WO2016207870A1

WO2016207870A1 - Method of production of fireproof polymer additive, fireproof polymer

Info

Publication number: WO2016207870A1
Application number: PCT/IB2016/053824
Authority: WO
Inventors: Jiří VYLIMEC; Roman Magdina
Original assignee: Moles Technology, A.S.
Priority date: 2015-06-26
Filing date: 2016-06-27
Publication date: 2016-12-29
Also published as: SK500342015A3; WO2016207870A4

Abstract

Fireproof polymer is created from the non-toxic components in such a way that pentaerythritol (5% to 90% of the mass share) is added into the water (30% to 90% of the mass share) with the temperature 15 °C to 25 °C; during the continuous mixing the solution is heated to 52 °C to 68 °C. Subsequently ammonium polyphosphate (5% to 90% mass share) is added to the solution and the solution is subsequently heated to the temperature above 92 °C. After this temperature is surpassed the melamine (5% to 90% mass share) is added to the solution and the solution is heated to the temperature 98 °C to 100 °C. After the cooling the water is separated from the solution and the polymer is dried so that the mass share of the water ranges from 2,5% to 8%. The dried granulate is then process to the desired size and packed into a hygroscopically resistant packaging.

Description

Method of production of fireproof polymer additive, fireproof polymer

Field of technology

Invention concerns the method of production of the fireproof additive for increasing of the fire resistance of the coatings, sealants, construction materials. The additive is not toxic, it has strong fireproof effect and it can have a form of the solution or powder.

State of the art

Polymers are often used in construction materials or during the production of the means of production, where high fire resistance is required. Such solutions are known, which use various dangerous substances as flame retardants, for example according to CN102924868 (A), or which use substances which degrade the original physical and mechanical features of the original polymer.

During the production of the construction materials the intumescent additives are commonly used, which increases the fire resistance. These additives create a surface foam during the burning; this foam serves as a heat isolation. Usually the intumescent additives are created by the source of the carbon for the purposes of foaming, the compound producing acid and the compound which produces gases during its decomposition.

The use of ammonium polyphosphate and melamine in the preparations for improvement of the fire resistance is know. The effects of these substances in the individual fireproof applications are well researched. Such substances are in their applications known as indissoluble powders. For their use as well as their use with other substances in the polymer materials it is desirable to produce between them a multifold addition without a by-product. The resulting polymer should only contain substances without any dangerous effects according to known scientific results and studies. The components entering the polymerization should be commercially available with the appropriate environmental classification in REACH.

Essence of the invention

The abovementioned deficiencies in the prior state of the art are significantly remedied by the method of production of the fireproof polymer additive for retardation and/or prevention of the burning according to this invention which essence lies in the fact that pentaerythritol is poured into the water with temperature ranging from 15 °C to 25 °C and during intensive mixing the solution is gradually heated to the temperature ranging from 52 °C to 68 °C; ammonium polyphosphate is then poured into this solution during intensive mixing and heated to the temperature above 92 °C. After surpassing this temperature, melamine is mixed into the solution and the solution is heated to the temperature ranging from 98 °C to 100 °C.

Components added to the solution can have the following ratio (excluding water):

- ammonium polyphosphate: mass share from 5% to 90%,

- pentaerythritol: mass share from 5% to 90%,

- melamine: mass share from 5% to 90%.

Water forming the environment for the polymerization of the components forms, at the beginning of the process, 30% to 95% of the overall solution.

Ammonium polyphosphate [NH₄ POs]_n is used as a food additive, emulsifier (E545). It is also known as flame retardant for polyolefins and polyurethanes.

Pentaerythritol, 2,2-Bis(hydroxymethyl)1 ,3-propanediol, C₅H ₂0 , CAS 1 15-77- 5, is white crystalline powder, tetravalent monotopic alcohol. It is used for the production of alkyd resins, emulsifiers, explosives, coatings, synthetic lubricating oils. It is considered to be an ecologic alternative to polychlorinated biphenyls (PCB).

Melamine, 2,4,6-triamino-1 ,3,5-triazine, C3-H₆-N₆, CAS 108-78-1 , is used mainly during production of plastics and nitrogen fertilizers. Melamine does not dissolve in the water, basically, and in its molecular structure it contains approx. 66% of nitrogen, which is released during burning and which thereby damping the fire. In small amount melamine is not toxic. Melamine is described as harmful in connection with its undesired presence in the food, but the toxic dose in the food is comparable with the table salt; it surpasses 3 g/kg of the live weight of an individual. From this point of view the use of melamine according to this invention is basically harmless.

In the solution with three abovementioned substances - ammonium polyphosphate, pentaerythritol, and melamine - a polymerization takes place, which results in the fireproof polymer with especially strong fireproof effect. Such combination of substances potentiate each other and cores of microintumescence are created in the mass of the polymer. Typical intumescence manifests itself by foaming on the surface of the material, which is usually accompanied by the loss of the original mechanical features of the material. With additive according to this invention a phenomenon has been perceived where little cores are created in the mass of the polymer and there is local inner intumescence surrounding them; the intumescence is relative in its size to the small dimensions of the cores, thereby the inventors have named this phenomenon "microintumescence". The fireproof additive prevents the process of burning by releasing CO₂ and nitrogen gases around the cores in the mass.

Combination of the abovementioned three active substances in the resulting polymer achieves not only high fire resistance, but thanks to microintumescence the polymer have even after being exposed to fire high, almost unchanged mechanical original characteristics.

After the solution reaches the temperature 98 °C to 100 °C, the solution is cooled. The resulting solution can be used in liquid state or it is processed by drying and the volume of the water is limited to 2,5% to 8% with the subsequent adjustment of the granulometry pursuant to the desired result. The fireproof polymer in the powder form is packed into a hygroscopically resistant packaging.

All required raw materials as well as resulting product are categorized in the REACH evidence as substances without any harmful effects on the man. That means that a method (or process) of polymerization and combination of safe substances have been found which lead to increased fire resistance at low costs and low energy demands on the process. The invention achieves high fireproof effects and does not use toxic substances.

Examples of realization Example 1

In this example the fireproof polymer is produced in the following way: 1 ,5 kg of the powder pentaerythritol is mixed into the water with temperature 20 °C. Solution is continuously mixed and heated to the temperature of 65 °C, when during the intensive mixing 2 kg of the ammonium polyphosphate in the powder form is slowly poured into the solution. Then the solution is heated to the temperature 94 °C. After surpassing this temperature, 1 ,5 kg of the melamine is mixed into the solution and the solution is heated to 100 °C. After this temperature is reached the heating is stopped in the overall volume of the solution and it is left to cool; then the water is separated from it. The resulting fireproof polymer has powder form. Example 2

Powder pentaerythritol is mixed in the water with temperature 25 °C. The liquid is heated to 65 °C, when the ammonium polyphosphate in the powder form is mixed in. The liquid is heated to 92 °C and this temperature is maintained for at least 10 minutes. Then the melamine is mixed in and monomeric reaction takes place. The liquid is heated to 100 °C while it is continuously mixed and it is maintained at this temperature during normal pressure for at least 5 minutes, during which the polymerization takes place. The amount of the water can range from 30% to 95% of the overall mass, pursuant to the presumed application of the polymer. The fireproof polymer according to this example is used in the liquid form. It can form an addition to water systems of the industrial substances, an additive to the composites, mordants, oil-based coatings, water and other solvents.

Industrial applicability

Industrial applicability is obvious. According to this invention it is possible to industrially and repeatedly produce and use fireproof polymer which does not contain toxic components and which is very effective.

Claims

P A T E N T C L A I M S

1. A method of production of a fireproof polymer additive for a retardation and/or prevention of a burning i s c h a r a c t e r i z e d b y t h e f a c t , that pentaerythritol is added to a water; during continuous mixing a solution is heated to a temperature ranging from 52 °C to 68 °C, then ammonium polyphosphate is added to the solution during intensive mixing and the solution is gradually heated to the temperature above 92 °C; after this temperature is surpassed a melamine is added to the solution and the solution is heated to the temperature ranging from 98 °C to 100 °C, whereby it is maintained at this temperature for at least 5 minutes during which a polymerization takes place; and the solution is finally cooled.

2. The method of production of the fireproof polymer additive for the retardation and/or prevention of the burning according to the claim 1 i s c h a r a c t e r i z e d b y t h e f a c t , that pentaerythritol is added to the water with the temperature ranging from 15 °C to 50 °C, preferably from 20 °C to 25 °C.

3. The method of production of the fireproof polymer additive for the retardation and/or prevention of the burning according to the claim 1 or 2 i s c h a r a c t e r i z e d b y t h e f a c t , that all components added to the water have powder form.

4. The method of production of the fireproof polymer additive for the retardation and/or prevention of the burning according to any of the claims 1 to 3 i s c h a r a c t e r i z e d b y t h e f a c t , that ammonium polyphosphate forms 5% to 90% mass share of components added to the water.

5. The method of production of the fireproof polymer additive for the retardation and/or prevention of the burning according to any of the claims 1 to 4 i s c h a r a c t e r i z e d b y t h e f a c t , that pentaerythritol forms 5% to 90% mass share of the components added to the water.

6. The method of production of the fireproof polymer additive for the retardation and/or prevention of the burning according to any of the claims 1 to 5 i s c h a r a c t e r i z e d b y t h e f a c t , that melamine forms 5% to 90% mass share of the components added to the water.

7. The method of production of the fireproof polymer additive for the retardation and/or prevention of the burning according to any of the claims 1 to 5 i s c h a r a c t e r i z e d b y t h e f a c t , that after the mixing of all powder components, the water forms 30% to 95% mass share of the solution.

8. The method of production of the fireproof polymer additive for the retardation and/or prevention of the burning according to any of the claims 1 to 7 i s c h a r a c t e r i z e d b y t h e f a c t , that after the cooling the water is separated from the solution and the polymer is dried so that the mass share of the water ranges from 2,5% to 8%.

9. The method of production of the fireproof polymer additive for the retardation and/or prevention of the burning according to the claim 8 i s c h a r a c t e r i z e d b y t h e f a c t , that a dried granulate is processed to a desired size and subsequently it is packed into a hygroscopically resistant packaging.

10. A fireproof polymer i s c h a r a c t e r i z e d b y t h e f a c t , that it is formed by a copolymerization of pentaerythritol, ammonium polyphosphate and melamine in a water solution.