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WO2016170469A1 - Additif ignifuge pour des polyuréthanes, polyuréthane ignifuge, procédé de production d'additif ignifuge - Google Patents

Additif ignifuge pour des polyuréthanes, polyuréthane ignifuge, procédé de production d'additif ignifuge Download PDF

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Publication number
WO2016170469A1
WO2016170469A1 PCT/IB2016/052211 IB2016052211W WO2016170469A1 WO 2016170469 A1 WO2016170469 A1 WO 2016170469A1 IB 2016052211 W IB2016052211 W IB 2016052211W WO 2016170469 A1 WO2016170469 A1 WO 2016170469A1
Authority
WO
WIPO (PCT)
Prior art keywords
fireproof
additive according
added
melamine
solution
Prior art date
Application number
PCT/IB2016/052211
Other languages
English (en)
Inventor
Roman Magdina
Jiří VYLIMEC
Radoslav BERNÁT
Original Assignee
Roman Magdina
Vylimec Jiří
Bernát Radoslav
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Roman Magdina, Vylimec Jiří, Bernát Radoslav filed Critical Roman Magdina
Publication of WO2016170469A1 publication Critical patent/WO2016170469A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings

Definitions

  • the invention concerns the additive which increases the fire resistance of the polymer materials, mainly polyurethanes and foam polyurethanes, which are used, for example, in construction materials, means of transport and so on.
  • the additive is not toxic and it has robust fireproof effect.
  • polyurethanes represent a wide group of polymer materials with various features; they are basis for the paints and coating materials, for flexible foams, for fibers, but also for hard elastomers.
  • Polyurethanes are produced by reactions between isocyanates and polyalcohols. Urethane group — NH— CO—CD- is common for polyurethanes. During the main reaction there can be side reactions, for example, the releasing of the CO2 during the production of the foam polyurethane. This one is often used in the function of the construction of the thermal insulator.
  • the common feature of the unrefined polyurethanes in the common forms is their low resistance to fire. The consumption of the polyurethanes increases by 5% per annum. From the overall volume, approx. 32% is consumed for the insulation of the buildings, 20% for the furniture and mattresses, 14% in car and aviation industry and 10% as coatings. Given the structure of the consumption of the polyurethanes, their fire resistance is highly desired.
  • JPS58222146 a use of pentaerythritol and ammonium polyphosphate in order to increase the fire resistance of polyurethane is known. Such combination has relatively weak effect.
  • the solution according to RU2040531 (C1 ) uses expandable graphite, which in itself is expensive in necessary concentration and not very effective, and which in high concentration undesirably affects other features of the polyurethane. Similar deficiencies accompany the solution according to DE4234374, DE10047024 with the use of melamine.
  • intumescent additives increasing the fire resistance are known. Such additives produce a surface foaming during the burning, whereby this foaming serves as a heat insulation.
  • the intumescent additives are composed of the source of the carbon for the foaming, the acid-producing compound and the compound which produces gases by its decomposition.
  • the walls of the individual cells are thin; they contain few materials in the contact layer and therefore the production of intumescence is difficult to realize.
  • a use of ammonium polyphosphate and melamine in the preparations for the improving of the fire resistance is known. Use of such substances in the individual fireproof applications is well-researched. The substances are in the applications used as indissoluble powders. For their use - as well as use with the other substances in polyurethanes - it is desirable to produce multiple additions between them without byproduct. The resulting polymer should only contain the substances without any dangerous effects according to all known results and studies. The ingredients entering the process of polymerization should be commercially available with the respective appropriate environmental categorization in the REACH classification.
  • the organic compound of saccharose in an additive according to this invention, the organic compound of saccharose
  • Saccharose is also well soluble in the aqueous solution; it can be used in crystalline form of a classical food sugar or in form of a liquid glucose and fructose.
  • the side-effect of the use of saccharose as an ingredient to polyurethane is an inhibition of the growth of the microorganisms, whereby this effect is achieved by the substance with no health hazard.
  • Copolymer of pentaerythritol, ammonium polyphosphate and melamine is created in such a way that pentaerythritol is poured into the water with temperature ranging from 15 °C to 25 °C; during continuous mixing the solution is heated up to the temperature of 52 °C to 68 °C; then during intensive mixing we pour ammonium polyphosphate to the solution and the solution is gradually heated to the temperature above 92 °C. After surpassing this temperature the melamine and the solution is heated to the temperature 98 °C to 100 °C
  • the ingredients added to the solution can have following ratios (not counting the water):
  • Saccharose will be added to the aqueous solution with the pre-produced copolymer, preferably before the cooling of the aqueous solution. Saccharose is added in the share of 5% to 70% of the overall mass of all ingredients without water. It is preferable if the saccharose is added after the addition of the ingredient to the polyurethane basis in the liquid form in the mass share ranging from 2% to 19% of the overall mass of the polyurethane mixture before foaming.
  • the resulting solution can be used in the liquid state or it is adapted by drying to the point where water forms 2,5% to 8% with the subsequent adjusting of the granulometry (or particles size) to the desired shape.
  • Ammonium polyphosphate [NH 4 POs] n is used as a food ingredient, an emulsifier (E545). It is also known to be a flame retardant for polyolefins and polyurethanes.
  • Pentaerythritol, 2,2-Bis(hydroxymethyl)1 ,3-propanediol, C 5 H 2 0 , 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 ecological alternative to polychlorinated biphenyls (PCB).
  • Melamine 2,4,6-triamino-1 ,3,5-triazine, C 3 -H 6 -N 6 , 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 damps 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; such dose must surpass 3 g to 1 kg of the live weight of an individual.
  • melamine is basically harmless, because receiving such dose from the treated polyurethane can be ruled out. Even during continuous contact of the treated polyurethane with skin the harmful dose will not be transferred. Melamine prevents the burning process also by releasing CO2 and nitrogen gases during heat. This lowers the amount of oxygen in the boundary layer of the polyurethane to 13%, which stops the process of burning.
  • the fireproof effects of the additive are heightened if such melamine is added to the aqueous solution which does not create copolymer with the other components, but it does increase the amount of nitrogen available for release during burning,
  • the additional melamine can present a mass share of 10% to 60% from the overall mass of the polyurethane mixture before foaming.
  • Triol in form of various hydroxyl derivates of hydrocarbons with three hydroxyl groups can form 40% to 80% of the mass of the polyurethane mixture.
  • the mass share of the polyol as alcohol with two or multiple hydroxyl groups can form 6% to 45% of the mass of the polyurethane mixture.
  • Polyurethane mixture can include triethyl phosphate (TEP, Ce H-
  • TEP triethyl phosphate
  • 5 0 4 P-i triethyl phosphate
  • a fine amorphous silicon dioxide powder S1O2 with a fraction below 5 pm, preferably below 1 pm.
  • Such fraction of an amorphous powder silicon dioxide has high specific surface, usually 12 000 to 35 000 m 2 /kg.
  • Such fraction of the ultra-fine silica fume is used for the refinement of the concrete, where it is called microsilica.
  • microsilica functions as a core of the starting point of the hydration of the cement.
  • Microsilica is a mineral substance which originally appeared as a waste in certain metallurgical plants. Silicone dioxide powder is nonflammable and its temperature of melting is approx. 1600 °C. It is generally known that the crystalline silicon can cause silicosis; however, in the additive according to this invention an amorphous silicone oxide is used, which is not considered harmful.
  • Fireproof additive with the microsilica according to this invention has unusually large surface of the grains of usually round shape.
  • the additive is capable even in very thin layer to fill in the surface of the cavities and voids in the polyurethane, thereby preventing the access of the oxygen.
  • Physical features of the microsilica - which in case of its application in the concrete mixtures ensure pozzolanic and rheological effect - in our case significantly ensure, after its connection with the surface of the polyurethane, its nonflammability.
  • Silicone dioxide powder can contain crystalline form and alien admixtures pursuant to the method of the production of the microsilica. It can therefore contain calcium oxide, magnesium oxide, aluminum oxide, sodium oxide.
  • the main part of microsilica (more than 50%) will be formed precisely by the amorphous silicone dioxide powder.
  • This invention ensures high fireproof effects, it uses non-toxic substances and it can be easily applied in the polyurethanes of various kinds.
  • the fireproof additive is produced in following way: 1 ,5 kg of the powder pentaerythritol are mixed to 5 kg of water heated to 20 °C.
  • the solution is continuously mixed and heated to the temperature of 65 °C, when we during intensive mixing slowly pour in 2 kg of the ammonium polyphosphate in the powder form. Then the solution is heated to 94 °C. After surpassing this temperature we mix 1 ,5 kg of the melamine into the solution and we heat it up to 100 °C. After achieving this temperature in the whole volume of the solution we finish heating and we let the solution cool below 65 °C, when we mix 2 kg of saccharose in the crystalline form into the solution.
  • Powder pentaerythritol is mixed in water with temperature of 25 °C.
  • the liquid is heated to the temperature of 65 °C when the ammonium polyphosphate in the powder form is mixed into it.
  • the liquid is heated to 92 °C and we maintain this temperature for at least 10 minutes.
  • the liquid is heated to 100 °C; we mix it continuously and we maintain this temperature during normal pressure for at least 5 further minutes, during which a polymerization takes place.
  • the amount of water can be chosen in the range of 30% to 95% of the mass share, based on the amount of the saccharose and additional melamine added later.
  • saccharose presents 19% of the mass share, the additional melamine 10%, the copolymer of pentaerythritol, ammonium phosphate and melamine 10% of the mass share in the total weight of the polyurethane mixture.
  • Other components forming the basis of the polyurethane mixture can vary.
  • Fireproof additive in this example is supplied by amorphous silicone dioxide powder in the amount of 15% of the mass share.
  • Additive and polyurethane with the additive can be advantageously used in construction, in manufacture of furniture, mattresses, paints and coatings, and sealants and in the automotive and aerospace industries.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un additif ignifuge qui ralentit ou arrête la combustion du polyuréthane. L'additif utilise un mélange de saccharose et d'un copolymère de pentaérythritol, de polyphosphate d'ammonium et de mélamine en solution aqueuse. Dans agencement préférable, l'additif peut contenir de la mélamine supplémentaire qui ne prend pas part à la polymérisation et qui fournit au lieu de cela principalement une source d'azote destinée à être libérée pendant le contact avec les flammes. Le saccharose, en association avec le copolymère, présente une fonction importante dans la création de la structure de surface qui forme le support mécaniquement assez résistant pour le processus intumescent. L'additif est créé à partir de constituants non toxiques, en ce qu'on ajoute, à de l'eau (part massique de 30 % à 90 %) présentant une température entre 15°C et 25°C, un pentaérythritol (part massique de 5 % à 90 %) ; pendant le mélange continu, la solution est progressivement chauffée à la température entre 52°C et 68°C. Ensuite, un polyphosphate d'ammonium (part massique de 5 % à 90 %) est ajouté à la solution pendant un mélange intensif et la solution est chauffée à la température au-dessus de 92°C. Après avoir dépassé cette température, de la mélamine (part massique de 5 % à 90 %) est ajoutée à la solution et la solution est chauffée à la température entre 98°C et 100°C. Ensuite, un saccharose est ajouté, ainsi que de la mélamine supplémentaire.
PCT/IB2016/052211 2015-04-19 2016-04-19 Additif ignifuge pour des polyuréthanes, polyuréthane ignifuge, procédé de production d'additif ignifuge WO2016170469A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SK50018-2015A SK500182015A3 (sk) 2015-04-19 2015-04-19 Protipožiarna prísada do polyuretánov, protipožiarny polyuretán, spôsob výroby protipožiarnej prísady
SKPP50018-2015 2015-04-19

Publications (1)

Publication Number Publication Date
WO2016170469A1 true WO2016170469A1 (fr) 2016-10-27

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Country Status (2)

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SK (1) SK500182015A3 (fr)
WO (1) WO2016170469A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017179029A1 (fr) * 2016-04-16 2017-10-19 Vylimec Jiří Procédé de production d'une substance d'imprégnation ignifuge, principalement pour des produits de construction, substance d'imprégnation ignifuge et son utilisation
CN110157040A (zh) * 2019-05-31 2019-08-23 安徽理工大学 一种新型膨胀阻燃成炭剂及其制备方法
CN113150671A (zh) * 2021-05-07 2021-07-23 华阳新材料科技集团有限公司 非离子型水性聚氨酯基膨胀型钢结构防火涂料及制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010131037A1 (fr) * 2009-05-12 2010-11-18 Tremco Illbruck Coatings Limited Composition intumescente
US20150004402A1 (en) * 2013-06-28 2015-01-01 Sabic Innovative Plastics Ip B.V. Intumescent coating composition comprising particulate poly(phenylene ether)
US9097011B1 (en) * 2009-06-05 2015-08-04 American Thermal Holdings Company Heat and fire resistant plastic foam

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010131037A1 (fr) * 2009-05-12 2010-11-18 Tremco Illbruck Coatings Limited Composition intumescente
US9097011B1 (en) * 2009-06-05 2015-08-04 American Thermal Holdings Company Heat and fire resistant plastic foam
US20150004402A1 (en) * 2013-06-28 2015-01-01 Sabic Innovative Plastics Ip B.V. Intumescent coating composition comprising particulate poly(phenylene ether)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
UNKNOWN: "Flame retardans-online; Intumenscent flame retardant systems", XP002759799, Retrieved from the Internet <URL:http://www.flameretardants-online.com/web/en/106/110.htm> [retrieved on 20160712] *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017179029A1 (fr) * 2016-04-16 2017-10-19 Vylimec Jiří Procédé de production d'une substance d'imprégnation ignifuge, principalement pour des produits de construction, substance d'imprégnation ignifuge et son utilisation
US10773415B2 (en) 2016-04-16 2020-09-15 Movychem, S.R.O Method of production of fire impregnation substance, mainly for construction products, fire impregnation substance and use of thereof
CN110157040A (zh) * 2019-05-31 2019-08-23 安徽理工大学 一种新型膨胀阻燃成炭剂及其制备方法
CN113150671A (zh) * 2021-05-07 2021-07-23 华阳新材料科技集团有限公司 非离子型水性聚氨酯基膨胀型钢结构防火涂料及制备方法
CN113150671B (zh) * 2021-05-07 2022-09-23 华阳新材料科技集团有限公司 非离子型水性聚氨酯基膨胀型钢结构防火涂料及制备方法

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Publication number Publication date
SK500182015A3 (sk) 2016-11-02

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