KR100469920B1 - Non-halogen fire retardant material and method thereof - Google Patents

Abstract

Disclosed are a new non-halogen flame retardant and a method of preparing the same, which can simultaneously synthesize inorganic oxides, hydroxides or other metal-based flame retardants and nitrogen-based flame retardants with phosphoric acid to satisfy each of the advantages and disadvantages. The non-halogen flame retardant and the method for preparing the same include phosphorus-based compounds including inorganic oxides, hydroxides or metal compounds in a nitrogen-phosphorus reaction process in which phosphorus is attached to existing nitrogen-based compounds such as melanin-based, urea-based, amine-based or amide-based compounds. It is achieved by providing a process for preparing a metal salted nitrogen-phosphorous flame retardant characterized by reacting a compound and then heat condensing it to a high temperature.

Description

Non-halogen flame retardant and its manufacturing method {Non-halogen fire retardant material and method

Polymers play a very important role in human life and have become a part of life that can be easily found around them. Therefore, the function of the polymer is becoming more diverse in daily life, and the function of flame retardant, which does not burn in the event of fire, has become a part of a very important factor related to human safety. Therefore, the flame retardancy of the polymer is becoming more diverse in terms of its function and performance. Conventional flame retardant is mainly used a halogen-based flame retardant containing bromine or chlorine.

This halogen flame retardant has a very excellent flame retardancy which stops combustion by stopping radicals of chain combustion and is still used a lot. And when used in combination with inorganic antimony system is characterized in that the effect is further improved. However, these halogen flame retardants are not only harmful to the human body due to the generation of toxic gases during combustion, but also adversely affect the environment. As a result, regulations on the use of halogen flame retardants have been strengthened, and legal regulations by countries as well as environmental organizations have recently been tightened. In addition, antimony-based compounds used with halogen flame retardants are also toxic and their use has been limited. Recently, research on non-halogen flame retardants has been actively conducted and various things have been developed. Examples of the non-halogen flame retardant include phosphorus, inorganic oxides and hydroxides, nitrogen compounds, and silicones. However, the development of flame retardants to match the performance of the halogen flame retardant has not been made so much research is necessary. Phosphorus-based flame retardants have been developed and used in various kinds of derivatives, good flame retardancy but many physically weak points in terms of properties, inorganic oxide or hydroxide-based flame retardant has a disadvantage of having to add a large amount.

Nitrogen compounds and silicones are also flame retardant to the extent that it is difficult to impart flame retardancy by itself. Therefore, it is necessary to develop a new flame retardant supplementing the advantages and disadvantages.

The present invention is to solve the above problems and to meet the need for the development of a new flame retardant, a flame retardant that can meet both of the advantages and disadvantages by synthesizing inorganic oxide, hydroxide or other metal flame retardant and nitrogen flame retardant simultaneously with phosphoric acid And a manufacturing method thereof. It is another object of the present invention to provide a method of applying the prepared flame retardant as a flame retardant for polymers and other uses.

Currently, non-halogen flame retardants include metal oxides, hydroxides, nitrogen compounds, phosphorus, and silicon. The non-halogen flame retardants used here have their advantages and disadvantages. Therefore, in order to prepare an effective composite flame retardant, each of the above non-halogen flame retardants were reacted together at the time of synthesis, so as to complement the disadvantages of each other and maximize the advantages. The basic base compound in the present invention uses the properties of products in which nitrogen compounds and phosphorus are combined, such as melamine phosphate, melamine pyrophosphate, melamine polyphosphate, ammonium phosphate, ammonium polyphosphate, etc., which are already used for various purposes. For example, the additive inorganic compound to be complex-reacted may be aluminum oxide or hydroxide, magnesium oxide or hydroxide, trioxide or antimony pentoxide, zinc oxide or zinc hydroxide, zinc borate, molybdenum oxide, zeolite, hydrotalcite, In general, inorganic materials that are used in polymers or can help to show flame retardancy are mainly used. That is, the inorganic non-halogen flame retardant type contributes to supplementing the shortcomings of melamine or ammonium phosphate, which are nitrogen-phosphorous flame retardants, and reacts them with phosphorus, thereby improving the physical properties and flame retardancy in the polymer. This is because the synthesis of the nitrogen-phosphorus flame retardant is superior to the flame retardancy than the addition of the inorganic compound and can increase the content of phosphorus relative to nitrogen. In addition, some inorganic compounds can increase the new flame retardant effect by reacting with the phosphorus compound, and have better grinding properties than the pulverization after the synthesis of nitrogen-phosphorus alone, and can solve the physical disadvantages of mixing. To produce. In particular, the physical properties of the polymer when added to it can be much improved than that of the existing nitrogen-phosphorus.

In order to achieve the above object of the present invention,

The present invention primarily includes an inorganic oxide, hydroxide, or other metal compound in the nitrogen-phosphorus reaction manufacturing process for attaching phosphorus to existing nitrogen-based (melamine-based, urea-based, amine-based, amide-based, etc.). A method of producing a metal salted nitrogen-phosphorus flame retardant by reacting with a compound and condensing it by heating it to a high temperature secondly. At this time, the manufacturing process of the first reaction is a mixture of one or two or more kinds of nitrogen-based materials (up to 0.1-99%) and one or two or more kinds of nitrogen-based compounds with inorganic oxides, hydroxides or other metal compounds. It is preferable to mix up to 0.1-99% by weight with respect to the mixture, and then proceed with the reaction between 0-150 ° C. while slowly adding phosphorus compounds (up to 1-3 moles of 1 mole of nitrogen compounds). Among the nitrogen-based compounds that can be used here are melamine, melam, melam, memel, melon, ammeline, ammelide, ureidomelamine, and 2-ureidomelamine. ), Methylene dimelamine, ethylenedimelamine, trimethylene dimelamine, tetramethylenedimelamine, hexamethylene dimelamine, decamethylenedimelamine, dodecamethylenedimelamine, p-phenylene dimelamine, 1,3-cyclohexylene Dimelamine, p-xylene dimelamine, diethylene trimelamine, triethylene tetramelamine, tetraethylenepentamamine and hexaethylene heptamelamine, melamine saanurate or at least one substituent is methyl, phenyl, carboxymethyl, 2-carboxy Melamine cyanurate compounds substituted with ethyl, cyanomethyl, 2-cyanoethyl, and the like.

Other nitrogen compounds that may be used include ammonium carbonate, alkyl carbamate, ammonium sulfamate, amine, ethylamine, diethylamine, amide, polyamide, amidine, aldimine, alkylanolamine, alkyl isocyanate, and sulfur Mixic acid, dicyanamide, urea, ureacarbonate, diethylaminourea, urea compound, thiourea, thiourea derivatives, nitrile, ketimine, ammonium carbonate, ammonium bicarbonate, aminoguanidine, acetoguanamine, acetoguanamine Guanamine (benzoguanamine), guanidine carbonate, guanidine, cyanuric acid and derivatives, phosphazenes and derivatives, and the like.

The kinds of metal compounds added to the reaction process may include aluminum oxide, hydroxide or carbonate, magnesium oxide or hydroxide or carbonate, calcium oxide or hydroxide or carbonate, zinc oxide or hydroxide or carbonate, silicon oxide, Hydroxide or carbonate, silica, alkali metal silicate, metal silicate, antimony trioxide or antimony pentoxide, barium oxide or hydroxide or carbonate, zinc borate, boric acid, boric compounds such as boric acid, molybdenum oxide or hydroxide, zeolite, Hydrotalcite, talc, graphite, graphite compounds, titanium oxide and the like can be used.

Phosphorous compounds reacted with the above compounds are phosphoric acid, olsophosphoric acid, pyrophosphoric acid, triphosphoric acid, metaphosphoric acid, phosphorus acid, hydrophosphorus acid, Phosphonic Acid, Phosphos Oxide, Phosphine Oxide, Phosphorustrihalide, Phosphorus Oxyhalide, Phosphorus Oxide, Monometal Hydrogen Phosphate, Ammonia Dihydrogen Phosphate, Bromate Phosphate, Alkaline Metal Dihydrogen Phosphates, halogenated phosphates, organophosphorus compounds, alkyl phosphines, alkyl chlorophosphines, alkyl phosphites, organic acid phosphates, dialkylhydrogen phosphates, arylhydrogen phosphates, hydroorganic diphosphonates, aryl phosphates Pit, Dialkyl Phosphate, Trialkyl Phosphite, Hal Geneyi lactide and the like phosphonate ester. After completion of the first reaction, it is preferable to completely dry the water or solvent at 150 ° C., and then gradually heat it, and then condensate sufficiently for 30 minutes to 10 hours according to each decomposition temperature characteristic up to 150-450 ° C. to complete the reaction. Do. Here, ammonia or other generated substances are removed under reduced pressure, and after completion of the reaction, are pulverized by various pulverizers and applied to polymer flame retardant. At this time, the finer the particle size is, the better the distribution is between 0.2-50 μm and the average particle size is 20 μm or less. This new flame retardant can be used with other organophosphorus flame retardants depending on the application. The phosphorus flame retardants can be used together with triphenyl phosphate, trialkylphenyl phosphate, tricrecylphosphate, Propylated triphenylphosphate, butylated triphenyl phosphate, triethylphosphate, tributyl phosphate, resorcinol diphosphate, bisphenol diphosphate

(bisphenoldiphosphate), dimethyl methyl phosphonate, polyphosphate ester, oligomeric organophosphate, ethyl pyrocatechol phosphate, dipyrocatechol biphosphate, polyethylethyleneoxy Phosphate (polyethylene ethyleneoxy phosphate), methyl neopentyl phosphate (methylneopentyl phosphate), pentaerythritol diethyl phosphate, penta erythritol diphenyl phosphate (pentaeritritol diphenyl phosphate), methyl neopentyl phosphonate (methylneopent dimethyl phosphate) dicyclopentyldiphosphate, dineopentylbiphosphate, and the like, and the polymers to which the non-halogen flame retardant of the present invention can be applied and applied include polyvinyl chloride, polyester, phenol resin, amine resin, polyethylene resin homo and block copolyol. Or copolymers thereof, polypropylene resin homo and block copolymers or copolymers, polyphenylene ether, polyphenylene oxide, polyurethane resin, heterocycle vinyl compound, polyethylene terephthalate, acrylonitrile resin, vinyl acetate and styrene Styrene copolymer, polycarbonate, polystyrene, acrylonitrile butadiene styrene copolymer, styrene acrylonitrile copolymer, polyether, high impact polystyrene, polybutadiene, aromatic vinyl compound, polysulfone, polyoxymethylene, vinyl acetate styrene Copolymer, Polyimide, Nylon Resin, Phenoplast, Aminoplast, Furan, Polyamide, Polytetrafluoroethylene, Methagrylonitrile Resin, Silicone Resin, Cyclic Unsaturated Resin, Urethane Silicate, Cellulose Ester, Chlorinate Tide rubber, cellulose ether, Such as a cyano ethyl cellulose, cellulose acetate. In addition to the polymer, it can be applied to papermaking, rubber, wood, paint, and the like.

Hereinafter, the present invention will be described through preferred embodiments.

(Example 1)

Melamine 200g and magnesium oxide 40g into a stainless reactor (1.5L) was stirred and mixed for 10-20 minutes. The reaction is slowly added with 155.3 g of 80% aqueous phosphoric acid. The moisture generated by the exotherm is opened to evaporate well. When the exothermic reaction is completed to some degree, the temperature is gradually increased to 150 ° C., and the water is completely evaporated. While continuing stirring in a powder state, the temperature was continuously raised to a high temperature (300-450 ° C.) for 1 hour or more, and then the temperature was gradually lowered to room temperature to obtain sample 1.

(Example 2)

200 g of melamine and 150 g of aluminum hydroxide were added to a stainless reactor (3 L).

Stir for 10-20 minutes and mix. 200g of 80% aqueous solution of phosphoric acid is slowly added, and the moisture generated by exotherm is opened to evaporate well. When the exothermic reaction is completed to some degree, the temperature is gradually increased to 150 ° C., and the water is completely evaporated. While continuing to stir in a powder state, the temperature is continuously raised to a high temperature (300-450 ° C.) for 1 hour or more, and then the temperature is gradually lowered to room temperature to obtain sample 2.

(Example 3)

200g of melamine, 97.96g of urea and 100g of ginkborate are added to a stainless reactor (3L) and mixed by stirring for 10-20 minutes. The reaction is performed by slowly adding 350 g of 80% aqueous phosphoric acid, and the moisture generated by the exotherm is opened to evaporate well. After the exothermic reaction is completed to some extent, the temperature is gradually increased to 150 ° C. to completely evaporate the moisture. While continuing to stir in a powder state, the temperature is continuously raised to a high temperature (300-450 ° C.) for 1 hour or more, and then the temperature is gradually lowered to room temperature to obtain sample 3.

(Example 4)

200 g of melamine, 97.96 g of urea and 80 g of magnesium hydroxide are added to a stainless reactor (3 L) and stirred for 10-20 minutes to mix. The reaction is slowly added with 320 g of 80% aqueous phosphoric acid, and the moisture generated by the exotherm is opened to evaporate well. When the exothermic reaction is completed to some degree, the temperature is gradually increased to 150 ° C., and the water is completely evaporated. While continuing to stir in a powder state, the temperature is continuously raised to a high temperature (300-450 ° C.), and the reaction is performed for 1 hour or more, and then the temperature is gradually lowered to room temperature to obtain sample 4.

(Flame retardancy evaluation)

The polypropylene (homopolymer, 500 ppm primary antioxidant, 1,000 ppm secondary antioxidant) was kneaded from Sample 1 to Sample 4 synthesized above at 200 ° C., followed by Twin-screw After pelleting in an extruder, a measurement sample was made.

▲ Metric

Flame retardancy UL-94 (Underlighter Laboratories Incorporation)

Oxygen index: Oxygen index according to ASTM D2863

▲ Test Table for Flame Retardants

(*) Polypropylene (Homopolymer, primary antioxidant Irganox 1010: 500 ppm,

Secondary antioxidant Irgafos 168: 1,000 ppm)

The present invention relates to a method for preparing an effective non-halogen flame retardant and its application in a polymer, and is an inorganic oxide oxide during a process for preparing nitrogen-phosphorus reaction which first attaches phosphorus to existing nitrogen-based (melamine-based, urea-based, amine-based, amide-based, etc.). Or a hydroxide or other metal compound together, react with a phosphorus compound, and condensate it by heating it to a high temperature for the second time to produce a metal salted nitrogen-phosphorus flame retardant. In other words, the inorganic non-halogen flame retardants contribute to supplementing the shortcomings of the melamine- or ammonium phosphate-based nitrogen-phosphorous flame retardant, and reacting them with phosphorus to improve the physical properties and flame retardancy in the polymer. This is superior to the flame retardancy than the addition of the inorganic compound after the synthesis of the nitrogen-phosphorous flame retardant and can increase the content of phosphorus relative to nitrogen. In addition, some inorganic compounds can increase the new flame retardant effect by reacting with the phosphorus compound, and have better grinding properties than the pulverization after the synthesis of nitrogen-phosphorus alone, and also solve the physical disadvantages of mixing, which is effective in many ways. to be. In addition, the new flame retardant has a high decomposition temperature and can be applied to paper, rubber, wood, paint, etc. in addition to polymers.

Claims (5)

In the nitrogen-phosphorus reaction process that attaches phosphorus to existing nitrogen-based compounds such as melamine-based, urea-based, amine-based or amide-based compounds, the inorganic compound, hydroxide or metal compound is included together to react the phosphorus-based compound and then heat-condensed at high temperature. Method for producing a metal salted nitrogen-phosphorous flame retardant characterized in that the. The process of claim 1, wherein the reaction step of the phosphorus compound is a mixture of one or two or more nitrogen compounds (up to 0.1% to 99%) with an inorganic oxide, hydroxide or metal compound mixed with the nitrogen compound. Of the metal salted nitrogen-phosphorous flame retardant, characterized by mixing at a weight ratio of 0.1 to 99%, and then reacting at a temperature of 150 ° C. or less while gradually adding a phosphorus compound to 1 to 3 moles relative to 1 mole of the nitrogen compound. Manufacturing method. The method of claim 1, wherein the high temperature heat condensation is a condensation reaction for 30 minutes to 10 hours depending on the decomposition temperature characteristics from 150 to 450 ℃ after completely reacting the phosphorus-based compound at 150 ℃ water or solvent Method for producing a metal salted nitrogen-phosphorous flame retardant, characterized in that. The method of claim 1, wherein the nitrogen-phosphorus reaction process is performed by stirring for 10-20 minutes in a stainless reactor. A non-halogen flame retardant prepared by the method of claims 1 to 4, which contains inorganic oxides, hydroxides or metal compounds.