SK500342015A3 - Process for producing polymer antifire ingredients and antifire polymer - Google Patents
Process for producing polymer antifire ingredients and antifire polymer Download PDFInfo
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- 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
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- 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
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- 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
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- 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
- C08K5/5205—Salts of P-acids with N-bases
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/10—Organic materials containing nitrogen
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Abstract
Opisuje sa spôsob, pri ktorom sa do vody s teplotou 15 °C až 25 °C pridá 5 % až 90 % hmotn. pentaerytritolu a za priebežného miešania sa roztok postupne zahrieva na teplotu 52 °C až 68 °C. Následne sa do roztoku za intenzívneho miešania pridá 5 % až 90 % hmotn. amonium polyfosfátu a roztok sa zahrieva na teplotu nad 92 °C. Po prekročení tejto teploty sa do roztoku pridá 5 % až 90 % hmotn. melamínu a roztok sa zohrieva na teplotu 98 °C až 100 °C. Po vychladnutí sa z roztoku oddelí voda a získaný polymér sa vysuší a granuluje.A method is described wherein 5% to 90% by weight of water at 15 ° C to 25 ° C are added to the water. pentaerythritol and with continuous stirring, the solution is gradually heated to 52 ° C to 68 ° C. Subsequently, 5% to 90% by weight of the solution is added to the solution with vigorous stirring. ammonium polyphosphate and the solution is heated to above 92 ° C. When this temperature is exceeded, 5% to 90% by weight is added to the solution. melamine and the solution is heated to 98 ° C to 100 ° C. After cooling, water is separated from the solution and the polymer obtained is dried and granulated.
Description
Vynález sa týka spôsobu výroby protipožiarnej prísady na zvýšenie požiarnej odolnosti náterových hmôt, tmelov, stavebných hmôt. Prísada je netoxická, má vysoký protipožiarny účinok a môže mať formu roztoku alebo prášku.The invention relates to a process for the production of a fire-fighting additive for increasing the fire resistance of paints, sealants, building materials. The additive is non-toxic, has a high fire-fighting effect and can be in the form of a solution or a powder.
Doterajší stav technikyBACKGROUND OF THE INVENTION
Polyméry sa často využívajú v stavebných výrobkoch, vo výrobe dopravných prostriedkov, kde sa vyžaduje vysoká odolnosť voči ohňu. Sú známe riešenia, ktoré používajú ako retardéry horenia rôzne nebezpečné látky, napríklad podľa CN 102924868 (A) alebo ktoré používajú látky, ktoré degradujú pôvodné fýzikálnomechanické vlastnosti pôvodného polyméru.Polymers are often used in construction products, in the manufacture of vehicles where high fire resistance is required. There are known solutions which use various hazardous substances as flame retardants, for example according to CN 102924868 (A) or which use substances which degrade the original physical-mechanical properties of the original polymer.
Pri výrobe stavebných materiáloch sa bežne používajú intumescentné prísady, ktoré zvyšujú požiarnu odolnosť. Tieto prísady vytvárajú pri horení povrchové napenenie, ktoré slúži ako tepelná izolácia. Zvyčajne sú intumescentné prísady tvorené zdrojom uhlíka na napenenie, zlúčeninou vytvárajúcou kyselinu a zlúčeninou, ktorej rozkladom vznikajú plyny.In building materials, intumescent additives are commonly used to increase fire resistance. These additives create a surface foaming during combustion which serves as thermal insulation. Typically, the intumescent ingredients are a carbon source for foaming, an acid-forming compound, and a gas-decomposing compound.
Je známe použitie amonium polyfosfátu a melaminu v prípravkoch na zvýšenie požiarnej odolnosti. Účinky týchto látok v samostatných protipožiarnych aplikáciách sú preskúmané. Tieto látky sú pri aplikácií známe ako nerozpustné prášky. Na ich použitie a tiež na ich použitie s ďalšími látkami v polymérnych materiáloch je žiaduce vytvoriť medzi nimi viacnásobnú adíciu bez vedľajšieho produktu. Výsledný polymér by mal obsahovať len látky bez akýchkoľvek nebezpečných účinkov podľa všetkých známych výskumných výsledkov a štúdií. Zložky vstupujúce do polymerizácie by mali byť komerčne dostupné s príslušným vhodným enviromentálnym zaradením v klasifikácií REACH.It is known to use ammonium polyphosphate and melamine in formulations to increase fire resistance. The effects of these substances in separate fire-fighting applications are investigated. These substances are known as insoluble powders when applied. For their use as well as for their use with other substances in polymeric materials, it is desirable to form a multiple addition between them without a by-product. The resulting polymer should contain only substances without any dangerous effects according to all known research results and studies. The components entering the polymerization should be commercially available with the appropriate appropriate environmental classification in the REACH classification.
Podstata vynálezuSUMMARY OF THE INVENTION
Nedostatky uvedené v doterajšom stave techniky podstatným spôsobom odstraňuje spôsob výroby protipožiarnej poiymérovej prísady na spomalenie a/alebo zabránenie horenia podľa tohto vynálezu, ktorého podstata spočíva v tom, že do vody s teplotou 15°C až 25 °C nasypeme pentaerytritol, za priebežného miešania roztok postupne zahrievame na teplotu 52 °C až 68 °C, do roztoku za intenzívneho miešania iThe drawbacks of the prior art are substantially eliminated by the process for the production of the fire retardant polymer additive for flame retardation and / or prevention according to the invention, which consists in pouring pentaerythritol into water at a temperature of 15 ° C to 25 ° C, stirring continuously. gradually heat to 52 ° C to 68 ° C, into the solution with vigorous stirring i
:, 499 nasypeme amonium polyfosfát a roztok postupne zahrievame na teplotu nad 92 °C. Po prekročení tejto teploty do roztoku primiešame melamin a roztok zohrievame na teplotu 98 °C až 100°C.499, add ammonium polyphosphate and gradually heat the solution to a temperature above 92 ° C. After exceeding this temperature, add melamine to the solution and heat the solution to a temperature of 98 ° C to 100 ° C.
Zložky pridávané do roztoku môžu mať nasledovný vzájomný pomer (bez vody):The components added to the solution may have the following ratio to each other (without water):
- amonium polyfosfát od 5% do 90% hmotn.,- ammonium polyphosphate from 5% to 90% by weight,
- pentaerytritol od 5% do 90% hmotn.,- pentaerythritol from 5% to 90% by weight,
- melamin od 5% do 90% hmotn..- melamine from 5% to 90% by weight.
Voda tvoriaca prostredie pre polymerizáciu zložiek predstavuje na začiatku procesu 30% až 95% celkového roztokuThe water forming the medium for the polymerization of the components represents 30% to 95% of the total solution at the start of the process
Amonium polyfosfát [NH4 PO3]n je používaný ako potravinárska prísada, emulgátor (E545). Je tiež známy ako retardér ohňa pre polyolefíny a polyuretány.Ammonium polyphosphate [NH 4 PO 3 ] n is used as a food additive, emulsifier (E545). It is also known as a fire retardant for polyolefins and polyurethanes.
Pentaerytritol, 2,2-Bis(hydroxymethyl)1,3-propanediol, C5H12O4, CAS 115-77-5 je biely kryštalický prášok, štvormocný monotopícký alkohol. Používa sa na výrobu alkydových živíc, emulgátorov, výbušnín, náterových hmôt, syntetických mazacích olejov. Považuje sa za ekologickú náhradu polyvinylchlorbifenylov (PCB).Pentaerythritol, 2,2-Bis (hydroxymethyl) 1,3-propanediol, C 5 H 12 O 4 , CAS 115-77-5 is a white crystalline powder, a tetravalent monotopic alcohol. It is used for the production of alkyd resins, emulsifiers, explosives, paints, synthetic lubricating oils. It is considered an ecological substitute for polyvinylchlorobiphenyls (PCBs).
Melamin, 2,4,6-triamino-1,3,5-triazin, sumárny vzorec C3-H6-N6, CAS číslo 10878-1 sa využíva najmä pri výrobe plastov a dusíkatých hnojív. Melamin sa vo vode v podstate nerozpúšťa, vo svojej molekulovej štruktúre obsahuje približne 66 % dusíku, ktorý sa pri horení uvoľňuje a tým tlmí oheň. Melamin je v malých dávkach netoxický. Melamin sa v spojitosti s jeho nežiaducou prítomnosťou v potravinách opisuje ako škodlivý, ale toxická dávka v potravinách je porovnateľná s kuchynskou soľou, presahuje 3 g na jeden kilogram živej hmotnosti jedinca. Z tohto pohľadu je použitie melamínu v prísade podľa tohto vynálezu neškodné.Melamine, 2,4,6-triamino-1,3,5-triazine, the molecular formula C 3 H 6 N 6, CAS No. 10878-1 is used mainly in the manufacture of plastics and nitrogen fertilizers. Melamine is essentially water-insoluble and contains approximately 66% nitrogen in its molecular structure, which is released by combustion and thus suppresses fire. Melamine is non-toxic in small doses. Melamine is described as harmful in connection with its undesirable presence in food, but the toxic dose in food is comparable to table salt, exceeding 3 g per kilogram body weight of the individual. In this regard, the use of melamine in the additive of the present invention is harmless.
V roztoku s uvedenými troma látkami - amonium polyfosfát, pentaerytritol, a melamin dochádza k polymerizácií, čoho výsledkom je protipožiarny polymér s obzvlášť vysokým protipožiarnym účinkom. Táto kombinácia látok sa vzájomne potencuje a v hmote polyméru dochádza k vytvoreniu jadier mikrointumescencie. Klasická intumescencia sa prejavuje napenením na povrchu hmoty, čo je zvyčajne spojené so stratou pôvodných mechanických vlastností hmoty. Pri prísade podľa tohto vynálezu sa vypozoroval jav, kedy sa v hmote polyméru vytvárajú malé jadrá, okolo ktorých dochádza k lokálnej vnútornej intumescencii, tá je svojou veľkosťou primeraná malým rozmerom jadier, preto vynálezcovia tento jav nazvali ako mikrointumescencia. Protipožiarna prísada bráni procesu horenia aj tým, že sa okolo jadier v hmote pôsobením tepla uvoľňuje CO2 a dusíkaté plyny.In the solution with the three substances - ammonium polyphosphate, pentaerythritol, and melamine, polymerization occurs, resulting in a fire-retardant polymer with a particularly high fire-retardant effect. This combination of substances potentiates each other and the nuclei of the microintumescence form in the bulk of the polymer. Classical intumescence is manifested by foaming on the surface of the mass, which is usually associated with the loss of the original mechanical properties of the mass. The additive of the present invention has seen the phenomenon of forming small cores in the polymer mass around which local internal intumescence occurs, which by its size is proportional to the small size of the cores, hence the inventors called this phenomenon as microintumescence. The fire-retardant also prevents the combustion process by releasing CO 2 and nitrogen gases around the cores in the mass by the action of heat.
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Kombinácia hore opísaných troch účinných látok vo výslednom polymére spôsobuje nielen dosiahnutie vysokej požiarnej odolnosti, ale vďaka mikrointumescencii má polymér aj po vystavení požiaru vysoké, takmer nezmenené pôvodné mechanické vlastnosti.The combination of the three active ingredients described above in the resulting polymer not only results in a high fire resistance, but due to microintumescence, the polymer has high, almost unchanged, original mechanical properties even after exposure to fire.
Po dosiahnutí teploty roztoku 98 °C až 100 °C sa roztok ochladí. Výsledný roztok je použiteľný v kvapalnom stave, alebo sa upraví sušením na obsah vody v rozmedzí 2,5% až 8% s následnou úpravou granulometrie podľa požadovaného výsledku. Protipožiarny polymér v práškovej forme sa balí do hygroskopicky odolných obalov.After reaching a solution temperature of 98 ° C to 100 ° C, the solution is cooled. The resulting solution is usable in the liquid state or is adjusted by drying to a water content in the range of 2.5% to 8%, followed by adjustment of the granulometry to the desired result. The fire-fighting polymer in powder form is packaged in hygroscopically resistant containers.
Všetky vstupné suroviny ako aj výstupný produkt sú v evidencii REACH vedené ako látky bez akýchkoľvek nebezpečných vplyvov na človeka. To znamená, že sa podarilo vynájsť postup polymerizácie a kombináciu bezpečných látok, ktoré vedú k zvýšeniu požiarnej odolnosti a to pri nízkych nákladoch a malej energetickej náročnosti procesu. Vynález dosahuje vysoké protipožiarne účinky, používa netoxické látky.All feedstocks and output products are listed in REACH as substances without any hazardous effects on humans. This means that we have succeeded in inventing a polymerization process and a combination of safe substances which lead to an increase in fire resistance at a low cost and low energy intensity of the process. The invention achieves high fire-fighting effects, using non-toxic substances.
Príklady uskutočnenia vynálezuDETAILED DESCRIPTION OF THE INVENTION
Príklad 1Example 1
V tomto príklade sa protipožiarny polymér vyrobil nasledovne. Do 5 kg vody teplej 20 °C sa vmieša 1,5 kg práškového pentaerytritolu. Roztok priebežne miešame a zahrievame na teplotu 65 °C, kedy do roztoku za intenzívneho miešania pomaly prisypeme 2 kg amonium polyfosfátu v práškovej podobe. Následne roztok zahrievame na teplotu 94 °C. Po prekročení tejto teploty do roztoku primiešame 1,5 kg melaminu a roztok zohrievame na teplotu 100 °C. Po dosiahnutí tejto teploty v celom objeme roztoku ukončíme zahrievanie, roztok necháme vychladnúť a následne z neho odlúčime vodu. Výsledný protipožiarny polymér má práškovú formu.In this example, the fire-fighting polymer was produced as follows. 1.5 kg of pentaerythritol powder are mixed into 5 kg of 20 ° C warm water. The solution is continuously stirred and heated to 65 ° C, when 2 kg of ammonium polyphosphate in powder form is slowly added to the solution with vigorous stirring. Heat the solution to 94 ° C. After exceeding this temperature, add 1.5 kg of melamine to the solution and heat the solution to 100 ° C. After reaching this temperature in the whole volume of the solution, stop heating, let the solution cool and then remove the water from it. The resulting fire-fighting polymer is in powder form.
Príklad 2Example 2
Práškový pentaerytritol rozmiešame vo vode o teplote 25 °C. Tekutinu zohrievame na teplotu 65 °C, kedy k nej primiešame amonium polyfosfát v práškovej podobe. Tekutinu zohrievame na 92°C, túto teplotu udržujeme aspoň 10 minút. Potom primiešavame melamin, pričom prebieha monomérna reakcia. Tekutinu zohrejeme na 100 °C, stále ju miešame a udržujeme na tejto teplote pri normálnom tlaku aspoň 5 minút, počas ktorých prebieha polymerizácia. Množstvo vody môže byť zvolené v rozsahu 30% až 95% hmotn. podľa predpokladanej aplikácie polyméru.Mix pentaerythritol powder in water at 25 ° C. Heat the liquid to 65 ° C, adding ammonium polyphosphate in powder form. Heat the liquid to 92 ° C for at least 10 minutes. Melamine is then mixed while the monomeric reaction takes place. Heat the liquid to 100 ° C, mix constantly and maintain at this temperature at normal pressure for at least 5 minutes, during which polymerization takes place. The amount of water may be selected in the range of 30% to 95% by weight. depending on the intended application of the polymer.
Protipožiarny polymér v tomto príklade je použitý v tekutej forme. Môže tak tvoriť prísadu do vodných systémov priemyselných látok, prísadu do kompozitov, do moridiel, náterov na báze olejov, vody alebo iných rozpúšťadiel.The fire-fighting polymer in this example is used in liquid form. It may thus form an additive for aqueous industrial substance systems, an additive for composites, mordants, oil, water or other solvent based coatings.
Priemyselná využiteľnosť ío Priemyselná využiteľnosť vynálezu je zjavná. Podľa tohto vynálezu je možné priemyselne a opakovane vyrábať a používať protipožiarny polymér, ktorý nemá toxické zložky a pritom je veľmi účinný.Industrial Applicability The industrial applicability of the invention is obvious. According to the present invention, it is possible to industrially and repeatedly produce and use a fire-fighting polymer which has no toxic components and yet is very effective.
.» <« · * , 3 ( Λ v#. »<« · *, 3 (Λ in #)
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SK50034-2015A SK500342015A3 (en) | 2015-06-26 | 2015-06-26 | Process for producing polymer antifire ingredients and antifire polymer |
PCT/IB2016/053824 WO2016207870A1 (en) | 2015-06-26 | 2016-06-27 | Method of production of fireproof polymer additive, fireproof polymer |
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SK288796B6 (en) * | 2016-04-16 | 2020-11-03 | Movychem S R O | Method of production of fire impregnation substance, mainly for construction products, fire impregnation substance and use of thereof |
CN111333849B (en) * | 2020-04-14 | 2022-03-04 | 中南大学 | Carbon-nitrogen-phosphorus intumescent flame retardant and preparation method thereof |
JP2023524850A (en) * | 2020-05-05 | 2023-06-13 | モビケム エス.アール.オー. | Fire resistant polymer additive and method of making and using same |
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SK5976Y1 (en) * | 2011-02-24 | 2011-12-05 | Moles Technology A S | Fireproof paint coat matter |
CN103937066A (en) * | 2014-01-24 | 2014-07-23 | 严兵 | Flame-retardant bast fiber-plastic composite material, and preparation method thereof |
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