ES2329873T3 - ANTISTTATIC AGENT. - Google Patents

Abstract

Polymer compositions contain at least one quaternary ammonium salt of a perfluoroalkylsulfonic acid. Polymer compositions (I) contain at least one quaternary ammonium salt of formula (1). R-SO3NR'R''R'''R'''' (1) R = 1-30(4-8)C perfluorinated linear, branched or unbranched carbon chain or 5-7C cyclic group; R' = 1-30(3-10)C alkyl or 5-7C cycloalkyl, optionally substituted by halogen, hydroxy, 5-7C cycloalkyl or 1-3C alkyl, preferably propyl, 1-butyl, 1-pentyl, hexyl, isopropyl, isobutyl, tert-butyl, neopentyl, 2-pentyl, iso-pentyl, iso-hexyl, cyclohexyl, cyclohexylmethyl or cyclopentyl; R'',R''',R'''' = 1-30(3-10)C alkyl or 5-7C cycloalkyl, optionally substituted by halogen, hydroxy, 5-7C cycloalkyl or 1-3C alkyl, preferably methyl, ethyl, propyl, 1-butyl, 1-pentyl, hexyl, isopropyl, isobutyl, tert-butyl, neopentyl, 2-pentyl, iso-pentyl, iso-hexyl, cyclohexyl, cyclohexylmethyl or cyclopentyl; whereby at least one of R'-R is not ethyl. Independent claims are included for: (1) preparation of polymer compositions (I) by the addition of a quaternary ammonium salt of a perfluoroalkylsulfonic acid before, during or after polymerization of the polymer; and (2) production of molded articles having antistatic properties using the composition (I).

Description

Antistatic agent

The request refers to molding masses formed by special quaternary ammonium salts of acids perfluoroalkylsulfonic and thermoplastic, which have an effect antistatic and that in processing do not show any yellowing

In the plastic molding bodies the dust accumulation, with formation of dust figures, is a widespread problem See in this regard, e.g., Saechtling, Kunststoff-Taschenbuch, 26th edition, Hanser Verlag, 1995, Munich, p. 140 ss. Especially disturbing and limiting the function is the accumulations of dust in molding bodies transparent. Molding bodies of this type are used eg. in the fields of optical data storage, electrical engineering, car construction, in the construction sector, for liquid containers or for other optical applications. For All these applications, a dust accumulation is undesirable and It may impair the function.

A known method to decrease dust accumulations on plastic bodies is the use of antistatic agents Agents have been described in the literature antistatic for thermoplastics (see eg Gächter, Müller, Plastic Additives, Hanser Verlag, Munich, 1996, p. 749 ss) that limit dust accumulations. These antistatic agents improve the electrical conductivity of the molding masses plastic and in this way derive the surface charges that They form in manufacturing and during use. In this way the dust particles suffer less attraction and, consequently, There is less dust accumulation.

In antistatic agents it is distinguished in general between internal and external. An antistatic agent External is applied on the plastic molding body after processing, an internal antistatic agent is added as an additive to the plastic masses. For economic reasons, the use of agents Internal antistatics is desirable in most cases since that no additional work steps are needed to apply the antistatic agent after processing.

The internal antistatic agents for thermoplastics described to date in the literature have in General one or more of the following disadvantages:

?

molecular weight reduction of thermoplastics

?

effectiveness only from high concentrations (> 0.5%)

?

cloudiness in thermoplastics transparent

?

not effective enough to electrostatic discharge e.g. make it possible after the injection and thereby prevent the accumulation of dust

?

color changes

A class of antistatic agents in Thermoplastics that have been described are often acid salts sulfonic JP-06 228 420 A 940 816, eg, describes ammonium salts of aliphatic sulfonic acids in  Polycarbonate as an antistatic agent. However, these Compounds lead to a reduction in molecular weight.

Acid quaternary ammonium salts perfluoroalkylsulfonic acids are known, as is their use in thermoplastics, such as in document DE 2 506 726. In this Patent application describes quaternary ammonium salts of perfluoroalkylsulfonic acids as mold release agents for polycarbonate However, the examples described in this request lead in the polycarbonate to a manifest coloration yellow during processing, which is undesirable in special for transparency and inking criteria in White.

WO 01/25326, which is a document according to article 54 (3) of the CPE, describes compositions antistatic containing a melt mixture of how minimum an ionic salt formed by a nitrogen onion ion and a organic fluoride anion.

WO 01/12713, which is also a document according to article 54 (3) of the CPE, describes the use  of fluorinated salts of alkylsulfonic acid as agent antistatic in plastics, as well as plastics that contain them and the molding bodies formed with them. Nor in WO 01/25326 nor in WO 01/12713 ammonium salts are described Quaternary claimed here.

The object of the invention is therefore facilitate antistatic agents that do not negatively influence the material properties of plastics.

It was surprisingly found that certain salts of perfluoroalkylsulfonic acids are especially good as antistatic agents for the manufacture of bodies of Injected and extruded molding. With small amounts of salt of perfluoroalkylsulfonic acid can already be manufactured bodies of molding that does not accumulate dust and that nonetheless does not present any of the drawbacks cited at the beginning of the agents conventional antistatic Therefore, the object of the The present invention is the use of the following ammonium salts quaternary to provide antistatic properties to plastics, preferably to polycarbonate or polycarbonate compositions, tetrapropylammonium salt of perfluorooctanesulfonic acid, salt of acid tetrapropylammonium perfluoro-butanesulfonic acid, tetrabutylammonium salt of perfluorooctanesulfonic acid, tetrabutylammonium salt of perfluorobutanesulfonic acid, tetrapentylammonium acid salt perfluorooctanesulfonic acid tetrapentylammonium salt perfluorobutanesulfonic acid, tetrahexylammonium acid salt perfluorooctanesulfonic acid, tetrahexylammonium acid salt perfluorobutanesulfonic acid, perfluorobutyl sulphonate N-methyl-tripropylammonium, perfluorobutyl sulphonate N-ethyl-tripropylammonium, tetrapropylammonium perfluorobutyl sulphonate, dimethyldiisopropylammonium perfluorobutyl sulphonate, perfluorobutyl sulphonate N-methyl-tributylammonium, cyclohexyldiethylmethylammonium perfluorobutyl sulphonate, perfluorobutyl sulphonate cyclohexyl-trimethylammonium, perfluorooctylsulfonate of N-methyltripropylammonium, perfluorooctylsulfonate of N-ethyl-tripropylammonium, tetrapropylammonium perfluorooctylsulfonate, dimethyldiisopropylammonium perfluorooctylsulfonate, perfluorooctylsulfonate of N-methyl-tributylammonium, cyclohexyldiethylmethylammonium perfluorooctylsulfonate, cyclohexyltrimethylammonium perfluorooctylsulfonate, alone or their mixtures, as well as plastic compositions, preferably polycarbonate or copolycarbonate, which contain at least one salt of quaternary ammonium as indicated above.

The plastic molding masses according to the invention optionally contain other polymer additives used  habitually.

Mixtures of acid salts are also preferred. sulfonic acid, especially sulfonic acid salts above  cited.

They are especially preferred N-methyltripropylammonium perfluorobutyl sulphonate, N-ethyltripropylammonium perfluorobutyl sulphonate, dimethyldiisopropylammonium perfluorobutyl sulphonate, methylethyldiisoripropylammonium perfluorobutyl sulphonate, N-methyltributylammonium perfluorobutyl sulphonate, alone or their mixtures.

Acid ammonium salts perfluoroalkylsulfonic are known or can be prepared according to known procedures Sulfonic acid salts can be prepared by mixing equimolar amounts of acids free sulfonic with the hydroxyl forms of the cation corresponding in water at room temperature and concentrating the solution. Other preparation procedures are described by example in documents DE 1 966 931 and NL 7 802 830.

Acid ammonium salts perfluoroalkylsulfonic are added to plastics preferably in amounts of 0.001 to 2% by weight, preferably 0.1 at 1% by weight.

It should be understood as suitable thermoplastics in the meaning of the invention in particular thermoplastics transparent, preferably polymerized monomers ethylenically unsaturated and / or polycondensates of compounds bifunctional reagents.

Especially suitable plastics are diphenol-based polycarbonates or copolycarbonates, of polyacrylates or copolycrylates and polymethacrylates or copolymethacrylates as for example and preferably methyl polymethacrylate, polymers or copolymers with styrene such as and preferably polystyrene or transparent polystyrene acrylonitrile (SAN), polyurethanes transparent thermoplastics, as well as polyolefins, as per example and preferably types of polypropylene or polyolefins a cyclic olefin base (for example TOPAS®, Hoechst), polycondensates or copolycondensates of terephthalic acid, as per example and preferably ethylene polyterephthalate or ethylene copolyterephthalate (PET or CoPET) or PET modified with glycol (PETG).

Especially preferred are polycarbonates or copolycarbonates, especially polycarbonates or copolycarbonates halogenated with molecular weights Mv of 500 to 100,000, preferably 10,000 to 50,000, especially preferably from 15,000 to 40,000.

Thermoplastic aromatic polycarbonates in the sense of the present invention are both homopolycarbonates and also copolycarbonates; polycarbonates can be so known linear or branched.

The polycarbonates of the present invention they may be present totally or partially brominated.

The preparation of these polycarbonates takes carried out in a known manner from diphenols, derived from carbonic acid, possibly chain switches and eventually branching.

The details about the preparation of Polycarbonates have been described for about 40 years in many patent memories. As an example, reference is made here only to Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, volume 9, Interscience Publishers, New York, London, Sydney 1964, to D. Freitag, U. Grigo, P. R. Müller, H. Nouvertne ', BAYER AG, "Polycarbonates" in Encyclopedia of Polymer Science and Engineering, volume 11, second edition, 1988, pages 648-718 and finally to doctors U. Grigo, K. Kirchner and P. R. Müller "Polycarbonate" in Becker / Braun, Kunststoff-Handbuch, volume 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag München, Wien 1992, pages 117-299.

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Preferred diphenols in the preparation of polycarbonates are: 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,1- bis- (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis- (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, bis- (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2-bis- (3, -dime-
til-4-hydroxyphenyl) -propane, bis- (3,5-dimethyl-4-hydroxyphenyl) -sulfone, 2,4-bis- (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,1 -bis- (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5- dibromo-4-hydroxyphenyl) -propane and 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

Especially preferred diphenols are 2,2-bis- (4-hydroxyphenyl) -propane,  he 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane,  he 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane  Y 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

Preferred branchers are triphenols, (trichloride) trimesic acid, cyanuric acid trichloride and 3,3-bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.

To get the plastic compositions improved, it is possible in the sense of the invention to incorporate thermoplastic plastics, preferably polycarbonates and copolycarbonates, an additional additive commonly present such as stabilizers (as described for example in documents EP 0 839 623 A1 or EP 0 500 496 A1) especially thermostabilizers, in particular phosphites or phosphines, by way of example and preferably triphenylphosphine, release agents, a by way of example and preferably fatty acid esters of the glycerin or tetramethanol methane, and can also be oxidized totally or partially unsaturated fatty acids, especially glycerin monostearate or pentaerythrite tetraestearate (PETS),  flame retardants, UV absorbers, by way of example and preferably hydroxybenzotriazole and hydroxytriazine, agents of filler, blowing agents, dyes, pigments, lighteners optics, transesterification catalysts and agents nucleization or the like, preferably in amounts up to 5%, preferably 0.01 to 5% referred to the total mixture, of especially preferably 0.01% by weight to 1% by weight referred to the amount of plastic.

The incorporation of acid salts perfluoroalkylsulfonic acid, as well as eventually the addition of additives or mixtures thereof, is generally produced by example before or during polymerization or by mixing back with plastic.

The plastic compositions obtained from this way they are usually present in the form of solutions, dispersions, emulsions, powders, granules, laminates or scales (molding masses) and are used for the manufacture of objects molded (molded bodies).

Molded objects are by way of example and preferably transparent objects for example and preferably light scattering lenses for motor vehicles, lenses as per example glasses, sheets, ribbons, plates, ribbed plates, plates multinervadas, containers, tubes and other profiles that are manufactured according to usual procedures, such as pressing on hot, spinning, extrusion or injection molding. The polymer compositions can also be processed to obtain molded sheets

Possible applications of the compositions of plastic according to the invention are:

one.

Safety glasses as you know they are necessary in many areas of buildings, vehicles and airplanes, as well as in helmet visors.

2.

Manufacture of extrusion sheets and of dissolution for screens or electric motors, as well as sheets for skis

3.

Blowing body manufacturing (see for example US Patent 2 964 794).

Four.

Manufacture of transparent plates, in special hollow chamber plates, such as for coating  buildings such as railway stations, greenhouses and lighting installations.

5.

For the manufacture of traffic light housings or signs of traffic.

6.

For the manufacture of spongy materials (see for example the DE-AS 1 031 507).

7.

For the manufacture of wires and wires (see for example the DE-AS 1 137 167 and DE-OS 1 documents 785 137).

8.

How translucent plastics containing glass fibers for the purpose of lighting technology (see for example the DE-OS document 1,554,020).

9.

For manufacture precision injection molding particles, as per example lens holders. For this, polycarbonates with a glass fiber content, which eventually also contains approximately 1-10% by weight of MoS2 based on weight total.

10.

Optical applications, such as memories (CD, DVD), goggles or camera lenses photographic and film cameras (see for example the document DE-OS 2 701 173).

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eleven.

How light transmission brackets, especially as power cables light transmission (see for example the document EP-A1 0 089 801).

12.

How electrical insulating materials for electrical conductors and for plug boxes and plug connectors.

13.

How bearing material for organic photoconductors.

14.

For the manufacture of lamps, for example, headlight lamps, such as called "head-lamps" ("lamps front ") or light scattering glasses or decks lamps.

fifteen.

For medical applications, for example oxygenators, dialyzers

16.

For food applications, such as bottles, dishes and chocolate molds.

17.

For applications in the automobile field, where it can occur contact with fuels and lubricants.

18.

For sporting goods, such as door sticks for example slalom.

19.

For household items, such as kitchen sinks and mailbox boxes.

twenty.

For housings, such as distribution cabinets, appliances Electrical appliances.

twenty-one.

Components of household items, electrical appliances and electronic devices.

22

For the manufacture of helmets for motorcyclists and helmets protectors

2. 3.

Auto parts, such as windows, dashboards, body parts and shock absorbers.

24.

For other applications, such as barn doors or cages animals, the use of plastic compositions being preferred according to the invention for

one.

Safety glasses as you know they are necessary in many areas of buildings, vehicles and airplanes, as well as in helmet visors.

2.

Manufacture of transparent plates, in special hollow chamber plates, such as for coating  buildings such as railway stations, greenhouses and lighting installations.

3.

Optical applications, such as memories (CD, DVD), goggles or camera lenses photographic and film cameras (see for example the document DE-OS 2 701 173).

Four.

For housings, such as distribution cabinets, appliances Electrical appliances.

5.

For the manufacture of lamps, for example, headlight lamps, such as called "head-lamps" ("lamps front ") or light scattering glasses or decks lamps.

6.

For the manufacture of helmets for motorcyclists and helmets protectors

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It is also interesting to use the plastic compositions according to the invention for the manufacture of multi-layer systems For this a thin layer is applied of the plastic composition according to the invention on an object molded that is not endowed with antistatic properties. The application can be done at the same time or immediately after shaping the molding body, for example by means of coextrusion or injection molding of multiple components. But the application can also happen on the basic body just molded, for example by lamination with a film or by coating with a solution.

For the manufacture of glass dispersers light for motor vehicles compositions are preferably used plastic containing acid ammonium salts perfluoroalkylsulfonic.

It is also of special interest to use plastic compositions containing acid salts perfluoroalkylsulfonic for the manufacture of plates, plates double ribbed, coextruded plates and sheets. It’s of interest, in addition, the use of perfluoroalkylsulfonic acid salts according to the invention in flame retardant thermoplastic molding masses.

The advantage of plastic molding bodies equipped with antistatic agents according to the invention is that they no longer recharged electrostatically, for example during manufacturing, when tearing off the protective sheets that usually used or during transport and storage.

Acid ammonium salts perfluoroalkylsulfonic acid according to the invention are especially suitable for transparency adjustments of thermoplastics, without However, they can also be gifted antistatically with the help of these additives settings covered.

The plastic compositions according to the invention they can also be obtained through the so-called "mixtures mother ", in which the composition has been previously mixed of additives desired. According to the desired composition of the plastic, then only the amounts are added to the polycarbonate corresponding to this mother mix, for example when combining or before the injection.

The following examples serve to explain the invention. The invention is not limited to the examples. The data from percentages mean hereafter percentages by weight.

Examples Dust test

To study the accumulation of dust in a laboratory test the injected plates are exposed to a swirling dust atmosphere. This is filled with dust (carbon powder / 20 g active carbon, Riedel-de Haen, Seelze, Germany, Article No. 18003) up to a height about 1 cm a beaker of 2 l with a rod 80 mm long magnetic stirrer and triangular section. With The help of a magnetic stirrer swirls the dust. After stop the stirrer the specimen is exposed for 7 seconds to this dust atmosphere. According to test tube used it is deposited on it more or less amount of dust.

The evaluation of dust deposits (figures of dust) is done visually. The plates that present figures of dust were evaluated as negative (-), the plates practically Dust-free figures were evaluated with (+).

Example 1

They are arranged in a 500 ml three mouth flask 6.25 g of neopentylamine, 28 g of tributylamine and 22 g of DMF. Be 40.8 g of methyl iodide are added dropwise to this mixture together with 14 ml of DMF and stir for 12 hours at temperature ambient. The solution is precipitated in ethyl acetate and dried. Be they obtain 2.4 g of colorless crystals. Neopentilamine may Obtained at Pfaltz & Bauer, Waterbury, CT, USA.

Example 2

9.6 g of the compound of example 1 are dissolved in 96 ml of water and passed through a column filled with 260 g of Lewatite M 500 in hydroxyl form. The solution obtained is neutralizes with perfluorooctanesulfonic acid (Fluka) and is Concentrate to dryness. You get salt from acid trimethyl-neopentylammonium perfluorobutanesulfonic.

Example 3

Acid trimethylphenylammonium salt is prepared perfluorobutanesulfonic acid neutralization perfluorobutanesulfonic acid and trimethylphenylammonium hydroxide in aqueous solution. Perfluorobutanesulfonic acid can be released leaving concentrated sulfuric acid on the potassium salt of sulfonic acid and be isolated by distillation. Salt Potassium can be obtained in Aldrich. Hydroxide Trimethylphenylammonium can be prepared from chloride trimethylphenylammonium (Aldrich) by ion exchange through of the anion exchanger Lewatit® 500 (Bayer AG).

Example 4

Acid benzyltrimethylammonium salt is prepared perfluorobutanesulfonic acid neutralization perfluorobutanesulfonic acid and hydroxide benzyltrimethylphenylammonium in aqueous solution. Hydroxide Benzyltrimethylphenylammonium can be obtained from Aldrich.

Example 5

Acid tetratrimethylammonium salt is prepared perfluorobutanesulfonic acid neutralization perfluorobutanesulfonic acid and tetramethylphenylammonium hydroxide in aqueous solution. Tetramethylphenylammonium hydroxide can Obtained at Aldrich.

Example 6

Acid tetrapropylammonium salt is prepared perfluorobutanesulfonic acid neutralization perfluorobutanesulfonic acid and tetrapropylammonium hydroxide in aqueous solution. Tetrapropylammonium hydroxide can be obtained in Aldrich.

Example 7

Acid tetrahexylammonium salt is prepared perfluorobutanesulfonic acid neutralization perfluorobutanesulfonic acid and tetrahexylammonium hydroxide in aqueous solution. Tetrahexylammonium hydroxide can be obtained in Fluka

Example 8 Test Tube Preparation

For the preparation of the specimens it is added to a twin screw extruder an unstabilized polycarbonate and Additive-free (Makrolon® 2808 from Bayer AG, Leverkusen) with a average molecular weight of approximately 30,000 (M v according to GPC) and a viscosity in solution: η = 1,293 a 290-300 ° C, mixed with the amounts of salts of sulfonic acid (according to example 2-7) and remaining additives indicated and in the end it is granulated.

Then, from this granulate is injection molded rectangular plates at 300 or 320 ° C mass temperature (155 mm x 75 mm x 2 mm). Then you visually check the color of the rectangular plates in front of the of rectangular plates prepared in parallel but without the salts of sulfonium according to the invention (example 8.1). Finally, they submit Rectangular dustproof plates. The results are indicated in table 2.

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TABLE 1 Plastic compositions

one

2

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TABLE 2 Results of dust and drawings test optical

3

The results in Table 2 indicate that versus to conventional sulfonium salts only sulfonium salts according to the invention have both an antistatic effect in the sense that no dust is deposited after injection, nor is it show additional yellowing after treatment.

Example 9

30.2 g of perfluorobutanesulfonyl fluoride (0.1 mol, Aldrich) and 6.0 g of dimethyldimethoxysilane (0.05 mol, Fluka) in 70 ml of tert-butyl methyl ether are placed in a 250 ml three-mouth flask Dry (Aldrich) and under nitrogen atmosphere are slowly mixed at room temperature with 14.3 g of tripropylamine (0.1 mol, Aldrich). The reaction solution is then heated with reflux for 3 h and finally the precipitated product is obtained by filtration, washed with ether and dried. Yield 32.6 g of white solid matter of N-methyl-tripropylammonium perfluorobutyl sulphonate.

Example 10

30.2 g of perfluorobutanesulfonyl fluoride (0.1 mol, Aldrich) and 8.8 g of diethyldiethoxysilane (0.05 mol, Fluka) in 70 ml of tert-butyl methyl ether are placed in a 250 ml three-mouth flask Dry (Aldrich) and under nitrogen atmosphere are slowly mixed at room temperature with 14.3 g of tripropylamine (0.1 mol, Aldrich). The reaction solution is then heated with reflux for 3 h and finally the precipitated product is obtained by filtration, washed with ether and dried. Yield 8 g of white solid matter of N-ethyl-tripropylammonium perfluorobutyl sulphonate.

Example 11

30.2 g of perfluorobutanesulfonyl fluoride (0.1 mol, Aldrich) and 7.3 g of methyltripropoxysilane (0.033 mol, Aldrich) in 70 ml of dry tert-butyl methyl ether are placed in a 250 ml three-mouth flask Aldrich) and under a nitrogen atmosphere are slowly mixed at room temperature with 14.3 g of tripropylamine (0.1 mol, Aldrich). The reaction solution is then heated with reflux for 8 h and finally the precipitated product is obtained by filtration, washed with ether and dried. Yield 19.3 g of white solid matter of tetrapropylammonium perfluorobutyl sulphonate.

Example 12

30.2 g of perfluorobutanesulfonyl fluoride (0.1 mol, Aldrich) and 6.0 g of dimethyldimethoxysilane (0.05 mol, Fluka) in 100 ml of dry cyclohexane (Aldrich) are placed in a 250 ml three-mouth flask ) and under nitrogen atmosphere mix slowly at room temperature with 11.52 g of N, N-diisopropylmethylamine (0.1 mol, Fluka). The reaction solution is then heated with stirring for 7 h and finally the precipitated product is obtained by filtration, washed with hexane and tert-butyl methyl ether and dried. Yield 14.4 g of white solid matter of dimethyldiisopropylammonium perfluorobutyl sulphonate.

Example 13

They are arranged in a 250 ml three mouth flask 30.2 g of perfluorobutanesulfonyl fluoride (0.1 mol, Aldrich) and 6.0 g of dimethyldimethoxysilane (0.05 mol, Fluka) in 100 ml of Dry cyclohexane (Aldrich) and under nitrogen atmosphere are mixed slowly at room temperature with 18.4 g of tributylamine (0.1 mol, Aldrich). The reaction solution is then heated. with stirring for 1 h and finally the filtration is obtained precipitated product, washed with ether and dried. Yield 6.5 g of white solid matter of perfluorobutyl sulphonate of N-methyl-tributylammonium.

Example 14

30.2 g of perfluorobutanesulfonyl fluoride (0.1 mol, Aldrich) and 6.0 g of dimethyldimethoxysilane (0.05 mol, Fluka) in 70 ml of tert-butyl methyl ether are placed in a 250 ml three-mouth flask Dry (Aldrich) and under nitrogen atmosphere are slowly mixed at room temperature with 15.5 g of N, N-diethylcyclohexylamine (0.1 mol, Aldrich). The reaction solution is then stirred for 1 h at room temperature, then heated under reflux for 3 h and finally the precipitated product is obtained by filtration, washed with ether and dried. Yield 40 g of white solid matter of cyclohexyldiethylmethylammonium perfluorobutyl sulphonate.

Example 15

30.2 g of perfluorobutanesulfonyl fluoride (0.1 mol, Aldrich) and 6.0 g of dimethyldimethoxysilane (0.05 mol, Fluka) in 70 ml of tert-butyl methyl ether are placed in a 250 ml three-mouth flask Dry (Aldrich) and under nitrogen atmosphere are slowly mixed at room temperature with 12.7 g of N, N-dimethylcyclohexylamine (0.1 mol, Aldrich). The reaction solution is then stirred for 8 h at room temperature and finally the precipitated product is obtained by filtration, washed with ether and dried. Yield 39 g of white solid matter of cyclohexyltrimethylammonium perfluorobutyl sulphonate.

Example 16

30.2 g of perfluorobutanesulfonyl fluoride (0.1 mol, Aldrich) and 6.0 g of dimethyldimethoxysilane (0.05 mol, Fluka) in 100 ml of tert-butyl methyl ether are placed in a 250 ml three-mouth flask Dry (Aldrich) and under nitrogen atmosphere are slowly mixed at room temperature with 8.7 g of N, N-dimethylisopropylamine (0.1 mol, Aldrich). The reaction solution is then stirred for 8 h at room temperature and finally the precipitated product is obtained by filtration, washed with ether and dried. Yield 33 g of white solid matter of isopropyltrimethylammonium perfluorobutyl sulphonate.

Example 17

30.2 g of perfluorobutanesulfonyl fluoride (0.1 mol, Aldrich) and 6.0 g of dimethyldimethoxysilane (0.05 mol, Fluka) in 100 ml of tert-butyl methyl ether are placed in a 250 ml three-mouth flask Dry (Aldrich) and under nitrogen atmosphere are slowly mixed at room temperature with 19.5 g of N, N-methyldicyclohexylamine (0.1 mol, Aldrich). The reaction solution is then stirred for 8 h at room temperature and finally the precipitated product is obtained by filtration, washed with ether and dried. Yield 38 g of white solid matter of dicyclohexyldimethylammonium perfluorobutyl sulphonate.

Example 18

They are arranged in a three-mouth flask of 1000 ml 212.5 g perfluorobutanesulfonyl fluoride (0.7 mol, Aldrich) and 42.2 g of dimethyldimethoxysilane (0.35 mol, Fluka) and low nitrogen atmosphere mix slowly at room temperature with 91 g of N, N-diisopropylethylamine (0.7 mol, Aldrich). The reaction solution is then stirred for 8 h at room temperature and finally the filtration is obtained precipitated product, washed with ether and dried. Yield 159 g of white solid matter of perfluorobutyl sulphonate of Methylethyldiisopropylammonium.

Example 19

In an analogous way to example 8, they are prepared rectangular plates by combination and subsequent molding by injection according to table 3 and undergo dust testing. In the Table 4 summarizes the results:

TABLE 3 Plastic compositions

4

TABLE 4 Results of dust and drawings test optical

5

The results in table 4 indicate that versus to conventional sulfonium salts the sulphonium salts according to the invention both have an antistatic effect in the sense of that no dust is deposited after injection, nor is it show additional yellowing after treatment.

Example 20

It is combined in the manner described in Example 8 Makrolon 2808 with 0.05% triphenylphosphine, 0.3% 2- (2'-hydroxy-3 '- (2-butyl) -5' - ( tert -butyl) - phenyl) -benzotriazole, 0.1% octadecyl-3- (3 ', 5'-di- tert -butyl-4'-hydroxyphenyl) -propionate and 1.5% dimethyldiisopropylammonium perfluorobutyl sulphonate (example 12).

Example 21

The granulate of the mixture is mixed by stirring Example 20 with granules of the Makrolon AI2647 polycarbonate type of Bayer AG according to table 5, is injection molded to give rectangular plates analogously to example 8 and subjected to Dust proof

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TABLE 5 Composition of rectangular plates and proof of powder

6

Table 5 indicates that with the help of a antistatic agent concentrate (pre-mix, "mix mother ") molding masses can also be prepared according to invention.

Claims (9)

1. Use of the following ammonium salts Quaternary to provide antistatic properties to plastics:

Get ouf of perfluorooctanesulfonic acid tetrapropylammonium,

Get ouf of perfluorobutanesulfonic acid tetrapropylammonium,

Get ouf of perfluorooctanesulfonic acid tetrabutylammonium,

Get ouf of perfluorobutanesulfonic acid tetrabutylammonium,

Get ouf of perfluorooctanesulfonic acid tetrapentylammonium,

Get ouf of perfluorobutanesulfonic acid tetrapentylammonium,

Get ouf of perfluorooctanesulfonic acid tetrahexylammonium,

Get ouf of perfluorobutanesulfonic acid tetrahexylammonium,

perfluorobutyl sulphonate N-methyl-tripropylammonium,

perfluorobutyl sulphonate N-ethyl-tripropylammonium,

perfluorobutyl sulphonate tetrapropylammonium,

perfluorobutyl sulphonate dimethyldiisopropylammonium,

perfluorobutyl sulphonate N-methyl-tributylammonium,

perfluorobutyl sulphonate cyclohexyldiethylmethylammonium,

perfluorobutyl sulphonate cyclohexyl trimethylammonium,

perfluorooctylsulfonate of N-methyl-tripropylammonium,

perfluorooctylsulfonate of N-ethyl-tripropylammonium,

perfluorooctylsulfonate of tetrapropylammonium,

perfluorooctylsulfonate of dimethyldiisopropylammonium,

perfluorooctylsulfonate of N-methyl-tributylammonium,

perfluorooctylsulfonate of cyclohexyldiethylmethylammonium,

perfluorooctylsulfonate of cyclohexyl trimethylammonium,

alone or their mixtures

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2. Use of the following ammonium salts quaternary according to claim 1:

perfluorobutyl sulphonate N-methyl-tripropylammonium,

perfluorobutyl sulphonate N-ethyl-tripropylammonium,

perfluorobutyl sulphonate dimethyldiisopropylammonium,

perfluorobutyl sulphonate methylethyldiisopropylammonium,

perfluorobutyl sulphonate N-methyltributylammonium, alone or mixtures thereof.

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3. Use of quaternary ammonium salts according to claim 1 to provide antistatic properties to Polycarbonate or copolycarbonate compositions. 4. Plastic compositions containing as at least one quaternary ammonium salt according to claim 1 or the claim 2. 5. Plastic composition according to claim 4, the polycarbonate plastic being or copolycarbonate Method for the preparation of plastic compositions as defined in claim 4, characterized in that at least one quaternary ammonium salt of a perfluoroalkylsulfonic acid is added before, during or after the polymerization of the plastics. 7. Use of plastic compositions that contain quaternary ammonium salts according to claim 1 for  the manufacturing of molding bodies. 8. Method for the manufacture of molding bodies with antistatic action, characterized in that at least one plastic composition as defined in claim 4 is used as starting materials. 9. Plastic molding bodies containing at least one quaternary ammonium salt according to claim one.