Patent Application
20080035894
The present invention will now be described for purposes of illustration and not limitation. Except in the operating examples, or where otherwise indicated, all numbers expressing quantities, percentages, and so forth in the specification are to be understood as being modified in all instances by the term “about.”
The present invention provides antistatic and electrically conductive, thermoset or thermoplastic polyurethanes, obtained by the reaction of an isocyanate with a compound containing NCO-reactive groups, with the optional addition of catalysts, blowing agents, auxiliary substances and additives, in which the polyurethanes contain (A) a conductive carbon black and (B) carbon fibers, the weight ratio of conductive carbon black (A) to carbon fibers (B) preferably being 1:2 to 1:15, more preferably 1:4 to 1:10, most preferably 1:4 to 1:8, and the total quantity of (A) and (B) preferably being 1 to 15 wt. %, more preferably 3 to 10 wt. %, most preferably 4 to 8 wt. %, based on the total weight of polyurethane.
The mixture of reaction components and additives used for the polyurethanes according to the invention has a viscosity sufficiently low that the mixture can be processed industrially. Under stress, the conductivity of the polyurethanes according to the invention is maintained.
Conductive carbon blacks with a surface area (measured by the BET method according to ASTM D 6556-04) of 600 to 1200 m2/g, with an absorption pore volume (according to ASTM D 2414-05a with n-dibutyl phthalate) of 300 to 450 cm3/100 g carbon black at about 23° C., a pour density (according to ASTM D 1513-05) of 20 to 250 kg/m3 and with an average particle size diameter of less than 50 nm, more preferably 10 to 50 nm, may be included.
The carbon fibers preferably have a diameter, as measured through their thickness, of 2 μm to 10 μm, more preferably of 6 μm to 10 μm. Both cut and ground carbon fibers can be used.
The polyurethanes according to the invention preferably have bulk densities of 200 kg/m3 to 1400 kg/m3, more preferably of 600 kg/m3 to 1400 kg/m3 and most preferably of 800 kg/m3 to 1400 kg/m3.
The polyurethanes are preferably not thermoplastic.
Solid polyurethanes, e.g. cast elastomers, are preferred.
The polyurethanes according to the invention can additionally contain fillers, such as e.g. chalks, silicates, dolomites and aluminum hydroxides. These non-conductive fillers known in polyurethane chemistry can be present in concentrations of up to 25 wt. %, based on the polyurethane.
Surprisingly, it has been found that a low viscosity and a good conductivity are obtained with mixtures of conductive carbon black particles and carbon fibers.
The conductive carbon blacks are marketed e.g. with the names PRINTEX XE 2B from Degussa AG and KETJENBLACK EC from Akzo Nobel Polymer Chemicals by. The cut or ground carbon fibers are marketed e.g. with the name SIGRAFIL from SGL Carbon Group.
The polyurethanes according to the invention are used e.g. for paintable, electrically shielding and/or electrostatically dissipating materials, e.g. for floor coverings, tires, rolls, rollers, electrical encapsulation materials, housing parts and other technical parts.
The present invention is further illustrated, but is not to be limited, by the following examples. All quantities given in “parts” and “percents” are understood to be by weight, unless otherwise indicated.
DESMODUR 44V10L (polyisocyanate mixture from the diphenylmethane series; NCO content: 31.5 wt. %; viscosity (25° C.): 100 mPas)
DESMODUR 44P90; NCO content: 28.5 wt. %; viscosity (25° C.): 130 mPas)
DESMODUR 15; 1,5-naphthalene diisocyanate
DESMODUR PF; prepolymer based on 4,4′-diphenylmethane diisocyanate and tripropylene glycol with an NCO content of 23 wt. % and a viscosity of 650 mPas at 25° C.
POLYOL COMPONENT 1 was stirred for 90 seconds with the carbon fiber SIGRAFIL C10 M250 UNS and ISOCYANATE 1 according to the composition given in the table, using a Pendraulik stirrer at a speed of 4500 rpm, and compacted in a closed mould to a bulk density of 500 kg/m3.
POLYOL COMPONENT 1 was stirred for 90 seconds with the conductive carbon black KETJENBLACK EC 600 JD and ISOCYANATE 1 according to the composition given in the table, using a Pendraulik stirrer at a speed of 4500 rpm, and compacted in a closed mould to a bulk density of 500 kg/m3.
POLYOL COMPONENT 1 was stirred for 90 seconds with the conductive carbon black KETJENBLACK EC 600 JD, the carbon fiber SIGRAFIL C10 M250 UNS and ISOCYANATE 1 according to the composition given in the table, using a Pendraulik stirrer at a speed of 4500 rpm, and compacted in a closed mold to a bulk density of 500 kg/m3.
An attempt was made to mix POLYOL COMPONENT 2 with carbon nanotubes (BAYTUBES C 150 P), the carbon fiber SIGRAFIL C10 M250 UNS and ISOCYANATE 2 according to the composition given in the table, using a Pendraulik stirrer. Processing was impossible, and so no moldings could be produced and no conductivity measurements could be taken.
It was attempted to mix POLYOL COMPONENT 2 with carbon nanotubes (BAYTUBES C 150 P), COND 8/96 graphite and ISOCYANATE 2 according to the composition given in the table, using a Pendraulik stirrer. Processing was impossible, and so no moldings could be produced and no conductivity measurements could be taken.
POLYOL COMPONENT 3 was mixed for 90 seconds with the conductive carbon black KETJENBLACK EC 600 JD and the conductive fiber SIGRAFIL C25 S006 PUT according to the composition given in the table, using a Pendraulik stirrer at 4500 rpm. This mixture was reacted at 127° C. with 25 parts by weight of 1,5-naphthalene diisocyanate. Crosslinking was performed with 5.0 parts by weight of 1,4-butanediol and a test plate was cast. The conductivities given in the table were determined on this plate in accordance with DIN IEC 60093.
100 parts by weight of POLYOL COMPONENT 3 were reacted at 127° C. with 25 parts by weight of 1,5-naphthalene diisocyanate. Crosslinking was performed with 5 parts by weight of 1,4-butanediol and a test plate was cast. The volume resistivity determined on this plate in accordance with DIN IEC 60093 was higher by a factor of 106 compared with Example 6.
96.87 parts by weight of POLYOL COMPONENT 4 were mixed with 0.54 parts by weight of KETJENBLACK EC 600 JD conductive carbon black and 2.15 parts by weight of SIGRAFIL C10 M250 UNS carbon fibers at room temperature. The mixture was dispersed for 60 minutes in vacuo (<1 mbar) in a high-speed mixer at 1100 rpm. The diameters of the container and disk of the high-speed mixer were 16 mm and 5 mm respectively. For the subsequent foaming to a bulk density of approx. 400 kg/m3, 0.45 wt. % water was added. The resulting mixture was flowable and pumpable.
62.44 parts by weight of ISOCYANATE COMPONENT 4 were mixed with 2.15 parts by weight of KETJENBLACK EC 600 JD conductive carbon black and 0.54 parts by weight of SIGRAFIL C10 M250 UNS carbon fibers at room temperature. The mixture was dispersed for over 90 minutes at room temperature and under a pressure of <1 mbar at 1100 rpm. The diameters of the container and disk of the high-speed mixer were 16 mm and 5 mm respectively. The resulting mixture was flowable and pumpable.
The polyol and isocyanate batches (including fibers and carbon black) were mixed in a ratio of 100:65.13 by high pressure injection mixing at a product temperature of 60° C. The reaction mixture was discharged into a closed mold, temperature-controlled at 60° C. The surface resistance and volume resistivity measurements were then taken on 10 mm thick plates in accordance with DIN IEC 60093. With 4×106 ohms for the surface resistance and 6×103 ohmcm for the volume resistivity, the values were significantly lower than those conventional for these polyurethanes (without the addition of carbon black and carbon fibers), i.e. 1010 to 1014 ohms and 1010 to 1014 ohmcm respectively.
6.1 parts by weight of COND 8/96 graphite and 2.2 parts by weight of BAYTUBES C 150 P (carbon nanotubes) were added to 94.3 parts by weight of polyol, with stirring. The dispersion thus obtained was homogenized three times using a high-pressure homogenizer (Micron Lab 40, APV, Unna) at 1000 bar. The polyol dispersion was not pumpable, and so industrial processing by machine was impossible.
The dispersion was stirred for 90 seconds with the ISOCYANATE 2 corresponding to the composition given in the table, using a Pendraulik stirrer at a speed of 4500 rpm. Processing was extremely difficult. The resistances listed in the table were determined on the reaction mixture poured out on to a plate.
In the Table below,
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 102006037582.3 | Aug 2006 | DE | national |
