Synthesis And Performance Test Of Flame Retardants Of Cyanuric Chloride Series

Polymer material has been widely used in aerospace,electrical and electronic,automobile,building decoration and other fields.However,polymer material is flammable when it is in fire,which can emit plenty of combustion heat and produce large numbers of droplets.Both combusition heat and droplets are the major factors that extend fire hazard which can cause grave social property losses.It is more severe that fire disaster usually release poisonous smoke smudge formed by suspendedsolids,dense liquid particle and high temperature flue gas.Generally,this kind of toxic smoke brings about low visibility,staff panic,bod damage,loss of activity or even suffocation to death.These problems seriously restrict the scope of application of polymer material.Therefore,adorning polymer material with flame retardant is very significant.Environment-friendly flame retardant which is containing a small amount of halogen or even no halogen,having low toxicity has become the pursuit of the goal.In this dissertation,cyanuric chloride used as the main raw material reacted respectively with diethylenetriamine,2,4,6-Tribromophenol,chitosan,diphenylguanidine,ethanolamine and PEPA.There were eight kinds of low halogen or halogen-free environment-friendly flame retardant numbered from FR-1 to FR-8 obtained through molecular design or ingredient design.The products were characterized by FTIR ? MS ?NMR ? EDX ? melting point test.Fire retardance of the products was investigated by means of TGA analysis,limiting oxygen index(LOI)test.and vertical burning test,:(a)Cyanuric chloride reacted with diethylenetriamine in the absolute THF solvent,using N,N-Diisopropylethylamine as acid binding agent.The reaction was carri-ed out for4 h at 0 ? and for another 48 h at room temperature.The product is lowhalogen flame retardant FR-1.The flame retardant FR-2 can be obtained by the reaction of FR-1 with taurine.Under the same additive amount of each flame retardant,the LOI of FR-1 is higher than the LOI of FR-2,filling amount reaching 25% of FR-1 and FR-2 made each flame retardant system flammable into combustible.In these two kinds of flame retardant system,only the flame retardant system which was added 30% FR-1 passed the vertical flame test reaching UL-94V-2.In terms of resistance to droplets,FR-2 flame retardant systembehaved better: dropping speed of droplets was slower and absorbent cotton firing frequency was less.(b)Cyanuric chloride reacted with tribromophenol by the molar ratio of 1:3.1 in ethyl acetate solvent,using sodium sulfite as decoloring agent,Na OH as acid binding agent.The product three(tribromophenyl)triazine,namely FR-3,was obtai-ned after the reaction carried out for 2.5h at 70 ?.FR-3 containing high halogen is a kind of efficient flame retardant.In order to reduce the use of halogen flame retardant,FR-3 was mixed with environment-friendly flame retardant poly ammonium phosphate(APP)and flame retardant synergist zinc borate compound.The total filing amount of Flame retardant was30%,adding amount of APP was fixed with 17% and changing the the amount of FR-3 and zinc borate.The LOI of flam-e retardant system(FR-3: APP: zinc borate = 10%: 17%: 3%)is the highest reaching 25.6.The LOI of other systems are all lower than this value,but are higher than 24.Three different ratio of flame retardants system,including 30:0:0,13:17:0and 10:17:3 passed the vertical flame test reaching UL-94V-1.The left two flame retardants system(7:17:6 and 4:17:9)passed the vertical flame test reaching UL-94V-2.Adding APP and zinc borate to FR-3 flame retardants system made the system less smoke when the tested sample was ignited and more friendly to environment.Nevertheless,the speed of droplets was still fast,which can extend fire hazard.(c)Cyanuric chloride was modified with chitosan to get a new kind of low halogen flame retardant FR-4.Hydrolyzing degenerative cyanuric chloride is to get1,3,5-Triazin-2,4,6-triol.Then,another kind of halogen free flame retardant FR-5 was synthetiseed by 1,3,5-Triazin-2,4,6-triol and diphenyl guanidine.Multihydroxyl compound3-THA,carbon forming agent,was synthetised by cyanogen chloride and ethanolamine.3-THA respectively reacted with HBO3 and Mg Cl2 to produce another two kinds of environmentally friendly inorganic-organic flame retardants FR-6 and FR-7.Thermal stability of 3-THA?FR-6?FR-7 was tested by TGA,the result show that when temperature rised 3-THA?FR-6?FR-7 dehydrated and carbon layer appeared.LOI of FR-4,FR-5,FR-7flame retardant system ascended when the addtion amount of co-rresponding flame retardants increased.There is a sharp contrast that LOI of FR-6 flame retardant system reached its own maximum when just added 15% FR-6 to its system.Although these 4kinds of flame retardant systems failed to passed the vertical flame test they all reduced the burning speed of tested samples and dropping speed of droplets obviously.More importantly they all did not produce toxic dense smoke when they were on fire.(d)Pentaerythritol reacted with diethylenetriamine by the molar ratio of 1:1.With a condenser used,the reaction was carried out at 95 ? for 7 h.PEPA is the recrystallization of the product.Cyanuric chloride reacted with PEPA by the molar ratio of 1:2.With a condenser used,the reaction was carried out at 15~20 ? for 0.5 h,and at 50 ? for another 6 h.Flame retardant FR-8 is the recrystallization of the product.Thermal stability of FR-8 was tested by TGA,the result show that when test temperature rised between329.05 ? and 454.91 ? FR-8 dehydrated rapidly.Carbon layer appeared at the same time.The final residual rate of carbon is as high as 40% above.These are illustrating that FR-8 own the property of forming carbon layer.The LOI tests have shown that filling amount,only reaching 15%,of FR-8 made the flame retardant system flammable into combustible and the combustion system began toappear carbon deposition.With the adding amount of FR-8 increased,LOI of the tested samples ascended up to 23.9 and the speed of droplets reduced gradually at the same time.Only the flame retardant system which was added 30% FR-8 passed the vertical flame test reaching UL-94V-2.