WO2017097385A1 - Complex halogen-free solid flame-retardant agent composition for polymer molding compounds, consisting of a reaction product of porous boron silicate glass particles which are produced by means of a high-temperature extrusion process and which melt at low temperatures, melamine, and ammonium nitrate, and method for producing same - Google Patents

Abstract

The invention relates to a complex halogen-free solid flame-retardant agent composition for polymer molding compounds, consisting of - 30 to 70 wt.% porous glass particles, which melt at a low temperature and which are made of a boron silicate glass foam produced by means of a high-temperature extrusion process, with an average particle size of 1.5 to 12 μm, - 30 to 70 wt.% melamine, and - 2 to 10 wt.% ammonium nitrate. The composition is obtained by - dry-mixing the porous glass particles made of a boron silicate glass foam and the melamine - uniformly distributing 2 - 10 wt.% of ammonium nitrate, which is dissolved in distilled water, in the mixture of the glass particles and the melamine - further mixing the components of the porous glass particles, the melamine, and the dissolved ammonium nitrate, - and temperature-treating the mixture at 90 to 120 °C for 90 to 240 minutes.

Description

 A complex halogen-free solid flame retardant composition for polymer molding compositions consisting of a reaction product of porous borosilicate glass particles, melamine and ammonium nitrate, produced by high-temperature extrusion and melting at low temperatures

Process for their preparation

The invention relates to complex halogen-free solid flame retardant compositions for polymer molding compositions. The invention further relates to flame-retardant polymer molding compositions which can be composed of one or more polymers and to moldings, fibers or films which can be produced from the novel flame-retardant molding compositions and to a process for the preparation thereof. In DE 10 2004 02 67 99 B4 is the compaction / granulation of

 Flame retardants with flame retardant synergists described as granulation aids. As Flammschutzsynergisten zinc phosphate compounds are claimed with a melting point between 40 and 250 ° C. DE 101 44 231 B4 claims a process for coating melamine cyanurate, in which the melamine cyanurate is mixed in solution with monomers, oligomers and / or polymers based on lactams. The disadvantage is that the mixing must be carried out in an aqueous medium and then filtration and

Drying is required.

DE 600 29 009 T2 claims a flame-retardant polyamide resin composition consisting of polyamide resin, a salt of polyphosphoric acid and melamine, and inorganic fillers. This is a combination of two known flame retardants for polyamides.

In DE 195 32 720 Al a flame-retardant thermoplastic molding composition is claimed which consists of polyamide, melamine cyanurate, with Siianverbindungen pretreated fibrous fillers and other additives and processing aids. In the example given there, 15% by weight of melamine cyanurate are used in order to achieve fire classification UL 94-V2 in the fire test.

CONFIRMATION COPY In EP 15 02 900 Bl or DE 60 2004 00 31 79 T2 is a

 Flame retardant composition and thermoplastic resin compositions containing described, consisting of a phosphate glass with a

Glass transition temperature between 300 and 400 ° C and a phosphate-containing

Flame retardant, wherein both components are previously mixed or kneaded. The phosphate glass consists of 5 to 35 mol% monovalent alkali metal oxides, 20 to 27 mol% P ₂ O ₅ , 3 to 20 mol% S0 ₃ , 10 to 55 mol% ZnO, 1 to 5 mol% Al ₂ 0 ₃ , 8-20 mol% B ₂ 0 ₃ and 0-15 mol% of divalent metal oxides other than zinc. With only 2% by weight of this flame retardant composition and 0.2% by weight of the antidripping agent PTFE, the V0 can be achieved in the polycarbonate.

In DE 10 2004 02 67 99 B4 are press granulated

 Flame retardant compositions and processes for their preparation and their use described. These are phosphinic salts and / or

Diphosphinic salts mixed with a fusible zinc phosphinate and optionally other additives or flame retardants and pressed.

In DE 10 2011 01 18 84 AI are porous, amorphous glass particles of continuously foamed glass, with other inorganic salts or organic

Compounds doped are described. The doped glass particles can as

Catalysts, siccatives, vulcanization activators, vulcanization accelerators or flame retardants can be used. There will be no

 Flame retardant composition of the glass particles with melamine and ammonium nitrate described. DE 10 2012 004 357 A1 discloses a flame retardant composition

Melamincyanurat and porous amorphous glass particles of borosilicate glass claimed. It also describes the preparation of flame retardant compositions by mixing melamine and cyanuric acid in the aqueous medium with the porous glass powder and subsequent heat treatment. Here, however, the components become melamine. and cyanuric acid produced by a thermal treatment at preferably 90 to 100 ° C melamine cyanurate.

DE 103 59 816 B4 claims flame retardant-stabilizer combinations which contain phosphinic acid salts and / or diphosphinic acid salts and / or their polymer and chain extender. As further components they can also contain glass powder. In DE 103 23 116 AI titanium-containing Phosphionatflammschutzmittel be claimed. Furthermore, molding compositions of thermoplastic or thermosetting polymers are claimed, which may contain other flame retardants and inorganic compounds such as glass powder.

The specifications DE 195 36 665 C2, DE 195 36 666 C2 and DE 195 45 065 C2 describe the production of glass foam produced continuously in the extruder.

The patent DE 102 52 693 B4 describes a process for producing platelet-shaped and irregular, 3-dimensionally or regularly shaped glass particles, which are produced from relaxing pressurized molten glass by adding propellants.

These glass particles are referred to below as porous glass particles.

It is essential that flame retardant be as homogeneous as possible in one

Polymer molding compound are distributed. Frequently, flame retardant finishes for polymer molding compositions consist of several components. The dosage of

Flame retardants from several individual components when incorporated into the

Polymer molding compounds in the extruder is difficult and often leads to inhomogeneous

Distribution of flame retardants in the polymer molding compounds. This in turn may be detrimental to the flame retardancy due to local underdosage and results in the flame retardants being used at a higher dosage to achieve consistent flame retardancy. The use of flame retardants in the polymer molding compositions also has a negative impact on the mechanical properties

 Characteristics. Therefore, the necessary amount of flame retardant should be as low as possible.

The task was therefore in the development of flame retardant compositions, consisting of several synergistic acting

Flame retardants.

A halogen-free solid flame retardant composition has been found which ensures stable flame retardancy in unfilled polymer molding compositions even with a small amount of use. In polyamide 6, for example, with the complex halogen-free flame retardant composition, the amount used Flame retardants compared to melamine cyanurate treated compounds for UL94 VO be reduced by 50%.

In filled with glass fiber polymer molding compounds can be found by the

Flame retardant composition in conjunction with others

 Flame retardant synergists, such as phosphorus-containing organic flame retardants, a flame retardant can be achieved. This allows the phosphorus-containing

Flame retardant known corrosion can be reduced. By partially replacing the expensive organic phosphorus-containing flame retardants, a reduction of the costs is possible.

The complex halogen-free solid flame retardant compositions for polymer compositions consist of:

 - 30 to 70 wt .-% porous, melting at low temperatures glass particles from a produced by high-temperature extrusion borosilicate glass foam having an average particle size of 1.5 to 12 pm

 - 30 to 70 wt .-% melamine and

 2 to 10% by weight of ammonium nitrate, obtainable by:

 dry mixing of the porous glass particles of the borosilicate glass foam and the melamine

 uniform distribution of 2-10% by weight of ammonium nitrate dissolved in distilled water

Water, in the mixture of the glass particles and the melamine

 - further mixing the components porous glass particles, melamine and dissolved ammonium nitrate

- Temperature treatment of the mixture at 90 to 150 ° C for at least 90 minutes.

The complex halogen-free solid flame retardant compositions for polymer compositions preferably consist of:

 40 to 60% by weight of porous, low-melting glass particles from a borosilicate glass foam produced by high-temperature extrusion with an average particle size of 2 to 6 μm

 - 40 to 60 wt .-% melamine and

 - 2 to 10 wt .-% ammonium nitrate, obtainable by

 dry mixing of the porous glass particles of a borosilicate glass foam and the melamine

 uniform distribution of 2-10% by weight of ammonium nitrate dissolved in distilled water

Water, in the mixture of the glass particles and the melamine - further mixing the components porous glass particles, melamine and dissolved ammonium nitrate

 - Temperature treatment of the mixture at 90 ° C to 120 degrees for 90 to 240 minutes. It was surprisingly found that at low temperature melting porous glass particles of borosilicate glass mixed with melamine and a dissolved

Ammonium nitrate and then temperature treated against the use of separate porous Borosilikatglaspartikeln and separate melamine to reduce the necessary flame retardant and lead to improved and uniform results in the flame retardancy.

In the unfilled polyamide 6, for example, the amount of flame retardant could be reduced by 50% compared to melamine cyanurate in order to achieve the UL94 V0.

Flame retardant compositions obtained from temperature treated

Mixtures of porous, low melting temperature glass particles and melamine using water also result in improvements over the use of melamine or melamine cyanurate and porous glass particles as

Individual components.

Melamine as a nitrogen-containing flame retardant has the disadvantage that it diffuses out of the polymer matrix of the polymer molding compositions equipped therewith.

Melamine cyanurate, however, has long been known as a flame retardant for engineering plastics. Especially in polyamides, but also in polyesters and others

Plastics, such as styrene-based polymers, find it widely used. The advantage of the melamine cyanurate is that it does not diffuse out of the polymer matrix (JP 00000 53 317 59 B2). This effect is on the two-dimensional, on

Attributed to hydrogen bonding network structure of Melamincyanurates. The disadvantage, however, is that thus important for flame retardant knit content of about 66 wt .-% in melamine to about 50 wt .-% in

Melamincyanurat is reduced and thus larger amounts are required.

By attaching the melamine in combination with the ammonium nitrate to the porous glass powder, the disadvantage of diffusion from the polymer molding compound is eliminated. The porous glass powder is at the same time carrier for the melamine and

Flammschutzsnergist, as it in case of fire to form a glass foam layer on the polymer molding compound comes. The reaction products of ammonium nitrate support the formation of the glass foam layer and stabilize it.

The melamine can be coupled to the surface of the porous glass particles by means of hydrogen bonding or via the OH ions present on the glass particle surface. Likewise, a dipole interaction between the glass particle surface and the melamine molecules is possible.

The polymer molding compounds are thermoplastic or thermosetting polymers or blends of the various polymers.

The claimed complex halogen-free flame retardant composition can also be used as a masterbatch, ie a compound with a high concentration of

Flame retardant composition are introduced into the polymer molding compositions. The masterbatch may contain further auxiliaries, such as plasticizers, nucleating agents,

 Release agents and lubricants, flow and processing aids, antioxidants, heat and light stabilizers, dyes, pigments and other flame retardants.

Thermoplastic molding compositions according to the invention, which with the

Flameproofing composition can be equipped, are homo- and

 Copolymers of olefinically unsaturated monomers such as polyfluoroethylene, polyethylene, polypropylene, ethylene / propylene copolymers, polyethylene ethers, polystyrenes, such as

Polystyrene HI, styrene / acrylonitrile copolymers, ABS (acrylonitrile-butadiene-styrene) polymer blends or PC / ABS (polycarbonate / acrylonitrile-butadiene-styrene), vinyl chloride homo- and copolymers, polyacrylates, vinyl acetate copolymers such as ethylene vinyl acetate, polyacetates , Polycarbonates, polyesters and polyamides.

As components of the thermoplastic molding compositions according to the invention may also contain elastomeric polymers. Preference is given here to call the so-called ethylene-propylene or ethylene-propylene-diene rubbers (ERM and EPDM rubber). The EPD and EPDM rubbers may also preferably be grafted with reactive carboxylic acids or their derivatives.

The thermoplastic polymer molding compositions are preferably polyamides, polyesters, polycarbonates, polyethylene ethers, polystyrene HI (high impact) and blends or polymer blends of the ABS (acrylonitrile-butadiene-styrene) or PC / ABS type (Polycarbonate / acrylonitrile-butadiene-styrene) without excluding other thermoplastic polymers.

The thermoplastic polyamide molding compositions can by polycondensation of

Lactams are obtained with 3- or multi-membered ring or polymerizable amino acids or by polycondensation between dibasic acids and diamines. Examples of the polyamides are polymers of ε-caprolactam, aminocaproic acid, β-lactam, γ-lactam, δ-lactam, ε-lactam, 7-aminoheptanoic acid, 11-aminodecanoic acid, pyridine, piperidone and the like, produced by the polycondensation between

Diamines such as hexamethylene nonamethylene, undecamethylene, dodecamethylene, m-xylylenediamine and dicarboxylic acids such as terephthalic, isophthalic, adipic, sebacic, dodecanedicarboxylic and glutaric acid or copolymers thereof. Specific examples of the polyamides are polyamide 4 (monomers pyrrolidone), polyamide 6 (monomer ε-caprolactam), polyamide 7 (monomers ethanolactam), polyamide 8 (monomer

Capryllactam), polyamide 9 (monomer 9-aminoperlagonic acid), polyamide 11 (monomer aminoundecanoic acid), polyamide 12 (monomer laurolactam), polyamide 46 (monomers tetramethylenediamine and adipic acid), polyamide 66 (monomers hexamethylenediamine and adipic acid), polyamide 69 (monomers hexamethylenediamine and Azelaic acid), polyamide 610 (monomers hexamethylenediamine and sebacic acid), polyamide 612 (monomers hexamethylenediamine and decanedicarboxylic acid), polyamide 613 (monomers hexamethylenediamine and undecanedicarboxylic acid), polyamide 1212 (monomers 1,12-dodecanediamine and decanedicarboxylic acid), polyamide 1313 (monomers 1, 13 - diaminotridecane and undecanedicarboxylic acid), polyamide 6T (monomers

Hexamethylenediamine and terephthalic acid), polyamide 9T (monomers 1,9-nonanediamine and terephthalic acid), polyamide MXD6 (monomers m-xylylenediamine and adipic acid), polyamide 61 (monomers hexamethylenediamine and isophthalic acid), polyamide 6-3-T (monomers trimethylhexamethylenediamine and terephthalic acid) , Polyamide 6 / 6T

(Mixture of PA6 and PA6T), polyamide 6/66 (mixture of PA6 and PA66), polyamide 6/12 (mixture of PA6 and PA12), polyamide 66/6/610 (mixture of PA66, PA6 and PA 610), polyamide 6I / 6T (mixture of PA6I and PA6T), polyamide PACM 12 (monomers

Diaminodicyclohexylmethane and laurolactam), PA 6I / 6T / PACM (mixture of PA6I, PA6T and the monomer diaminodicyclohexylmethane), PA12 MACMI (monomers laurolactam, dimethyldiaminodicyclohexylmethane and isophthalic acid), PA 12MACMT (monomers laurolactam, dimethyldiaminodicyclohexylmethane and terephthalic acid) and PDA -T (monomers phenylenediamine and terephthalic acid) without further exclusion.

Particularly preferred are polyamide 6 and polyamide 6.6 and mixtures thereof. Polybutylene terephthalate (PBT) and polyethylene terephthalate (PET) are preferred in the polyesters. The thermoset polymers are preferably epoxy, formaldehyde, melamine / phenolic resin polymers and / or polyurethanes.

Preferred flame-retardant polymer molding compositions consist of:

 40.0 to 98.0% by weight of polymers or polymer mixtures,

2.0 to 12.0% by weight of the complex halogen-free solid

 Flame retardant composition,

 - 0 to 30 wt .-% auxiliaries

Preferred flame-retardant polymer molding compositions consist of:

40.0 to 96.0% by weight of polymers or polymer mixtures,

 2.0 to 12.0% by weight of the complex halogen-free solid

Flame retardant composition,

 1.0 to 20.0% by weight of flame retardant synergists

 - 0 to 30 wt .-% auxiliaries

Preferred flame-retardant polymer molding compositions consist of:

 40.0-96.0% by weight of polymers or polymer mixtures,

 - 4.0 - 20.0 wt .-% of the flame retardant composition

 - 0 to 50.0 wt .-% fillers and reinforcing agents

- 0 - 20 wt .-% of other flame retardant synergists

 - 0 - 30 wt .-% excipients

The porous glass particles are made of glass foam. For this purpose, a glass melt is produced from glass pellets in a melting funnel, which then in a

Single-screw extruder is drawn under hydrostatic pressure. The glass melt is mixed in the single-screw extruder at 800 to 1000 ° C under pressure with steam as blowing agent. There are 1 to 5 g of water vapor, preferably 2 to 4 g, per kg of glass melt used as a blowing agent. Particularly preferred are pellets of a borosilicate glass following

Composition used for the molten glass: Oxides content in% by weight

Na ₂ 0 9.5 - 13.5

K ₂ 0 1.0 - 4.0

 MgO 0-2.0

 CaO 1.0 - 5.0

AI ₂ Q ₃ 4.0 - 7.0

Si0 ₂ 55.0 - 60.0

B ₂ 0 ₃ 8.0 - 11.0

Fe ₂ 0 ₃ <0.2

 ZnO 2.0 - 5.0

 BaO 3.0 - 6.0

F ₂ <1.0

More preferably, the processing temperature in the single screw extruder for this glass composition is 850 to 920 ° C in the individual heating zones. At the Extruderaustrittsdüse, diameter 2 to 5 mm, the relaxation of the mixture of molten glass and blowing agent and it forms a fine-pored

Glass foam having a density of 0.05 to 0.30 g / cm ³ , preferably 0.10 to 0.20 g / cm ³ .

The glass foam strand is not relaxed, but cools under the action of

Ambient air. It consists of closed pores, which, however, partially break up as a result of the rapid cooling. As a result, the glass foam strand breaks down into

irregular fragments.

Furthermore, the irregular fragments are pre-shredded in a roll crusher (EMDE) with a 7 mm perforated sieve. Then the grinding takes place

(Ball mill) and classification (Windradsichter) of pre-broken glass foam pieces to average particle sizes (d ₅₀ ) between 1 and 100 μιτι, preferably between 2 and 6 pm. The porous glass particles contain in micropores (<2 nm), mesopores (2 to 50 nm), and macropores (<50 nm) still residues of the propellant water, whereby upon heating of the glass particles to temperatures of 360-600 ° C, re-foaming he follows. Due to the strong surface activation during the grinding process, the particles sinter together already in this temperature range. Melamine (2,4,6-triamino-1,3,5-triazine) with the molecular formula C ₃ H ₆ N ₆ is a heterocyclic aromatic compound with nitrogen. The nitrogen content of the melamine is about 66 wt .-%. Melamine is produced by trimerization of urea. Ammonium nitrate (NH ₄ I \ 10 ₃ ) is a salt produced by neutralization of ammonia with nitric acid and is very soluble in water.

The complex halogen-free solid flame retardant compositions are prepared by adding 20-80% by weight, preferably 40-60% by weight, of the porous

Borosilicate glass powder with 20 to 80 wt .-% melamine powder, preferably 40 to 60% by weight, dry blended. Commercially available mixers such as Lodige mixers, Henschel mixers or Banbury mixers may be used. The mixture is then sprayed with 2 to 20 wt .-%, preferably 2 to 10 wt .-%, ammonium nitrate, which was previously dissolved under heat in distilled water, while still mixing. The weight ratio of ammonium nitrate to the distilled water used for the solution may be 3: 1 to 1: 2, wherein a

Ratio of 2: 1 to 1: 1 is preferred to obtain a mixture, although moist, but not lumpy. The necessary mixing time is chosen so that a homogeneous distribution of the dissolved ammonium nitrate in the mixture of porous borosilicate glass powder and melamine is achieved. The mixing time is preferably 40 minutes. Subsequently, the wet mixture of the porous glass powder, the melamine and the dissolved ammonium nitrate is subjected to a temperature treatment. This may preferably be done in the mixer or in a separate oven. The mix is exposed for at least 90 minutes, preferably for 180 minutes, to a temperature of at least 90 ° C and at most 150 ° C, preferably at least 90 ° C and at most 120 ° C. It comes to the reaction between the porous glass powder, the melamine and the ammonium nitrate. It releases ammonia. The resulting complex halogen-free flame retardant composition has a residual moisture content below 1.0, preferably below 0.5 wt .-%.

In a particular embodiment can be dispensed with the component ammonium nitrate and it is dry mixed with the melamine only the porous glass powder and then sprayed with distilled water. Subsequently, the temperature treatment, as described above. It is a powdery product having an average particle size (d ₅₀ ) of 1.0 to 50.0 μιη, preferably 3.0 to 12.0 μιτι obtained. Agglomerates can be deagglomerated by milling, for example in a ball mill, planetary mill or tooth colloid mill. The complex However, halogen-free solid flame retardant composition can also be incorporated without deagglomeration in the polymer molding compositions, since then the

Dust is lower and the deagglomeration can be done in the compound production.

The complex, halogen-free, solid according to the invention

 Flame retardant compositions are preferably used in compounds which are used to produce polymer moldings. The complex, halogen-free, solid according to the invention

 Flame retardant compositions can be made into thermoplastic polymers

incorporated by e.g. the flame retardant compositions with the additives and the fillers as powder and / or granules are premixed in a mixer and then mixed in a compounding unit (for example twin-screw extruder) in the polymer melt and homogenized.

Preference is given to twin-screw extruders. The melt is usually withdrawn as a strand, cooled and granulated. The components can also be supplied separately via a dosing system directly into the compounding unit.

It is also possible to admix the flame retardants to a finished polymer granulate or powder and to process the mixture directly on an injection molding machine to form parts. The complex, halogen-free, solid according to the invention

 Flame retardant compositions may also be blended into the monomers or prepolymers of the polymer molding compositions.

The compounds may contain other auxiliaries such as plasticizers, nucleating agents, antistatic agents, mold release agents and lubricants, flow and processing aids,

 Antioxidants, heat and light stabilizers, dyes, pigments, coupling agents, such as various silanes, anti-dripping agents such as polytetrafluoroethylene, dispersion aids such as ethylene glycol, 1,2-propanediol or 1,3-propanediol and other flame retardants.

Fillers and reinforcing agents are glass fibers (short, long or continuous fibers), glass beads, glass powder, glass cloth, glass mats, talc, feldspar, quartz, mica, Kaolin, chalk, calcium carbonate, magnesium carbonate, titanium oxide, silicates such as wollastonite, phyllosilicates, clay minerals such as bentonites, montmorillonites, hectorites, saponites, precipitated, pyrogenic, crystalline or amorphous silicas, metal oxides and hydroxides, barium sulfate, fibers or flours of natural products, synthetic Fibers, carbon fibers, aramid fibers, soot and graphites without other fillers

excluded. The fillers and reinforcing materials may also be surface-treated. In the case of fibers as fillers, an introduction of these is only shortly before the

Extruderaustrag preferred to minimize the comminution of the fibers.

The preparation of the flame-retardant compounds is preferably carried out by the complex halogen-free, solid flame retardant composition with the

Polymer granules and other additives and fillers and mixed on one

Twin-screw extruder is processed at temperatures of 230 to 260 ° C (PBT), from 260 ° C (PA6) or from 260 to 280 ° C (PA66). A separate feeder of

Flame retardant composition via a side dosing is also possible. Other polymer molding compounds may require different temperatures in the preparation of the compounds in the twin-screw extruder. The homogenized polymer strand is stripped off, preferably cooled in a water bath, and then granulated.

The invention also relates to polymer moldings, films, filaments and fibers comprising the complex halogen-free solid

Flame retardant compositions included.

Examples

 Hereinafter, the present invention will be described in detail, however, the

Invention is not limited thereto.

Production of the porous glass particles

From a borosilicate glass with the described chemical composition was using water vapor (2.5 g per kg glass melt) as a blowing agent in

Single-screw extruder manufactured at a glass melt temperature of 880 ° C glass foam.

This is followed by pre-shredding the glass foam in a roll crusher (EMDE) to glass foam particles <7 mm. In a subsequent combined grinding and screening process (ball mill and Windradsichter, Helmut Kreutz GmbH) comminution is carried out to a mean particle size of 3.0 μητι (Particle size distribution: di ₀ = 0.9 μητι; d ₅₀ = 3.0 μηη; d ₇₅ = 5.0 μιτι; d ₉₀ = 7.2 μπτι and d ₉₉ <12.0 μητι). The determination of the particle size distribution was carried out by means of

Laser diffraction (Sympatec Helos) according to DIN ISO 1332-1. D ₅₀ is the particle size at which 50 percent of the particles are less than or equal to the specified value.

The pH of the porous glass particles was determined in a 10% aqueous suspension at room temperature in accordance with DIN EN ISO 787-9. Unlike the standard, the eluate was prepared from 10 g of glass powder and 90 g of distilled water. The pH and conductivity of the suspension were then measured with the pH laboratory kit with conductivity electrode (Hach Lange GmbH). The moisture content of the glass particles was in accordance with ISO 787-2 after 2 hours of drying in

Convection oven at 105 ° C determined.

The following values were determined for the porous borosilicate glass powder used in the examples with a d ₅₀ of 3.0 μm.

 pH: 10.3

 Conductivity: 0.7 mS / cm

 Residual moisture: 0.4%.

Preparation of the complex halogen-free, solid flame retardant composition

 Example A

4.7 kg of the porous glass particles with a d ₅₀ of 3.0 pm and 4.7 kg of melamine powder (supplier Penpet Petrochemical Trading GmbH) are weighed out and filled in a flysch mixer (type VM 60 A). Then mix for 10 minutes. 600 g of ammonium nitrate ACS (supplier Carl Roth GmbH & Co. KG) are mixed in 500 ml

dissolved distilled water. This is done by means of heatable magnetic stirrer, since the solution is strongly endothermic.

The ammonium nitrate solution was filled in a 2 liter pressure vessel. The container was pressurized with 2.5 bar by means of compressed air. The mixture of glass powder and melamine in the mixer was sprayed with the ammonium nitrate solution by means of a silt nozzle, with further mixing. After a total mixing time of 60 minutes, the moist product was removed and spread on stainless steel plates, covered with a silicone mat, the layer height being at most 2 cm. The filled sheets were pushed in a trolley and pushed into the oven preheated to 90 ° C. After reaching the target temperature of 90 ° C, the sheets remained for 180 minutes at 90 ° C in the oven. The trolley with the sheets was then removed from the oven removed and after 60 minutes, the complex halogen-free flame retardant was removed as a powder from the sheets.

The complex halogen-free flame retardant was then used to prepare eluates. Contrary to the standard DIN EN ISO 787-14, 10 g of the powder were eluted in 90 g of distilled water. The pH of the eluate was 6.2 and the conductivity 9.4 mS / cm, measured with the pH laboratory kit with conductivity electrode (Hach Lange GmbH). The moisture content of the complex halogen-free flame retardant was determined in accordance with ISO 787-2 after drying for 2 hours in a convection oven at 105 ° C and was 0.25%.

Example B

In a further embodiment, 5.0 kg of the porous glass particles were weighed out with a d ₅₀ of 3.0 μm and 5.0 kg of melamine powder (supplier Penpet Petrochemical Trading GmbH) and filled in a flysch mixer (type VM 60 A). It was then mixed for 10 minutes.

400 ml of distilled water was placed in a 2 liter pressure vessel. The container was pressurized with 2.5 bar by means of compressed air. The mixture of glass powder and melamine in the mixer was sprayed by means of a silt nozzle with the distilled water, wherein the mixture is still mixed. After a total mixing time of 60 minutes, the moist product was removed and spread on stainless steel plates, covered with a silicone mat, the layer height being at most 2 cm. The filled sheets were pushed in a trolley and pushed into the oven preheated to 90 ° C. After reaching the target temperature of 90 ° C, the sheets remained 90 minutes at 90 ° C in the oven. The trolley with the sheets was then removed from the oven and after 60 minutes the complex halogen-free flame retardant could be removed as a powder from the sheets. Eluates were then prepared from the halogen-free flame retardant prepared from porous borosilicate glass powder and melamine. Contrary to the standard DIN EN ISO 787-14, 10 g of the powder were eluted in 90 g of distilled water. The pH of the eluate was 10.2 and the conductivity 0.4 mS / cm, measured with the pH laboratory kit with conductivity electrode (Hach Lange GmbH). The moisture content of the halogen-free, made of porous borosilicate glass powder and melamine

 Flame retardant was according to ISO 787-2 after 2 hours of drying in

Umluftschrank determined at 105 ° C and was 0.20%. The following components were used to prepare the compounds:

CompoDesign Product Manufacturer / Supplier Supplier

A PBT Ultradur B4520 BASF

B PTFE powder HEROLUB ™ C Heroflon

 Spa.

C PA6; relative viscosity 2.70, Tarnamid T-27 PolyOne measured in

96% H ₂ S0 ₄ as 0.5%

 Solution at 25 ° C according to DIN ISO

307; Density 1.14 g / cm ³ ;

 D Glass fiber Vetrotec EC 10 983 Vetrotec

 S.R.L.

E Phosphorus-containing EXOLIT OP 1240 Clariant SE

 Flame retardants

F Porous Borosilikatglaspartikel, TROVO ^® powder B- Trovotech d ₅₀ = 3.0 μιη coated with K3 SÜ.5-2 GmbH 1.5 wt .-% Dynasylan 1189

 G Complexes halogen-free according to Trovotech

 Flammschutzmittelzusammense Example A GmbH tion of 47 wt .-% porous

Borosilicate glass particles with d ₅₀

 = 3.0 μητι, 47 wt .-% melamine,

 6% by weight of ammonium nitrate

 ACS

H complexes halogen free according to Trovotech

 Flammschutzmittelzusammense Example B GmbH tion of 50 wt .-% porous

Borosilicate glass particles with d ₅₀

 = 3.0 μητι, 50 wt .-% melamine

 I melamine cyanurate MC25J Nordmann

 Rassmann GmbH

J Porous borosilicate glass particles, TROVO®powder B- Trovotech d ₅₀ = 3.0 pm K3 GmbH κ Porous borosilicate glass particles, TROVO®powder B- Trovotech d ₅₀ = 3.0 μm, coated with K3-SÜ.5 GmbH 1.5% by weight of Dynasylan 1175

 L 47% by weight GP B3-5-M-WI Trovotech

Borosi Ii katg laspa rti kel, GmbH ground from solid glass, d ₅₀ =

 3.0 μιτι, 47 wt .-% melamine, 6

 Wt% ammonium nitrate ACS,

 Temperature treatment 180

 Minutes at 90 ° C

M 47 wt .-% porous TROVO ^® powder K3 Trovotech

Float glass particles with d ₅₀ = 3.0 M-WI GmbH pm, 47 wt .-% melamine, 6

 Wt% ammonium nitrate ACS,

 Temperature treatment 180

 Minutes at 90 ° C

N 94 wt .-% porous TROVO ^® powder B- Trovotech

Borosilicate glass particles with d ₅₀ K3-WI GmbH = 3.0 μm, 6% by weight

 Ammonium nitrate ACS,

 Temperature treatment 45

 Minutes at 330 ° C

 0 PA66 Ultramid A28 BASF SE

 P Phosphorus-containing EXOLIT OP 1240 Clariant SE

 Flame retardants

The PA6 compounds were produced at a cylinder temperature of 270 to 280 ° C in a twin-screw extruder ZSK 32 (manufacturer Werner and Pfleiderer). The PBT compounds were produced at a cylinder temperature of 250 to 260 ° C in one

Twin screw extruder ZSK 32 (manufacturer Werner and Pfleiderer) produced.

After sufficient drying were from the molding compositions on a

Injection molding machine (Arburg 320C Allrounder) at melt temperatures of 240 to 270 ° C (PBT) and from 270 to 280 ° C (PA6) produced the test specimens for various investigations. The fire test was conducted in accordance with UL94 "Tests for Flammability of Plastic Materials for Parts in Devices and Applications" by Underwriters Laboratories (UL), which has meanwhile been included in the IEC / DIN standards For this test bars of the dimensions 125 mm x 13 mm xs mm are produced, the thickness s may be different and is indicated in the classification.

Comparative Examples

Examples (claim)

 Component Example 1 Example 2 Example 3 Example 4 Example 5

A 54.7 49.7 54.7 54.7

C 94.0 D 25.0 30.0 25.0 25.0

 G 6.0 6.0 6.0 10.0 6.0

 H 6.0

 E 14.0 14.0 14.0 10.0

 B 0.3 0.3 0.3 0.3

Results of the tests

Compare Compare Compare Compare Compare Compare 7 8 9 10 11 12

UL94, 48h, 23 ° C,

 50% rel. LF, 0.8

 mm

 UL94, 48h, 23 ° C, V2 VO V2 V2 V2 HB 50% rel. LF. 1.6

 mm

 UL94, 48h, 23 ° C, VO

 50% rel. LF, 3.0

 mm

 UL94, 168h, 23 ° C,

 70%, 0.8 mm

 UL94, 168h, 23 ° C,

70%, 1.6 mm

In the PBT compounds of Comparative Examples 1 and 2 filled with glass fibers, only a VI according to UL94 was achieved with a combination of a phosphorus-containing flame retardant and porous borosilicate glass particles with a d ₅₀ of 3.0 μm coated with an adhesion promoter. The afterburning times were too long in both cases. However, instead of the porous borosilicate glass particles coated with the adhesion promoter, the claimed complex flame retardant consisting of the porous borosilicate glass particles and melamine (Example 2) or consisting of the porous borosilicate glass particles, melamine and ammonium nitrate (Examples 1 and 3) was used UL94 can be achieved. In Example 4, with a reduction of the use of the phosphorus-containing flame retardant by 50% and simultaneous replacement by the claimed complex flame retardant, the classification V0 according to UL94 was also achieved.

In polyamide 6 could be combined with a combination of melamine cyanurate and porous

 Borosilikatglaspartikeln (Comparison 3 and 4) only the V2 to UL94 can be achieved, although in comparison 5 each 5 wt .-% of both components were used. When using 8 wt .-% melamine cyanurate (Comparison 7) could also be achieved only the V2 to UL94. Only with 12 wt .-% melamine was then achieved in the PA6 compound V0 to UL94. Comparison 9 shows that when using

Borosilicate glass particles milled from solid glass with an average particle size of 3.0 μηι instead of the porous glass particles obtained from glass foam also only a V2 to UL94 could be achieved. Likewise, in comparison with only a V2 according to UL94 when using porous glass particles made of float glass (soda lime glass) instead of the porous glass particles made of borosilicate glass foam only a V2 according to UL94 can be achieved. When, as in Comparison 11, the porous borosilicate glass particles were treated only with ammonium nitrate, only V2 according to UL94 was also achieved. By contrast, with the claimed halogen-free flame retardant composition it was possible to achieve V0 according to UL94 in PA6 even when using 6.0% by weight, as example 5 shows. In Figure 1, a transmission electron micrograph of the porous

 Borosilicate glass particles made from glass foam produced by high-temperature extrusion. The porous structure of the glass particles with pore sizes between 5 and 25 nm is easy to recognize. Figure 2 shows a transmission electron micrograph of the complex halogen-free flame retardant composition of the claim.

Claims

claims:

Claim 1:

 Complex halogen-free solid flame retardant composition for

Polymer molding compounds consisting of

 30 to 70% by weight of porous, low-temperature melting glass particles from a borosilicate glass foam produced by high-temperature extrusion having an average particle size of 1.5 to 12 μm

 - 30 to 70 wt.% Melamine and

- 2 to 10 wt .-% ammonium nitrate, which by

 dry mixing of the porous glass particles of a borosilicate glass foam and the melamine

 uniform distribution of 2-10% by weight of ammonium nitrate dissolved in distilled water

Water, in the mixture of the glass particles and the melamine

- further mixing the components porous glass particles, melamine and dissolved ammonium nitrate

 - Temperature treatment of the mixture at 90 to 120 ° C for 90 to 240 minutes is obtained. Claim 2:

 Flame-retardant polymer molding compositions containing:

 40.0 to 98.0% by weight of polymers or polymer mixtures,

 2.0 to 12.0% by weight of the flame retardant composition according to claim 1,

- 0 to 30 wt .-% auxiliaries

Claim 3:

 Flame-retardant polymer molding compositions containing:

 40.0 to 96.0% by weight of polymers or polymer mixtures,

 - 4.0 to 20.0 wt .-% of the flame retardant composition according to claim 1, - 0 to 50.0 wt .-% fillers and reinforcing agents

 0 to 20% by weight of further flame retardant synergists

 - 0 to 30 wt .-% auxiliaries

Claim 4:

Polymer form according to claim 2 and 3 wherein the auxiliaries plasticizers, nucleating agents, antistatic agents, mold release agents and lubricants, flow and

Processing aids, antioxidants, heat and light stabilizers, dyes, Pigments, coupling agents such as various silanes, anti-drip agents such as polytetrafluoroethylene, dispersion aids such as ethylene glycol, 1,2-propanediol or 1,3-propanediol and other flame retardants are. Claim 5:

 Polymer molding compositions according to claim 3, wherein the contained filler and

Reinforcing materials glass fibers (short, long or continuous fibers), glass beads, glass powder, glass cloth, glass mats, talc, feldspar, quartz, mica, kaolin, chalk,

Calcium carbonate, magnesium carbonate, titanium oxide, silicates such as wollastonite,

Phyllosilicates, clay minerals, e.g. Bentonites, montmorillonites, hectorites, saponites, precipitated, pyrogenic, crystalline or amorphous silicas, metal oxides and hydroxides, barium sulfate, fibers or flours of natural products, synthetic fibers,

Carbon fibers, aramid fibers, carbon black and graphites are excluded without other fillers.

Claim 6:

 Polymer molding compositions according to claim 3, which in addition to the complex halogen-free

Flame retardant composition according to claim 1 contain further flame retardant synergists and anti-drip agents.

Claim 7:

 Polymer molding compositions according to claim 6, wherein the further flame retardant synergists are organic phosphorus compounds. Claim 8:

 A polymer mold according to claim 6, in which as anti-dripping agent

Polytetrafluoroethylene is used as a powder or suspension.

Claim 9:

complex non-halogenated solid fire retardant composition for

 Polymer molding compositions according to claim 1, which is coated with an adhesion promoter for better Deagglomeration and integration into the polymer molding compositions.

Claim 10:

Polymer molding compositions according to claim 2, which is formed from polyamides Claim 11:

 Polymer molding compositions according to claim 3, which is formed from polyesters such as polyethylene terephthalate or polybutylene terephthalate. Claim 12:

 Use of flame-retardant polymer molding compositions according to Claims 2 and 3 for the production of moldings, fibers or films.

Claim 13:

Process for the preparation of complex halogen-free solid flame retardants for polymer compositions with the process steps

 dry mixing of porous glass particles of a borosilicate glass foam and melamine

 uniform distribution of 2-10% by weight of ammonium nitrate dissolved in distilled water in the mixture of the glass particles and the melamine

 - further mixing the mixture of porous glass particles, melamine and dissolved ammonium nitrate

 - Temperature treatment of the mixture at 90 to 120 ° C for 90 to 240 minutes