Phenolic aldehyde colophony regards a kind of commonly used high polymer polymer as material, have cost craft of low, synthesis is convenient wait for an advantage, often wait for material to apply extensively in the domain such as industry of electric equipment industry, construction as heat preservation, adiabatic, insulation. But the limitation that phenolic aldehyde colophony also puts in easy combustion, anti-flammability to differ, make its are in industry is produced and restriction accepts in daily application. To raise flame retardation of phenolic aldehyde resinous, add to the middle of phenolic aldehyde colophony normally flame retardant material, for example bittern department fire retardant, 3 oxidation 2 antimony, phosphor is fire retardant, in order to raise anti-flammability of phenolic aldehyde resinous. But, these are flame retardant when material burns release noxiousness gas easily, cause a harm to the environment. Accordingly, need seeks a kind of environmental protection model fire retardant material raises flame retardation of phenolic aldehyde colophony. Oxidation cerium (CeO2) serves as a kind new-style flame retardant additive, have the good point that freedom radical captures and combustion catalysis becomes charcoal, can become phosphor is fire retardant to replace content, in using its at polymer material of ameliorable material flame retardant and characteristic. Join CeO2 Wu Wei epoxy resin, in order to promote the flame retardation of epoxy resin, the experiment makes clear: CeO2 can increase limiting oxygen index of epoxy resin flaming (LOI) , reduce initiative decompose temperature, conduce to the flame retardation that raises epoxy resin. Add CeO2 Feng Houjun to acrylic colophony, make value of acrylic resinous LOI is as high as 30% , increase combustion thermal stability. But, add CeO2 to phenolic aldehyde colophony, to composite material flame retardant the report of heat proof quality is less. This experiment adds CeO2 to phenolic aldehyde colophony, colophony of preparation phenolic aldehyde / CeO2 composite material, the influence of research CeO2 dosage to function of the flame retardation of composite material, heat preservation. 1 experiment part formaldehyde of 1.1 main raw material, the analysis is simple, jinan fine horse vacates chemical limited company; Phenol, the analysis is simple, dark blue city limited company of 3 model liability; Oxyhydrogen changes sodium, the analysis is simple, limited company of pharmacy of traditional Chinese medicine; Oxidation cerium (CeO2) , analyse KH-560 of coupling agent of alkyl of pure, silicon, purity 99% , close Europeanize of Tianjin city family learns reagent limited company. 1.2 instruments and beater of equipment magnetic force, h550, shanghai jumps over limited company of numerous instrument equipment; Vacuum sweatbox, VO-6020T, instrument of Shanghai lamp Mao creates limited company; Create an opportunity, XSN-3, peaceful starts city luck heavenly body rubber-plastic and mechanical limited company; Ball mill, TJGN-450, only science and technology of Tianjin city Oriental weather expands limited company; Hot press, PLC, frit becomes ultrasonic technology (Shanghai) limited company; Scanning electron microscope (SEM) , s4800, japanese day establishs a company; Hot heavy analyzer (TGA) , q600 SDT, american TA company; Cone-shaped quantity heats up appearance, BT300-2J, suzhou humble Ni Kesi is qualitative check instrument limited company; Perpendicular combustion appearance, CZF-6, nanjing river analyses instrument limited company rather; Appearance of limiting oxygen index (LOI) , HVI, shanghai tastes limited company of chief Electromechanical science and technology; Measuring instrument of coefficient of thermal conductivity, DRE-2B, limited company of instrument of Xiangtan city instrument. In 3 flask that preparation of colophony of phenolic aldehyde of 1.3.1 of 1.3 sample preparation joins formaldehyde of 46mL phenol, 138mL 500mL, join 36mL to go to the middle of flask ionic water, agitate 60min mixes with assuring formaldehyde, phenol and water even, the oxyhydrogen that joins 1g to the middle of solution changes sodium and undertake to mixing solution agitate is handled heating, heat when temperature achieves 70 ℃ , undertake supersonic processing 240min to reaction solution, put into vacuum sweatbox to heat to undertake to 130 ℃ vacuum evaporation is handled, use the machine that build bead to become cut of phenolic aldehyde colophony bead. In 3 flask that preparation of 1.3.2 modified CeO2 joins CeO2 100mL, join the KH-560 of the distilled water of 50mL and 1.5mL, agitate heats to have reaction to 60 ℃ , react agitate stops after 30min, get modified CeO2 through smoking filter, hand-in-hand travel room temperature heats stoving processing. Colophony of 1.3.3 phenolic aldehyde / preparation of CeO2 composite material is expressed 1 for colophony of different phenolic aldehyde / the recipe of CeO2 composite material. According to the watch 1 recipe undertakes raw material and modified CeO2 mixture, choose ball mill both abrade hot pressing undertakes in stainless steel pattern is being put after mixing. To 30min of hot press warm-up, put phenolic aldehyde colophony and CeO2 into the mould to undertake heating up solidify, hot press warms up to be taken out to room temperature to refrigeration of 30min of 150 ℃ heat preservation, get phenolic aldehyde resin / CeO2 composite material.

1.4 function test and token SEM analyse: Sample with liquid nitrogen refrigerant fragile break, to processing of sample gush gold, voltage 5kV. TG analysis: Kind quality measures 0.5g, n2 atmosphere, temperature limits 400 ℃ of 30 ～ , rate-of-rise of air temperature 2 ℃ / Min. Taper measures the test that heat up appearance: Press ISO5660-1:2015 have a test, power 50kW/m2, sample size 80mm×80mm×20mm. Perpendicular combustion checks: Have a test by GB/T 8333—2008, sample size 100mm×10mm×3mm, choose methane to regard fire as the source, ignite time 10s, record phenomenon of the spontaneous combustion time of blaze and frit drop. LOI checks: Have a test by GB/T2406.2—2009, sample size 120mm×6mm×3mm. Coefficient of thermal conductivity checks: Have a test by GB/T3139—2005, sample size 30mm×20mm×5mm, test temperature 37 ℃ . 2 results and discuss colophony of 2.1 phenolic aldehyde / the SEM of CeO2 composite material analyses a scheme 1 for modified CeO2, phenolic aldehyde colophony and phenolic aldehyde colophony / the SEM photograph of CeO2 composite material. From the graph 1a can see, the bead diameter of modified CeO2 is 1μm about. From the graph 1b can see, surface of colophony of pure phenolic aldehyde is slick. From graph 1c ～ graph 1f can see, join the addition of the quantity as CeO2, phenolic aldehyde colophony / CeO2 composite material begins to rough, the CeO2 of excessive appears in phenolic aldehyde colophony reunite phenomenon. SEM result makes clear: Right amount CeO2 can disperse equably in phenolic aldehyde colophony, as a result of the existence of coupling agent, make phenolic aldehyde colophony can be mixed union is close together between CeO2. But the affiliation of GeO2 is measured overmuch, occurrence CeO2 grain reunites phenomenon.

Colophony of 2.2 phenolic aldehyde / the thermal stability of CeO2 composite material analyses a scheme 2 for colophony of pure CeO2, phenolic aldehyde and colophony of different phenolic aldehyde / the TG curve of CeO2 composite material. From the graph 2 can see, pure CeO2 is in 400 ℃ of 30 ～ the weightlessness extent inside limits is inferior, show CeO2 has taller thermal stability. And to colophony of pure phenolic aldehyde, the quality that controls in 225 ℃ drops apparently; As temperature elevatory, around 340 ℃ TG curve does not produce change. In 225 ～ inside 340 ℃ limits, phenomenon of degradation of occurrence heat of phenolic aldehyde colophony, main show is the hydrocarbon in fragrant black silk ribbon kind decompose and the process that become charcoal. In joining CeO2 phenolic aldehyde colophony, phenolic aldehyde colophony / the initiative pyrolysis temperature of CeO2 composite material is elevatory, and CeO2 adds a capacity from 0 add to 40% , its are initiative pyrolysis temperature is added from 225 ℃ to 307 ℃ , increase about 36.4% . Make clear CeO2 introduce the initiative thermal stability that can improve composite material apparently. CeO2 becomes charcoal reaction in resinous of phenolic aldehyde of the catalysis in combustion process, form aerobic separator and capture the freedom that combustion produces base restrain combustion. Of coupling agent introduce also increase phenolic aldehyde colophony and enhance the combinative performance between body, make phenolic aldehyde matrix resolves need more energy, also increase the thermal stability of composite material thereby.

Colophony of 2.3 phenolic aldehyde / the flame retardation of CeO2 composite material analyses a scheme 3 for phenolic aldehyde colophony and colophony of different phenolic aldehyde / the LOI value of CeO2 composite material. From the graph 3 can see, join the addition of the quantity as CeO2, the LOI of composite material of phenolic aldehyde colophony is worth Gaokeda to arrive 29.2% , LOI of resinous of purer phenolic aldehyde is worth (21.3%) increases 7.9% , the affiliation that makes clear CeO2 can better land increases anti-flammability. CeO2 can promote matrix of phenolic aldehyde colophony to form charcoal layer in the catalysis in combustion process, the existence of charcoal layer can keep apart the interface of oxygen and phenolic aldehyde matrix effectively to accumulate, can raise composite material flame retardation thereby, and CeO2 still is had capture the action of freedom radical raises flame retardation likewise.

Graph 4 for phenolic aldehyde colophony and colophony of different phenolic aldehyde / the combustion total heat of CeO2 composite material releases a quantity (time of spontaneous combustion of THR) , perpendicular combustion (TTI) , heat releases rate (HRR) curve.

From the graph 4a can see, THR of colophony of pure phenolic aldehyde is 107.8MJ/m² high, show combustion of phenolic aldehyde colophony releases higher quantity of heat. CeO2 is joined in phenolic aldehyde colophony, phenolic aldehyde colophony / the THR of CeO2 composite material is reduced apparently, and phenolic aldehyde colophony / the THR of 30% CeO2 is low, for 64.0MJ/m² . Relative to colophony of pure phenolic aldehyde, phenolic aldehyde colophony / the THR of 30% CeO2 is reduced 40.6% . As a result of phenolic aldehyde colophony / when CeO2 burns, layer of CeO2 stimulative charcoal is formed and capture freedom radical, the combustion that checks data and release quantity of heat, the presence that indicates CeO2 is helpful for raising flame retardation of phenolic aldehyde resinous. From the graph 4b can see, join CeO2 fire retardant to the middle of the system, blaze is initiative TTI is added from 49s to 72s, lengthen 46.9% . From the graph 4c can see, phenolic aldehyde colophony / the heat of 30% composite material releases rate peak value (PHRR) under phenolic aldehyde colophony / 40% composite material. The time that adds the composite material of phenolic aldehyde colophony of CeO2 to achieve PHRR is shorter, show CeO2 can raise flame retardation of phenolic aldehyde resinous. Combinative SEM analysis is knowable, what add a capacity as a result of CeO2 is overmuch, the more CeO2 in bringing about matrix of phenolic aldehyde colophony appears reunite, more hole appears in phenolic aldehyde matrix, combustion is participated in to react in making oxygen enters phenolic aldehyde matrix more easily. Accordingly, join right amount CeO2 to be helpful for promoting phenolic aldehyde resinous flame retardation, add a capacity when CeO2 for 30% , the flame retardation beautiful of composite material of phenolic aldehyde colophony. Express the 2 combustion condition that are phenolic aldehyde colophony and composite material of phenolic aldehyde colophony and order and degree. From the watch 2 can see, time of spontaneous combustion of resinous of pure phenolic aldehyde is 33s, appear obvious melt thing is drippy phenomenon, explain its are easy combustion, UL-94 checks off grade. And joining CeO2, material of colophony of purer phenolic aldehyde reduces the photograph of spontaneous combustion time of composite material of phenolic aldehyde colophony apparently, but because combustion reaction makes CeO2 and matrix of phenolic aldehyde colophony combine a gender,reduce, the desquamation of occurrence CeO2 phenomenon, as the addition that CeO2 adds a capacity composite material falls off the phenomenon is more apparent. Phenolic aldehyde colophony / of 30% CeO2 composite material flame retardant and characteristic good, spontaneous combustion time falls to 5s, reduce than time of spontaneous combustion of colophony of pure phenolic aldehyde 84.8% , do not burn fall off thing is less, have relative to taller anti-flammability, UL-94 test reachs V-0 level. Accordingly, phenolic aldehyde colophony / the flame retardation that 30% CeO2 composite material has fine.

Colophony of 2.4 phenolic aldehyde / the CeO2 of analysis of heat proof quality of CeO2 composite material serves as a kind of inorganic additive, its coefficient of thermal conductivity is taller. Colophony heat proof quality can be reduced in joining CeO2 phenolic aldehyde colophony. Express 3 for phenolic aldehyde colophony and colophony of different phenolic aldehyde / the thermal conductance of CeO2 composite material. From the watch 3 can see, join the addition of the quantity as CeO2, phenolic aldehyde colophony / the thermal conductance of CeO2 composite material increases. When the affiliation of CeO2 the quantity is 30% , the thermal conductance of composite material of phenolic aldehyde colophony is 0.3954W/(m·K) , have inferior heat conduction property, make clear CeO2 introduce won't right phenolic aldehyde colophony / the heat proof quality of CeO2 composite material produces bigger effect.

3 conclusion (1) mix CeO2 and phenolic aldehyde colophony, shape through hot pressing colophony of preparation phenolic aldehyde / CeO2 composite material. TG result makes clear: The CeO2 of 40% joins phenolic aldehyde colophony in, can raise phenolic aldehyde resinous initiative pyrolysis temperature, decompose temperature to increase about 36.4% , ceO2 increases thermal stability of phenolic aldehyde resinous. (2) phenolic aldehyde colophony / the flame retardation of 30% CeO2 composite material is good, resorcinol of purer phenolic aldehyde does not reduce its THR and TTI photograph 40.6% with 84.8% , prove CeO2 can raise anti-flammability of phenolic aldehyde resinous as fire retardant. (3) the affiliation of CeO2 brings about thermal conductance of phenolic aldehyde resinous to reduce, but phenolic aldehyde colophony / the thermal conductance of 30% CeO2 composite material is 0.3954W/(m·K) , thermal conductance is inferior. Accordingly, composite material of phenolic aldehyde colophony can be used at building the insulation material of establishment as heat preservation heat-insulating material.