DE102012010766A1 - Plastic material, useful in molding and fire protection coating, comprises a binder made from polymer, and an energetic compound with positive linkage enthalpy, where the compound is decomposed exothermically under the influence of heat - Google Patents

Abstract

Fire-stable plastic material comprises a binder made from at least one polymer, and 0.1-15 mass% of at least an energetic compound with positive linkage enthalpy, where the compound is decomposed exothermically under the influence of heat, without undergoing a chemical reaction with other potential reaction partners in order to before-damage the polymer structure of the binder.

Description

The invention relates to a fire-resistant plastic material which contains a binder of at least one polymer.

Fire-resistant plastic materials are widely used to minimize a risk of fire, especially in the construction sector, where they are used on the one hand in the form of coating materials, on the other hand as moldings, for example in the form of components. The polymer matrix of such fire-resistant plastic materials usually contains one or more flame retardants, which may comprise a multiplicity of substances which unfold a different chemical and / or physical action.

Thus, the chemical protective effect of some conventional flame retardants based on the one hand by in the pyrolysis of the flame retardant released gases, which are capable of trapping the radicals in the gas phase radical scavengers and thereby inhibit the radical chain mechanism of the combustion process, the so-called gas phase mechanism.

On the other hand, the chemical protective effect of some conventional flame retardants based on the fact that the flame retardant causes at least surface enhanced carbonization of the polymer matrix and in this way a kind of protective layer of carbonized material is constructed, which prevents the ingress of oxygen and heat and thus also inhibits the combustion process. Such a protective layer can be formed in particular as a result of the so-called Intumeszenzeffektes, accordingly a voluminous, insulating foam layer is constructed. Such flame retardants usually comprise a foam-forming filler combination of a carbon source, a catalyst and a blowing agent. However, in order for the desired "protective foam" to form, the polymer matrix must soften or degrade over a very narrow temperature range, severely limiting the use of intumescent flame retardants. In addition, crosslinkable polymer binders, in particular, considerably inhibit the desired foam formation, with the result that virtually exclusively epoxy resins (EP) or intumescent gel coats based on epoxy resins and polyesters (PE) have existed hitherto. On the other hand, the polymeric binder material often has to be resistant to water and weathering and, in particular in industrial applications, often has further individual requirements, such as the prevention of electrostatic charging of fire-protected components, which additionally complicates the selection of suitable binder materials.

Another - both chemical and physical - effect of conventional flame retardants is based on the cooling of the potential combustion zone by flame retardants decomposing endothermically in the event of fire, ideally below a temperature required to maintain the combustion process.

Another - also chemical and physical - effect of conventional flame retardants is that the latter release in the case of fire largely inert, non-combustible gases and dilute the combustible gases in this way.

The above-mentioned conventional flame retardants can be subdivided in this case mainly in halogen-containing and halogen-free means in chemical terms. The former include z. As polybrominated diphenyl ethers such as decaBDE, tetrabromobisphenol-A (TBBPA) or hexabromocyclodecane (HBCD) and derivatives thereof. Halogen-free flame retardants in particular include organic and inorganic phosphorus compounds, such as TCEP (tris (chloroethyl) phosphate), TCPP (tris (chloropropyl) phosphate), TDCPP (tris (dichloroisopropyl) phosphate), TPP (triphenyl phosphate), TEHP (tris (2-ethylhexyl) phosphate), TKP (tricresyl phosphate), ITP (isopropylated triphenyl phosphate), mono-, bis- and tris (isopropylphenyl) phosphates of different isopropylation grade, RDP (resorcinol bis (diphenyl phosphate)), BDP (bisphenol A bis (diphenyl phosphate)), ammonium phosphate (NH ₄ ) ₃ PO ₄ ) and the like, nitrogen-based flame retardants such as urea, melamine and the like, as well as metal oxides, hydroxides or salts, boron, zinc and silicon compounds such as aluminum hydroxide (Al (OH) ₃ , "Aluminum trihydrate ATH"), magnesium hydroxide (Mg (OH) ₂ , "magnesium dihydrate, MDH"), ammonium sulfate ((NH ₄ ) ₂ SO ₄ ), zinc borates, slaked lime (Ca (OH) ₂ ) and the like.

The DE 10 2004 023 166 A1 describes another flame retardant based on ceramizing additives such as disodium tetraborate, boron oxide and silica, which z. B. may be incorporated in a paint on polybutadiene or melamine / formaldehyde base.

The invention has for its object to propose a novel flame retardant for a fire resistant plastic material of the type mentioned, which increases the selection of possible polymer binders while ensuring reliable fire protection properties and in particular should be combined with conventional flame retardants.

According to the invention this object is achieved in a fire-resistant plastic material of the type mentioned above in that it contains between 0.1 and 15 wt .-% based on the total fire-resistant plastic material, at least one energetic compound with positive binding enthalpy, which is under Thermal decomposition exothermically decomposes without entering into a chemical reaction with other potential reactants in order to thermally pre-dam the polymer structure of the binder.

The flame retardants of the invention, which are referred to in the present disclosure with "energetic compounds", therefore, on the one hand have a positive binding enthalpy, on the other hand they require for their - exothermic - decomposition no other reactants, but react with themselves and thereby release the heat to thermally pre-dam the polymer matrix of the binder material. The mode of action of these energetic compounds is consequently based on the fact that the thermally initiated, exothermic decomposition of the energetic compounds leads to a degradation of the binder polymer in the form of a charring reaction and in this way to a lower formation of combustible decomposition products. The type of binder is largely arbitrary, wherein the decomposition temperature of the energetic compound should be adapted only to that of the binder, especially in an early stage of fire, in which the polymer matrix itself would withstand the fire, a decomposition of the polymer in not or only to initiate badly combustible products. Both thermoplastics and thermosetting polymers, including their copolymers and polymer blends or blends, are suitable for the binder. In the case of thermoplastic high-melt binder matrices, the thermoplastic can be thermally pre-damaged in a still solid state, whereas in the case of thermoplastic low-melting binder matrices an effect on the molten phase is possible, which on the one hand prevents the melting away, on the other hand influence on the semi-liquid phase can be taken, which is crucial in particular in the case of intumescent additives for effective foam formation. In the case of thermosetting polymer matrices, the energetic compounds are able to ensure decomposition already below the actual decomposition temperature of the polymer. The energetic compounds according to the invention make the use of polymeric binders which hitherto appear to be unsuitable in fire-resistant plastic materials possible, it also being possible to obtain, in particular, water-resistant plastic materials, insofar as, in particular, largely water-insoluble energetic compounds are used as flame retardants.

The energetic compound should preferably be present in a proportion of between 0.5 and 12.5% by weight, in particular in a proportion of between 1 and 10% by weight, based on the total fire-resistant plastic material, in the latter to fulfill their intended function.

• – kovalente Verbindungen; und
• – ionische Verbindungen, von welchen wenigstens eines ihrer Ionen eine positive Bindungsenthalpie aufweist und sich unter Wärmeeinwirkung exotherm zersetzt, ohne eine chemische Reaktion mit anderen potenziellen Reaktionspartnern einzugehen,

umfasst. Beispiele solcher Verbindungen sind weiter unten im Einzelnen angegeben.The flame retardant based on energetic compounds of the above definition according to the invention may, for example, be selected from a group which

• - covalent compounds; and
• Ionic compounds of which at least one of their ions has a positive binding enthalpy and decomposes exothermically under the action of heat, without undergoing a chemical reaction with other potential reactants,

includes. Examples of such compounds are detailed below.

As already indicated, an advantageous embodiment provides that the energetic compound has a decomposition temperature between 100 ° C and 350 ° C, in particular between 120 ° C and 325 ° C, preferably between 140 ° C and 300 ° C, wherein the decomposition temperature should be suitably lower than the flash point and / or the decomposition temperature of the polymeric binder in order to influence its decomposition in an early stage of fire can.

While the energetic compounds according to the invention can in principle also be used as the sole flame retardant, an advantageous embodiment of the invention provides that the fire-resistant plastic material further contains at least one conventional flame retardant, which activates in particular by the exothermic reaction of the energetic compounds also in an early fire stage can be.

• – wenigstens eine Kohlenstoffquelle;
• – wenigstens einen Katalysator; und
• – wenigstens ein unter Wärmeeinwirkung nicht entflammbare Gase freisetzendes Treibmittel

enthält. Derartige intumeszierende Flammschutzzusammensetzungen sind als solche bekannt und umfassen als Kohlenstoffquelle beispielsweise Kohlehydrate und/oder insbesondere mehrwertige (Poly)alkohole, wie Mono-, Di- oder Tripentaerythrit und dergleichen, als Katalysator beispielsweise zur Abspaltung von Phosphorsäure geeignete phosphorhaltige Verbindungen, z. B. Ammoniumpolyphosphat und dergleichen, und als Treibmittel beispielsweise Melamin, Dicyandiamid und dergleichen. Die erfindungsgemäßen energetischen Substanzen vermögen hierbei infolge ihrer Vorschädigung der Polymermatrix die Schaumbildung zu verbessern, wobei einige Vertreter derselben, z. B. ionische Flüssigkeiten mit Dicyanamid-, Tricyanmethanid- oder 5-Cyanotetrazolat-Anionen (s. u.), überraschenderweise selbst voluminöse Schäume ausbilden können. Ferner kann die Aktivierungstemperatur der jeweiligen intumeszierenden Flammschutzzusammensetzung durch den Einsatz von energetischen Verbindungen mit entsprechend geringerer Aktivierungstemperatur herabgesetzt werden, indem die bei deren Zersetzung frei werdende Wärme das Intumeszenzsystem frühzeitig zu aktivieren vermag. Zugleich weist die Polymermatrix des Binders infolge der durch die energetischen Verbindungen bewirkten Verkohlungsreaktion eine geringere Brennbarkeit auf und wird die Bildung brennbarer Zersetzungsprodukte somit weitestgehend minimiert. Die energetischen Verbindungen schädigen hierbei durch ihre exotherme Zersetzung auch vernetzte Polymerbinder, wie duroplastische Polymere, unterhalb deren Zersetzungstemperatur und ermöglichen der intumeszierenden Flammschutzmittelzusammensetzung eine effektivere Schaumbildung, wobei lediglich beispielhaft energetische Verbindungen in Form von 1-Allyl-3-methylimidazolium Dicyanamid mit einer Zersetzungstemperatur von 259°C, 1-Allyl-4-amino-1,2,4-triazolium Dicyanamid mit einer Zersetzungstemperatur von 160°C oder Trihexyltetradecylphosphonium Dicyanamid mit einer Zersetzungstemperatur von 190°C° erwähnt seien. A particularly preferred embodiment of the fire-resistant plastic material is characterized in this context by the fact that it is intumescent and in particular

• - at least one carbon source;
• At least one catalyst; and
• - At least one under the action of heat non-flammable gases releasing propellant

contains. Such intumescent flame retardant compositions are known as such and include as carbon source, for example, carbohydrates and / or in particular polyhydric (poly) alcohols, such as mono-, di- or tripentaerythritol and the like, as a catalyst, for example, for the removal of phosphoric acid suitable phosphorus compounds, eg. For example, ammonium polyphosphate and the like, and as blowing agents, for example, melamine, dicyandiamide and the like. The energetic substances according to the invention are able to improve the foam formation as a result of their prior damage to the polymer matrix, with some representatives of the same, for. As ionic liquids with Dicyanamid-, Tricyanmethanid- or 5-cyanotetrazolate anions (see below), surprisingly even voluminous foams can form. Furthermore, the activation temperature of the respective intumescent flame retardant composition can be reduced by the use of energetic compounds with a correspondingly lower activation temperature, in that the heat released by their decomposition can activate the intumescence system at an early stage. At the same time, as a result of the charring reaction caused by the energetic compounds, the polymer matrix of the binder has a lower combustibility and thus the formation of combustible decomposition products is minimized as far as possible. Due to their exothermic decomposition, the energetic compounds also damage crosslinked polymer binders, such as thermoset polymers, below their decomposition temperature and allow the intumescent flame retardant composition to foam more effectively, with energetic compounds in the form of 1-allyl-3-methylimidazolium dicyanamide having a decomposition temperature of only 259 ° C, 1-allyl-4-amino-1,2,4-triazolium dicyanamide having a decomposition temperature of 160 ° C or Trihexyltetradecylphosphonium dicyanamide having a decomposition temperature of 190 ° C ° be mentioned.

According to an advantageous embodiment of the invention, it is provided that the energetic compound is selected from the group of energetic ionic liquids (EILs). Such energetic compounds have the further advantage that they have antistatic properties and prevent electrostatic charging, which allows them in particular for use in fire protection coatings for industrial purposes.

• – quartäre Ammonium-Kationen der allgemeinen Formel [NRR₁R₂R₃]⁺;
• – Phosphonium-Kationen der allgemeinen Formel [PRR₁R₂R₃]⁺;
• – Boronium-Kationen der allgemeinen Formel [BRR₁R₂R₃]⁺;
• – Imidazolium-Kationen der allgemeinen Formel
  
  einschließlich der Imidazolium-Kationen der vorgenannten Formel analogen isomeren Imidazolinium- und Imidazolidinium-Kationen;
• – H-Pyrazolium-Kationen der allgemeinen Formel
  
  einschließlich der 3H-Pyrazolium-Kationen, der 4H-Pyrazolium-Kationen, der 1-Pyrazolinium-Kationen, der 2-Pyrazolinium-Kationen und der 3-Pyrazolinium-Kationen;
• – Pyridinium-Kationen;
• – Pyridazinium-Kationen;
• – Pyrimidinium-Kationen;
• – Pyrazinium-Kationen;
• – Pyrrolidinium-Kationen;
• – Triazinium-Kationen der allgemeinen Formel
  
• – 1,3,4-Oxadiazolium-Kationen der allgemeinen Formel
  
• – 1,2,4-Triazolium-Kationen und 1,2,3-Triazolium-Kationen der allgemeinen Formel
  
• – Tetrazolium-Kationen der allgemeinen Formeln
  
• – wenigstens fünfgliedrige, insbesondere wenigstens sechsgliedrige, heterocyclische Kationen, welche wenigstens ein Phosphor- und/oder Stickstoffatom sowie gegebenenfalls wenigstens ein Sauerstoff- und/oder Schwefelatom aufweisen, insbesondere aus der Gruppe der Thiazolium-, der Oxazolium-, der 1,2,3-Triazin-Kationen, der 1,2,4-Triazin-Kationen und der 1,3,5-Triazin-Kationen, wobei die genannten heterocyclischen Kationen insbesondere einen fünf- bis sechsgliedrigen Heterocyclus besitzen, welcher ein, zwei, drei oder vier Stickstoffatome sowie ein Schwefelatom und/oder ein Sauerstoffatom aufweist;

wobei es sich bei R, R₁, R₂, R₃, R₄ um Wasserstoff oder um einen organischen Rest, insbesondere aus der Gruppe der Alkyl-, der Allyl-, der Vinyl-, der Ethinyl-, der Hydroxyalkyl-, der Azido-, der Alkyl-, der Acryl- sowie der homocyclischen und/oder der heterocyclischen Substituenten handelt.In this connection, it can be provided that the energetic compound is an ionic compound of which at least its cation has a positive binding enthalpy and exothermally decomposes under heat without undergoing a chemical reaction with other potential reactants, the cation selected from the following group is:

• Quaternary ammonium cations of the general formula [NRR ₁ R ₂ R ₃ ] ⁺ ;
• - Phosphonium cations of the general formula [PRR ₁ R ₂ R ₃ ] ⁺ ;
• - Boronium cations of the general formula [BRR ₁ R ₂ R ₃ ] ⁺ ;
• - Imidazolium cations of the general formula
  
  including the imidazolium cations of the aforementioned formula, analogous isomeric imidazolinium and imidazolidinium cations;
• - H-pyrazolium cations of the general formula
  
  including the 3H-pyrazolium cations, the 4H-pyrazolium cations, the 1-pyrazolinium cations, the 2-pyrazolinium cations, and the 3-pyrazolinium cations;
• - pyridinium cations;
• - pyridazinium cations;
• - pyrimidinium cations;
• - pyrazinium cations;
• - pyrrolidinium cations;
• - Triazinium cations of the general formula
  
• - 1,3,4-oxadiazolium cations of the general formula
  
• - 1,2,4-triazolium cations and 1,2,3-triazolium cations of the general formula
  
• - Tetrazolium cations of the general formulas
  
• At least five-membered, in particular at least six-membered, heterocyclic cations which have at least one phosphorus and / or nitrogen atom and optionally at least one oxygen and / or sulfur atom, in particular from the group of thiazolium, oxazolium, 1,2,3 Triazine cations, the 1,2,4-triazine cations and the 1,3,5-triazine cations, said heterocyclic cations especially having a five- to six-membered heterocycle having one, two, three or four nitrogen atoms and a sulfur atom and / or an oxygen atom;

where R, R ₁ , R ₂ , R ₃ , R ₄ is hydrogen or an organic radical, in particular from the group of the alkyl, the allyl, the vinyl, the ethynyl, the hydroxyalkyl, the Azido, the alkyl, the acrylic and the homocyclic and / or the heterocyclic substituent.

• – Dinitramid-Anionen ((N(NO₂)₂)^–);
• – Pikrat-Anionen
  
• – Dicyanamid-Anionen ((N≡C-N-C≡N)^–);
• – Tricyanmethanid-Anionen ((C(CN)₃)^–);
• – Imidazolat-Anionen der allgemeinen Formel
  
• – 1,2,4-Triazolat-Anionen und 1,2,3-Triazolat-Anionen der allgemeinen Formel
  
  insbesondere in Form von 4,5-Dicyano-1,2,3-triazolat;
• – Tetrazolat-Anionen der allgemeinen Formeln
  
  insbesondere in Form von 5-Cyanotetrazolat, 5-Methyltetrazolat und/oder 5,5-Bistetrazolat;
• – Borat-Anionen der allgemeinen Formel [BRR₁R₂R₃]^–, wobei es sich bei R, R₁, R₂ und R₃ insbesondere um einen organischen Rest aus der Gruppe der heterocyclischen Substituenten handelt;
• – Phosphat-Anionen der allgemeinen Formel [OPOROR₁O]^–, wobei es sich bei R und R₁ insbesondere um einen organischen Rest aus der Gruppe
  
  einschließlich deren Homologen handelt; sowie
• – Azidoalkylsulfate der allgemeinen Formel [ROSO₃]^–, wobei es sich bei R um einen organischen Rest, insbesondere aus der Gruppe
  
  einschließlich deren Homologen sowie
  
  wobei R_A1 und R_A2 aus der Gruppe
  
  einschließlich deren Homologen gewählt ist, handelt;

wobei es sich bei R, R₁, R₂, R₃, R₄ um Wasserstoff oder um einen organischen Rest, insbesondere aus der Gruppe der Alkyl-, der Allyl-, der Vinyl-, der Ethinyl-, der Hydroxyalkyl-, der Azido-, der Alkyl-, der Acryl- sowie der homocyclischen und/oder der heterocyclischen Substituenten handelt.Alternatively or additionally, it can be provided that the energetic compound is an ionic compound of which at least its anion has a positive binding enthalpy and decomposes exothermally under heat without undergoing a chemical reaction with other potential reactants, wherein the anion selected from the following group is:

• Dinitramide anions ((N (NO ₂ ) ₂ ) ^- );
• - Picrate anions
  
• - dicyanamide anions ((N≡CNC≡N) ^- );
• Tricyanomethane anions ((C (CN) ₃ ) ^- );
• - Imidazolate anions of the general formula
  
• - 1,2,4-triazolate anions and 1,2,3-triazolate anions of the general formula
  
  in particular in the form of 4,5-dicyano-1,2,3-triazolate;
• - Tetrazolate anions of the general formulas
  
  in particular in the form of 5-cyanotetrazolate, 5-methyltetrazolate and / or 5,5-bistetrazolate;
• - borate anions of the general formula [BRR ₁ R ₂ R ₃ ] ^- , wherein R, R ₁ , R ₂ and R _{3 are} in particular an organic radical from the group of heterocyclic substituents;
• - Phosphate anions of the general formula [OPOROR ₁ O] ^- , wherein it is in particular R and R ₁ is an organic radical from the group
  
  including their homologs; such as
• - Azidoalkylsulfate of the general formula [ROSO ₃ ] ^- , wherein it is an organic radical R, in particular from the group
  
  including their homologs as well
  
  where R _A1 and R _{A2 are selected} from the group
  
  including their homologs is selected acts;

where R, R ₁ , R ₂ , R ₃ , R ₄ is hydrogen or an organic radical, in particular from the group of the alkyl, the allyl, the vinyl, the ethynyl, the hydroxyalkyl, the Azido, the alkyl, the acrylic and the homocyclic and / or the heterocyclic substituent.

Of course, the aforementioned anions and cations can also be combined with each other so that the energetic compound is an ionic compound having at least one of said cations and at least one of said anions. Examples of such compounds are exemplified by 1-allyl-3-methylimidazolium dicyanamide, 1-allyl-4-amino-1,2,4-triazolium dicyanamide (AATT), trihexyltetradecylphosphonium dicyanamide, 1-methyl-4-amino-1,2, 4-triazolium 2-azidopropane sulfate, 1-vinyl-4-methyl-1,2,4-triazolium dicyanamide or mixtures thereof mentioned. On the other hand, it is of course also possible to combine the abovementioned anions or cations with cations or anions which have a negative binding enthalpy, but preferably also decompose exothermically, so that it is only around one ion (the anion or the cation) is one which has a positive binding enthalpy and decomposes exothermally under heat without undergoing a chemical reaction with other potential reactants. By way of example, mention may be made here of ionic compounds which have at least one cation from the abovementioned group, while their anion is, for example, nitrate antions (NO ₃ ^- ), perchlorate anions (ClO ₄ ^- ) or the like.

• – physikalisch oder chemisch an die Polymermatrix des Binders gebunden ist; oder
• – physikalisch oder chemisch an ein energetisches Polymer, insbesondere aus der Gruppe der Glycidylazidopolymere (GAP) und 3,3-Bis(azidomethyl)oxethan (BAMO), welches in die Polymermatrix des Binders eingebracht ist, gebunden ist.

According to one embodiment of the invention it can be provided that the energetic compound is an ionic compounds, of which the cation and / or the anion is at least one functional group, in particular from the group of allyl, vinyl, azido, epoxide and ethynyl Groups, wherein the functional group of the cation and / or the anion

• - is physically or chemically bound to the polymer matrix of the binder; or
• - Physically or chemically bound to an energetic polymer, in particular from the group of glycidyl azido (GAP) and 3,3-bis (azidomethyl) oxoethane (BAMO), which is incorporated in the polymer matrix of the binder.

und dergleichen umfassen. Beispiele solcher Anionen können

und dergleichen umfassen.Examples of such cations can

and the like. Examples of such anions may be

and the like.

In this case, it is therefore possible to incorporate the functionalized anions and / or cations of the energetic compounds according to the invention, in particular in the form of energetic ionic liquids (EILs), by physical or chemical bonding in the polymer matrix of the binder, wherein the with functional Groups provided anions and / or cations of the energetic compounds, for example, by chemical polymerization thereof in the polymer matrix of the binder, by chemical linkage with the polymer matrix of the binder or by incorporating the energetic compounds are polymerized into the polymer matrix of the binder to the polymer.

In addition, it is alternatively or additionally possible to provide the functional groups provided with anions and / or cations of the energetic compounds, in particular in the form of energetic ionic liquids (EILs), z. B. to crosslink with energetic polymers of the aforementioned type and to introduce into the polymer matrix of the binder and to perform a curing and / or post-curing, for example by means of 1,3-dipolar cycloaddition.

Accordingly, an embodiment variant of the invention can provide that the anions and / or the cations of the ionic energetic compound, in particular in the form of energetic ionic liquids (EILs), via their functional group (s) with the at least one energetic polymer, in particular from the group of glycidyl azido (GAP) and 3,3-bis (azidomethyl) oxethane (BAMO), crosslinked are, wherein the crosslinked by means of the ionic energy compounds energetic polymer is incorporated in the polymer matrix of the binder of the fire-resistant plastic material.

The energetic compound used according to the invention as a flame retardant does not necessarily have to be of ionic structure, but according to an advantageous further embodiment variant of the invention may also be selected from the group of covalent compounds.

Advantageous representatives of such covalent energetic compounds, which also have a positive binding enthalpy and can decompose exothermally under heat, without entering into a chemical reaction with other potential reactants, for example, from the group of nitrates, azides, nitroamino compounds, dinitramine, glycidyl azido polymers (GAP), in particular GAP diol and / or GAP triol and triaminoguanidine nitrate (TAGN).

In this respect, according to a development of the invention, it may be provided that the covalent energetic compound has at least one functional group, in particular from the group of the allyl, vinyl, azido, epoxide and ethynyl groups, where the functional group is the covalent energetic compound is physically or chemically bonded to the polymer matrix of the binder.

In particular, if a chemical and / or physical binding of the energetic compound - be it ionic or covalent construction - is desired, the binder of the fire-resistant plastic material should expediently contain or at least be formed from a polymer containing functional groups, in particular Hydroxy groups, amino groups, amide groups, carboxylic acid groups, anhydride groups, azide groups, epoxide groups, alkynyl groups, especially ethynyl groups, or the like.

By way of example may be mentioned in this context polymeric binder materials containing at least one polymer from the group of polyurethane, polyurea, epoxy, acrylic, aldehyde and rubbers, in particular polybutadiene, including their copolymers and polymer blends or are formed entirely from this.

As also mentioned above, the fire-resistant plastic material according to the invention can be used on the one hand for fire-resistant molded parts made of such a plastic material, on the other hand for one of the claims fire protection coatings of such a plastic material.

Exemplary embodiments of inventive fire-resistant plastic materials are reproduced below.

Example 1:

Fire-resistant plastic material based on a thermosetting polymer binder and an energetic compound in the form of an energetic ionic liquid (EIL):

- Polymeric binder:

• 5-30 mass% of polyurethane and / or polyurea resin;

- Energetic connection:

• 1-10 mass% of 1-allyl-3-methylimidazolium dicyanamide (allyl-Im-DCA);

- Harder:

• 5-30 mass% isocyanate;

- Conventional flame retardants:

• – 5–20 Mass.-% Melamin (Treibmittel),
• – 5–20 Mass.-% Pentaerythritol (Kohlenstoffquelle),
• – 5–40 Mass.-% Ammoniumpolyphosphat (Phosphorsäurelieferant als Katalysator);

Intumescence composition

• 5-20% by weight of melamine (blowing agent),
• 5-20% by weight of pentaerythritol (carbon source),
• 5-40 mass% ammonium polyphosphate (phosphoric acid supplier as catalyst);

- Further additives:

• 0.1-3% by mass of silica (SiO ₂ ),
• 1-5 mass% titanium dioxide (TiO ₂ ),
• 0-10 mass% organic solvent,
• 0-5 Mass .-% defoamers, cell formers and flow additives.

Example 2:

Fire-resistant plastic material based on a thermoplastic polymer binder and an energetic compound in the form of an energetic ionic liquid (EIL):

- Polymeric binder:

• 5-40 mass% urea / aldehyde resin;

- Energetic connection:

• 1-10 mass% of 1-allyl-3-methylimidazolium dicyanamide (allyl-Im-DCA);

- Conventional flame retardants:

• – 5–20 Mass.-% Melamin (Treibmittel),
• – 5–20 Mass.-% Pentaerythritol (Kohlenstoffquelle),
• – 5–40 Mass.-% Ammoniumpolyphosphat (Phosphorsäurelieferant als Katalysator);

Intumescence composition

• 5-20% by weight of melamine (blowing agent),
• 5-20% by weight of pentaerythritol (carbon source),
• 5-40 mass% ammonium polyphosphate (phosphoric acid supplier as catalyst);

- Further additives:

• 0.1-3% by mass of silica (SiO ₂ ),
• 1-5 mass% titanium dioxide (TiO ₂ ),
• 1-6 mass% expandable graphite,
• 10-30 mass% organic solvent,
• 0-5 mass% cell former.

Example 3:

Fire-resistant plastic material with a covalent energetic compound, which can be chemically bound to the functional groups of the binder:

- Polymeric binder:

• 20-40 mass% hydroxy-terminated polybutadiene;

- Energetic connection:

• 1-10 mass% glycidyl azide copolymer (GAP diol);

- Harder:

• 2-8 mass% isophorone diisocyanate (IPDI);

- Conventional flame retardants:

• – 5–20 Mass.-% Melamin (Treibmittel),
• – 5–20 Mass.-% Pentaerythritol (Kohlenstoffquelle),
• – 5–40 Mass.-% Ammoniumpolyphosphat (Phosphorsäurelieferant als Katalysator).

Intumescence composition

• 5-20% by weight of melamine (blowing agent),
• 5-20% by weight of pentaerythritol (carbon source),
• 5-40 mass% ammonium polyphosphate (phosphoric acid supplier as catalyst).

QUOTES INCLUDE IN THE DESCRIPTION

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Cited patent literature

• DE 102004023166 A1 [0008]

Claims (20)

Fire-resistant plastic material containing: A binder of at least one polymer; and Between 0.1 and 15% by mass, based on the total fire-resistant plastic material, of at least one energetic compound with positive binding enthalpy, which decomposes exothermally under the action of heat, without entering into a chemical reaction with other potential reactants, in order to improve the polymer structure of the polymer Thermally pretend binder. Fire-resistant plastic material according to claim 1, characterized in that it contains the energetic compound in an amount between 0.5 and 12.5 mass%, in particular in a proportion between 1 and 10 mass%, based on the total fire-resistant Plastic material, contains. Fire-resistant plastic material according to claim 1 or 2, characterized in that the energetic compound is selected from a group which - covalent compounds; and Ionic compounds of which at least one of their ions has a positive binding enthalpy and decomposes exothermically under the action of heat, without undergoing a chemical reaction with other potential reactants, includes. Fire-resistant plastic material according to one of claims 1 to 3, characterized in that the energetic compound has a decomposition temperature between 100 ° C and 350 ° C, in particular between 120 ° C and 325 ° C, preferably between 140 ° C and 300 ° C, having. Fire-resistant plastic material according to one of claims 1 to 4, characterized in that the energetic compound has a decomposition temperature which is lower than the flash point and / or the decomposition temperature of the binder. Fire-resistant plastic material according to one of claims 1 to 5, characterized in that it further comprises at least one conventional flame retardant. Fire-resistant plastic material according to one of claims 1 to 6, characterized in that it is intumescent and - at least one carbon source; At least one catalyst; and - At least one under the action of heat non-flammable gases releasing propellant contains. Fire-resistant plastic material according to one of claims 1 to 7, characterized in that the energetic compound is selected from the group of energetic ionic liquids (EILs). Fire-resistant plastic material according to one of claims 1 to 8, characterized in that the energetic compound is an ionic compounds, of which at least their cation has a positive binding enthalpy and decomposes exothermically under heat, without entering into a chemical reaction with other potential reactants, wherein the cation is selected from the group consisting of: quaternary ammonium cations of the general formula [NRR ₁ R ₂ R ₃ ] ⁺ ; - Phosphonium cations of the general formula [PRR ₁ R ₂ R ₃ ] ⁺ ; - Boronium cations of the general formula [BRR ₁ R ₂ R ₃ ] ⁺ ; - Imidazolium cations of the general formula

including the imidazolium cations of the aforementioned formula, analogous isomeric imidazolinium and imidazolidinium cations; - H-pyrazolium cations of the general formula

including the 3H-pyrazolium cations, the 4H-pyrazolium cations, the 1-pyrazolinium cations, the 2-pyrazolinium cations, and the 3-pyrazolinium cations; - pyridinium cations; - pyridazinium cations; - pyrimidinium cations; - pyrazinium cations; - pyrrolidinium cations; - Triazinium cations of the general formula

- 1,3,4-oxadiazolium cations of the general formula

- 1,2,4-triazolium cations and 1,2,3-triazolium cations of the general formula

- Tetrazolium cations of the general formulas

At least five-membered, in particular at least six-membered, heterocyclic cations which contain at least one phosphorus and / or nitrogen atom and optionally at least one oxygen and / or Have sulfur atom, in particular from the group of thiazolium, the oxazolium, the 1,2,3-triazine cations, the 1,2,4-triazine cations and the 1,3,5-triazine cations, wherein the heterocyclic cations mentioned in particular have a five- to six-membered heterocycle having one, two, three or four nitrogen atoms and a sulfur atom and / or an oxygen atom; where R, R ₁ , R ₂ , R ₃ , R ₄ is hydrogen or an organic radical, in particular from the group of the alkyl, the allyl, the vinyl, the ethynyl, the hydroxyalkyl, the Azido, the alkyl, the acrylic and the homocyclic and / or the heterocyclic substituent. Fire-resistant plastic material according to one of Claims 1 to 9, characterized in that the energetic compound is an ionic compound of which at least its anion has a positive binding enthalpy and decomposes exothermically under the action of heat, without entering into a chemical reaction with other potential reactants, wherein the anion is selected from the group consisting of: - dinitramide anions ((N (NO ₂ ) ₂ ) ^- ); - Picrate anions

- dicyanamide anions ((N≡CNC≡N) ^- ); Tricyanomethane anions ((C (CN) ₃ ) ^- ); - Imidazolate anions of the general formula

- 1,2,4-triazolate anions and 1,2,3-triazolate anions of the general formula

in particular in the form of 4,5-dicyano-1,2,3-triazolate; - Tetrazolate anions of the general formulas

in particular in the form of 5-cyanotetrazolate, 5-methyltetrazolate and / or 5,5-bistetrazolate; - borate anions of the general formula [BRR ₁ R ₂ R ₃ ] ^- , wherein R, R ₁ , R ₂ and R _{3 are} in particular an organic radical from the group of heterocyclic substituents; - Phosphate anions of the general formula [OPOROR ₁ O] ^- , wherein it is in particular R and R ₁ is an organic radical from the group

including their homologs; and - azidoalkyl sulfates of the general formula [ROSO ₃ ] ^- , where R is, in particular, an organic radical from the group

including their homologs as well

where R _A1 and R _{A2 are selected} from the group

including their homologs is selected acts; where R, R ₁ , R ₂ , R ₃ , R ₄ is hydrogen or an organic radical, in particular from the group of the alkyl, the allyl, the vinyl, the ethynyl, the hydroxyalkyl, the Azido, the alkyl, the acrylic and the homocyclic and / or the heterocyclic substituent. A fire resistant plastic material according to any one of claims 1 to 10, characterized in that the energetic compound is an ionic compound having at least one cation according to claim 8 and at least one anion according to claim 9. Fire-resistant plastic material according to one of claims 1 to 11, characterized in that the energetic compound is an ionic compounds, of which the cation and / or the anion at least one functional group, in particular from the group of allyl, vinyl, azido -, epoxide and ethynyl groups, wherein the functional group of the cation and / or the anion - is physically or chemically bound to the polymer matrix of the binder; or - Physically or chemically bound to an energetic polymer, in particular from the group of glycidyl azido (GAP) and 3,3-bis (azidomethyl) oxoethane (BAMO), which is incorporated in the polymer matrix of the binder. Fire-resistant plastic material according to claim 12, characterized in that the anions and / or the cations of the ionic energetic compound via their functional group (s) with the at least one energetic polymer, in particular from the group of glycidyl azido (GAP) and 3,3-bis (azidomethyl) oxoethane (BAMO), are crosslinked. Fire-resistant plastic material according to one of claims 1 to 7, characterized in that the energetic compound is selected from the group of covalent compounds. Fire-resistant plastic material according to claim 14, characterized in that the covalent energetic compound from the group of nitrates, azides, nitroamino compounds, the Dinitramine, the glycidyl azido polymers (GAP), in particular GAP diol and / or GAP triol and triaminoguanidine nitrate (TAGN) is selected. Fire-resistant plastic material according to claim 14 or 15, characterized in that the covalent energetic compound has at least one functional group, in particular from the group of allyl, vinyl, azido, epoxide and ethynyl groups, wherein the functional group the covalent energetic compound is physically or chemically bound to the polymer matrix of the binder. Fire-resistant plastic material according to one of claims 1 to 16, characterized in that the binder contains at least one functional group, in particular hydroxyl and / or amino groups, containing polymer or is formed entirely thereof. Fire-resistant plastic material according to one of claims 1 to 17, characterized in that the binder comprises at least one polymer from the group of polyurethane, polyurea, epoxy, acrylic, aldehyde and rubbers, in particular polybutadiene, including their copolymers and polymer blends contains or is formed entirely from it. Fire-resistant molded part made of a fire-resistant plastic material according to one of claims 1 to 18. Fire protection coating made of a fire-resistant plastic material according to one of claims 1 to 18.