CN104072940B - Nano titanium nitride-phenolic aldehyde composite foam material and preparation method thereof - Google Patents
Nano titanium nitride-phenolic aldehyde composite foam material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Nano titanium nitride-phenolic aldehyde composite foam material and preparation method thereof. material is made up of Nano titanium nitride, free-phenol, free formaldehyde, surfactant, curing agent, sodium chloride and phenolic resins, and the particle diameter of Nano titanium nitride is wherein 5～50nm, method is first by the ultrasonic Nano titanium nitride formalin or the mixed liquid of paraformaldehyde or formalin and paraformaldehyde being dispersed under stirring, obtain mixed solution, again by mixed solution, phenol and alkaline solution mixing post-polymerization, obtain phenolic resins prepolymer, afterwards, first phenolic resins prepolymer is carried out to acid neutralization, decompression distillation processing, obtain neutral intermediate product, again by neutral intermediate product, blowing agent and surfactant stir after mixing, obtain hybrid resin, finally, first in hybrid resin, add curing agent and stir, be placed on again in mould and solidify and foam, make object product. its thermal conductivity factor under normal temperature and high and low temperature is all lower, can be widely used in heat preservation and insulation field.
Description
Technical field
The present invention relates to a kind of composite foam material and preparation method, especially a kind of Nano titanium nitride-phenolic aldehydeComposite foam material and preparation method thereof.
Background technology
The mankind entered after 21 century, the new demand proposing along with the continuous progress of society with to environmental protection, peopleIn different fields, the demand of heat-insulating material is also constantly being promoted. There is the poly-of fine occupation rate of marketThough the type thermoplastic resin foamed materials such as ethene, polystyrene, polyurethane also possess good heat-proof quality,But slight flaw in white jade is to exist the defects such as easy firing, thermal conductivity factor is high, water imbibition is poor. Comparatively speaking,Phenol foam has possessed the advantages such as difficult combustion, good water absorption, but, but its thermal conductivity factor summaryHigher than polyethylene, polystyrene, polyurethane foamed material. Accordingly, people are in order to solve this difficult problem,Some trials and effort are done, if Chinese invention patent application CN103194041A is in July, 2013A kind of flexibilizer for toughness reinforcing obturator phenolic aldehyde foam plastic and the application thereof of within 10, announcing. This patent of inventionThe obturator phenolic aldehyde foam plastic of mentioning in application comprises the material component of following weight portion: resol100 parts, 4～8 parts of blowing agents, 10～20 parts, curing agent, 1～5 part, surfactant, polyethylene pyrrole4～15 parts of pyrrolidone or vulcabond; Preparation method adopts blend to send out. , no matter be closed pore phenolFormaldehyde foam plastic, or its preparation method, all exist weak point, and first, product is under normal temperatureThermal conductivity factor is still unsatisfactory, and in especially high temperature lower time, the decline of thermal conductivity factor is more without advantage; Secondly,Preparation method can not obtain the product compared with low thermal conductivity.
Summary of the invention
The technical problem to be solved in the present invention, for overcoming weak point of the prior art, provides a kind of heat conductionNano titanium nitride-phenolic aldehyde composite foam material that coefficient is low.
Another technical problem that the present invention will solve is for providing a kind of above-mentioned Nano titanium nitride-phenolic aldehyde compoundThe preparation method of foamed material.
For solving technical problem of the present invention, the technical scheme adopting is: Nano titanium nitride-phenolic aldehyde is compoundFoamed material comprises phenolic resins, particularly,
In described composite foam material, also contain Nano titanium nitride, free-phenol, free formaldehyde, surperficial livingProperty agent, curing agent and sodium chloride, described Nano titanium nitride, free-phenol, free formaldehyde, surface-activeThe percentage by weight of agent, curing agent and sodium chloride is 0.1～8wt%:2.5～3.5wt%:0.4～0.6wt%:6～8wt%:15～19wt%:12～16wt%, surplus is phenolic resins;
The particle diameter of described Nano titanium nitride is 5～50nm.
Further improvement as Nano titanium nitride-phenolic aldehyde composite foam material:
Preferably, surfactant be sorbitan, aliphatic acid lipid, siloxy group epoxy heterocycle altogetherPolymers, castor oil ethylene oxide, alkylphenol polyethylene glycol oxide ether, polyethylene glycol oxide methyl-silicone oil,OP-7, a kind of in OP-10, Tween-20, Tween-40, Tween-60, Tween-80, DC-193 orTwo or more mixtures.
Preferably, curing agent is one in p-methyl benzenesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acidPlant or two or more mixtures.
For solving another technical problem of the present invention, another technical scheme adopting is: above-mentioned receivingThe preparation method of rice titanium nitride-phenolic aldehyde composite foam material comprises batch process, and particularly completing steps is as follows:
Step 1, the Nano titanium nitride that is first 5～50nm by particle diameter is 1:6～140 according to weight ratioRatio, ultrasonic being dispersed to stirred mixing of lower formalin or paraformaldehyde or formalin and paraformaldehydeIn liquid, obtain mixed solution, then the alkalescence that is 15～25wt% by mixed solution, phenol and concentration successivelySolution is placed at least 2.5h of polymerisation at 70～90 DEG C after mixing, wherein, and the formaldehyde in mixed solutionThe weight ratio of mixed liquid, phenol and the alkaline solution of solution or paraformaldehyde or formalin and paraformaldehyde is0.4～1.7:1:0.3～0.7, obtains phenolic resins prepolymer;
Step 2, first carries out acid neutralization and decompression to the room temperature phenolic resins prepolymer under stirring successivelyDistillation is processed, and obtains neutral intermediate product, then is 50:3.5～5.5:1.8～2.2 according to weight ratioRatio stir at least 1min after neutral intermediate product, blowing agent and surfactant are mixed, obtainHybrid resin;
Step 3 first adds curing agent and stirs at least 1min in hybrid resin, wherein, and hybrid resinWith the weight ratio of curing agent be 10:0.9～1.1, obtain mixture, then mixture be placed in to mould,At 60～85 DEG C, solidify at least 30min that foams, make Nano titanium nitride-phenolic aldehyde composite foam material.
Further improvement as the preparation method of Nano titanium nitride-phenolic aldehyde composite foam material:
Preferably, alkaline solution is sodium hydroxide solution, barium hydroxide solution, potassium hydroxide solution, ammoniaThe mixture of one or more in water.
Preferably, when sour neutralisation treatment acid used be in hydrochloric acid, sulfuric acid, nitric acid one or both withOn mixture, the rotating speed of stirring is 200r/min.
Preferably, pressure≤0.08MPa, time >=20min when decompression distillation is processed.
Preferably, blowing agent is fluorochloroparaffins, pentane, azodicarbonamide, P-toluene sulfonyl hydrazide, benzeneThe mixture of one or more in sulfohydrazide.
Preferably, surfactant be sorbitan, aliphatic acid lipid, siloxy group epoxy heterocycle altogetherPolymers, castor oil ethylene oxide, alkylphenol polyethylene glycol oxide ether, polyethylene glycol oxide methyl-silicone oil,OP-7, a kind of in OP-10, Tween-20, Tween-40, Tween-60, Tween-80, DC-193 orTwo or more mixtures.
Preferably, curing agent is one in p-methyl benzenesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acidPlant or two or more mixtures.
Beneficial effect with respect to prior art is:
One, uses respectively ESEM to the object product making, thermogravimetric analyzer and the resistance to heat flow method of speedingHeat transfer analysis instrument characterizes, and from its result, the distribution of cells of object product is even and size is neatStandardized. It is by Nano titanium nitride, free-phenol, free formaldehyde, surfactant, curing agent, chlorinationSodium and phenolic resins form, wherein, Nano titanium nitride, free-phenol, free formaldehyde, surfactant,The percentage by weight of curing agent and sodium chloride be 0.1～8wt%:2.5～3.5wt%:0.4～0.6wt%:6～8wt%:15～19wt%:12～16wt%, surplus is phenolic resins; The particle diameter of Nano titanium nitride whereinBe 5～50nm, surfactant be sorbitan, aliphatic acid lipid, siloxy group epoxy heterocycle altogetherPolymers, castor oil ethylene oxide, alkylphenol polyethylene glycol oxide ether, polyethylene glycol oxide methyl-silicone oil,OP-7, a kind of in OP-10, Tween-20, Tween-40, Tween-60, Tween-80, DC-193 orTwo or more mixtures, curing agent is p-methyl benzenesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acidIn one or more mixture. This is main body by phenolic resins, dopen Nano titanium nitride,The object product of free-phenol, free formaldehyde, surfactant, curing agent and sodium chloride assembling, both protectedThe advantages such as the original difficult combustion of phenolic resins, good water absorption are stayed; Again because the existence of alloy makes its abscessDistribution more even, the average-size of abscess diminishes.
Its two, use the resistance to heat flow method heat transfer analysis instrument of speeding to characterize to phenol formaldehyde foam and object product respectively,Its comparing result is as shown in the table,
As seen from the above table, the thermal conductivity factor of object product under normal temperature and high and low temperature all obtained largelyReduce.
Its three, preparation method's science, efficient, has not only made the low object product of thermal conductivity factor---receiveRice titanium nitride-phenolic aldehyde composite foam material, also because doping and the dispersed object that makes of Nano titanium nitride are producedThe thermal conductivity factor of thing is minimized, and has had the inside that distribution of cells is even and size is uniform simultaneouslyStructure; More there is the feature that preparation cost is low; And then make object product very easily various in being widely used inHeat preservation and insulation field, make its central air conditioner system, light thermal-insulation color steel, external wall heat-barrier material,Petrochemical pipe has a wide range of applications with fields such as insulation materials.
Brief description of the drawings
Fig. 1 is that the object product respectively phenol formaldehyde foam and preparation method being made uses ESEM (SEM)One of result characterizing. Wherein, the SEM image that Fig. 1 a is phenol formaldehyde foam; Fig. 1 b is that object is producedThe SEM image of thing. As seen from Figure 1, the distribution of cells of object product is more even than phenol formaldehyde foam,And aperture is little.
Fig. 2 uses thermogravimetic analysis (TGA) (TGA) instrument to characterize to phenol formaldehyde foam and object product respectivelyOne of result. Can be found out by TGA curve map, the decomposition temperature of object product has improved 25.29 DEG C, pointTemperature when solution is the fastest has improved 7 DEG C, and the amount (59.590%) of residue is also far away more than phenol after 700 DEG CAldehyde foam (24.471%).
Fig. 3 uses model to be to phenol formaldehyde foam and object product respectively in the time that environment temperature is-20 DEG COne of result that the resistance to heat flow method heat transfer analysis instrument of speeding of HFM436 characterizes. As seen from Figure 3, objectThe thermal conductivity factor of product in the time of-20 DEG C reduced 7.92mW/mK.
Fig. 4 uses model to be to phenol formaldehyde foam and object product respectively in the time that environment temperature is 20 DEG COne of result that the resistance to heat flow method heat transfer analysis instrument of speeding of HFM436 characterizes. As seen from Figure 4, objectThe thermal conductivity factor of product in the time of 20 DEG C reduced 10.98mW/mK.
Fig. 5 for using model to be to phenol formaldehyde foam and object product respectively in the time that environment temperature is 60 DEG COne of result that the resistance to heat flow method heat transfer analysis instrument of speeding of HFM436 characterizes. As seen from Figure 4, objectThe thermal conductivity factor of product in the time of 60 DEG C reduced 17.04mW/mK.
Below in conjunction with accompanying drawing, optimal way of the present invention is described in further detail.
First buy from market or make by conventional method:
Particle diameter is the nano silicon nitride of 5～50nm; Formalin; Paraformaldehyde; Formalin and poly firstThe mixed liquid of aldehyde; Phenol; As sodium hydroxide solution, barium hydroxide solution, the potassium hydroxide of alkaline solutionSolution and ammoniacal liquor; As sour hydrochloric acid, sulfuric acid and nitric acid; As the fluorochloroparaffins of blowing agent, pentane,Azodicarbonamide, P-toluene sulfonyl hydrazide, benzene sulfonyl hydrazide; As sorbitan, the fat of surfactantFat acid lipid, siloxy group epoxy heterocyclic copolymer, castor oil ethylene oxide, alkylphenol polyoxygenatedVinethene, polyethylene glycol oxide methyl-silicone oil, OP-7, OP-10, Tween-20, Tween-40, Tween-60,Tween-80, DC-193; As p-methyl benzenesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, the second of curing agentAcid. Then,
Embodiment 1
The concrete steps of preparation are:
Step 1, the ratio that the Nano titanium nitride that is first 5nm by particle diameter is 1:6 according to weight ratio, ultrasonicBe dispersed in the formalin under stirring, obtain mixed solution. Again successively by mixed solution, phenol and denseAfter the alkaline solution that degree is 15wt% mixes, be placed in polymerisation 3.5h at 70 DEG C; Wherein, mixed solutionIn the weight ratio of formalin, phenol and alkaline solution be 0.4:1:0.7, alkaline solution is hydrogen-oxygenChange sodium solution, obtain phenolic resins prepolymer.
Step 2, first carries out acid neutralization and decompression to the room temperature phenolic resins prepolymer under stirring successivelyDistillation is processed; Wherein, when sour neutralisation treatment, acid used is hydrochloric acid, and the rotating speed of stirring is 200r/min,Pressure≤0.08MPa, time >=20min when decompression distillation is processed, obtain neutral intermediate product. AgainThe ratio that is 50:3.5:2.2 according to weight ratio is by neutral intermediate product, blowing agent and surfactantAfter mixing, stir 1min; Wherein, blowing agent is pentane, and surfactant is Tween-80, is mixedResin.
Step 3 first adds curing agent and stirs 1min in hybrid resin; Wherein, hybrid resin is with solidThe weight ratio of agent is 10:0.9, and curing agent is p-methyl benzenesulfonic acid, obtains mixture. Again mixture is putIn mould, at 60 DEG C solidify foaming 40min, make and be similar to shown in Fig. 1, and as Fig. 2,Nano titanium nitride-phenolic aldehyde composite foam material shown in curve in Fig. 3, Fig. 4 and Fig. 5.
Embodiment 2
The concrete steps of preparation are:
Step 1, the ratio that the Nano titanium nitride that is first 16nm by particle diameter is 1:39 according to weight ratio is superSound is dispersed in the formalin under stirring, and obtains mixed solution. Again successively by mixed solution, phenol andConcentration is, after the alkaline solution of 18wt% mixes, to be placed in polymerisation 3.3h at 75 DEG C; Wherein, mix moltenThe weight ratio of formalin, phenol and alkaline solution in liquid is 0.7:1:0.6, and alkaline solution is hydrogenSodium hydroxide solution, obtains phenolic resins prepolymer.
Step 2, first carries out acid neutralization and decompression to the room temperature phenolic resins prepolymer under stirring successivelyDistillation is processed; Wherein, when sour neutralisation treatment, acid used is hydrochloric acid, and the rotating speed of stirring is 200r/min,Pressure≤0.08MPa, time >=20min when decompression distillation is processed, obtain neutral intermediate product. AgainThe ratio that is 50:4:2.1 according to weight ratio is mixed by neutral intermediate product, blowing agent and surfactantClose rear stirring 2min; Wherein, blowing agent is pentane, and surfactant is Tween-80, is mixedResin.
Step 3 first adds curing agent and stirs 2min in hybrid resin; Wherein, hybrid resin is with solidThe weight ratio of agent is 10:0.95, and curing agent is p-methyl benzenesulfonic acid, obtains mixture. Again by mixtureBe placed in mould, at 69 DEG C solidify foaming 38min, make and be similar to shown in Fig. 1, and as Fig. 2,Nano titanium nitride-phenolic aldehyde composite foam material shown in curve in Fig. 3, Fig. 4 and Fig. 5.
Embodiment 3
The concrete steps of preparation are:
Step 1, the ratio that the Nano titanium nitride that is first 28nm by particle diameter is 1:73 according to weight ratio is superSound is dispersed in the formalin under stirring, and obtains mixed solution. Again successively by mixed solution, phenol andConcentration is, after the alkaline solution of 20wt% mixes, to be placed in polymerisation 3h at 80 DEG C; Wherein, mixed solutionIn the weight ratio of formalin, phenol and alkaline solution be 1.0:1:0.5, alkaline solution is hydrogen-oxygenChange sodium solution, obtain phenolic resins prepolymer.
Step 2, first carries out acid neutralization and decompression to the room temperature phenolic resins prepolymer under stirring successivelyDistillation is processed; Wherein, when sour neutralisation treatment, acid used is hydrochloric acid, and the rotating speed of stirring is 200r/min,Pressure≤0.08MPa, time >=20min when decompression distillation is processed, obtain neutral intermediate product. AgainThe ratio that is 50:4.5:2 according to weight ratio is mixed by neutral intermediate product, blowing agent and surfactantClose rear stirring 3min; Wherein, blowing agent is pentane, and surfactant is Tween-80, is mixedResin.
Step 3 first adds curing agent and stirs 3min in hybrid resin; Wherein, hybrid resin is with solidThe weight ratio of agent is 10:1, and curing agent is p-methyl benzenesulfonic acid, obtains mixture. Again mixture is placed inIn mould, at 73 DEG C, solidify foaming 35min, make as shown in Figure 1, and as Fig. 2, Fig. 3, figure4 and Fig. 5 in curve shown in Nano titanium nitride-phenolic aldehyde composite foam material.
Embodiment 4
The concrete steps of preparation are:
Step 1, the ratio that the Nano titanium nitride that is first 39nm by particle diameter is 1:106 according to weight ratio,In the ultrasonic formalin being dispersed under stirring, obtain mixed solution. Again successively by mixed solution, phenolAfter mixing with the concentration alkaline solution that is 23wt%, be placed in polymerisation 2.8h at 85 DEG C; Wherein, mixThe weight ratio of formalin, phenol and alkaline solution in solution is 1.3:1:0.4, and alkaline solution isSodium hydroxide solution, obtains phenolic resins prepolymer.
Step 2, first carries out acid neutralization and decompression to the room temperature phenolic resins prepolymer under stirring successivelyDistillation is processed; Wherein, when sour neutralisation treatment, acid used is hydrochloric acid, and the rotating speed of stirring is 200r/min,Pressure≤0.08MPa, time >=20min when decompression distillation is processed, obtain neutral intermediate product. AgainThe ratio that is 50:5:1.9 according to weight ratio is mixed by neutral intermediate product, blowing agent and surfactantClose rear stirring 4min; Wherein, blowing agent is pentane, and surfactant is Tween-80, is mixedResin.
Step 3 first adds curing agent and stirs 4min in hybrid resin; Wherein, hybrid resin is with solidThe weight ratio of agent is 10:1.05, and curing agent is p-methyl benzenesulfonic acid, obtains mixture. Again by mixtureBe placed in mould, at 79 DEG C solidify foaming 33min, make and be similar to shown in Fig. 1, and as Fig. 2,Nano titanium nitride-phenolic aldehyde composite foam material shown in curve in Fig. 3, Fig. 4 and Fig. 5.
Embodiment 5
The concrete steps of preparation are:
Step 1, the ratio that the Nano titanium nitride that is first 50nm by particle diameter is 1:140 according to weight ratio,In the ultrasonic formalin being dispersed under stirring, obtain mixed solution. Again successively by mixed solution, phenolAfter mixing with the concentration alkaline solution that is 25wt%, be placed in polymerisation 2.5h at 90 DEG C; Wherein, mixThe weight ratio of formalin, phenol and alkaline solution in solution is 1.7:1:0.3, and alkaline solution isSodium hydroxide solution, obtains phenolic resins prepolymer.
Step 2, first carries out acid neutralization and decompression to the room temperature phenolic resins prepolymer under stirring successivelyDistillation is processed; Wherein, when sour neutralisation treatment, acid used is hydrochloric acid, and the rotating speed of stirring is 200r/min,Pressure≤0.08MPa, time >=20min when decompression distillation is processed, obtain neutral intermediate product. AgainThe ratio that is 50:5.5:1.8 according to weight ratio is by neutral intermediate product, blowing agent and surfactantAfter mixing, stir 5min; Wherein, blowing agent is pentane, and surfactant is Tween-80, is mixedResin.
Step 3 first adds curing agent and stirs 5min in hybrid resin; Wherein, hybrid resin is with solidThe weight ratio of agent is 10:1.1, and curing agent is p-methyl benzenesulfonic acid, obtains mixture. Again mixture is putIn mould, at 85 DEG C solidify foaming 30min, make and be similar to shown in Fig. 1, and as Fig. 2,Nano titanium nitride-phenolic aldehyde composite foam material shown in curve in Fig. 3, Fig. 4 and Fig. 5.
Select respectively the more mixed liquid of formalin or paraformaldehyde or formalin and paraformaldehyde, as alkaliProperty solution sodium hydroxide solution, barium hydroxide solution, potassium hydroxide solution, ammoniacal liquor in a kind of or twoKind of above mixture, as one or more the mixture in sour hydrochloric acid, sulfuric acid, nitric acid,In the fluorochloroparaffins of blowing agent, pentane, azodicarbonamide, P-toluene sulfonyl hydrazide, benzene sulfonyl hydrazideOne or more mixture, as the sorbitan of surfactant, aliphatic acid lipid,Siloxy group epoxy heterocyclic copolymer, castor oil ethylene oxide, alkylphenol polyethylene glycol oxide ether, poly-Ethylene oxide methyl-silicone oil, OP-7, OP-10, Tween-20, Tween-40, Tween-60, Tween-80,The mixture of one or more in DC-193, as p-methyl benzenesulfonic acid, hydrochloric acid, the sulphur of curing agentThe mixture of one or more in acid, phosphoric acid, nitric acid, acetic acid, repeats above-described embodiment 1～5,Make equally as or be similar to as shown in Fig. 1, and as the Curves in Fig. 2, Fig. 3, Fig. 4 and Fig. 5Nano titanium nitride-phenolic aldehyde the composite foam material showing.
Obviously, those skilled in the art can be to Nano titanium nitride-phenolic aldehyde composite foam material of the present inventionAnd preparation method thereof carry out various changes and modification and do not depart from the spirit and scope of the present invention. Like this, ifIf to of the present invention these amendment and modification belong to the claims in the present invention and equivalent technologies thereof scope itIn, the present invention be also intended to comprise these change and modification interior.
Claims (7)
1. a preparation method for Nano titanium nitride-phenolic aldehyde composite foam material, comprises batch process, its spyLevy and be that completing steps is as follows:
Step 1, the Nano titanium nitride that is first 5～50nm by particle diameter is 1:6～140 according to weight ratioRatio, ultrasonic being dispersed to stirred mixing of lower formalin or paraformaldehyde or formalin and paraformaldehydeIn liquid, obtain mixed solution, then the alkalescence that is 15～25wt% by mixed solution, phenol and concentration successivelySolution is placed at least 2.5h of polymerisation at 70～90 DEG C after mixing, wherein, and the formaldehyde in mixed solutionThe weight ratio of mixed liquid, phenol and the alkaline solution of solution or paraformaldehyde or formalin and paraformaldehyde is0.4～1.7:1:0.3～0.7, obtains phenolic resins prepolymer;
Step 2, first carries out acid neutralization and decompression to the room temperature phenolic resins prepolymer under stirring successivelyDistillation is processed, and obtains neutral intermediate product, then is 50:3.5～5.5:1.8～2.2 according to weight ratioRatio stir at least 1min after neutral intermediate product, blowing agent and surfactant are mixed, obtainHybrid resin;
Step 3 first adds curing agent and stirs at least 1min in hybrid resin, wherein, and hybrid resinWith the weight ratio of curing agent be 10:0.9～1.1, obtain mixture, then mixture be placed in to mould,At 60～85 DEG C, solidify at least 30min that foams, make Nano titanium nitride-phenolic aldehyde composite foam material;
Described Nano titanium nitride-phenolic aldehyde composite foam material by Nano titanium nitride, free-phenol, free formaldehyde,Surfactant, curing agent, sodium chloride and phenolic resins composition, wherein, Nano titanium nitride, free benzeneThe percentage by weight of phenol, free formaldehyde, surfactant, curing agent and sodium chloride is 0.1～8wt%:2.5～3.5wt%:0.4～0.6wt%:6～8wt%:15～19wt%:12～16wt%, surplus is phenolic aldehydeResin, the particle diameter of Nano titanium nitride is 5～50nm.
2. the preparation method of Nano titanium nitride-phenolic aldehyde composite foam material according to claim 1,It is characterized in that alkaline solution is in sodium hydroxide solution, barium hydroxide solution, potassium hydroxide solution, ammoniacal liquorOne or more mixture.
3. the preparation method of Nano titanium nitride-phenolic aldehyde composite foam material according to claim 1,While it is characterized in that sour neutralisation treatment acid used be in hydrochloric acid, sulfuric acid, nitric acid one or moreMixture, the rotating speed of stirring is 200r/min.
4. the preparation method of Nano titanium nitride-phenolic aldehyde composite foam material according to claim 1,It is characterized in that pressure≤0.08MPa, time >=20min when decompression distillation is processed.
5. the preparation method of Nano titanium nitride-phenolic aldehyde composite foam material according to claim 1,It is characterized in that blowing agent is fluorochloroparaffins, pentane, azodicarbonamide, P-toluene sulfonyl hydrazide, benzene sulfonylThe mixture of one or more in hydrazine.
6. the preparation method of Nano titanium nitride-phenolic aldehyde composite foam material according to claim 1,It is characterized in that surfactant be sorbitan, aliphatic acid lipid, siloxy group epoxy heterocyclic copolymer,Castor oil ethylene oxide, alkylphenol polyethylene glycol oxide ether, polyethylene glycol oxide methyl-silicone oil, OP-7,One or both in OP-10, Tween-20, Tween-40, Tween-60, Tween-80, DC-193 withOn mixture.
7. the preparation method of Nano titanium nitride-phenolic aldehyde composite foam material according to claim 1,It is characterized in that curing agent be a kind of in p-methyl benzenesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid orTwo or more mixtures.
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