DE102012200684A1 - Dispersion, useful as lubricant, comprises radiation-chemically and/or plasma-chemically modified PTFE particles in an aryl phosphate, where after the reactive reaction, the particles are negatively charged - Google Patents

Abstract

Dispersion comprises radiation-chemically and/or plasma-chemically modified PTFE particles in an aryl phosphate or its mixture, where after a reactive reaction, the aryl phosphate is covalently or chemically bonded to the PTFE particle surface and the PTFE particles are negatively charged. An independent claim is included for the preparation of the dispersion comprising in situ dispersion of radiation chemically and/or plasma-chemically modified PTFE particles with persistent perfluoro(peroxy)radicals and/or functional groups in the form of carbonyl fluoride, carboxylic acid and/or perfluoroalkylene aryl phosphate groups or its mixture with at least one aryl phosphate coupling active groups, under mechanical stress.

Description

The invention relates to the field of polymer chemistry and relates to aryl phosphate PTFE dispersions, such as, for example, as a lubricant, as an additive in lubricants and plastics or as a dispersion or as hydraulic oil in hydraulic systems in mechanical engineering, in vehicle technology or in aerospace engineering can be used.

Are known from the DE 10 2007 055 927 A1 Long-term stable oil-PTFE dispersion, which can be used, for example, in gearboxes or bearings. This PTFE oil dispersion consists of PTFE particles and a single or multiple olefinically unsaturated hydrocarbon-based oil, where molecules of the olefinically unsaturated oil are covalently / chemically coupled to PTFE (primary) particle surfaces via radical reactions, a permanent charge separation between the PTFE Particle surfaces and the coupled oil molecules and a fine dispersion of the PTFE particles in the oil or oil mixture is present. These long-term stable PTFE oil dispersions are prepared by mixing modified PTFE (emulsion) polymers with persistent perfluoro (peroxy) radicals together with an olefinically unsaturated oil and subsequently subjecting the modified PTFE (emulsion) polymers to mechanical stress become.

Furthermore, from the DE 103 51 813 A1 a free-radically coupled PTFE polymer powder is known which consists of radiation-chemically and / or plasma-modified PTFE powders whose particle surface homo-, co- or ter-polymers are radically coupled via a reactive reaction in dispersion or in substance. Such a powder is prepared by reactive reaction of PTFE powder with reactive perfluoroalkyl (peroxy) radical centers after dispersion by chemical and / or plasma chemical means in dispersion or in substance with the addition of polymerizable, olefinically unsaturated monomers Implementation of a polymer synthesis reaction is realized.

From the DE 103 51 812 A1 are known modified perfluorocarbons consisting of modified perfluoropolymers whose surface simultaneously -COOH and / or -COF groups and reactive perfluoroalkyl (peroxy) radical centers, wherein on the groups and / or to the centers more low molecular weight and / or oligomeric and / or polymeric substances and / or olefinically unsaturated monomers and / or oligomers and / or polymers are coupled. These plastics are produced by reacting modified perfluoropolymers, which simultaneously have -COOH and / or -COF groups and reactive perfluoroalkyl (peroxy) radical centers, by substitution reactions and / or by addition reactions and / or by free-radical reactions with further substances be implemented.

And continue to be out of the DE 10 2004 016 876 A1 Free-radically coupled perfluoropolymer polymer materials which consist of perfluoropolymers, to whose perfluoropolymer chains olefinically unsaturated monomers and / or macromers and / or oligomers and / or polymers in dispersion are chemically radically coupled via a reactive reaction. These materials are prepared by dispersing perfluoropolymers with persistent active or reactivatable perfluoroalkyl (peroxy) radicals and / or radicals from thermally decomposed groups not originating from an irradiation process and / or a plasma treatment with the addition of olefinically unsaturated monomer (s) ) and / or macromer (s) and / or oligomer (s) and / or polymer (s) are reactively reacted.

From the DE 69 209 168 T2 Furthermore, organic phosphates and their preparation are known. These organic phosphates are said to be used as wear inhibitors in fuels, lubricants and oil-based functional fluids.

According to the GB-A-1,146,173 Triaryl phosphates are known which are prepared by reacting a phenol with an alkylating agent in a first stage and then reacting the mixture of alkylated and still present unalkylated phenol with a phosphorylating agent in a second stage. They are useful as plasticizers, in the formulation of hydraulic or other functional fluids, as ignition control agents or as other additives for fuels, as well as extreme pressure (EP) additives or other additives for lubricants.

A disadvantage of the known solutions is that aryl phosphates can not sufficiently meet the tribological requirements in the respective field of use.

The object of the present invention is to deliver an aryl phosphate PTFE dispersion which reduces the sliding friction and the wear in tribological applications, and a method for producing such a dispersion, which is simple and inexpensive to implement.

The object is achieved by the invention specified in the claims. Advantageous embodiments are the subject of the dependent claims.

The aryl phosphate-PTFE dispersion according to the invention comprises PTFE-particles modified by radiation chemistry and / or plasma chemistry in aryl phosphate or in an aryl phosphate mixture in which, after a reactive reaction in a dispersion, aryl phosphate (s) are covalently / chemically coupled to the PTFE particle surface and the PTFE particles are negatively charged.

Advantageously, aryl phosphate (s) are covalently / chemically coupled to the PTFE particle surface via radical reactions and / or substitution reactions and / or addition reactions.

Also advantageously, aryl phosphate (s) are present on the PTFE particle surface via carbon-carbon bonds and / or via carbon-nitrogen-carbon bonds as the amine and / or imine and / or amide and / or imide group and / or via carbon-oxygen-carbon bonds as ether and / or ester group and / or via carbon-sulfur-carbon bonds as thioether and / or thioester group covalently / chemically coupled before.

Further advantageously, 50% by mass to 0.1% by mass of PTFE are present in the dispersion.

It is also advantageous if as coupled (s) aryl phosphate (s) PTFE {-X-Ar ¹ -O- [PO (-O-Ar ² ) -O-Ar ³ -O-] _m -PO (-O-Ar ⁴ ) (-O-Ar ⁵ )} _n with Ar ¹ , Ar ³ ... phenylene, arylene, advantageously bis-phenylene-A, bis-phenylene-F, O xy-bis-phenylene, bis-phenylene sulfone, bis-phenylene sulfide, diphenylenes, substituted phenylenes, preferably alkyl-substituted and or alkylene-substituted phenylenes, and / or substituted arylenes, preferably alkyl-substituted and / or alkylene-substituted arylenes,
Ar ² , Ar ⁴ , Ar ⁵ ... phenyl, aryl = substituted phenyls, preferably alkyl-substituted and / or alkylene-substituted phenyls
X ... CC bond as direct C _PTFE -C _alkylene bond and / or CNC bond as amine ([-NR-] and / or [-NR-R * -]) and / or imine ([= N -] and / or [= NR * -]) and / or amide ([-CO-NR-] and / or [-CO-NR-R * -] and / or [-NR-CO-] and / or [-NR-CO-R * -]) and / or imide ([-CO-N (-R * bond to Ar ¹ ) -CO-] and / or [-CO-N (bond to Ar ¹ ) -CO-]) and / or COC bonds as ethers ([-O-] and / or [-OR * -]) and / or esters ([-CO-O-] and / or [-CO-OR * -] and / or [-O-CO-] and / or [-O-CO-R * -]) and / or CSC bonds as thioethers ([-S-] and / or [-SR * -]) and / or thioesters ([-CO-S-] and / or [-CO-SR * -] and / or [-S-CO-] and / or [-S-CO-R *])
m ≥ 0
n> 0
R ... H, alkyl
R * ... alkylene (alkylene bridge to Ar ^{1 of} the aryl phosphate) PTFE ... PTFE particles
is available.

It is also advantageous if the PTFE particles are present as primary particles of a radiation- and / or plasma-modified emulsion PTFE in the aryl phosphate PTFE dispersion.

In the process according to the invention for producing an aryl phosphate PTFE dispersion, radiation-modified and / or plasma-chemically modified PTFE particles having persistent perfluoro- (peroxy) radicals and / or functional groups in the form of carbonyl fluoride and / or carboxylic acid groups and / or perfluoroalkylene Groups in aryl phosphate or in a Arylphosphatgemisch, wherein on at least one aryl phosphate coupling active groups are present and / or are formed during the reactive dispersion in situ, reactive dispersed under mechanical stress.

Advantageously, the aryl phosphate or the Arylphosphatgemisch or be it as aryl phosphate or as Arylphosphatgemisch Y-Ar ¹ -O- [PO (-O-Ar ² ) -O-Ar ³ -O-] _m -PO (-O-Ar ⁴ ) (-O-Ar ⁵ ) with Ar ¹ , Ar ³ ... phenylene, arylene advantageously bis-phenylene-A, bis-phenylene-F, oxybis-phenylene, bis-phenylene sulfone, bis-phenylene sulfide, diphenylenes, substituted phenylenes, preferably alkyl-substituted and / or alkylene-substituted phenylenes, and / or substituted arylenes, preferably alkyl-substituted and / or alkyl-substituted arylenes,
Ar ² , Ar ⁴ , Ar ⁵ ... phenyl, aryl = substituted phenyls, preferably alkyl-substituted and / or alkylene-substituted phenyls
Y ... -OH, -R * -OH, -NHR, -R * -NHR, -SH, -R * -SH, -allyl, -O-allyl, -R * -O-allyl, -NR- Allyl, -R * -NR-allyl, -N (allyl) ₂ , -R * -N (allyl) ₂ , -S-allyl, -R * -S-allyl-O-oleyl, -R * -O- Oleyl, -O-CO-oleyl, -R * -O-CO-oleyl, -CO-O-oleyl, -R * -CO-O-oleyl, -NR-oleyl, -R * -NR-oleyl, - NR-CO-oleyl, -R * -NR-CO-oleyl, -NH-CO-H, -R * -NH-CO-H, -NH-CO-R ***, -R * -NH-CO -R **, -NH-CO-OR **, -R * -NH-CO-OR **, -CO-O-allyl, -R * -CO-O-allyl, -CO-NR-allyl, -R * -CO-NR-allyl, -CO-N (allyl) ₂ , -R * -CO-N (allyl) ₂ , -CO-NR-oleyl, -R * -CO-NR-oleyl, -SO ₂ -NHR, -SO ₂ -NHR **
m ≥ 0
R ... H, alkyl
R * ... alkylene
R ** ... alkyl, aryl, allyl, oleyl
R *** ... alkyl, allyl, oleyl
added.

Also advantageously, the aryl phosphate or the Arylphosphatgemisch or when as aryl phosphate or as Arylphosphate mixture singly or in admixture o-allylphenyl-diphenylphosphate and derivatives and / or bis (o-allylphenyl) -phenylphosphate and derivatives and / or p-acetamidobenzyl-diphenylphosphate and derivatives and / or p-aminophenyl-diphenylphosphate and derivatives and / or p- Aminomethylphenyl-diphenylphosphate and derivatives and / or p-oleamic acid amidophenyl-diphenylphosphate and derivatives and / or p-hydroxymethylphenyl-diphenyl phosphate and derivatives and / or p-thiohydroxymethylphenyl-diphenylphosphate and derivatives and / or bisphenol-A-diphenylphosphate and derivatives and / or resorcinol Diphenyl phosphate and derivatives added.

Further advantageously, aryl phosphates based on phenol and / or phenol derivatives and / or bisphenol A bis (diphenyl phosphate) and / or resorcinol bis (diphenyl phosphate) are added to the aryl phosphate or the aryl phosphate mixture individually or in a mixture.

And advantageously also radiation-chemically and / or plasma-chemically treated PTFE emulsion polymers are used.

It is also advantageous if the radiation-chemical treatment of the PTFE particles is carried out under the influence of oxygen.

It is also advantageous when a shearing stress is applied as a mechanical stress that is even more advantageously applied by an Ultra-Turrax ^® and / or by a toothed disk is.

It is also advantageous if dispersion aids and dispersion stabilizer (s) are added.

With the solution according to the invention, it is possible for the first time to specify a stable aryl phosphate-PTFE dispersion which reduces the sliding friction and the wear in tribological applications.

This is achieved by an aryl phosphate PTFE dispersion which consists of radiation-chemically and / or plasma-chemically modified PTFE particles in aryl phosphate or in an aryl phosphate mixture, and in which after a reactive reaction in a dispersion aryl phosphate (e) to the PTFE Particle surface covalently / chemically coupled and the PTFE particles are negatively charged.

Aryl phosphate or the aryl phosphate mixtures are the dispersant in the dispersion according to the invention.

In this case, the covalent chemical coupling via radical reactions and / or substitution reactions and / or addition reactions by formation of carbon-carbon bonds and / or via carbon-nitrogen-carbon bonds as amine and / or imine and / or amide and / or or imide group and / or coupled via carbon-oxygen-carbon bonds as ether and / or ester group and / or via carbon-sulfur-carbon bonds as thioether and / or thioester group.

To form the covalent / chemical coupling, it is necessary that, on the one hand, the PTFE particles have coupling-active groups or radicals. This is achieved by the radiation-chemical and / or plasma-chemical modification.

On the other hand, at least aryl phosphates or aryl phosphate mixtures must also be used which have at least partially coupling-active and / or coupling-activatable groups. Coupling activatable groups are those groups formed in situ during the reactive dispersion.

Aryl phosphates or aryl phosphate mixtures having such coupling active and / or coupling activatable groups are advantageously Y-Ar ¹ -O- [PO (-O-Ar ² ) -O-Ar ³ -O-] _m -PO (-O-Ar ⁴ ) (-O-Ar ⁵ ) with Ar ¹ , Ar ³ ... phenylene, arylene advantageously bis-phenylene-A, bis-phenylene-F, oxybis-phenylene, bis-phenylene sulfone, bis-phenylene sulfide, diphenylenes, substituted phenylenes, preferably alkyl-substituted and / or alkylene-substituted phenylenes, and / or substituted arylenes, preferably alkyl-substituted and / or alkyl-substituted arylenes,
Ar ² , Ar ⁴ , Ar ⁵ ... phenyl, aryl = substituted phenyls, preferably alkyl-substituted and / or alkylene-substituted phenyls
Y ... -OH, -R * -OH, -NHR, -R * -NHR, -SH, -R * -SH, -allyl, -O-allyl, -R * -O-allyl, -NR- Allyl, -R * -NR-allyl, -N (allyl) ₂ , -R * -N (allyl) ₂ , -S-allyl, -R * -S-allyl-O-oleyl, -R * -O- Oleyl, -O-CO-oleyl, -R * -O-CO-oleyl, -CO-O-oleyl, -R * -CO-O-oleyl, -NR-oleyl, -R * -NR-oleyl, - NR-CO-oleyl, -R * -NR-CO-oleyl, -NH-CO-H, -R * -NH-CO-H, -NH-CO-R ***, -R * -NH-CO -R **, -NH-CO-OR **, -R * -NH-CO-OR **, -CO-O-allyl, -R * -CO-O-allyl, -CO-NR-allyl, -R * -CO-NR-allyl, -CO-N (allyl) ₂ , -R * -CO-N (allyl) ₂ , -CO-NR-oleyl, -R * -CO-NR-oleyl, -SO ₂ -NHR, -SO ₂ -NHR **
m ≥ 0
R ... H, alkyl
R * ... alkylene
R ** ... alkyl, aryl, allyl, oleyl
R *** ... alkyl, allyl, oleyl.

In particular, such aryl phosphates or aryl phosphate mixtures are those coupling-active and / or coupling-activatable groups have o-allylphenyldiphenylphosphate and derivatives and / or bis (o-allylphenyl) -phenylphosphate and derivatives and / or p-acetamidobenzyl-diphenylphosphate and derivatives and / or p-aminophenyl-diphenylphosphate and derivatives and / or p- Aminomethylphenyldiphenylphosphate and derivatives and / or p-oleamidophenyl-diphenylphosphate and derivatives and / or p-hydroxymethylphenyl-diphenylphosphate and derivatives and / or p-thiohydroxymethylphenyl-diphenylphosphate and derivatives and / or bisphenol-A-diphenylphosphate and derivatives and / or resorcinol-diphenylphosphate and Derivatives added as a dispersing agent.

According to the invention, however, it is also possible to add other aryl phosphates or aryl phosphate mixtures which have no coupling-active and / or coupling-activatable groups, such as aryl phosphates based on phenol and / or phenol derivatives (for example cresol, dimethylphenol and isopropyl alcohol) and / or bisphenol -A bis (diphenyl phosphate) and / or resorcinol bis (diphenyl phosphate),

These aryl phosphates or aryl phosphate mixtures can be used, for example, to adjust the viscosity index VI (VI describes the temperature dependence of the kinematic viscosity), i. the rheological properties of the dispersion are used.

The dispersion according to the invention is very stable and remains largely unchanged as dispersion over weeks and months. This stability is achieved, on the one hand, by the covalent bonding of the aryl phosphate (s) to the particle surface of the PTFE particles and, on the other hand, by the negative charge of the PTFE particles, which repel on approach and thereby maintain dispersion.

The negative charge of the PTFE particles is due to "frictional charging" during reactive shear / shear application in a dispersion. The charge, ie the potential of the PTFE particles in a dispersion can be determined by acoustophoresis. The electrostatic charging of plastics and especially PTFE by frictional and shear stress is well known to those skilled in the art. PTFE is one of the most highly chargeable materials [ www.kleinwaechtergmbh.de/cms/upload/downloads/allgemein/ESD_Anleitung.pdf] , The friction charging of PTFE is used technically, for example, in powder painting (tribo process).

Compaction of the dispersion without sedimentation occurs essentially only by the action of gravity and can easily be whirled up or redispersed.

The dispersion according to the invention consists of the PTFE-modified PTFE particles which have been advantageously modified by electron and / or gamma irradiation. Further advantageously used as radiation-modified PTFE in the presence of (air) oxygen irradiated PTFE.

The use of aryl phosphate as a flame retardant hydraulic fluid (special lubricant) in moving parts with tribological requirements leads to the reduction of sliding friction and wear. To improve the lubricant properties of aryl phosphate, the solid lubricant component PTFE should be used as an additive finely dispersed in aryl phosphate.

This aryl phosphate PTFE specialty lubricant has an increased potential for improving the run-in and run-flat properties of moving components through electrostatic and / or adhesive interactions of the modified PTFE component with the rubbing contact partners.

The use of aryl phosphate as an additive, for example as an EP additive, in lubricants for tribological requirements is known to reduce sliding friction and wear. To improve these properties in the lubricant system, instead of the aryl phosphate, the aryl phosphate PTFE dispersion according to the invention is added or added as an additive. The aryl phosphate-modified PTFE solid lubricant component of the aryl phosphate PTFE dispersion is likewise finely dispersed in the lubricant system and improves the tribo properties in the lubricant system with regard to sliding friction and wear by electrostatic and / or adhesive interactions of the aryl phosphate-modified PTFE particles with the friction contact partners. This increased interaction is achieved in addition to the electrostatic charging of the PTFE particles by the PTFE-coupled aryl phosphate (s), so that the combined interactions in the system improved sliding friction and wear properties can be realized.

For the purposes of this invention, finely dispersed PTFE is to be understood as meaning a finely divided and distributed PTFE which is stably dispersed in a medium such as, for example, aryl phosphate or lubricant, and which does not agglomerate almost completely or not.

It is advantageous if the aryl phosphate is completely or only partially, ie in the concentration range of 100 to 0.1% by mass with functional / coupling active and / or coupling-activatable groups on the aryl phosphate is used, wherein the aryl phosphate can be used as a pure substance or as an aryl phosphate mixture.

As functional or coupling-active groups on the aryl phosphate molecule it is preferred to use aromatic hydroxyl groups / phenol groups. For example, aryl phosphates with olefinically unsaturated double bonds, such as, for example, can also be used as coupling-active agents. with coupled allyl and / or oleyl groups and / or with aliphatic and / or alkylaromatic and / or aromatic hydroxy groups and / or with aliphatic and / or aromatic thiol groups and / or with aliphatic and / or aromatic amino groups and / or with aliphatic amide groups and / or with aliphatic and / or aromatic imide groups as the pure substance or as a substance mixture or as an additive to a non-functionalized aryl phosphate.

Important for the reactive dispersion is the use of a dispersing tool, which exerts a sufficient mechanical stress on the dispersion. In particular, should be used as a mechanical stress shearing stress. Preferably, toothed disk and / or Ultra-Turrax ^® are at a peripheral speed of v _u ≥ 15 m / s, preferably v _u ≥ 20 m / s, and more preferably v _u ≥ 23 m / s employed.

PTFE has been and is widely used as an additive in oils and lubricants, but previously primarily in physical mixture. Chemically compatibilized oil / grease PTFE products were only available in DE 10 2007 055 927 described which were prepared by reactive dispersion of radiation-chemically and / or plasma-modified PTFE in olefinically unsaturated oils.

A dispersion of PTFE in aryl phosphate without mechanical stress, both with and without dispersion aids or additives / auxiliaries, led to an aryl phosphate PTFE product, in which the PTFE settled down after a short time. This sedimented PTFE is usually difficult to fluidize / redisperse. This corresponds to the known physical mixtures.

In the reactively dispersed, stable aryl phosphate PTFE dispersions according to the invention, on the other hand, the reactive dispersed PTFE in the aryl phosphate or aryl phosphate mixture is compacted only by gravity according to the PTFE concentration slowly to a certain dispersion layer thickness or dispersion concentration, without any sedimentation occurring or a sediment layer is formed.

This densified aryl phosphate PTFE dispersion then remains as a stable dispersion in this state for long periods of time without deposition of a PTFE sediment. Even when diluted, stable aryl phosphate-PTFE dispersions show only a compression caused by gravity, and also form only a "compacted" dispersion layer without sedimentation phenomena. As a result, the modified / dispersed PTFE remains active in the system even without additional (dispersion aid) agents or additional redispersing units or circulates actively in the (lubricating) material circulation system. The functionalization and charging of the PTFE particles causes these enhanced interactions with a substrate.

Such dispersions / concentrates can be advantageously further processed into fats, which have the property that the PTFE is no longer agglomerated and / or phase-separated.

The phenomenon of dispersion stability is attributed, as already stated, to the coupling of aryl phosphate (s) to the PTFE particle surface and the electrostatic charging of the PTFE particles under shear conditions during the reactive dispersion by charge separation, which is analogous to DE 10 2007 055 927 for the reactively dispersed, stable oil-PTFE dispersions, and what was not expected for aryl phosphates due to the polarity. The polarity of the phosphoric acid ester molecules is based on the tetrahedral structure. Aryl phosphates can be considered as molecules with aprotic dipolar properties at the phosphoric acid ester centers. In contrast to the aryl phosphates, mineral oils and PAO are considered to be non-polar and ester oils to be of low polarity.

The advantage over the prior art is the preparation and provision of stable aryl phosphate PTFE modified PTFE dispersions by reactive dispersion / reaction with aryl phosphate or an aryl phosphate mixture to produce concentrates which are concentrated or diluted for use, e.g. as a flame retardant special oil for the hydraulic sector can come.

This aryl phosphate-PTFE material system is stable without further additives / additives and / or auxiliaries for redispersing in aryl phosphate-equipped tribosystems.

Such aryl phosphate-PTFE concentrates according to the invention can be used concentrated or diluted, for example as an additive in lubricants such as oils, fats and waxes or as an additive in plastics.

Analogous to DE 10 2007 055 927 This (lubrication) material system has an especially beneficial effect on slowly running aggregates, ie at low sliding speeds. If the aryl phosphate is displaced from the friction gap by the pressure of the aggregate components, the components rub to a greater or lesser degree by solid friction / in direct contact as well as in the mixed friction region. The increased friction leads to energy losses and increased wear.

The modified PTFE particles as a solid lubricant component in the stable aryl phosphate PTFE dispersions or in the lubricants and greases produced from them ensure the reduction of energy losses through friction and wear as well as the reduction of wear overall. Although under the conditions of solid-state friction, the aryl phosphate is displaced in the gap, the PTFE particles with the anti-adhesive properties as a solid lubricant component in the friction gap contribute to the reduction of friction and wear.

Under pressure between the component surfaces, a fixed friction-reducing PTFE film advantageously forms on the friction surfaces.

Comparative Example 1

To 17 g PTFE micropowder TF 9205 (Dyneon) (wetted with acetone), 173 g of aryl phosphate ISO VG 100 added. While stirring with a paddle and under pure nitrogen gassing is heated to 180 ° C and stirred at 180 ° C for 6 hours. After stopping the stirrer and cooling the dispersion, the sedimentation of the PTFE begins.

The re-stirred / homogenized dispersion of aryl phosphate TF9205 is tested in a Brugger test apparatus. Similar to the pure aryl phosphate, Brugger values of 22 to 27 MPa are obtained with this dispersion / physical mixture.

Example 1:

17 g of PTFE micropowder Zonyl ^® MP1100 (DuPont) are wetted with acetone and 173 g are aryl phosphate ISO VG 100 added. With stirring and under pure nitrogen gassing is heated to 180 ° C and this reaction mixture with a Ultra-Turrax ^{® for} 2 hours at 180 ° C reactively dispersed. After parking the Ultra-Turrax ^® and cooling the dispersion no sedimentation is observed. After standing for 7 days, the dispersion has "compacted" very slowly and only slightly downwards, ie in this dispersion a clear aryl phosphate layer has formed above without sedimentation of the PTFE.

The stable dispersion of aryl phosphate MP1100 is rehomogenized by brief stirring in a Brugger test apparatus similar to Comparative Example 1 examined. With this reactively dispersed aryl phosphate MP1100 dispersion, Brugger values of 145 to 150 MPa were obtained. An aryl phosphate MP1100 dispersion diluted to 3 wt% PTFE still gave Brugger values of 57 to 65 MPa.

Example 2:

To 17 g PTFE micropowder Zonyl ^® MP1100 (DuPont) (wet with acetone) are aryl phosphate 173 g ISO VG 100 added. With stirring and under pure nitrogen gassing is heated to 180 ° C and this reaction mixture with a dissolver (Dispermat, Zahnscheibenrührer) for 6 hours at 180 ° C reactively dispersed. After stopping the dissolver and cooling the dispersion, no sedimentation is observed analogously to Example 1. After standing for 7 days, the dispersion has "compacted" slowly, but somewhat more strongly than in example 1, ie in this dispersion a slightly larger, clear aryl phosphate layer has formed above without sedimentation of the PTFE.

The stable dispersion of aryl phosphate MP1100 is rehomogenized by brief stirring in a Brugger test apparatus similar to Comparative Example 1 examined. With this reactively dispersed aryl phosphate MP1100 dispersion, Brugger values of 125 to 133 MPa were obtained.

Example 3

17 g of PTFE micropowder TF2025 (Dyneon / 3M) gamma irradiated at 700 kGy under air atmosphere [TF2025 (700γ)] are wetted with acetone and 173 g of aryl phosphate are obtained ISO VG 100 added. With stirring and under pure nitrogen gassing is heated to 180 ° C and this reaction mixture with a Ultra-Turrax ^{® for} 2 hours at 180 ° C reactively dispersed. After stopping the Ultra-Turrax ^® and cooling the dispersion, no sedimentation is observed analogous example 1. After standing for 7 days, the dispersion has "compacted" very slowly and only slightly downwards, ie in this dispersion a clear aryl phosphate layer has formed above without sedimentation of the PTFE.

The stable dispersion of aryl phosphate TF2025 (700γ) is rehomogenized by brief stirring in a Brugger test apparatus similar to Comparative Example 1 examined. With this reactively dispersed aryl phosphate TF2025 (700γ) - Dispersion were obtained Brugger values of 185 to 195 MPa. An aryl phosphate TF2025 (700γ) dispersion diluted to 3 wt% PTFE yielded Brugger values of 80 to 85 MPa.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 102007055927 A1 [0002]
• DE 10351813 A1 [0003]
• DE 10351812 A1 [0004]
• DE 102004016876 A1 [0005]
• DE 69209168 T2 [0006]
• GB 1146173 A [0007]
• DE 102007055927 [0046, 0051, 0055]

Cited non-patent literature

• www.kleinwaechtergmbh.de/cms/upload/downloads/allgemein/ESD_Anleitung.pdf] [0036]
• ISO VG 100 [0058]
• ISO VG 100 [0060]
• ISO VG 100 [0062]
• ISO VG 100 [0064]

Claims (14)

Aryl phosphate PTFE dispersion, consisting of radiation-chemically and / or plasma-modified PTFE particles in aryl phosphate or in an aryl phosphate mixture in which after a reactive reaction in a dispersion aryl phosphate (e) covalently / chemically coupled to the PTFE particle surface and present the PTFE particles are negatively charged. An aryl phosphate PTFE dispersion according to claim 1, wherein aryl phosphate (s) are covalently / chemically coupled to the PTFE particle surface via radical reactions and / or substitution reactions and / or addition reactions. Aryl phosphate PTFE dispersion according to claim 1, wherein the aryl phosphate (s) on the PTFE particle surface via carbon-carbon bonds and / or via carbon-nitrogen-carbon bonds as amine and / or imine and / or amide and / or imide group and / or via carbon-oxygen-carbon bonds as ether and / or ester group and / or via carbon-sulfur-carbon bonds as thioether and / or thioester group covalently / chemically coupled. An aryl phosphate PTFE dispersion according to claim 1 wherein 50% to 0.1% by weight of PTFE is present in the dispersion. An aryl phosphate PTFE dispersion according to claim 1, wherein as coupled aryl phosphate (s) PTFE {-X-Ar ¹ -O- [PO (-O-Ar ² ) -O-Ar ³ -O-] _m -PO (-O-Ar ⁴ ) (-O-Ar ⁵ )} _n with Ar ¹ , Ar ³ ... phenylene, arylene, advantageously bis-phenylene-A, bis-phenylene-F, oxy-bis-phenylene, bis-phenylene sulfone, bis-phenylene sulfide, diphenylenes, substituted phenylenes, preferably alkyl-substituted and / or Alkylene-substituted phenylenes, and / or substituted arylenes, preferably alkyl-substituted and / or alkylene-substituted arylenes, Ar ² , Ar ⁴ , Ar ⁵ ... phenyl, aryl = substituted phenyls, preferably alkyl-substituted and / or alkylene-substituted phenyls X ... C-C bond as direct C _PTFE -C _alkylene bond and / or CNC bond as amine ([-NR-] and / or [-NR-R * -]) and / or imine ([= N-] and / or [= NR * -]) and / or amide ([-CO-NR-] and / or [-CO-NR-R * -] and / or [-NR-CO-] and / or [-NR-CO-R * -]) and / or imide ([-CO-N (-R * bond to Ar ¹ ) -CO-] and / or [-CO-N (bond to Ar ¹ ) -CO-]) and / or COC bonds as ethers ([-O-] and / or [-OR * -]) and / or esters ([-CO-O-] and / or [-CO-OR * -] and / or [-O -CO-] and / or [-O-CO-R * -]) and / or CSC bonds as thioeth he ([-S-] and / or [-SR * -]) and / or thioester ([-CO-S-] and / or [-CO-SR * -] and / or [-S-CO-] and / or [-S-CO-R *]) m ≥ 0 n> 0 R ... H, alkyl R * ... alkylene (alkylene bridge to Ar ^{1 of} the aryl phosphate) PTFE ... PTFE particle is present. Aryl phosphate PTFE dispersion according to claim 1, wherein the PTFE particles are present as primary particles of a radiation- and / or plasma-modified emulsion PTFE in the aryl phosphate PTFE dispersion. A process for the preparation of an aryl phosphate-PTFE dispersion, in the radiation-chemically and / or plasma-modified PTFE particles having persistent perfluoro (peroxy) radicals and / or functional groups in the form of carbonyl fluoride and / or carboxylic acid groups and / or perfluoroalkylene groups in aryl phosphate or in an aryl phosphate mixture, wherein coupling active groups are present on at least one aryl phosphate and / or are formed in-situ during the reactive dispersion, are reactive-dispersed under mechanical stress. The method of claim 7, wherein the aryl phosphate or the Arylphosphatgemisch or when the aryl phosphate or as Arylphosphatgemisch Y-Ar ¹ -O- [PO (-O-Ar ² ) -O-Ar ³ -O-] _m -PO (-O-Ar ⁴ ) (-O-Ar ⁵ ) with Ar ¹ , Ar ³ ... phenylene, arylene advantageously bis-phenylene-A, bis-phenylene-F, oxybis-phenylene, bis-phenylene sulfone, bis-phenylene sulfide, diphenylenes, substituted phenylenes, preferably alkyl-substituted and / or alkylene-substituted phenylenes, and / or substituted arylenes, preferably alkyl-substituted and / or alkyl-substituted arylenes, Ar ² , Ar ⁴ , Ar ⁵ ... phenyl, aryl = substituted phenyls, preferably alkyl-substituted and / or alkylene-substituted phenyls Y ... -OH, -R * - OH, -NHR, -R * -NHR, -SH, -R * -SH, -allyl, -O-allyl, -R * -O-allyl, -NR-allyl, -R * -NR-allyl, - N (allyl) ₂ , -R * -N (allyl) ₂ , -S-allyl, -R * -S-allyl-O-oleyl, -R * -O-oleyl, -O-CO-oleyl, -R * -O-CO-oleyl, -CO-O-oleyl, -R * -CO-O-oleyl, -NR-oleyl, -R * -NR-oleyl, -NR-CO-oleyl, -R * -NR -CO-oleyl, -NH-CO-H, -R * -NH-CO-H, -NH-CO-R ***, -R * -NH-CO-R **, -NH-CO-OR **, -R * -NH-CO-OR **, -CO-O-allyl, -R * -CO-O-allyl, -CO-NR-allyl, -R * -CO-NR-allyl, - CO-N (allyl) ₂ , -R * -CO-N (allyl) ₂ , -CO-NR-oleyl, -R * -CO-NR-oleyl, -SO ₂ -NHR , -SO ₂ -NHR ** m ≥ 0 R ... H, alkyl R * ... alkylene R ** ... alkyl, aryl, allyl, oleyl R *** ... alkyl, allyl, oleyl be added. A process according to claim 7, wherein the aryl phosphate or the aryl phosphate mixture or the aryl phosphate or aryl phosphate mixture singly or in admixture comprises o-allylphenyldiphenyl phosphate and derivatives and / or bis (o-allylphenyl) phenyl phosphate and derivatives and / or p-acetamidobenzyl diphenyl phosphate and derivatives and / or p-aminophenyl-diphenyl phosphate and derivatives and / or p-aminomethylphenyl-diphenylphosphate and derivatives and / or p-oleamic amidophenyl-diphenylphosphate and derivatives and / or p-hydroxymethylphenyl-diphenylphosphate and derivatives and / or p-thiohydroxymethylphenyl-diphenylphosphate and derivatives and / or bisphenol A diphenyl phosphate and derivatives and / or resorcinol diphenyl phosphate and derivatives may be added. Process according to Claim 7, in which aryl phosphates based on phenol and / or phenol derivatives and / or bisphenol A bis (diphenyl phosphate) and / or resorcinol bis (diphenyl phosphate) are added to the aryl phosphate or the aryl phosphate mixture individually or in a mixture , A method according to claim 7, in which radiation-chemically and / or plasma-chemically treated PTFE emulsion polymers are used. The method of claim 7, wherein the radiation-chemical treatment of the PTFE particles is carried out under the influence of oxygen. The method of claim 7, wherein a shear stress is applied as a mechanical stress, which is advantageously applied by a Ultra-Turrax ^® and / or by a toothed disc stirrer. A method according to claim 7, wherein dispersion aid and dispersion stabilizer (s) are added.