scattering it particles are in different directions. At a certain angle is a

Photomultiplier, which detects the scattered light. The detected signal is then evaluated. Suitable measuring devices are commercially available; it can

For example, a HORIBA LB-500 can be used.

The type and origin of the nanoparticles is not limited; the particles may be inorganic or organic in nature. As organic nanoparticles, for example, oligomeric silsesquioxanes can be used. However, nanoparticles in the form of a metal, a metal oxide, a metal boride, a metal carbide, a metal carbonate, a metal nitride, a

Metal phosphate, a metal chalcogenide (in particular a sulfide, selenide or telluride), a metal sulfate and / or a metal halide present.

The metal may preferably be Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Ag, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and / or Bi.

In particular, a metal oxide containing the elements Si, Al, Ti, Fe, Ce, In, Sb, Sn, Zn, Y and / or Zr may be preferred. It may be particularly advantageous if the dispersion used in the invention metal mixed oxides such as

Indium tin oxide, antimony tin oxide or matrix-domain-mixed oxides such as described in EP-A-1 284 485 or in EP-A-1 468 962. In particular, the dispersion according to the invention may also contain a metal oxide prepared by precipitation, as described, for example, in WO00 / 14017.

The nanoparticles can also be surface-modified. The

Surface modification includes adsorption, surface reactions or complexation of or with inorganic and / or organic reagents.

As nanoparticles are preferably doped indium oxide, doped tin oxide, doped antimony oxide, silica, alumina, zinc oxide, titanium dioxide,

Barium titanate, ceria, zirconia, aluminum nitride and lanthanum hexaboride into consideration.

In a preferred embodiment, the nanoparticles are laser-sensitive. Particularly suitable laser-sensitive additives are indium tin oxide (ITO) or antimony tin oxide (ATO), doped indium or antimony tin oxides and lanthanum hexaboride. Indium tin oxide is particularly preferred, and in turn, the "blue" indium tin oxide obtainable by a partial reduction process. The unreduced "yellow" indium-tin oxide may at higher concentrations and / or particle sizes in the upper region of a visually perceptible slightly yellowish hue of

Plastic material, while the "blue" indium tin oxide leads to no discernible color change.

The nanoparticles to be used according to the invention are known per se and also in nanoscale form, ie as discrete particles with sizes below 1 μm and

in particular in the here preferred size range commercially available, typically in the form of dispersions or in the form of easily redispersible powdery agglomerates of nanoscale particles. As a rule, the nanoparticles in their form of delivery are present as agglomerated particles, for example as agglomerates whose particle size can be between 1 μm to several mm. When preparing a dispersion, the agglomerates must be broken down into the nanoscale primary particles with the aid of suitable measures, for example high shear and / or the action of ultrasound. Nanoscale particles, in particular metal oxides, can be prepared, for example, by pyrolytic processes. Such processes are described, for example, in EP 1 142 830 A, EP 1 270 51 1 A or DE 103 1 1 645. Furthermore, nanoscale metal oxides can be produced by precipitation processes, as described for example in DE 100 22 037.

The choice of the dispersant depends on the polymer to be modified, although the particles of the polymer may be softened by the dispersant, but the polymer may not be completely soluble therein. Depending on the polymer, the dispersant may, for example, be an alcohol (eg 1,4-butanediol, butanol, ethanol, n-propanol), an ester (eg ethyl acetate), an alkane (eg heptane), a cycloalkane ( eg cyclohexane), an aromatic (eg toluene or xylene), an amide (eg dimethylformamide) or in individual cases also water. It is often advantageous to use mixtures of various such solvents as dispersants. The selection of suitable dispersants is the expert by orienting

Hand tests easily possible. In many cases, suitable dispersions of nanoparticles are also commercially available; There, the nanoparticle concentration is typically at least 10 wt .-% and in particular at least 40 wt .-% and at most 70 wt .-%. It is important to ensure that the dispersed

Nanoparticles do not reagglomerate when diluted to the technically useful concentration (so-called solvent shock), but this does not occur, for example, when using typical alcohols or alkanediols, at least in the case of metal oxides or mixed oxides. Concentration and amount of

Nanoparticle dispersion should be chosen so that, on the one hand, a sufficient

Wetting of the plastic particles with the nanoparticle dispersion in step b) is achieved, on the other hand, the desired in the molding composition nanoparticle concentration of 0.0001 to 10 wt .-% is achieved. The low nanoparticle concentrations of 0.0001 to 1 wt .-% are preferably selected when the molding material is to be processed directly into moldings; the higher concentrations of 1 to 10 wt .-% are useful if the concentrate formed in another

Compounding be reworked into the actual molding composition, for example, if further additives are required, which can not be incorporated in a solid phase (for example, rubbers, other polymers, glass fibers or flame retardants) or if the concentrate is to be used as a masterbatch. In a first preferred embodiment, the molding composition contains a

transparent microcrystalline or semicrystalline polyamide, for example PA PACM10 or PA PACM12 based on a 4,4'-diaminodicyclohexylmethane with a trans, trans isomer content of 35 to 65% (EP 0 619 336 A2) and

Nanoparticles in an amount of 0.0001 to 5.0 wt .-%, preferably 0.001 to 2.0 wt .-% and particularly preferably 0.01 to 0.1 wt .-%.

In a second preferred embodiment, the molding composition comprises an amorphous polyamide, for example one of the abovementioned types, for example the polyamide based on 1,12-dodecanedioic acid and 4,4'-diaminocyclohexylmethane with a trans-trans isomer content of less than 35% or (Co) polyamide of 1, 12-dodecanedioic acid or sebacic acid, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and optionally laurolactam or caprolactam and nanoparticles in an amount of 0.0001 to 5.0 wt .-%, preferably 0.001 to 2.0 wt .-% and particularly preferably 0.01 to 0.1 wt .-%.

In a third preferred embodiment, the molding composition contains

Polymethyl methacrylate (PMMA) and nanoparticles in an amount of 0.0001 to 10 wt .-%, preferably 0.0001 to 5.0 wt .-%, particularly preferably 0.0001 to 2.0 wt .-%, particularly preferably 0.001 to 1, 0 wt .-% and most preferably 0.01 to 0.1 wt .-%.

Typical procedures are, for example: - On a laboratory scale: wetting the molding material particles, for example granules, shot or powder, in a rotary evaporator, for. B. Rotavapor (typical working volume 0.1 I to 5 I at a granulate, shot or powder use of 0.1 to 2 kg), then impregnating the mechanically agitated

Molding material particles at 60 to 150 ° C and drying the molding material particles at 100 to 170 ° C in vacuo.

In pilot scale or production scale: Wetting of the molding material particles, for example granules, shot or powder, in a tumble dryer

(typical volume 0.1 m ³ to 30 m ³ in a granule, shot or

Powder input from 10 to 15,000 kg), then impregnating the mechanical moving molding material particles at 60 to 150 ° C and drying the

Molding compound particles at 100 to 170 ° C.

In pilot plant or production scale alternatively: wetting the

Molding material particles, for example granules, shot or powder, in a paddle dryer (typical volume 0.005 m ³ to 10 m ³ at a granulate, meal or powder 1 to 2000 kg), then impregnating the mechanically agitated molding compound particles at 60 to 150 ° C. and drying the molding material particles at 100 to 170 ° C.

The following examples are intended to illustrate the invention in more detail, but in no way limit it.

A. Laboratory tests in a rotary evaporator:

Example 1: Modification of semicrystalline PA PACM12

There were 80 g of a PA PACM12 granules with a proportion of 48% trans, trans-isomer in the PACM used and 1, 0 g of a 40 wt .-% dispersion of ITO with d ₅₀ = 76 nm, dispersed in n-butanol, was used to obtain a desired nanoparticle concentration of 0.5% by weight.

Polymer and dispersion were homogenized at room temperature (23 ° C) with mechanical agitation in a rotary evaporator within 2 hours under a gentle nitrogen flow of 10 l / h. Then the temperature was raised to 130 ° C within 30 minutes and maintained at this temperature with further mechanical movement for another 10 hours while passing 10 l / h of nitrogen until the dispersant was removed.

The resulting polymer-nanoparticle compound was dust-free and non-chalking. SEM and light micrographs showed that the nanoparticles were fixed in a thin surface layer of the granules.

Example 2 Modification of Amorphous PA PACM 12

In order to obtain a desired nanoparticle concentration of 0.01% by weight, 55.0 g of a PA PACM12 granulate with a content of 22% trans, trans. Isomerem in the PACM used and 0.014 g of a 40 wt .-% dispersion of ITO with d ₅₀ = 76 nm, dispersed in n-butanol, diluted with 5.0 g of 1, 4-butanediol, used. Polymer and dilute dispersion were stirred at room temperature with mechanical agitation in a rotary evaporator within 2 hours

Nitrogen stream of 10 l / h homogenized. The temperature was then raised to 80 ° C over 30 minutes and maintained at this temperature with further mechanical agitation for a further 24 hours while passing 20 l / h of nitrogen until the dispersant was removed.

Again, the nanoparticles were fixed abrasion resistant in a thin surface layer of the granules. Example 3: Modification of polymethyl methacrylate (PMMA)

In order to obtain a desired nanoparticle concentration of 0.2 wt .-%, 70.0 g of PMMA granules (PLEXIGLAS ^® 7N) and 0.35 g of a 40 wt .-% were separated

Dispersion of ITO with d ₅₀ = 76 nm, dispersed in n-butanol used. Polymer and dispersion were homogenized at room temperature with mechanical agitation in a rotary evaporator within 2 hours under a stream of nitrogen of 10 l / h. Then, the temperature was increased to 130 ° C within 30 minutes and maintained under further mechanical movement for another 7.5 hours at this temperature while passing 10 l / h of nitrogen until the

Dispersant was removed.

Again, the nanoparticles were fixed in a thin surface layer of the granules, which leaves no markings when rubbed on paper.

Example 4: Modification of a thermoplastic PA12 elastomer

To obtain a desired nanoparticle concentration of 0.15 wt .-%, 100.0 g of a PA12 elastomer granules (65 wt .-% of a soft block based on polypropylene glycol diamine having a number average molecular weight of 2000 and 0.375 g of a 40 wt .-% dispersion of ITO with d ₅₀ = 76 nm, dispersed in n-butanol used. Polymer and dispersion were homogenized at room temperature with mechanical agitation in a rotary evaporator within 3 hours under a stream of nitrogen of 10 l / h. Then the temperature was increased to 45 ° C within 30 minutes, then applied 20 mbar vacuum and maintained at 45 ° C for 5 hours, then within 30 minutes, the temperature increased to 60 ° C and at this temperature and 20 mbar for another 8 hours then, within 30 minutes, raise the temperature to 80 ° C and hold at less than 3 mbar vacuum and temperature for a further 2 hours until the dispersant was completely removed.

Again, the nanoparticles were fixed in a thin surface layer of granules, which leaves no markings when rubbed with paper.

B. Experiments in 0.25 m ³ tumble dryer

Example 5: Modification of semicrystalline PA PACM12

There were 100 kg of a PA PACM12 granules with a proportion of 48% trans, trans-isomer in the PACM used, 25 g of a 40 wt .-% dispersion of ITO with d ₅₀ = 76 nm, dispersed in n-butanol, and 250 g of n-butanol was used to obtain a desired nanoparticle concentration of 0.01% by weight.

The batch was homogenized at room temperature, passing 500 l / h of nitrogen and 3 revolutions per minute in a tumble dryer. After homogenization for 2 hours, the tumble dryer temperature was increased to 100 ° C and the nitrogen flow increased to 1250 l / h; these conditions were kept for 10 hours. Thereafter, the tumble dryer with the compound was cooled to less than 50 ° C within 4 hours.

The resulting compound was dust-free and non-chalking. The nanoparticles were fixed abrasion-resistant in a thin surface layer of the granules.

C. Experiments in the paddle dryer

Examples 6 to 8: Modification of Polyphenylsulfone (PPSU), Polysulfone (PSU) and

Polycarbonate (PC) In these examples, a nanoparticle concentration of 0.1% by weight was desired. For this purpose, in each case 20.0 kg of polymer in the form of shot, 222 g of a 9 wt .-% dispersion of antimony tin oxide (ATO) in isopropanol (d ₅₀ = 85 nm), diluted with further 3 l of isopropanol, placed in the paddle dryer and homogenized at room temperature, about 0.1 bar nitrogen overpressure and mechanical agitation for 2 hours. Then, the temperature was raised to 60 ° C within one hour, a vacuum of 100 mbar was applied, and these conditions were maintained with mechanical agitation for 16 hours. Subsequently, the impeller with the compound was cooled to below 40 ° C within 2 hours.

Again, the nanoparticles were in a thin surface layer of the

Shot particles fixed abrasion-resistant. The polymer-nanoparticle compounds prepared in Examples 1 to 8 can with the classical processing methods, for. B. extrusion, injection molding or blow molding. So z. B. the compound obtained in Example 5 are processed on all conventional injection molding machines.

Here, the screw temperature at 255 to 310 ° C and the

Tool temperature at 60 - 80 ° C, while the temperature of

Feed zone between 40 and 80 ° C should be. In the extrusion of this

Compounds, z. Example, with a conventional three-zone screw (length> 24D), the melt temperature should be 265-295 ° C, with a decreasing to the screw tip temperature profile. The catchment area must be cooled.

The moldings thus obtained can, for. B. with a laser wavelength of 532 nm or 1064 nm, laser marking on the surface according to WO 2005084956. They can also be laser-engraved three-dimensionally with a laser wavelength of 532 nm according to WO 2006094881.

Claims

Process for the preparation of a nanoparticle-containing molding composition which comprises the following steps:

a) A thermoplastic molding material in the form of compact particles is

provided;

b) a dispersion of nanoparticles in a dispersant is applied to the surface of the molding material particles;

c) it is waited until the dispersion in the edge zone of

Trapped molding compound particles;

d) the dispersant is removed at a temperature of at least 50 ° C.

Method according to claim 1,

characterized in that

- In step b) the molding material particles are at a temperature level of 0 ° C to 160 ° C and / or

- In step c), the mixture is at a temperature level of 20 ° C to 180 ° C and / or

- In step d) the temperature is in the range of 80 ° C to 170 ° C.

Method according to one of the preceding claims,

characterized in that

- In step b) the molding material particles are at a temperature level of 20 ° C to 80 ° C and / or

- In step c), the mixture is at a temperature level of 60 ° C to 150 ° C and / or

- In step d) the temperature is in the range of 100 ° C to 160 ° C.

Method according to one of the preceding claims,

characterized,

that step d) is carried out by melting in a conveying unit and applying a vacuum. Method according to one of the preceding claims, characterized

the molding composition comprises one or more polymers selected from the group of polyamides, poly (meth) acrylates, polycarbonate, thermoplastic polyesters, polyester carbonate, polyimides, polyetherimides, polymethacrylimides, polysulfone, styrene polymers, polyolefins, olefin-maleimide copolymers,

Polyvinylcyclohexane, polyarylene ether ketone and polyvinyl chloride.

Method according to one of the preceding claims,

characterized,

the nanoparticles are either of an organic nature or are selected from the group metal oxide, metal boride, metal carbonate, metal nitride,

Metal phosphate, metal chalcogenide, metal sulfate and / or metal halide.

Method according to one of the preceding claims,

characterized,

the nanoparticles are laser-sensitive and are preferably selected from the group indium tin oxide (ITO), antimony tin oxide (ATO), doped indium or. Antimony tin oxides and lanthanum hexaboride.

Method according to one of the preceding claims,

characterized,

the nanoparticles have an average diameter d ₅₀ , determined according to ISO 13321 by means of photon correlation spectroscopy, of less than 400 nm.

Method according to claim 8,

characterized,

the average diameter d _{50 of} the nanoparticles is in the range from 20 to 250 nm.

Method according to claim 9,

characterized,

the average diameter d _{50 of} the nanoparticles is in the range from 30 to 170 nm.

1 1. Method according to one of the preceding claims,

characterized,

the concentration and the amount of the nanoparticle dispersion are chosen such that a nanoparticle concentration of 0.0001 to 10% by weight is achieved in the resulting molding composition.

12. Molding composition particles which are obtained by a process according to any one of claims 1 to 3 and 5 to 1 1, wherein step d) was carried out without melting the molding material particles.

13. Method for producing a molded part or semifinished product,

characterized,

that molding material particles according to claim 12 directly without

Intermediate granulation are processed by a shaping process via the melt to form part or semi-finished.