PL232158B1 - Polymer composition for metallic, wooden and plastic substrates - Google Patents

Description

The subject of the invention is a polymer composition for metal, wooden and plastic substrates, in particular water-soluble and water-soluble paints or varnishes, and varnish coatings, including pigment and adhesive joints.

Addition of CNT in an amount below 1 wt.% uniquely improves various properties of polymeric materials such as electrical and thermal conductivity as well as mechanical properties. However, in order for the carbon nanofiller to fulfill its function, it must be properly dispersed in the polymer material. Ultrasonic mixing (sonication) is one of the most effective methods of dispersing CNTs in liquid systems. This dispersion method, however, cannot be used directly to disperse nanofillers in coating compositions based on polymer emulsions / suspensions as it causes irreversible phase separation of the system. In addition, the sonication method is normally limited to mixing not very large volumes of dispersion (up to approx. 10 dm ³ ) and poses various risks when used on an industrial scale. Thus, in order to incorporate the carbon nanofiller into the polymer composition, it is separately dispersed in a dispersing medium, e.g. water, by sonication in the presence of a surfactant (SPC). The prepared dispersion (premix) of carbon nanofiller can then be mixed mechanically with the polymer emulsion / suspension, thus obtaining a nanofiller dispersion in a liquid polymer composition. Continuous work is underway to improve the methods of ultrasonic dispersion of carbon nanostructures.

Chinese patent specification CN102303862 describes the process of ultrasonic carbon nanofiller dispersion in water in the presence of hydrophilic coronene derivatives as SPC, carried out at a temperature of 10-40 ° C; no other process parameters were specified. It is known from US2013341570 to use a salt of a chondroitin derivative for ultrasonic dispersion of CNTs in water; process temperature 0-5 ° C, device power 100 W, time 0.5 h. Chinese patent description CN102911531 describes the method of ultrasonic CNT and graphene (GN) dispersion in organic solvents in the presence of epoxy resin synthesized from natural polyphenol - gallic acid under the following conditions : wave frequency 10-100 kHz, device power 80-170 W, process time 0.5-10 h. No other additives influencing the dispersing efficiency were used. Chinese patent specification CN102709523 relates to a method of dispersing CNT in a viscous non-Newtonian solution of poly (vinylpyrrolidone) in N-methylpyrrolidone by mechanical mixing in the presence of electrically conductive microfillers (such as lithium and iron orthophosphate or metallic nickel) as dispersion aids. The mixing speed as described herein is 900-1800 rpm. and the mixing time is 1-1.5 h. From the Polish patent application P.395835 there is known a method of dispersing CNT in the presence of a hydrophytic ionic liquid (1-ethyl-3-methylimidazolium diethylphosphate) in an ultrasonic bath. The indicated optimal process parameters are the temperature of 60-65 ° C and the time 4-5 hours.

Polymer composition for metal, wood and plastic substrates according to the invention, containing an epoxy and / or polyurethane binder and / or acrylic and / or alkyd and / or polyvinyl acetate and / or polyvinyl alcohol) and fillers and / or or pigments and / or dyes and / or plasticizers and / or co-solvents and / or defoamers and / or coalescents and / or catalysts and / or thickeners and / or biocides and carbon nanotubes, characterized by containing carbon nanotubes in the form of dispersion in water and / or organic liquids, wherein the amount of water and / or organic liquids in the total dispersion is from 39 to 99.4% by weight, the dispersion being obtained by ultrasonic dispersion in the presence of a nanoparticle dispersion aid with dielectric properties. The polymer composition comprises carbon nanotubes in an amount from 0.01 wt% to 5 wt% of the sum of all non-volatile components of the polymer composition. As a carbon nanotube dispersion aid, the polymer composition contains solids such as silicon oxide and / or alumina and / or titanium oxide and / or cerium oxide and / or silicon carbide in the form of a powder with particle sizes from 5 to 200 nm. The content of the dispersion aid in the carbon nanotube dispersion used in the composition is from 0.5 to 55% by weight. the mass of the entire dispersion of carbon nanotubes. Preferably, the polymer composition contains natural and synthetic fillers such as silica and silicates, alumina, iron oxides, calcium carbonate, calcium and magnesium carbonate, talc, kaolin, mica, barium sulfate, wollastonite, halloysite in an amount from 0.01% by weight to 85%. % by weight of the sum of all non-volatile components of the polymer composition. Preferably, the polymer composition contains natural and / or synthetic pigments, such as aluminum and / or calcium and / or zinc and / or magnesium phosphate, titanium dioxide, iron oxides in an amount from 0.01% by weight to 85% by weight of the sum of all non-volatile components of the polymer composition.

Surfactants used in the process of obtaining the dispersion used in the composition according to the invention are chemical compounds containing in their structure an organophilic and hydrophilic part, in particular such as: dodecylbenzenesulfonic acid and its salts, phenyl-, benzyl- and naphthyl-oligoxyalkylene ethers - including aromatic ring alkyl ethers; and polymeric compounds.

The energy of the ultrasound wave is transferred to the nanoparticles of the dispersing aid, which, while moving at high speed, help to break up agglomerates of carbon nanotubes. Due to this phenomenon, a much better dispersion degree of carbon nanofiller is obtained than in the analogous process carried out without the use of a dispersing aid. This requires much less energy consumption (it allows the dispersion energy to be reduced by at least 50%), as the energy supplied to the system is used in an optimized manner thanks to nanomechanical grinding / dispersion processes with the aid of the dispersing aid. In addition, the nanoparticles of the inorganic substance remain in the dispersion system after the dispersion process and are a useful additive to the polymer composition, enabling e.g. the improvement of the properties of the final coating materials or adhesives with the aid of carbon nanotube dispersion. The polymer composition containing the dispersion of carbon nanotubes obtained by the ultrasonic dispersion method in the presence of a dispersing aid, allows to obtain coatings, films and adhesive joints characterized by increased electrical conductivity compared to systems obtained with methods known so far and increased transparency compared to reference materials with the same composition obtained with the use of classical CNT dispersions.

The polymer composition according to the invention is used for the production of antistatic, electrically dissipative, electrically conductive and electromagnetic radiation shielding coatings, films and adhesive joints.

The solution according to the invention is presented in the working examples and in the drawing showing the graphs for the coatings prepared according to the procedures C and D of the first example, in which Fig. 1 shows the effect of the ultrasonic stirrer power on the surface resistivity of the coatings made of water-soluble acrylic lacquer containing the dispersion of carbon nanotubes obtained according to the invention with the use of nanoparticle SiO2 (dispersion time 30 minutes, temperature 20 ° C), Fig. 2 shows the effect of the dispersion time on the surface resistivity of coatings made of water-soluble acrylic varnish containing the dispersion of carbon nanotubes obtained according to the invention with nanoparticle SiO2 (ultrasonic stirrer power 70 W / g , temperature 20 ° C), Fig. 3 shows the effect of the dispersion process temperature on the surface resistivity of coatings made of water-soluble acrylic lacquer containing the dispersion of carbon nanotubes obtained according to the invention with the use of nanoparticle SiO2 (m o the agitator 70 W / g, dispersion time 30 minutes).

P r z k ł a d 1

The example shows the preparation of a dispersion of carbon nanotubes in water using nanoparticle silicon oxide as a dispersion aid and the application of the obtained carbon nanotube dispersion to a water-based acrylic lacquer.

For the purposes of comparison, two compositions were obtained with the method known from the state of the art by adding SiO2 nanoparticles after the sonication process.

Procedure A (comparative procedure).

Multi-walled carbon nanotubes (MWCNT; diameter -10 nm, ratio 1 / d ~ 160) were introduced into the water containing the dissolved surfactant (sodium dodecylbenzene sulfonate), and then the system was sonicated for 30 minutes at 20 ° C using an ultrasonic stirrer ( frequency 24 kHz, power 180 W / g). After the sonication process, the MWCNT dispersion was introduced into a mixture of an aqueous dispersion of acrylic copolymer (copolymer content 50% by weight, viscosity 250 mPa.s), an aqueous dispersion of SiO2 nanoparticles (with an average particle size of 40 nm) and water. Two coating compositions were obtained, denoted by the symbols A1 and A2, with the weight fractions of the components given in Table 1.

PL232 158 Β1

Procedure Β (comparative procedure).

The MWCNT dispersion was prepared in the same way as in procedure A, with the difference that the power of the ultrasonic stirrer was reduced to 70 W / g. Coating compositions denoted by the symbols B1 and B2 were obtained with the same composition as the corresponding compositions A1 and A2 with the weight fractions of the components given in Table 1.

Procedure C (according to the invention).

MWCNT (diameter ~ 10 nm, ratio 1 / d -160) was introduced into the aqueous nanoparticle S1O2 dispersion (with an average particle size of 40 nm) containing the dissolved surfactant (sodium dodecylbenzene sulphonate) and the system was sonicated for 30 minutes at 20 ° C for % using an ultrasonic stirrer (24 kHz, 180 W / g) to obtain aqueous dispersions containing 0.16-0.2 wt. % nanotubes and 40 wt. silicon oxide. The thus prepared MWCNT dispersion was mixed with an aqueous dispersion of acrylic copolymer (50 wt.%, 250 mPa · s). Two coating compositions denoted by the symbols C1 and C2 were obtained with the same composition as the respective compositions A1 and A2 (Table 3).

Procedure D (according to the invention).

The MWCNT dispersion was prepared in the same way as in procedure C with the difference that the power of the ultrasonic stirrer was reduced to 70 W / g. Two coating compositions were obtained, denoted by the symbols D1 and D2, with the same composition as the corresponding compositions A1 and A2 (Table 3).

Varnishes prepared according to procedures A, B, C and D were applied to transparent substrates (glass and polyester with PET) using a slot applicator to obtain nanocomposite polymer films with a thickness of 40 μηΊ. The electrical surface resistivity of coatings on a glass substrate (according to PN-E-04405) and the transparency of coatings on a polyester substrate (by UV-Vis spectrophotometry) were tested.

Table 1 shows the composition of water-borne acrylic varnishes with dispersions of carbon nanotubes prepared with the use of nanoparticulate silicon oxide and the properties of the obtained coatings.

Table 1

Sample symbol Composition k binder and arnpo; [% CNT position by weight SPC MWło ] S1O2 H ₂ O CNT content [wt%] ^b Stirrer power [W / gr Surface resistivity [£ 2 | ^d Transparency L%] ^e Al comparative 23.65 0.1 0.19 23.93 52.13 0.2 180 8.5-10 ¹¹ 65 BI comparative 70 2.2-10 ¹³ 65 Cl 180 2.5-10 ¹⁰ 73 Dl 70 1.0-10 ' 73 A2 comparative 23.6 0.12 0.24 23.96 52.07 0.25 180 9.1-10 ⁷ 55 B2 comparative 70 4.5-10 ¹⁰ 55 C2 180 2.3-10 ⁷ 62 D2 70 9.0 10 ⁵ 62

a - refers to the dry weight of the binder, b - dry matter content of the coating;

c - power per 1 g of dispersed carbon nanotubes; d - for a test voltage of 10 V;

e - at 700 nm light wave

Example 2

The example shows the preparation of a dispersion of carbon nanotubes in water using nanoparticle alumina as a dispersion aid and the application of the resulting dispersion to a water-based acrylic varnish.

For comparative purposes, the composition was prepared in a manner known from the state of the art by adding Al2O3 nanoparticles after the sonication process.

PL232 158 Β1

Procedure Ε (comparative procedure).

Single-walled carbon nanotubes (SWCNT; diameter -2 nm, ratio 1 / d -1000) were introduced into the water containing the dissolved surfactant (sodium dodecylbenzene sulphonate), and then the system was sonicated for 30 minutes at 20 ° C using an ultrasonic stirrer (24 kHz, 200 W / g). After the sonication process, the SWCNT dispersion was introduced into a mixture of an aqueous dispersion of acrylic copolymer (copolymer content 50% by weight, viscosity 250 mPa.s), aqueous dispersion of Al2O3 nanoparticles (with an average particle size of 40 nm), silicone skimmer and water. A coating composition marked with the symbol E1 was obtained with the following weight fractions of components:

- water: 569.8 parts weight,

- acrylic copolymer: 181 parts weight,

- surfactant: 6.4 parts weight,

- from the foamer: 3 parts weight,

- aluminum oxide: 236.6 parts weight,

- carbon nanotubes: 3.2 parts wt.

Procedure F (according to the invention).

SWCNT (diameter -2 nm, ratio 1 / d -1000) was introduced into the aqueous dispersion of nanoparticle Al2O3 (40 nm) containing the dissolved surfactant (sodium dodecylbenzene sulfonate) and the system was sonicated for 30 minutes at 20 ° C using an ultrasonic stirrer ( 24 kHz, 100 W / g) to obtain a dispersion with the following composition:

- carbon nanotubes: 0.74 parts weight,

- surfactant: 1.48 parts weight,

- aluminum oxide: 55 parts weight,

- water: 42.78 parts wt.

The dispersion of nanotubes prepared in this way was mixed with an aqueous dispersion of acrylic copolymer (50% by weight, 250 m-Pas), water and a silicone skimmer. A coating composition denoted by the symbol F1 having the same composition as composition E1 was obtained.

Water-soluble acrylic varnishes, prepared according to procedures E and F, were applied to a transparent substrate (glass and polyester with PET) using a slot applicator to obtain nanocomposite polymer films with a thickness of 40 μη μ. The surface electrical resistivity of the obtained coatings on a glass substrate (in accordance with PN-E-04405) and the transparency of coatings on a polyester substrate (by UV-Vis spectrophotometry) were tested.

Table 2 shows the conditions for dispersing carbon nanotubes with nanoparticle alumina and the properties of coatings made of a water-based acrylic lacquer containing a dispersion of carbon nanotubes.

Table 2

Sample symbol Stirrer power [W / g] ^a CNT content [wt%] ^b Surface resistivity [Ω] c Transparentity [%] ^d El comparative 200 0.74 3.6-10 ⁷ 57 FI 100 1.5-10 ⁶ 62

a - power per 1 g of dispersed carbon nanotubes; b - dry matter content of the coating; c - for a test voltage of 10 V; d - at 700 nm light wave

Example 3

The example shows the preparation of a dispersion of carbon nanotubes in a water-ethanol mixture using nanoparticulate silicon oxide as a dispersion aid and the application of the resulting dispersion to a water-based varnish with a polyvinyl acetate binder.

For comparative purposes, the composition was obtained with the method known from the state of the art by adding S1O2 nanoparticles after the sonication process.

Procedure G (reference procedure).

Polywall carbon nanotubes were introduced into an equilibrium mixture of water and ethanol containing dissolved surfactant (sodium dodecylbenzene sulfonate)

PL232 158 Β1 (MWCNT; diameter ~ 20 nm, ratio 1 / d -100), then the system was sonicated for 30 minutes at 0 ° C using an ultrasonic stirrer (24 kHz, 180 W / g). After the sonication process, the MWCNT dispersion was introduced into the mixture of an aqueous polyvinyl acetate dispersion (polymer content 50% by weight, viscosity 2200 mPa-s), S1O2 nanoparticle dispersion in ethanol (with an average particle size of 5 nm), filler (kaolin), water and ethanol . A varnish marked with the symbol G1 was obtained with the following components by weight:

- water: 48.98 parts weight,

- ethanol: 22.37 parts weight,

- poly (vinyl acetate): 15.90 parts weight,

- kaolin: 0.01 part weight,

- surfactant: 1.6 parts weight,

- silicon oxide: 10.98 parts weight,

- carbon nanotubes: 0.16 parts wt.

Procedure H (according to the invention).

MWCNT (diameter -20 nm, ratio 1 / d -100) was introduced into the mixture consisting of the dispersion of nanoparticle S1O2 in ethanol (5 nm) with an aqueous solution of the surfactant (sodium dodecylbenzenesulfonate) and the system was sonicated for 30 minutes at 0 ° C using an ultrasonic stirrer (24 kHz, 90 W / g) to obtain a dispersion with the following composition:

- carbon nanotubes: 0.37 parts weight,

- surfactant: 3.7 parts weight,

- silicon oxide: 25.44 parts weight,

- water: 32.62 parts weight,

- ethanol: 37.87 parts wt.

The thus prepared MWCNT dispersion was mixed with a mixture of an aqueous dispersion of polyvinyl acetate (50 wt.%, 2200 mPa · s), water, ethanol and a filler. The obtained varnish, marked with the symbol H1, has the same composition as the varnish G1.

Varnishes prepared according to procedures G and H were applied to a transparent substrate (glass and PET) with a slot applicator in order to obtain nanocomposite polymer films with a thickness of 40 μηΊ. The electrical surface resistivity of coatings on a glass substrate (according to PN-E-04405) and the transparency of coatings on a polyester substrate (by UV-Vis spectrophotometry) were tested.

Table 3 shows the conditions for dispersing carbon nanotubes with nanoparticle silicon oxide and the properties of coatings of water-borne polyvinyl acetate varnish containing carbon nanotube dispersion.

T a b el a 3

Sample symbol Stirrer power [W / g] ^a CNT content [wt%] ^b Surface resistivity [Ω [c Transparency [%] ^d Comparative G1 180 0.55 1.8-10 ⁹ 31 HI 90 2.4-10 ⁸ 33

a - power per 1 g of dispersed carbon nanotubes; b - dry matter content of the coating; c - for a test voltage of 10 V; d - for a light wave length

700 nm

Example 4

The example shows the preparation of a dispersion of carbon nanotubes in water using nanoparticulate cerium oxide as a dispersion aid and the application of the obtained nanotube dispersion to a water-borne polyurethane paint.

For comparative purposes, the composition was obtained with the method known from the state of the art by adding CeO2 nanoparticles after the sonication process.

Procedure J (comparative procedure).

Multi-walled carbon nanotubes (MWCNT; diameter -20 nm, ratio 1 / d -100) were introduced into the water containing the dissolved surfactant (sodium dodecylbenzene sulphonate), and then the system was sonicated for 60 minutes at 20 ° C using an ultrasonic stirrer

PL232 158 Β1 (24 kHz, 180 W / g). After the sonication process, the CNT dispersion was introduced into a mixture of an aqueous solution of a polyurethane copolymer (copolymer content 40% by weight, viscosity 140 mPa-s), an aqueous dispersion of CeC> 2 nanoparticles (with an average particle size of 10 nm), water, fillers (talc, calcium carbonate and magnesium, halloysite, wollastonite), pigment (titanium white), silicone skimmer, plasticizer (trimethylhydroxypentyl isobutyrate) and biocide. A polymer composition marked with the symbol J1 was obtained with the following composition:

- water: 579.40 parts weight,

- polyurethane copolymer: 59.39 parts weight,

- calcium and magnesium carbonate: 307.40 parts weight,

- talc: 30.66 parts weight,

- halloysite: 9.90 parts weight,

- wollastonite: 9.37 parts weight,

- titanium white: 0.05 parts weight,

- skimmer: 0.11 parts weight,

- plasticizer: 0.47 parts by weight,

- biocidal agent: 0.10 part weight,

- surfactant: 0.44 parts weight,

- cerium oxide: 2.47 parts weight,

- carbon nanotubes: 0.05 parts wt.

Procedure K (according to the invention).

MWCNT (diameter ~ 20 nm, ratio 1 / d -100) was introduced into the aqueous nanoparticle CeC> 2 dispersion (10 nm) containing the dissolved surfactant (sodium dodecylbenzene sulphonate) and the system was sonicated for 60 minutes at 20 ° C with a stirrer ultrasonic (24 kHz, 90 W / g) to obtain a dispersion with the following composition:

- carbon nanotubes: 0.01 parts weight,

- surfactant: 0.09 parts weight,

- cerium oxide: 0.5 part weight,

- water: 99.4 parts wt.

The thus prepared MWCNT dispersion was mixed with a mixture of an aqueous solution of a polyurethane copolymer (40 wt.%, 140 mPas), fillers, pigment, defoamer, plasticizer and biocidal agent. As a result, a polymer composition marked with the symbol K1 having the same composition as composition J1 was obtained.

Water-soluble polyurethane paints prepared according to procedures J and K were applied to a transparent substrate made of poly (ethylene terephthalate) with a slot applicator to obtain nanocomposite polymer films with a thickness of 40 μηΊ. The electrical surface resistivity of the coatings was tested (according to PN-E-04405).

Table 4 shows the dispersion conditions for carbon nanotubes with the participation of nanoparticulate cerium oxide and the properties of polyurethane paint coatings containing the dispersion of carbon nanotubes.

Table 4

Sample symbol Stirrer power [W / g] ³ CNT content [wt%] ^b Surface resistivity [Ω] ' comparative 180 0.0l ι, ο-ιο ¹⁴ KI 90 ^{4.110 ΙΛ}

a - power per 1 g of dispersed carbon nanotubes;

b - dry matter content of the coating; c - for a test voltage of 10 V;

Example 5

The example shows the preparation of a dispersion of carbon nanotubes in a mixture of xylene and butanol using nanoparticulate silicon oxide and silicon carbide as a dispersion aid, and the application of the resulting carbon nanotube dispersion to a solvent-based epoxy adhesive.

PL 232 158 B1

For comparative purposes, the composition was obtained with the method known from the state of the art by adding SiO2 and SiO nanoparticles after the sonication process.

Procedure L (comparative procedure).

To the mixture of xylene with butanol (weight ratio 8: 2), containing the dissolved surfactant (polyether with nonylphenyl substituent), carbon nanotubes (MWCNT, diameter ~ 10 nm, ratio 1 / d ~ 160) were introduced into sonicated for 5 minutes at 90 ° C using an ultrasonic stirrer (24 kHz, 250 W / g). After the sonication process, the CNT dispersion was introduced into a mixture of epoxy resin based on bisphenol A (viscosity 25,000 mPas), epoxy diluent (butanediol diglycidyl ether, viscosity 150 mPas), plasticizer (polyether diol), fillers and pigments (mica, sulphate barium, aluminum phosphate), rheology modifier (montmorillonite) and dispersion of Si O2 nanoparticles (with an average particle size of 90 nm) and SiC (with an average particle size of 200 nm) in a mixture of xylene with butanol (8: 2). A polymer composition marked with the symbol L1 was obtained with the following weight percentages of components:

- epoxy resin: 33.43 parts weight,

- epoxy thinner: 16.21 parts by weight,

- xylene: 14.31 parts weight,

- butanol: 3.58 parts weight,

- plasticizer: 2.0 parts weight,

- mica: 1 part weight,

- barium sulphate: 2.5 parts weight,

- aluminum phosphate: 4.0 parts weight,

- montmorillonite: 0.5 parts weight,

- surfactant: 2.56 parts weight,

- silicon oxide: 5.96 parts weight,

- silicon carbide: 5.96 parts weight,

- carbon nanotubes: 0.83 parts wt.

Procedure M (according to the invention).

MWCNT (diameter ~ 10 nm, ratio 1 / d ~ 160), SiO2 (90 nm) and SiC (200) were introduced into a mixture of xylene with butanol (weight ratio 8: 2) containing dissolved surfactant (polyether with nonylphenyl substituent). nm) and then the system was sonicated for 5 minutes at 90 ° C using an ultrasonic stirrer (24 kHz, 120 W / g) to obtain a dispersion with the following composition:

- carbon nanotubes: 2.5 parts weight,

- surfactant: 7.7 parts weight,

- silicon oxide: 18 parts weight,

- silicon carbide: 18 parts weight,

- xylene: 43 parts weight,

- butanol: 10.8 parts wt.

The prepared MWCNT dispersion was mixed with a mixture of epoxy resin based on bisphenol A (25,000 mPa · s), epoxy diluent (butanediol diglycidyl ether, 150 mPa · s), plasticizer, fillers, pigments, rheology modifier and solvents. A polymer composition denoted by the symbol M1 was obtained having the same composition as that denoted by L1.

Polymer compositions prepared according to procedures L and M were mixed with the hardener - triethylenetetramine in the amount of 7.16 parts. wt. The liquid adhesives were applied to the steel substrate (in order to assess the volume electrical resistivity in accordance with PN-E-04405) using a slot applicator. The samples were cured at ambient temperature for 14 days.

PL232 158 Β1

The dispersion conditions of carbon nanotubes and the electrical properties of the obtained adhesive are presented in Table 5.

Table 5

Sample symbol Stirrer power [W / g] ^a CNT content [wt%] ^b Volume resistivity '[Ω-m] ^e LI 250 1 7.5-10 ⁶ Comparative Ml 120 4.5-10 ^s

a - power per 1 g of dispersed carbon nanotubes;

b content in dry matter of the coating; c - for a test voltage of 10 V;

Example 6

The example shows the preparation of a carbon nanotube dispersion in white spirit using nanoparticle alumina as a dispersion aid and the application of the resulting carbon nanotube dispersion to a solvent based alkyd paint.

For comparative purposes, the composition was prepared in a manner known from the state of the art by adding Al2O3 nanoparticles after the sonication process.

Procedure N (comparative procedure).

Multi-walled carbon nanotubes (MWCNT; diameter ~ 10 nm, ratio 1 / d -160) were introduced into the white spirit, containing the dissolved surfactant (naphthyl-oligoxyethylene ether), and the system was sonicated for 30 minutes at 20 ° C for using an ultrasonic stirrer (24 kHz, 160 W / g). After the sonication process, the CNT dispersion was introduced into a mixture consisting of a medium-greasy alkyd resin solution in white spirit, filler (calcium carbonate), pigment (iron black), siccative (cobalt and zirconium), anti-skinning agent and aluminum oxide dispersion (average particle size 40 nm) ) in white spirit. The paint marked with the symbol N1 was obtained with the following composition:

- alkyd resin: 14.82 parts weight,

- white spirit: 58.17 parts weight,

- calcium carbonate: 0.4 parts weight,

- iron black: 2.16 parts weight,

- siccatives: 2.04 parts weight,

- anti-skinning agent: 0.52 part weight,

- surfactant: 2.09 parts weight,

- aluminum oxide, 20.92 parts weight,

- carbon nanotubes: 2.09 parts wt.

Procedure P (according to the invention).

MWCNT (-10 nm diameter, ratio 1 / d -160) and aluminum oxide (average particle size 40 nm) and aluminum oxide (average particle size 40 nm) were introduced into the white spirit, containing the dissolved surfactant (naphthyl-oligoxyethylene ether), and the system was sonicated for 30 minutes. at 10 ° C using an ultrasonic stirrer (24 kHz, 80 W / g) to obtain a dispersion with the following composition:

- carbon nanotubes: 5 pcs. weight,

- surfactant: 5 parts weight,

- aluminum oxide: 50 parts weight,

- white spirit: 40 parts wt.

The thus prepared MWCNT dispersion was added to a mixture of a medium fatty alkyd resin solution in white spirit with the filler, pigment, siccatives and anti-skinning agent mentioned in procedure N. As a result, the paint P1 was obtained with the same composition as composition N1.

The coating compositions prepared according to the procedures N and P were applied to the steel substrate (in order to evaluate the electrical resistivity according to PN-E-04405) using a slot applicator.

PL232 158 Β1

The dispersion conditions of carbon nanotubes and the electrical properties of the obtained coatings are presented in Table 6.

Table 6

Sample symbol Stirrer power [W / gP CNT content [wt%] ^b Volume resistivity [Ω-m] ^c NI comparative 160 5 1.0- JO ³ PI 80 7.3-10 ²

a - power per 1 g of dispersed carbon nanotubes;

b - dry matter content of the coating; c - for a test voltage of 10 V;

Example 7

The example shows the preparation of a dispersion of carbon nanotubes in water using nanoparticulate titanium oxide as a dispersion aid and the application of the obtained nanotube dispersion to an aqueous solution of polyvinyl alcohol.

For comparative purposes, the composition was obtained with the method known from the state of the art by adding TiO 2 nanoparticles after the sonication process.

Procedure R (comparative procedure).

Multi-walled carbon nanotubes (MWCNT; diameter ~ 20 nm, ratio 1 / d -100) were introduced into the water containing the dissolved surfactant (sodium dodecylbenzene sulphonate), and then the system was sonicated for 10 minutes at 40 ° C using an ultrasonic stirrer (24 kHz, 250 W / g). After the sonication process, the CNT dispersion was introduced into a mixture of an aqueous solution of polyvinyl alcohol (polymer content 10% by weight, viscosity 650 mPa.s), an aqueous dispersion of nanoparticles T1O2 (with an average particle size of 25 nm), water and a filler (silica). The paint marked with the symbol R1 was obtained with the following composition:

- water: 84.94 parts by weight,

- poly (vinyl alcohol): 7.04 parts weight,

- silica: 5.07 parts weight,

- surfactant: 0.05 parts weight,

- titanium oxide: 2.45 parts weight,

- carbon nanotubes: 0.49 parts wt.

Procedure S (according to the invention).

MWCNT (diameter -20 nm, ratio 1 / d -100) was introduced into the aqueous dispersion of nanoparticle T1O2 (25 nm), containing the dissolved surfactant (sodium dodecylbenzenesulfonate), and the system was sonicated for 10 minutes at 40 ° C with a stirrer ultrasonic (24 kHz, 120 W / g) to obtain a dispersion with the following composition:

- carbon nanotubes: 2 parts weight,

- surfactant: 0.02 parts weight,

- titanium oxide: 10 parts weight,

- water: 87.98 parts wt.

The thus prepared MWCNT dispersion was mixed with a mixture of an aqueous solution of polyvinyl alcohol (10 wt.%, 650 mPa · s), water and a filler. As a result, a polymer composition designated S1 with the same composition as composition R1 was obtained.

Polyvinyl alcohol compositions) prepared according to the procedures R and S were applied to a transparent substrate made of poly (ethylene terephthalate) with a slot applicator in order to obtain nanocomposite polymer films with a thickness of 40 μηΊ. The electrical volume resistivity of firns was tested (according to PN-E-04405). The conditions for dispersing carbon nanotubes with nanoparticle titanium oxide and the properties of polyvinyl alcohol films containing the dispersion of carbon nanotubes are summarized in Table 7.

PL232 158 Β1

Table 7

Sample symbol Stirrer power [W / g] * CNT content [wt%] ^h Volume resistivity [Qm] ^c R1 comparative 250 1 3.2-10 ⁶ SI 120 7.1 · 10 ⁵

a - power per I g of dispersed carbon nanotubes; b - content in the dry matter of the film; c - for a test voltage of 10 V;

Patent claims

Claims (3)

1. Polymer composition for metal, wood and plastic substrates, containing an epoxy and / or polyurethane and / or acrylic and / or alkyd binder and / or polyvinyl acetate and / or polyvinyl alcohol) and fillers and / or pigments and / or or dyes and / or plasticizers and / or co-solvents and / or defoamers and / or coalescents and / or catalysts and / or thickeners and / or biocides and carbon nanotubes, characterized in that it contains carbon nanotubes in the form of dispersions in water and / or liquids organic, where the amount of water and / or organic liquids in the total dispersion is from 39 to 99.4% by weight, the dispersion being obtained by ultrasonic dispersion, in the presence of a nanoparticulate dispersing aid with dielectric properties in the form of solid substances such as silicon oxide , and / or aluminum oxide and / or titanium oxide and / or cerium oxide and / or silicon carbide, in the form of a powder with particle sizes from 5 to 200 nm, the composite The content of carbon nanotubes in an amount of from 0.01 wt% to 5 wt% of the sum of all non-volatile components of the polymer composition, and the content of the dispersion aid in the dispersion of the carbon nanotubes is from 0.5 to 55 wt%. the mass of the entire dispersion of carbon nanotubes. 2. The polymer composition of claim 1 1, characterized in that it contains natural and synthetic fillers such as silica and silicates, aluminum oxide, iron oxides, calcium carbonate, calcium and magnesium carbonate, talc, kaolin, mica, barium sulphate, wollastonite, halloysite in an amount from 0.01% by weight up to 85% by weight of the sum of all non-volatile components of the polymer composition. 3. The polymer composition according to claim A composition according to claim 1, characterized in that it contains natural and / or synthetic pigments, such as aluminum and / or calcium and / or zinc and / or magnesium phosphate, titanium dioxide, iron oxides in an amount from 0.01% by weight to 85% by weight the sum of all non-volatile components of the polymer composition.