DE102014012736A1 - Polymeric materials based on polyurethanes, epoxy resins, polymeric siloxanes or silicones or thermoplastic polymers, process for their preparation and their use - Google Patents

Abstract

The invention relates to polymer materials based on polyurethanes, epoxy resins, polymeric siloxanes or silicones or thermoplastic polymers, a process for their preparation and their use. The object of the invention is now to provide a polymer material and a process for its preparation available whose color or color changed by the action of an electrical potential difference and an electric current. According to the invention, the object is achieved with polymer materials based on polyurethanes, epoxy resins, polymeric siloxanes or silicones or thermoplastic polymers, which are characterized in that polymers of the general formula PX- (S) -YF are contained, where P is a polymer fraction based on of P1 polyurethanes having active OH and / or NH, NH 2 groups, P2 epoxy resins having active OH and / or NH, NH 2 groups, P 3 polymeric siloxanes or silicones having active OH and / or NH, NH 2 Groups or P4 thermoplastic polymers having active OH and / or NH, NH 2 groups, S is a spacer based on S1 diisocyanates O = C =N-R 1 -N =C =O, where R 1 is alkyl, cycloalkyl, Aralkyl or aryl groups, or S2 diepoxides C2 (O) -R2-C2 (O), where R2 are alkyl, aralkyl, cycloalkyl and / or aryl groups, F is a dye bonded to S with active OH and / or NH, NH2 groups based on F1 triphenylmethane dyes F2 polyanilines F3 spiropyranes F4 anthraquinonefa X is a urethane group -NH-COO-, a urea group -NH-CO-N (R3, H) - or an ether group -O- and R3 is an alkyl, cycloalkyl and / or aryl group and Y is a urethane group -NH-COO-, a urea group -NH-CO-N (R3, H) - or an ether group -O-, wherein R3 is an alkyl, cycloalkyl and / or aryl group. and with uses as indicators of electric currents, creepage currents in electrical installations and effluent discharges from electrostatic charging.

Description

The invention relates to polymer materials based on polyurethanes, epoxy resins, polymeric siloxanes or silicones or thermoplastic polymers, a process for their preparation and their use.

Polymer-based indicators indicating the flow of electrical currents or potential differences due to color changes are not known. In particular, insulating materials such as potting compounds or the like., Which are used in electrical equipment for the protection of live parts and for the protection of persons use and are enabled by doping with certain compounds in the situation by color change the flow of electrical currents, such as breakdowns and leakage currents , not known.

Electroactive polymers are known. Electroactive polymers (EAP) are polymers which, when stimulated by an electric field, undergo changes in shape, size or shape. The most common applications of EAP of this material group are sensors or actuators, i. H. The materials are subject to considerable deformation, or even capacitors, solar cells, electromagnetic shielding, electrostatic or corrosion-inhibiting coatings or diodes for emitting radiation (usually light). Another area is artificial muscle. Color changes, which are due here to the effect of electrical currents are not described.

The coloring of polymers can be done in different ways, eg. B. simply by adding pigments to the polymer, by adding insoluble (usually organic dyes) to the polymer (see, eg. DE 69 53 0488 T2 ), by dissolving dyes in the polymer or a starting material for its preparation, by copolymerization of dyes having double bonds in polymers ( DE 2003384A ) or by reaction on the polymer. The dyeing of the polymer can also be carried out directly during the production, as shown by the example of dyed silk by feeding the silkworms with luminescent dyes ( US 2012/0039813 ).

Furthermore, a process for dyeing thermosets is known by using, with a polymeric liquid, reactive dyes which are incorporated into the resin to form covalent bonds ( US 4284729 A ).

For electrochromic plates and electrolytes are used, the discolourable metal oxides, eg. As tungsten trioxide, and metal ions ( US 5,379,146 ).

A flexible electrochromic arrangement based on polyaniline doped with dl-camphor-10-sulfonic acid and polystyrenesulfonic acid is described as a coloring electrode Li-Ming Huang, Cheng-Hou Chen, Ten-Chin Wen, Development and characterization of flexible electrochromic devices based on polyaniline and poly (3,4-ethylenedioxythiophene) -poly (styrene sulfonic acid) Electrochimica Acta, Volume 51, No. 26 , Pages 5858-5863 (2006) , Electrically conductive layers with a relatively long reaction time based on electrically conductive ferroelectric liquid crystal polymers are described in: K Artelj I. Drevensek-Olenik, Bertil Helgee, Lachezar Komitov, Switching of Electrically Commanded Alignment Layers Probed by Optical Second Harmonic Generation, Mol. Cryst. Liq. Cryst. 450 (1), 127-139 (2006) ,

Furthermore, electrically conductive gels are known, which may be colored by the nature of the polymers or added dyes and are referred to as intelligent materials, see, for. B. Toshihiro Hirai, Mitsuhiro Hirai, Electrically Induced Strain in Polymer Gel Swollen with Non-Ionic Organic Solvents, Polymer Sensors and Actuators, Macromolecular Systems - Materials Approach 2000, pp 245-258 , Furthermore, it is known that dyes which occur in the form of a base and a salt can discolor under the influence of electric current, for. Polyanilines such as emeraldine (the base is blue, the salt is green), see e.g. B. Jin-Chih Chiang, Alan G MacDiarmid, 'Polyaniline': Protonic acid doping of the emeraldine form to the metallic regime, Synthetic Metals, Volume 13, Issues 1-3, January 1986, Pages 193-205 , Furthermore, electrochromic arrangements based on polyanilines are known, see, for. B. Li-Ming Huang, Cheng-Hou Chen, Ten-Chin Wen, Development and characterization of flexible electrochromic devices based on polyaniline and poly (3,4-ethylenedioxythiophene) -poly (styrene sulfonic acid), Electrochimica Acta, Vol. 51, No 26, pages 5858-5863 ,

However, there are no known anhydrous or nonionic polymers that change their color under the action of an electric current and thus can be used to display electric current in the material, eg. For example, to indicate leakage currents, electrostatic charges or faulty circuits.

The object of the invention is now to provide a polymer material and a process for its preparation available whose color or color changed by the action of an electrical potential difference and an electric current.

According to the invention, the object is achieved with polymer materials based on polyurethanes, epoxy resins, polymeric siloxanes or silicones or thermoplastic polymers, which are characterized in that polymers of the general formula PX- (S) -YF are contained
P is a polymer fraction based on
P1 polyurethanes with active OH and / or NH, NH ₂ groups,
P2 epoxy resins with active OH and / or NH, NH ₂ groups,
P3 polymeric siloxanes or silicones having active OH and / or NH, NH ₂ groups or
P4 thermoplastic polymers with active OH and / or NH, NH ₂ groups,
S a spacer based on
S1 diisocyanates O = C = NR ¹ -N = C = O, where R ^{1 are} alkyl, cycloalkyl, aralkyl or aryl groups,
or S2 diepoxides C ² (O) -R ² -C ² (O), where R ^{2 are} alkyl, aralkyl, cycloalkyl and / or aryl groups,
F is a dye bonded to S with active OH and / or NH, NH ₂ groups based on
F1 triphenylmethane dyes
F2 polyanilines
F3 spiropyranes
F4 anthraquinone dyes or
F5 aniline colors
X is an urethane group -NH-COO-, a urea group -NH-CO-N (R ³ , H) - or an ether group -O- and R ^{3 is} an alkyl, cycloalkyl and / or aryl group and
Y is a urethane group -NH-COO-, a urea group -NH-CO-N (R ³ H) - or an ether group -O-, wherein R ³ is an alkyl, cycloalkyl and / or aryl group.

In addition, the object is achieved with a process for the preparation of the polymer materials characterized by monomers, oligomers, prepolymers and / or polymer constituents P1, P2 or P3 or of liquid polymers of polymer fractions P4 with a spacer S1 or S2 and with a dye F1, F2, F3 or F4 are mixed in the presence of catalysts and reacted between 20 and 200 ° C, wherein
P1 polyurethanes with active OH and / or NH, NH ₂ groups,
P2 epoxy resins with active OH and / or NH, NH ₂ groups,
P3 polymeric siloxanes or silicones having active OH and / or NH, NH ₂ groups or
P4 thermoplastic polymers with active OH and / or NH, NH ₂ groups,
S is a P-binding spacer based on
S1 diisocyanates O = C = N-R1-N = C = O, where R1 is alkyl, cycloalkyl, aralkyl and / or aryl groups, or
S2 diepoxides C2 (O) -R2-C2 (O), where R2 is alkyl, cycloalkyl, aralkyl and / or aryl groups,
F is an S-binding dye having active OH and / or NH, NH ₂ groups based on
F1 triphenylmethane dyes, F2 polyanilines, F3 spiropyranes,
F4 anthraquinone dyes or F5 aniline dyes
and
Catalysts are organotin compounds,
and with uses as indicators of electric currents, creepage currents in electrical installations and effluent discharges from electrostatic charging. Advantageous developments are specified in the subclaims.

Thereafter, 0.01 to 50 wt .-% polymers of the general formula P-X- (S) -Y-F in the polymer materials. P1 are linear or branched or crosslinked polyurethanes, to whose main chain the dye F is bound via the spacer S.

P4 are thermoplastic polymers having attached to the main chain hydroxyl groups such as polyvinyl alcohol, polyvinyl acetate or polyvinyl butyral, which are prepared by polymerization of vinyl acetate or mixtures with it and subsequent partial saponification and optionally acetalization.

P2 are epoxy resins based on bisphenol F diglycidyl ether, bisphenol F diglycidyl ether, cyclohexanedicarboxylic acid diglycidyl ether and diamines such as bis (2-aminoethyl) methylamine or isophoronediamine,
P3 are gel-like or elastic silicones with free hydroxyl groups.

S1 is toluylene-2,4-disocyanate, tolylene-2,6-disocyanate or mixtures thereof, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate or mixtures thereof, m-xylylene diisocyanate, p Xylylene diisocyanate or mixtures thereof, phenylene-1,4-diisocyanate, hexane-1,6-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, the biuret of hexane-1,6-diisocyanate, the symmetrical or asymmetric trimers of hexane 1,6-diisocyanate, the symmetrical or asymmetric trimers of 4,4'-dicyclohexylmethane diisocyanate and prepolymers of a diisocyanate and one or more diols of molecular weight 62 to 2000 are.

S2 are bis-3,3 '- [(2,3-epoxypropoxy) 4-phenyl] -propane or mixtures thereof with oligomers thereof (commercial bisphenol A diglycidyl ether types such as Araldite GY 2600, Araldite GY 6010, Araldite GY 6020, Araldite MY 790-1, Araldite LY 1556 etc.), higher molecular weight solid epoxy resins based on bisphenol A diglycidyl ether (commercial types such as Araldite GT 6097, Araldite GT 6243, Araldite GT 6248, Araldite GT 7013), Bis-3 , 3 '- [(2,3-epoxy-propoxy) 4-cyclohexyl] -propane or mixtures with Oligomers thereof (commercial Araldite GY 281, Araldite GY 282, Araldite GY 285, Araldite PY 306, Araldite PY 302 etc.), epoxy-phenol novolacs (commercial Araldite GY 289, Araldite EPN 1138, Araldite EPN 1139, Araldite EPN 1179, Araldite EPN 1180, Araldite EPN 9850, Araldite EPN 9880, Araldite EPN 9881, Araldite PY 307, etc.), epoxy cresol novolaks (commercial Araldite ECN 1273, Araldite ECN 1280, Araldite ECN 1299, Araldite ECN 9511, etc.), glycidyl Amine epoxy resins (eg, commercial Araldite MY 0500, Araldite MY 0510, Araldite MY 0600, Araldite MY 0610, Araldite MY 720, Araldite MY 721, Araldite MY 725, Araldite MY 9512, etc.), 1,6-naphthalenedicarboxylic acid -diglycidester or 1,6-naphthalene diglycidyl ether (commercially available, for example, Araldite MY 0816), dicyclopentadiene-based epoxides (commercially available, for example, Tactix 556, Tactix 756, etc.), cyclohexane-1,2-dicarboxylic acid diglycidyl esters or mixtures on the basis of which (commercially available, for example, Araldite CY 179, Araldite CY 184, Araldite CY 1 92, Araldite CY 5622, Araldite CY 9729, etc.), butane-1,4-diol diglcidyl ether, cyclohexane-dimethanol diglycidyl ether, mixtures of C ₁₀ to C ₁₈ diglycidyl ethers, neopentyl diglycidyl ether, hexahydrophthalic acid diglycidyl ether, 4-glycidyloxy-N, N-diglycidylaniline, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane-carboxylate, polytetrahydrofuran-diglycid-ether and addition products of diepoxides to a deficit or excess of di- and / or polyamines.

F1 are Solvent Blue 70, solvent violet 31, F2 emeraldine base, F3 spiro [4H-pyranoxindole] or 2'-amino-2 ', 5'-dioxo-5,6,7,8-tetrahydro-spiro [ chromen-4,3'-indoline] -3-carbonitrile and F4 Solvent Red 111, Solvent Red 149, Solvent Red 172, Solvent Red 168, Solvent Red 207, Solvent Red 19, Solvent Blue 59, Solvent Blue 101, Solvent Blue 68 , Solvent Blue 78, Disperse Violet 17, Solvent Violet 12, Solvent Violet 14, Solvent Violet 26, Solvent Orange 86 and F5 Solvent Black 5 or Solvent Black 7.

In advantageous developments P1 is a weakly crosslinked polyurethane based on polyether alcohols of molecular weight 1000 to 6000, one or more chain extenders such as butane-1,4-diol, dipropylene glycol, 2-ethyl-1,3-hexanediol or 1,6-hexanediol , an organotin catalyst and a trimerized aliphatic or cycloaliphatic diisocyanate, S1 is an aliphatic or cycloaliphatic diisocyanate and F is selected from the group F1 to F5,
P4 is a polyvinyl butyral having 0.01 to 12% hydroxyl groups on the chain, S1 is a prepolymer of a diisocyanate and one or more diols and F is selected from the group F1 to F5,
P3 is a silicone composed of dichlorosilane building blocks of the formula Cl ₂ SiR ₂ , where R is identical or different alkyl, cycloalkyl, aralkyl or (optionally substituted) aryl groups. In further embodiments, P3 is a siloxane composed of dichlorosilane building blocks of the formula Cl ₂ Si (OR ₂ ), where R is identical or different alkyl, cycloalkyl, aralkyl or (optionally substituted) aryl groups,
P3 is a gelatinous or elastic, crosslinked silicone, S1 is a prepolymer selected from a diisocyanate and one or more diols and F is selected from the group F1 to F5 and
P2 is an amine-cured epoxy resin based on a diepoxide and one or more diamines, S2, a diepoxide such as butane-1,4-diol-diglcidether, cyclohexane dimethanol diglycidyl ether, mixtures of C ₁₀ to C ₁₈ diglycidyl ethers, neopentyl diglycidyl ether, hexahydrophthalic acid -diglycidyl ether and F is selected from the group F1 to F5.

• (a) von Diisocyanaten und Diolen und ggf. Triolen,
• (b) von Umsetzungsprodukten von Diisocyanaten mit Wasser (Biuretisocyanate),
• (c) von teilweise symmetrisch oder asymmetrisch trimerisierten Isocyanaten und als flüssige Polymere von Polymeranteilen P werden PVB in der Schmelze mit 1 ppm bis 5% eines Farbstoffs F1 bis F5 versetzt und anschließend mit S1 Spacern in Form von Prepolymeren aus Diisocyanaten und einem oder mehreren Diolen und Katalysatoren umgesetzt.

Als Monomere werden weiterhin Diepoxyde, Diamine oder Dicarbonsäureanhydride, als Oligomere Prepolymere auf der Basis

• (d) von Diepoxyden mit Diaminen oder Dicarbonsäureanhydriden,
• (e) Reaktionsprodukte der Diepoxyde aus der Herstellung mit einem Anteil an Oligomeren

eingesetzt.The inventive method has various advantageous developments. Thereafter, the dye F is dissolved in an amount of 1 ppm to 5% in one or more reaction components. In a further embodiment, monomers are diisocyanates, diols, polyether alcohols or diamines,
Oligomers are prepolymers based

• (a) of diisocyanates and diols and optionally triols,
• (b) reaction products of diisocyanates with water (biuretisocyanates),
• (c) of partially symmetrically or asymmetrically trimerized isocyanates and as liquid polymers of polymer fractions P PVB in the melt with 1 ppm to 5% of a dye F1 to F5 are added and then with S1 spacers in the form of prepolymers of diisocyanates and one or more diols and catalysts implemented.

Other monomers used are diepoxides, diamines or dicarboxylic acid anhydrides, based on prepolymers based on oligomers

• (d) diepoxides with diamines or dicarboxylic acid anhydrides,
• (e) reaction products of Diepoxyde from the production with a proportion of oligomers

used.

An embodiment is characterized in that
the starting material is mixed with other components including the components participating in the following reactions,
other additives such as catalysts and / or fillers, in particular nanoscale fillers, are incorporated into this mixture and
this mixture is reacted with one or more spacer diisocyanates or diepoxides,
whereby a colored polymer is formed with dye molecules bound via spacers in the side chain. In one embodiment of the method according to the invention are in a mixture of Polyether alcohols and diols 1 ppm to 5% of the dye F dissolved in this mixture 1 ppm to 1% of a catalyst is mixed and this mixture is reacted with a diisocyanate as a spacer. In a further development, the diisocyanate is a prepolymer of a diisocyanate and a diol. In a further embodiment, reactive components such as diols, triols, di- or polyamines are mixed before further reaction. A development is characterized in that the dyes are dissolved in a reaction component.

Polymers are used on whose main and / or side chains or on the chains of crosslinked polymers are attached via a spacer dye molecules having a functional group reactable with a reactive group of the spacer, the dye molecules must form at least two modifications having different colors , which can be generated by an electric current.

Surprisingly, it has been found that certain dye molecules bound to polymer chains react to electrical stimulation when the coloring structure is not limited in its response to external agents. Such dyes are z. For example, those, in addition to the aromatic system at least one functional group, eg. A hydroxyl, amino, epoxy or thiol group, which in turn is capable of reacting with another species having a reactive group, e.g. B. an isocyanate, carboxyl, epoxy or silane grouping. At least one further group is located on the polymer chain, which in turn reacts with a group of the spacer, so that the dyes are bound directly to the macromolecular chain via the spacer.

In one embodiment, triphenylmethane dyes having a functional group, e.g. As crystal violet, dissolved in a mixture of polyether alcohols and short-chain diols and this solution optionally reacted in the presence of catalysts with di- and / or polyisocyanates, so that polyurethane gels, polyurethane elastomers or polyurethane casting compounds are formed. These usually have the color of the present in amounts of 1 ppm to 5% dye. By applying a voltage of 0.1 to 1000 V, the color changes from red to green depending on the voltage level.

In another embodiment, polyanilines, e.g. B. emeraldine base, leucoemeraldine or nigraniline, dissolved in a mixture of polyether alcohols and short-chain diols and this solution optionally reacted in the presence of catalysts with di- and / or polyisocyanates, so that polyurethane gels, polyurethane elastomers or polyurethane casting compounds be formed. These usually have the color of the present in amounts of 1 ppm to 5% dye. By applying a voltage of 0.1 to 1000 V, the color changes from brown to yellow depending on the voltage level.

In a further embodiment, spiropyranes functionalized with hydroxyl or amino groups are dissolved in a mixture of polyether alcohols and short-chain diols and this solution is optionally reacted with di- and / or polyisocyanates in the presence of catalysts, so that polyurethane gels, polyurethane elastomers or polyurethane -Vergussmassen be formed. These usually have the color of the present in amounts of 1 ppm to 5% dye. By applying a voltage of 0.1 to 1000 V, the color changes from reddish to green-yellow depending on the voltage level. Of the spiropyrans their thermochromic or phorochromic properties are known, however, the dependence of color by electric current has not been detected.

In another embodiment, hydroxylated or amino-functionalized spiropyrans or polyanilines are adsorbed onto nanoscale metal oxides (the adsorption can be carried out in aqueous solution or by vapor deposition) and these coated nanoparticles are dissolved in a mixture of polyether alcohols and short-chain diols and this solution is optionally present of catalysts reacted with di- and / or polyisocyanates, so that polyurethane gels, polyurethane elastomers or polyurethane casting compounds are formed. These usually have the color of the present in amounts of 1 ppm to 5% dye. By applying a voltage of 0.1 to 1000 V, the color of the metal oxides coated with spiropyranes changes from reddish to green-yellow depending on the voltage level of the polyaniline-coated metal oxides in brownish to dark yellow depending on the voltage. As metal oxides, aluminum oxide, aluminum oxide hydroxide, magnesium oxide, zinc oxide, indium zinc oxide having a maximum particle diameter diameter of 2 to 200 nm can be used for this embodiment of the process according to the invention.

In a further embodiment, one of the dyes mentioned in a low molecular weight diol, z. As butane-1,4-diol or hexane-1,6-diol or 2-ethyl-1,3-hexanediol, dissolved, incorporated this solution in PVB at a temperature of 60 to 200 ° C and kneading or in the reaction extruder this mixture with one or more di- and / or polyisocyanates, preferably so-called. prepolymers of di- or triisocyanates and diols of molecular weight 62 to 2000 or and diaminopolyethers of the molecular weight 200 to 2500, reacted at temperatures of 140 to 220 ° C within 15 s to 15 min. This gives a dyed with the respective color of the dye base polymer with shape memory properties. When a voltage of 0.1 to 1000 V is applied, the color of the colored polymers changes markedly.

In another embodiment, functionalized with hydroxyl or amino spiropyranes or triphenylmethane dyes having a functional group, eg. Crystal violet, in a natural oil having functional groups, e.g. As castor oil, or in a functionalized oil, for. B. epoxidized castor oil or epoxidized soybean oil and short-chain diols and this solution optionally reacted in the presence of catalysts with di- and / or polyisocyanates, so that polyurethane gels, polyurethane elastomers or polyurethane casting compounds are formed. These usually have the color of the present in amounts of 1 ppm to 5% dye. By applying a voltage of 0.1 to 1000 V, the color changes from red to green depending on the voltage level.

In another embodiment, functionalized with hydroxyl or amino spiropyranes or triphenylmethane dyes having a functional group, eg. Crystal violet, in a natural oil having functional groups, e.g. As castor oil, or in a functionalized oil, for. As epoxidized castor oil or epoxidized soybean oil, and these mixtures to Epoxydharzkomponenten (usually to the resin component) added and cured with the respective hardener.

In another embodiment, functionalized with hydroxyl or amino functional spiropyranes or triphenylmethane dyes having a functional group in the resin component of an epoxy resin system, for. As bisphenol A diglycidyl ether, hexahydrophthalic diglycidester, bisphenol F diglycidyl ether, etc., dissolved with 1 ppm to 5 wt .-% and this mixture then with the hardener, z. Example, an amine hardener such as dipropylene triamine, bis (4-amino-cyclohexyl) methane, isophorone diamine or an acid hardener such as hexahydrophthalic, hexahydrophthalic anhydride, hexahydroendomethylene phthalic acid, hexahydroendomethylene phthalic anhydride, etc., reacted to form an epoxy resin composition which when applied a voltage with color change reacts.

The compositions of the invention can be used as such, as potting compounds, coatings or cellular materials for the isolation of electrical components, cables, electronic components, assemblies, etc. In case of an error, e.g. B. a short circuit or a Spnnungsleckage, this is visible in the component by a color change, so that the location of the repair requirement can be located quickly and clearly.

embodiments

example 1

In a mixer with an anchor stirrer and a volume of 0.36 m ³ 5.6 kg of dipropylene glycol and 25 kg of polypropylene glycol 2000 (Lupranol ^® 1000 from BASF AG) are initially introduced, beschleiert with nitrogen and the stirrer started. To this mixture are added 0.4 kg dibutyltin bis (2-ethylhexyl thioglycolate) and 0.4 kg Solvent Red 111 (F4). The mixture is stirred for 2 hours at 60 min ^-1 . Thereafter, to this mixture a further 175 kg of polypropylene glycol (P1) are added to 2000 (Lupranol ^® 1000 from BASF AG) and stirred for a further three hours under nitrogen veil. 25 kg of the premix thus prepared are filled into the reservoir for the A component of a Isotherm ^® mixer, into the reservoir of the B component 15 kg of polyphenyl-polymethylene-polyisocyanate (polymer-MDI, p-MDI) (Lupranat ^® M20 S from BASF AG) (S1). The mixing ratio of the Isotherm ^® mixer is set to 100: 11 and the machine started. It is dispensed via a static mixer in PTFE molds. A red-dyed polyurethane elastomer of Shore 0 hardness 35 is obtained. When 1 V of direct voltage is applied, the elastomer turns purple within 30 minutes, dark green at 10 V, green at 30 V.

Example 2

In a 5 liter dissolver, 100 g of Emeraldine base (F2) are dissolved in 2.5 kg of hexane-1,6-diol under nitrogen at 160 min ^-1 in 30 min. In a kneading chamber of 350 ml content, 180 g of polyvinyl butyral (PVB) (P4) are added and melted at 170 ° C. To the PVB is added 0.25 g of dibutyltin bis (2-ethylhexyl thioglycolate), 1.25 g of nanoscale alumina hydroxide (average particle diameter 12 nm) and 17.5 g of the solution prepared above. The mixture is kneaded at 170 ° C for 60 minutes. To the mixture are added 22.5 g of a prepolymer (S1) prepared from 4,4'-diphenylmethane diisocyanate and tripropylene glycol with 27.5% NCO content and kneaded for a further 15 minutes. The hot mixture is placed in a PTFE mold to form a 4 mm thick plate. A brown colored polymer of Shore A hardness 67 is obtained. When 1 V of direct voltage is applied, the polymer turns reddish brown within 30 minutes, dark red at 10 V, deep red in color at 30 V.

Example 3

20 g of Emeraldine base (F2) are dissolved in 1.5 kg of epoxidized soybean oil (S2) under nitrogen at 30 ° C. in a 5 l dissolver at 160 min ^-1 in 30 min. 2.5 g of the mixture are added to 250 g of 4-epoxycyclohexanemethyl-3,4-epoxycyclohexanecarboxylate (P2) and mixed for 30 minutes at 120 min ^-1 . To this mixture is added 100 g of a mixture of isophoronediamine and benzenedimethanamine. This mixture is poured into PTFE molds of 200 × 200 × 4 mm and then cured at 120 ° C for 4 hours. A light brown colored polymer plate of Shore D hardness 41 is obtained. When 1 V of DC voltage is applied, the polymer turns brown within 30 minutes, dark brown at 10 V, dark red at 30 V.

Example 4

The experiment of Example 3 is repeated with 2'-amino-2 ', 5'-dioxo-5,6,7,8-tetrahydro-spiro [chromen-4,3'-indoline] -3-carbonitrile (F3). It is worked under the same conditions. A light brown colored polymer plate of Shore D hardness 42 is obtained. When 1 V of DC voltage is applied, the polymer turns to a deeper brown within 30 minutes, dark brown at 10 V, dark red to 30 V in voltage.

Example 5

In a dissolver at 1000 g Geniosil ^® XL 70 (Wacker AG) (P3) 7 (F5) dissolved 8 g Solvent Black at 45 ° C under nitrogen. To 200 g Silres ^® BS 66 (Wacker AG) (P3) are added 10 g of this solution and 3.7 g of the prepolymer of Example 2 (S1) and mixed thoroughly. The mixture is poured onto a PTFE plate to a 4 mm layer and cured under air humidity in 24 hours. A gray-colored polymer plate of Shore A hardness 74 is obtained. When 1 V DC is applied, the polymer turns gray-blue within 30 minutes, dark blue at 10 V, dark blue at 30 V.

Example 6

To 200 g of the silicone resin Silres H62C ^® (Wacker AG) (P3) are added 5 g of the solution from Example 5 and 3.7 g of the prepolymer of Example 2 (S1) and in the kneader at 45 ° C for 30 min mixed. The resulting mixture is placed in a PTFE mold and cured at 145 ° C for 6 hours. A gray colored Shore A hardness 86 polymer plate is obtained. When 1 V DC is applied, the polymer turns gray-blue within 30 minutes, dark blue at 10 V, dark blue at 30 V.

Example 7

In a 5 l volume dissolver, 0.19 kg of Solvent Blue 70 (F1) are dissolved in 2.7 kg of 2-ethyl-1,3-hexanediol and then 0.8 kg of dibutyltin bis (2-ethylhexyl thioglycolate) are added. It is stirred for 4 hours. This solution is 2000, a mixer of 350 l capacity with anchor stirrer 96.5 kg of polypropylene glycol (Lupranol ^® 1000 from BASF AG) (P1) was slowly added under stirring and nitrogen veil. 25 kg of the premix thus prepared are filled into the reservoir for the A component of a Isotherm ^® mixer, in the reservoir of the B component 15 kg of a 1:10 - mixture of hexane-1,6-diisocyanate (S1) and trimerized hexane-1,6-diisocyanate (Desmodur ^® N3600 from Bayer AG) is filled. The mixing ratio of the Isotherm ^® mixer is set to 100: 15 and the machine started. It is dispensed via a static mixer in PTFE molds. A light blue polyurethane elastomer of Shore 00 hardness 30 is obtained. When 1 V of direct voltage is applied, the elastomer turns purple within 30 minutes, dark red at 10 V, and red at 30 V.

Example 8

In a 5 l volume dissolver, 0.15 kg of solvent violet 31 (F1) are dissolved in 3.8 kg of dipropylene glycol and then 0.15 kg of dibutyltin bis (2-ethylhexyl thioglycolate) are added. It is stirred for 4 hours. This solution is added to a mixer of 350 l capacity with anchor stirrer to 73.5 kg of castor oil (P1) and further to 9.6 kg of polypropylene glycol 2000 (Lupranol ^® 1000 from BASF AG), 8.0 kg Caradol 585 ^® (P1) added slowly with stirring and nitrogen veil. 25 kg of the premix thus prepared are filled in the reservoir for the A-component of an isothermal ^® blender, into the reservoir of the B-component contains 15 kg of polymeric MDI (Lupranat M20S ^® from BASF AG) (S1) is filled. The mixing ratio of the Isotherm ^® mixer is set to 100: 50 and the machine started. It is dispensed via a static mixer in PTFE molds. A blue violet colored polyurethane casting resin of Shore D hardness 50 is obtained. When 1 V of direct voltage is applied, the elastomer turns green-blue within 30 minutes, red at 10 V, red-violet at 30 V.

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 69530488 T2 [0004]
• DE 2003384A [0004]
• US 2012/0039813 [0004]
• US 4284729 A [0005]
• US 5379146 [0006]

Cited non-patent literature

• Li-Ming Huang, Cheng-Hou Chen, Ten-Chin Wen, Development and characterization of flexible electrochromic devices based on polyaniline and poly (3,4-ethylenedioxythiophene) -poly (styrene sulfonic acid) Electrochimica Acta, Volume 51, No. 26 , Pages 5858-5863 (2006) [0007]
• K Artelj I. Drevensek-Olenik, Bertil Helgee, Lachezar Komitov, Switching of Electrically Commanded Alignment Layers Probed by Optical Second Harmonic Generation, Mol. Cryst. Liq. Cryst. 450 (1), 127-139 (2006) [0007]
• Toshihiro Hirai, Mitsuhiro Hirai, Electrically Induced Strain in Polymer Gel Swollen with Non-Ionic Organic Solvents, Polymer Sensors and Actuators, Macromolecular Systems - Materials Approach 2000, pp. 245-258 [0008]
• Jin-Chih Chiang, Alan G MacDiarmid, 'Polyaniline': Protonic acid doping of the emeraldine form to metallic regime, Synthetic Metals, Volume 13, Issues 1-3, January 1986, Pages 193-205 [0008]
• Li-Ming Huang, Cheng-Hou Chen, Ten-Chin Wen, Development and characterization of flexible electrochromic devices based on polyaniline and poly (3,4-ethylenedioxythiophene) -poly (styrene sulfonic acid), Electrochimica Acta, Vol. 51, No 26, pages 5858-5863 [0008]

Claims (17)

Polymer materials based on polyurethanes, epoxy resins, polymeric siloxanes or silicones or thermoplastic polymers, characterized in that polymers of the general formula PX- (S) -YF are contained, wherein P is a polymer fraction based on P1 polyurethanes with active OH and / or NH, NH ₂ groups, P2 epoxy resins having active OH and / or NH, NH ₂ groups, P3 polymeric siloxanes or silicones having active OH and / or NH, NH ₂ groups or P4 thermoplastic polymers with active OH and / or NH, NH ₂ groups, S is a spacer based on S1 diisocyanates O = C =NR ¹ -N =C =O, where R ^{1 is} alkyl, cycloalkyl, aralkyl or aryl groups or die dieoxides C2 (O) -R ² -C ² (O), where R ^{2 are} alkyl, aralkyl, cycloalkyl and / or aryl groups, F is a dye bonded to S with active OH and / or NH- , NH ₂ groups based on F1 triphenylmethane dyes, F2 polyanilines, F3 spiropyranes, F4 anthraquinone dyes or F5 aniline dyes, X is an Ur ethane group -NH-COO-, a urea group -NH-CO-N (R ³ , H) - or an ether group -O- and R ^{3 is} an alkyl, cycloalkyl and / or aryl group and Y is a urethane group -NH-COO -, a urea group -NH-CO-N (R ³ , H) - or an ether group -O-, wherein R ^{3 is} an alkyl, cycloalkyl and / or aryl group are. Polymer materials according to claim 1, characterized in that 0.01 to 50 wt .-% polymers of the general formula PX- (S) -YF are included. Polymer materials according to claim 1 or 2, characterized in that P1 are linear or branched or crosslinked polyurethanes, to whose main chain the dye F are bonded via the spacer S, that P4 are thermoplastic polymers having attached to the main chain hydroxyl groups such as polyvinyl alcohol, polyvinyl acetate or polyvinyl butyral prepared by polymerization of vinyl acetate or mixtures therewith and subsequent partial saponification and optionally acetalization, that P2 epoxy resins based on bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, cyclohexanedicarboxylic acid diglycidyl ether and diamines such as bis (2) Aminoethyl) -methylamine or isophoronediamine, and that P3 are gel-like or elastic silicones with free hydroxyl groups. Polymer materials according to one of claims 1 to 3, characterized in that S1 is toluene-2,4-disocyanate, tolylene-2,6-disocyanate or mixtures thereof, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2 'Diphenylmethane diisocyanate or mixtures thereof, m-xylylene diisocyanate, p-xylylene diisocyanate or mixtures thereof, phenylene-1,4-diisocyanate, hexane-1,6-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, the biuret of hexane-1, 6-diisocyanate, the symmetrical or asymmetric trimers of hexane-1,6-diisocyanate, the symmetrical or asymmetric trimers of 4,4'-dicyclohexylmethane diisocyanate, that S1 are prepolymers of a diisocyanate and one or more diols of molecular weight 62 to 2000, S2 bis-3,3 '- [(2,3-epoxypropoxy) 4-phenyl] -propane or mixtures thereof with oligomers thereof (commercial bisphenol A diglycidyl ether types such as Araldite GY 2600, Araldite GY 6010, Araldite GY 6020, Araldite MY 790-1, Araldite LY 1556, etc.), hi hermolecular solid epoxy resins based on bisphenol A diglycidyl ether (commercial types such as Araldite GT 6097, Araldite GT 6243, Araldite GT 6248, Araldite GT 7013), bis-3,3 '- [(2,3-epoxy-propoxy) 4- cyclohexyl] -propane or mixtures thereof with oligomers thereof (commercial Araldite GY 281, Araldite GY 282, Araldite GY 285, Araldite PY 306, Araldite PY 302 etc.), epoxy phenol novolaks (commercial Araldite GY 289, Araldite EPN 1138, Araldite EPN 1139, Araldite EPN 1179, Araldite EPN 1180, Araldite EPN 9850, Araldite EPN 9880, Araldite EPN 9881, Araldite PY 307 etc.), epoxy cresol novolaks (commercial Araldite ECN 1273, Araldite ECN 1280, Araldite ECN 1299, Araldite ECN 9511, etc.), glycidyl amine epoxy resins (e.g. Commercially available Araldite MY 0500, Araldite MY 0510, Araldite MY 0600, Araldite MY 0610, Araldite MY 720, Araldite MY 721, Araldite MY 725, Araldite MY 9512, etc.), 1,6-naphthalenedicarboxylic acid diglycide ester, and 1.6, respectively Naphthalene diglycidyl ethers (commercially available, for example, Araldite MY 0816), dicyclopentadiene-based epoxies (commercially available, for example, Tactix 556, Tactix 756, etc.), cyclohexane-1,2-dicarboxylic acid diglycidyl esters, or mixtures based thereon (commercially available, for example, from US Pat. Araldite CY 179, Araldite CY 184, Araldite CY 192, Araldite CY 5622, Araldite CY 9729, etc.), butane-1,4-diol diglycidyl ether, cyclohexane-dimethanol diglycidyl ether, mixtures of C ₁₀ to C ₁₈ diglycidyl ethers, Neopentyl diglycidyl ether, hexahydrophthalic acid diglycidyl ether, 4-glycidyloxy-N, N-diglycidylaniline, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane-carboxylate, polytetrahydrofuran diglycidyl ether, and S2 Addition products of Diepoxyden to a deficit or excess of di- and / or polyamines. Polymer materials according to one of claims 1 to 4, characterized in that F1 Solvent Blue 70, solvent violet 31, F2 emeraldine base, F3 spiro [4H-pyranoxindole] or 2'-amino-2 ', 5'-dioxo 5,6,7,8-tetrahydro-spiro [chromen-4,3'-indoline] -3-carbonitrile and F4 Solvent Red 111, Solvent Red 149, Solvent Red 172, Solvent Red 168, Solvent Red 207, Solvent Red 19 , Solvent Blue 59, Solvent Blue 101, Solvent Blue 68, Solvent Blue 78, Disperse Violet 17, Solvent Violet 12, Solvent Violet 14, Solvent Violet 26, Solvent Orange 86 and F5 Solvent Black 5 or Solvent Black 7 are. Polymer materials according to one of claims 1 to 5, characterized in that P1 is a weakly crosslinked polyurethane based on polyether alcohols of molecular weight 1000 to 6000, one or more chain extenders such as butane-1,4-diol, dipropylene glycol, 2-ethyl-1, 3-hexanediol or 1,6-hexanediol, an organotin catalyst and a trimerized aliphatic or cycloaliphatic diisocyanate, S1 is an aliphatic or cycloaliphatic diisocyanate and F is selected from the group F1 to F5, P4 is a polyvinyl butyral with 0.01 to 12% hydroxyl groups the chain, S1 is a prepolymer of a diisocyanate and one or more diols and F is selected from the group F1 to F5, that P3 is a silicone composed of dichlorosilane building blocks of the formula Cl ₂ SiR ₂ , where R is identical or different alkyl, Cycloalkyl, aralkyl or (optionally substituted) aryl groups, is that P3 is a siloxane, built up from dichlorosilane building blocks of the formula Cl ₂ Si (OR ₂ ), where i R is the same or different alkyl, cycloalkyl, aralkyl or (optionally substituted) aryl groups, is that P3 is a gel-like or elastic, crosslinked silicone, S1 is a prepolymer of a diisocyanate and one or more diols and F is selected from the group F1 to F5 and P2 is an amine-hardened epoxy resin based on a Diepoxyds and one or more diamines, S2 is a Diepoxyd as butane-1,4-diol diglcidether, cyclohexane-dimethanol diglycidether, mixtures of C ₁₀ to C ₁₈ diglycidyl ethers, neopentyl diglycidyl ether, hexahydrophthalic diglycidyl ether and F from the group F1 to F5 is selected. Process for the preparation of polymer materials based on polyurethanes, epoxy resins, polymeric siloxanes or silicones or thermoplastic polymers according to Claims 1 to 6, characterized in that monomers, oligomers, prepolymers and / or liquid polymers of polymer proportions P1, P2, P3 or P4 mixed with a spacer S1 or S2 and with a dye F1, F2, F3 or F4 in the presence of catalysts and reacted between 20 and 200 ° C, wherein P1 polyurethanes having active OH and / or NH, NH ₂ groups, P2 epoxy resins with active OH and / or NH, NH ₂ groups, P3 polymeric siloxanes or silicones with active OH and / or NH, NH ₂ groups or P4 thermoplastic polymers with active OH and / or NH-, NH ₂ groups, S is a spacer based on S1 diisocyanates O = C = N-R1-N = C = O, where R1 is alkyl, cycloalkyl, aralkyl and / or aryl groups, or S2 diepoxides C2 (O ) -R2-C2 (O), where R2 is alkyl, cycloalkyl, aralkyl and / or aryl groups si nd, F is an S-binding dye having active OH and / or NH, NH ₂ groups based on F1 triphenylmethane dyes F2 polyanilines F3 spiropyranes or F4 anthraquinone dyes F5 and catalysts are organotin compounds. A method according to claim 7, characterized in that the dye F is dissolved in an amount of 1 ppm to 5% in one or more reaction components. A method according to claim 7 or 8, characterized in that as monomers diisocyanates, diols, polyether alcohols or diamines as oligomers prepolymers based on (f) of diisocyanates and diols and optionally triols, (g) of reaction products of diisocyanates with water (biuretisocyanates) , (h) of partially symmetrically or asymmetrically trimerized isocyanates and added as liquid polymers of polymer moieties P ... - - that PVB is melt-blended with 1 ppm to 5% of a dye F1 to F5 and then reacted with S1 Spacers in the form of prepolymers of diisocyanates and one or more diols and catalysts containing as monomers diepoxides, diamines or dicarboxylic anhydrides, as oligomers prepolymers based on (i) diepoxides with diamines or dicarboxylic acid anhydrides, (j) reaction products of diepoxides from the preparation with be used a proportion of oligomers. Method according to one of claims 7 to 9, characterized in that this starting material is mixed with other components including participating in the following reactions components, other additives such as catalysts and / or fillers, in particular nanoscale fillers are incorporated into this mixture and this mixture with one or more acting as a spacer diisocyanates or diepoxides is reacted, whereby a colored polymer is formed with spacer molecules in the side chain bonded dye molecules, that PVB is added in the melt with 1 ppm to 5% of a dye F1 to F5 and then reacted with S1 Spacers in the form of prepolymers of diisocyanates and one or more diols and catalysts. Method according to one of claims 7 to 10, characterized in that in a mixture of polyether alcohols and diols 1 ppm to 5% of the dye F are dissolved in this mixture 1 ppm to 1% of a catalyst is mixed and this mixture with a diisocyanate as Spacer is implemented. Method according to one of claims 7 to 11, characterized in that the diisocyanate is a prepolymer of a diisocyanate and a diol. A method according to claim 7, characterized in that they are mixed with other reactive components such as diols, triols, di- or polyamines prior to further reaction. Polymer materials with color-changing property according to claim 1, characterized in that the dyes are dissolved in a reaction component. Use of the materials according to claim 1 as indicators of electrical currents. Use of the materials according to claim 1 as indicators of leakage currents in electrical installations. Use of the materials according to claim 1 as an indicator of effluent streams from electrostatic charging.