DE3833977A1 - Adducts of phosphonates and amines and their use for preventive fire protection - Google Patents

Abstract

Adducts of phosphonates of the formula (I) <IMAGE> in which M stands for a metal of groups II to VIII of the Periodic Table, R stands for an aliphatic radical having 1 to 6 C atoms or an aromatic radical having 6 to 10 C atoms, R' stands for hydrogen, an aliphatic radical having 1 to 6 C atoms or an aromatic radical having 6 to 10 C atoms and x stands for an integer corresponding to the valency of M and amines, there being 0.05 to 1 mol of an amine to one equivalent of OR' groups contained in the phosphonate of the formula (I> and their use for preventive fire protection.

Description

The present invention relates to adducts of phosphonates and amines and their use as preventative Fire protection.

From EP-A 245 207 it is known that metal salts of Phosphonic acids serve as flame retardants for polymers can. They improve the oxygen index measured as Flammability. The afterburning behavior so equipped However, polymer is poor because of so-equipped polymers release combustible gases.

Adducts of phosphonates and amines have now been found, in which the phosphonate component of a phosphonate of the formula (I)

in the
M is a metal from groups II to VIII of the periodic table,
R is an aliphatic radical having 1 to 6 C atoms or an aromatic radical having 6 to 10 C atoms,
R 'is hydrogen, an aliphatic radical having 1 to 6 C atoms or an aromatic radical having 6 to 10 C atoms and
x represents an integer corresponding to the valence of M
and wherein to one equivalent in the phosphonate of the formula (I) contained -OR 'groups come from 0.05 to 1 mole of an amine.

In formula (I), M is preferably aluminum, Magnesium or calcium, R preferably methyl and R 'is preferably hydrogen or methyl. Both Phosphonates of the formula (I) may be uniform or mixed compounds, i. H. R and R ', in particular R ', can from one

vary to another. As examples of phosphonates of the formula (I) may be mentioned as follows:

When in formula (I) M represents a polyvalent metal, z. As aluminum, so must in the corresponding phosphonates not all valences of M with

be saturated. Of the present invention are Also includes such phosphonates, which in the case of M = polyvalent Metal next to it

also contain OH groups. As an example of such Phosphonates is

called.

There are also phosphonates, which are made Phosphonates of the formula (I) by intermolecular cleavage derive from R'-O-R '. As an example of such Phosphonates is

called.  

Preferred amines are those which have one molecule per molecule or more NH₂ groups. As examples may be mentioned: ammonia, ethylenediamine, polyethylene polyamines such as triethylenetetramine, melamine, guanidine, Urea, dicyandiamide, aniline-formaldehyde condensates, Ethanolamine and dimethylaminopropylamine. Especially preferred are ammonia, ethylenediamine and melamine, in particular Melamine.

But there are also secondary, tertiary and possibly Phosphorus-containing amines into consideration. When Examples include:

The ratio of in the phosphonates of the formula (I) contained OR 'groups to amine is preferably 0.25 to 0.75 moles of amine per equivalent of OR 'groups. It are in principle also amine amounts of more than 1 mol per Equivalent OR 'groups in the phosphonate of the formula (I) possible, however, this does not generally improve the fire properties of the phosphonate-amine adducts.

The phosphonates of the formula (I) can be, for example be prepared by hydroxides or oxides of Formulas (IIa) or (IIb)

M (OH) _x (IIa)

MO _{x / 2} (IIb)

in which
M and x have the meaning given for formula (I),
with stoichiometric amounts of a phosphonate compound of the formula (III)

in the
R and R 'have the meaning given in formula (I),
in the presence of water at temperatures in the range 120 to 200 ° C, optionally in closed vessels, reacted.

The adducts of phosphonates and Amines can be obtained by taking the two Components at 0 to 300 ° C, preferably at 15 to 200 ° C brings together. If and if so which Reaction (s) occur in the adduct formation is not been examined in detail. The components can as such, but also in dissolved and / or suspended State be brought together. It can also be water be present.  

With special ways of working one can look for one of the proceed as follows:

• - When using plastics with adducts according to the invention wants to equip it, so it is enough, the two components to incorporate into the plastic, with the adduct formation if necessary, only in case of fire.
• - You can also separately mix the components, if necessary in the aqueous medium, after adduct formation by drying the adduct and win this, if necessary after grinding, in plastics, paints, Incorporating impregnating agents, etc.
• The preparation of adducts according to the invention in aqueous Medium and the preparation of adducts according to the invention for use in casting resin systems is preferably carried out at temperatures in the range 0 to 100 ° C.
• The preparation of adducts according to the invention for use in thermoplastics is preferably carried out at temperatures in the range 100 to 250 ° C.

Particularly preferred adducts according to the invention are obtained in a simple way, if you put melamine in a 20 to 40% aqueous solution of aluminum methylphosphonate (= Ic) at 15 to 40 ° C enters. The water solubility The formed adducts depends on the molar ratio of Components off. Filtered off as solids and dried  Adducts of this type are particularly easy to handle during incorporation into epoxy resins, polyurethane foams, Rubber compounds, unsaturated polyester resins and thermoplastics.

Other particularly preferred adducts according to the invention are obtained one, when aqueous solutions of aluminum methylphosphonate (= Ic) neutralized with ammonia or ethylenediamine. Such adducts are generally included pH values from 7 to 9 are readily soluble in water and can be used directly as an aqueous solution, as in the preparation accumulates or after removing parts of the water as Soak for textiles or paper or as a paint to be used for wood.

Inventive adducts of phosphonates and amines can be used for preventive fire protection. The substrates equipped with it fire-proof can be of a very different kind. As substrates, for example, textiles, paper, Plastics, rubbers, casting resins, thermoplastics, polyester resins, Polyurethanes, epoxy resins, wood and metals in question. The adducts according to the invention give in Fire trap a carbonizing, intumescent (i.e. foaming) and flame-extinguishing effect. The forming Intumescent foam ceramizes and forms a fine-pored, oxidation-resistant and protective framework, which is often temperature resistant up to more than 1000 ° C.

Adducts according to the invention can be used as solutions or dispersions, optionally together with other usual ones  Components used for paints and impregnations become. Cast resins and multi-component reaction resins adducts according to the invention can be added, as long as they are still liquid. In thermoplastics and rubbers may optionally adducts according to the invention together with other additives on kneaders, Melt-mixing extruders or rolling mills incorporated become.

The adducts of the invention may, for. Also as such, z. B. in aqueous formulation, as putty, mortar or coatings used with fire protection effect become.

The fire protection effect is generally the better the more adducts according to the invention the respective ones contains protective substrate. For example, 10 to 400 wt .-% adducts according to the invention, based on the respective substrate can be used. Preferably this amount 25 to 250 wt .-%.

Of course, adducts according to the invention also in combination with other flame and fire retardants be used.  

Examples

In the following the invention will be explained by way of example. The specified parts and percentages refer to the Weight unless otherwise stated. The specified Formulas indicate the gross compositions.

A. Preparation of phosphonates of the formula (I) example 1

74 parts of Ca (OH) ₂ and 250 parts of dimethyl methylphosphonate (= DMMP) were made up with 500 parts of water for 4 hours Heated 170 ° C in an enamel autoclave. there has been a clear solution of the salt

receive.

Example 2

40 parts of MgO were mixed with 250 parts of DMMP and 500 parts Water in an enamel autoclave for 5 hours Heated to 190 ° C. It became a clear solution of the salt  

receive.

Example 3

81 parts ZnO and 250 parts DMMP were mixed with 500 parts Water in an enamel autoclave for 4 hours Heated to 180 ° C. It became a clear solution of the salt

receive.

Example 4

58 parts of Mg (OH) ₂ were mixed with 250 parts of DMMP and 500 Dissolve water in an autoclave for 4 hours Heated to 135 ° C. A suspension was obtained whose Water phase has a solids content of less than 2% would have. The suspension was evaporated to dryness at 120 ° C. The solid thus obtained consisted essentially out  

According to IR spectrum, NMR spectrum and titration results were 15% of the theoretically present P-OCH₃ groups been saponified to P-OH groups.

Example 5

78 parts of Al (OH) ₃ (Apyral® B 90 from Bayer AG) were with 124 parts of DMMP and 400 parts of water in an autoclave Heated to 150 ° C for 5 hours. there has been a Suspension obtained whose water phase has a solids content less than 2%. The suspension was concentrated at 60 ° C in vacuo. The resulting solid consisted according to carbon analysis, IR spectrum, NMR spectrum and a titration study to 70%

and to 30% off

Example 6

78 parts of Al (OH) ₃, as used in Example 5 were with 250 parts of DMMP and 500 parts of water in an autoclave Heated to 150 ° C for 5 hours. One received a suspension whose water phase has a solids content less than 2%. The suspension was in vacuo concentrated at 70 ° C. After the analytical investigations the solid was 70%

and to 30% off

Example 7

78 parts Al (OH) ₃, as used in Example 5 were with 373 parts DMMP and 800 parts water for 5 hours heated to 150 ° C in an autoclave. One received one Suspension whose water phase is less than 5% solids contained. The suspension was at 80 ° C under reduced Concentrated pressure. The resulting solid corresponded after analytical investigations of the salt  

in which 17% of the P-OCH₃ groups saponified to P-OH groups were.

Example 8

The procedure was as in Example 7, the Reaction temperature in the autoclave, however, was 180 ° C elevated. A clear solution of the salt was obtained

in which, according to analytical investigations, less than 10% of the P-OH groups still unsaponified as P-OCH₃ groups templates.

B. Preparation of adducts according to the invention Example 9

A 20% aqueous solution of the salt from Example 8 was mixed with a 20% solution of ethylenediamine in  Adjusted with stirring to a pH of 7.5. The resulting clear solution was water pump vacuum at 70 ° C to a solids content of 40% concentrated and then as a paint for wood used.

Example 10

312 parts of the salt from Example 8 were as 20% Solution in water with 42 parts of melamine. The Mixture thickened under warming. It was heated Reaction mixture for 10 minutes at 100 ° C and dried at 100 to 120 ° C. Then the material was on one Ball mill pulverized.

Example 11

The procedure was as in Example 10, but under Addition of 126 parts of melamine.

Example 12

The procedure was as in Example 10, but under Addition of 180 parts of melamine.

Example 13

350 parts of the salt from Example 7 were dissolved in 1000 parts Suspended water, with a pH of 3.5 revealed. Then it was adjusted to pH with triethanolamine set to 7.5 and dried.  

Example 14

It was worked as in Example 13, but was adjusted to a pH of 7.5 with aqueous ammonia.

Example 15

350 parts of the salt from Example 7 were in 1000 Divide water and add 84 parts while stirring Melamine heated to 100 ° C for 10 minutes. Then it became dried at 120 ° C and pulverized.

Example 16

240 parts of the salt from Example 6 were in 600 parts Suspended water and stirring with 84 parts Melamine heated to 100 ° C for 10 minutes. Then it became dried at 120 ° C and pulverized in a ball mill.

Example 17

240 parts of the salt from Example 6 were in a Mixer thoroughly mixed with 24 parts of ethylenediamine. The forming powder was free-flowing and odorless. In an aqueous slurry, the pH was 7.5.  

Example 18

180 parts of the salt from Example 5 were used with 126 Divide melamine in aqueous suspension for 10 minutes Boiled reflux and then dried at 100 to 130 ° C.

Example 19

240 parts of the salt of Example 4 were in 1000 Divide water and suspend the suspension with ethylene diamine to a pH of 7.5 set. Then it was dried and in a ball mill pulverized.

Example 20

240 parts of the salt from Example 4 were mixed with 120 Divide melamine and 1000 parts of water for 30 minutes Boiled reflux, then dried and pulverized.

Example 21

260 parts of the salt from Example 3 were used with 130 Dissolve melamine and 800 parts water for 10 minutes Heated to 100 ° C, then dried and pulverized.

Example 22

220 parts of the salt from Example 2 were as 20% Solution in water mixed with 42 parts of melamine, the viscous mixture stirred for 10 minutes at 100 ° C and then dried at 100 to 120 ° C and pulverized.  

Example 23

240 parts of the salt from Example 1 were as 20% aqueous solution with 84 parts of melamine stirred at 100 ° C. dried and then pulverized.

Example 24

240 parts of the salt from Example 1 were found to be 10% aqueous solution with 240 parts of melamine stirred, at 100 dried to 120 ° C and then pulverized.

C. Assessment of fire behavior Example 25 (for comparison)

On a rolling mill were in 100 parts of an ethylene-vinyl acetate copolymer of trade (Levapren® 8338, Bayer AG, ethylene content approx. 30%) 200 parts of the phosphonate from Example 8 incorporated in powder form.

• a) Examination of the O₂ index according to ISO 4589 (1984) gave a value of 40.5%.
• b) Furthermore, a 2 mm thick plate from the so obtained material with an edge length of 20 × 20 mm on a wire mesh with square Meshes of 1.9 × 1.9 mm mesh size 20 mm above the burner surface of a natural gas surface burner (16 mm Mecker Burner, Type 1431, Fa. Juchheim OHG,  5550 Bernkastel-Kues) horizontally centered and underside Flamed for 30 seconds. Then the burner became cleared and the afterburning of the sample observed. There was a after burning of 15 seconds (average of 5 measurements).

As far as the following examples on measurements of the O₂ index and measurements of the afterburning time proceed analogously.

Example 26 (for comparison)

The procedure was as in Example 25, but 200 were Parts of the phosphonate from Example 7 in the copolymer incorporated. It was an O₂ index of 41.8% and a Afterburn time of 14 seconds determined.

Example 27

The procedure was analogous to Example 25, but was as Solid used the adduct prepared according to Example 11. It has an O₂ index of 45.5% and an afterburning time determined by 3 seconds.

This experiment confirms that over the phosphonate Example 8 significantly improved fire protection effect of Adduct from Example 11.

Example 28

The procedure was analogous to Example 26, but as a solid product the adduct of Example 15 is used. It was  the O₂ index to 46.2% and the afterburner with 4 Seconds determined.

This experiment also demonstrates that over the phosphonate from Example 7 improved fire protection effect of Adduct from Example 15.

Example 29

A 2 mm thick spruce wood board was used with the 20% Solution of the phosphonate from Example 8 for 24 hours soaked, then wiped off and dried. The same was treated with a 20% aqueous solution of the adduct made from Example 9. The at 22 ° C up to constant Weight dried wood panels became a provision subjected to the afterburning time. For the phosphonate from example 8, an afterburn time of 21 seconds was determined in the adduct of Example 9, an afterburning time only 9 seconds.

Example 30

On a pill press, as used for making Potassium bromide compacts for IR spectroscopy usual were from the adducts according to Examples 10, 11 and 12 one pill each with a diameter of 1 cm and a thickness of 2 mm. These compacts were placed in a preheated to 500 ° C oven and Leave for 30 minutes. After cooling, the measured intumescent volume increase. She lay with  Adduct from Example 10 at 600 vol .-%, the adduct of Example 11 at 300 vol .-% and the adduct of Example 12 at 200 vol .-%.

Example 31

100 parts of the adduct of Example 11 were at 18 ° C stirred with 200 parts of water for 24 hours. It revealed a suspension in which the solids content in the Water phase was less than 5%. The phosphonate off Example 8, from which the adduct of Example 11 was prepared is freely mixable with water, so totally soluble. It is therefore easily due to moisture or Water dischargeable. That from the phosphonate of the example 8 prepared adduct of Example 11 is due its difficult solubility much more difficult Humidity or water dischargeable.

Example 32

There were the O₂ index values of compounds with different Adducts which according to Example 25 in a Ethylene-vinyl acetate copolymer has been incorporated were determined as follows:

Adduct from example O₂ index (%) 24 44.3 23 46.9 22 45.0 21 46.1 20 42.7 19 43.1 17 44.2 16 47.4 14 51.0 13 42.2

Example 33

In 100 parts of an ethylene-ethyl acrylate copolymer (Acrylate content 30%) were on a rolling mill 250 parts of the adduct of Example 11 incorporated. The determination of the O₂ index gave 39.3%, the determination of the afterburning time a value of 4 seconds.

A test specimen, as used for determining the afterburn time was used (see Example 25b), was 5 hours long in a ventilated muffle furnace at 600 ° C heated. Then the test piece was removed from the oven. It was about 600 vol.% Foamed, white and fine-pored, ceramized Foam scaffold with good strength. The Carbon content had been oxidized out. To this Available foam body have a density of about 100 g / l and are suitable for insulation.  

Example 34 a) for comparison

A cable was made with a standard flame retardant mixture from 45% vinyl acetate-containing ethylene-vinyl acetate copolymer (Levapren® 450, Bayer AG) and 200% Al (OH) ₃ coated (based on copolymer) and a 10 cm long piece of it 2 hours in a muffle furnace kept at 500 ° C. After that, the cable piece was in itself collapsed and the carbon largely oxidized away.

b) according to the invention

An identical cable was made with a flame retardant Mixture as in a) jacketed, but contained the flame-retardant coating instead of Al (OH) ₃ a corresponding Amount of the adduct of Example 15. After 2 hours in Muffle furnace at 500 ° C, the cable structure was fully preserved, the outer layer had the structure of a voluminous, solid and fine-pored foam and the Oxidation of carbon only incomplete and only of done the front sides.

Example 35

In a cold-curing epoxy resin reaction mixture (Lekutherm®, Bayer AG) were 50% (based on the Total amount) of the adduct of Example 15 incorporated. After curing, an O₂ index of 55% was measured.  

Example 36

In a polyether polyol (100 parts) by addition of ethylene oxide was produced on glycerol and having an OH number of 250, 150 parts were pulverized Adduct stirred from Example 11. Then were 0.2 parts of water, 0.2 parts of a commercial Silicone stabilizer, 0.3 parts of tin octoate and 65 parts a commercially available polyisocyanate based on Aniline-formaldehyde reaction products (Desmodur® 44 V 40, Bayer AG). In the course of 5 minutes foaming a polyurethane with a formed Volume weight of 300 g / l. In the flame test was a After burning of 3 seconds. With persistent Flaming became more stable as volume increased, ceramified, flame-retardant foam obtained. such Polyurethanes and polyurethane foams are for insulation and roofing suitable.

Example 37

The procedure was as in Example 34b), but was instead of the adduct from Example 15, a mixture of 80 parts of phosphonate from Example 7 and 20 parts Melamine used. In the muffle furnace here were the same good properties for such a jacketed Cable determined as in Example 34b). The O₂ index of Cable jacket material was determined to be 48%.

Example 38

A commercial alkyd resin clearcoat was 150%  (based on paint solids) of the milled, also in Example 37 used mixture of phosphonate and Melamine mixed and as a 1 mm thick layer on a 5 mm thick spruce wood board applied. After this Drying was the coated side of the plate with the flame of the natural gas burner (see example 25) flamed. For more than 10 minutes continued flame treatment formed from the coating about 4 mm thicker, the flame supplied Intumeszenzschaum feinporigem ceramized material, the underlying Areas of wood from further flame attack protected.

The same test procedure was observed as in place of the phosphonate / melamine mixture used Mixture of 70 parts of the phosphonate from Example 3 and 30 parts of melamine was used.

A comparison sample in which the paint instead of the precursors contained chalk for an adduct of the invention, burned as much as possible under the same test conditions from.

Example 39

A 30% aqueous solution of the phosphonate from Example 8 (solid) was with 25% aqueous ammonia Stirring adjusted to a pH of 8. It originated a viscous clear solution of the adduct. This solution was similar to Example 29 for flame retardant equipment used by wood. As a result of the fire test was determined an afterburn time of 11 seconds.  

Example 40

100 parts of the solid from Example 7 were in a Mixer (Lödige company) to saturation with ammonia gas added. It sounded the initial warming, from which adduct formation was accompanied. The powdery product had a water solubility at 20 ° C less than 3%. In water, the pH rose from 4.5 on 8 at.

It was dried in vacuo at 80 ° C and also Excess ammonia removed.

In 100 parts of an ethylene-vinyl acetate copolymer (about 45% Ethlyen) were 200% of the adduct on the Roller incorporated. A flexible coat was obtained. Its oxygen index was determined to be 52%. The Afterburning time was less than 3 seconds.

In a similar comparative experiment was instead the adduct used only the solid from Example 7. It was an oxygen index of 41% and a After-burn time of 19 seconds determined.

Example 41

6300 parts of Al (OH) ₃ (Apyral® B 90, Bayer AG) were with 4000 parts DMMP, 10 160 parts melamine and 40 000 parts Water in an autoclave for 5 hours at 150 ° C. heated with stirring. After cooling, it became a dispersion obtained directly as a fire-retardant for Wood and mineral wool products can be used.  

After distilling off the present in the dispersion Methanol left behind a spreadable more viscous Dispersion, which can also be used as a fire-retardant paint is, but now no flammable solvents contained more. It contained film-forming parts, the for a good adhesion of the intumescent paint on wood, mineral wool or other, preferably provide absorbent substrates.

The originally obtained neutral dispersion was added 120 ° C evaporated to dryness. The obtained powdery Material had a water-soluble content at 22 ° C 11%. 250 parts of the powdery material were in 100 Parts of an ethylene-vinyl acetate copolymer (vinyl acetate content 70%) incorporated on the roll at 90 ° C. The thus-obtained flexible polymer material had a O₂ index of 61%. The afterburning time became less determined as 3 seconds. When using an ethylene copolymer with 30% ethyl acrylate in the same amount an oxygen index of 58% was found.

Pattern of the so filled flexible polymers were placed in a heated to 500 ° C oven, where an intumescent foam with a volume increase of more than 300 vol .-% formed. This intumescence property makes the filled polymers particularly suitable for the production of closure bodies for fire protection cable penetrations (Cable bulkheads).

Claims (10)

1. adducts of phosphonates and amines in which the phosphonate consists of a phosphonate of the formula (I) in the
M is a metal from groups II to VIII of the periodic table,
R is an aliphatic radical having 1 to 6 C atoms or an aromatic radical having 6 to 10 C atoms,
R 'is hydrogen, an aliphatic radical having 1 to 6 C atoms or an aromatic radical having 6 to 10 C atoms and
x represents an integer corresponding to the valence of M
and to one equivalent in the phosphonate of formula (I) contained -OR 'groups come from 0.05 to 1 mole of an amine. 2. Adducts according to claim 1, characterized in that in formula (I) M is aluminum, magnesium or calcium,
R for methyl and
R 'are preferably hydrogen or methyl and
the amine has one or more NH₂ groups per molecule. 3. Adduct according to Claims 1 and 2, characterized that the amine is ammonia, Ethylene diamine, polyethylene polyamines, melamine, Guanidine, urea, dicyandiamide, aniline-formaldehyde condensates, Ethanolamine or dimethylaminopropylamine is. 4. Process for the preparation of adducts from phosphonates and amines according to claim 1, characterized in that that you have the two components in the corresponding quantitative ratio at 0 to 300 ° C. brings together. 5. Use of adducts of phosphonates and amines according to claim 1 for preventive fire protection. 6. Use according to claim 5, characterized that with the adducts textiles, paper, plastics, Rubbers, casting resins, thermoplastics, polyester resins, Polyurethanes, epoxies, wood or Preventive metals are fire protected.   7. Use according to claims 5 and 6, characterized that the adducts of phosphonates and Amines as solutions or dispersions, optionally along with other common components for Paints and impregnations. 8. Use according to claims 5 and 6, characterized that the adducts of phosphonates and Amines to casting resins or multi-component reaction resins adds as long as these are still fluid are. 9. Use according to claims 5 and 6, characterized that the adducts of phosphonates and Amines optionally together with other additives incorporated into thermoplastics or rubbers. 10. Use according to claims 5 to 9, characterized that from 10 to 400 wt .-% of the adducts Phosphonates and amines based on the respective Substrate used.