CN105111433A - Low dielectric constant polyamide aerogel thermal insulation material and preparation method thereof - Google Patents
Low dielectric constant polyamide aerogel thermal insulation material and preparation method thereof Download PDFInfo
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- CN105111433A CN105111433A CN201510641913.6A CN201510641913A CN105111433A CN 105111433 A CN105111433 A CN 105111433A CN 201510641913 A CN201510641913 A CN 201510641913A CN 105111433 A CN105111433 A CN 105111433A
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Abstract
The invention discloses a low dielectric constant polyamide aerogel thermal insulation material and a preparation method thereof. According to the low dielectric constant polyamide aerogel thermal insulation material, aromatic oxalyl chloride and aromatic diamine are taken as raw materials, polyamine or polybasic acyl chloride are taken as a cross-linking agent, a sol-to-gel process is adopted to prepare and obtain polyamide gel with a three-dimensional net structure, and the low dielectric constant polyamide aerogel thermal insulation material is obtained by carrying out CO2 supercritical drying on the polyamide gel. The aromatic oxalyl chloride is TPC or IPC or a mixture of the TPC and the IPC; the aromatic diamine is ODA or pPDA; the polyamine is TAB or OAPS; the polybasic acyl chloride is BTC. The thermal insulation material provided by the invention is relatively low in dielectric constant, low in density, low in heat conductivity and good in heat-insulating property; the preparation method provided by the invention has the advantages that a preparation process is simple, the raw materials are easy to obtain, the cost is relatively low, the requirement on environment is relatively low, a whole technological process is short in consumed time, and the material is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of lagging material and preparation method thereof, particularly relate to a kind of low-k polymeric amide aerogel heat-insulating material and preparation method thereof.
Background technology
In recent years, along with constantly reducing of super large-scale integration size, metal interconnected resistance, capacitance delays increase [functional materials with approximate quadratic power, 2000,31 (5): 452-455], cause signal transmission delay and crosstalk, directly affect the performance of device.Causing the increase of power consumption in order to reduce signal transmission delay and crosstalk and dissipation loss, meeting the high speed of signal transmission, improve the function of electronic circuit further, the materials demand with lower specific inductivity is urgent.
Aerogel is a kind of nanoporous network structure of mutually assembling formation with nanometer scale colloidal particle, and in hole, be full of a kind of high dispersive solid-state material of gaseous state dispersion medium.This constitutional features aerogel is become solid material that at present density is minimum in the world (minimumly reaches 0.0002gcm
-3), also be solid material (normal temperature thermal conductivity is the 0.013W/mK) [J.Mate.Proc.Technol. that current known thermal conductivity is minimum, 2008,199:10-26], and there is lower specific inductivity (specific inductivity of silica aerogel can be low to moderate 1.008) [ACSAppl.Mater.Interfaces2012,4,6346-6353].Above-mentioned characteristic makes aerogel can as a kind of desirable materials application in the field such as aerospace and electric and electronic.
General material cannot meet the requirement of lightweight, low-k, if the specific inductivity of polyimide is about 3.4, can not meet the dielectric constant values required for submicron component far away.Inorganic aerogels material is (as SiO
2aerogel) the lower specific inductivity that has and heat-proof quality preferably, but its shortcoming to be matter crisp, frangible, in use dry linting, fall slag, dust pollution is serious, cannot meet the requirement of electron device no dust pollution.Polyimide aerogels has good mechanical property, light weight, and specific inductivity can be low to moderate about 1.2, but its cost intensive, suitability for industrialized production has certain limitation.
Etc. MaryA.B. the specific inductivity introducing the polyimide aerogels obtained containing fluorine structure is 1.24[ACSAppl.Mater.InterfacesA-G], specific inductivity is lower, but raw materials source is narrow, and cost is high, is unfavorable for suitability for industrialized production.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of low-k polymeric amide aerogel heat-insulating material and preparation method thereof.
Low-k polymeric amide aerogel heat-insulating material of the present invention is for raw material with aromatic diacid chlorides and aromatic diamine, polyamine or polynary acyl chlorides are linking agent, adopt the polyamide gels with three-dimensional net structure that the process of sol-gel prepares, polyamide gels is through CO
2low-k polymeric amide aerogel heat-insulating material is obtained after supercritical drying.
Described aromatic diacid chlorides is the mixture of p-phthaloyl chloride (terephthaloylchloride is called for short TPC) or m-phthaloyl chloride (isophthaloylchloride is called for short IPC) or TPC and IPC; When adopting the mixture of TPC and IPC, the mole number of TPC accounts for 5% ~ 95% of TPC and IPC total mole number.
Described aromatic diamine is 4,4 '-diaminodiphenyl oxide (4,4 '-diaminodiphenylether, be called for short ODA) or Ursol D (p-phenylenediamine is called for short pPDA);
Described polyamine is 1,3,5-tri-(4-amino-benzene oxygen) benzene (1,3,5-triaminophenoxybenzene is called for short TAB) or eight (aminophenyl) polysilsesquioxane (OAPS), preferred TAB; Polynary acyl chlorides is 1,3,5-benzene three formyl chloride (1,3,5-benzenetricarbonyltrichloride is called for short BTC); When taking polyamine as linking agent, the mol ratio of aromatic diacid chlorides, aromatic diamine is (1.00 ~ 1.10): 1.00, when with polynary acyl chlorides for linking agent time, the mol ratio of aromatic diacid chlorides, aromatic diamine is (0.90 ~ 1.00): 1.00; The mol ratio that polyamine and institute add aromatic diamine is (0.017 ~ 0.033): 1.000, and polynary acyl chlorides is (0.017 ~ 0.033) with the mol ratio of the aromatic diamine added: 1.000.Polymeric amide aerogel heat-insulating material structure prepared by TPC, ODA and BTC tri-kinds of material copolymerizations is such as formula shown in I; Polymeric amide aerogel heat-insulating material structure prepared by TPC, ODA and TAB tri-kinds of material copolymerizations is such as formula shown in II; Polymeric amide aerogel heat-insulating material structure prepared by IPC, ODA and BTC tri-kinds of material copolymerizations is as shown in formula III; Polymeric amide aerogel heat-insulating material structure prepared by IPC, ODA and TAB tri-kinds of material copolymerizations is such as formula shown in IV; Polymeric amide aerogel heat-insulating material structure prepared by TPC, pPDA and TAB tri-kinds of material copolymerizations is such as formula shown in V; Polymeric amide aerogel heat-insulating material structure prepared by TPC, pPDA and BTC tri-kinds of material copolymerizations is such as formula shown in VI; Polymeric amide aerogel heat-insulating material structure prepared by IPC, pPDA and TAB tri-kinds of material copolymerizations is such as formula shown in VII; Polymeric amide aerogel heat-insulating material structure prepared by IPC, pPDA and BTC tri-kinds of material copolymerizations is such as formula shown in VIII; Polymeric amide aerogel heat-insulating material structure prepared by TPC, IPC, ODA and BTC tetra-kinds of material copolymerizations is such as formula shown in IX; Polymeric amide aerogel heat-insulating material structure prepared by TPC, IPC, ODA and TAB tetra-kinds of material copolymerizations is such as formula shown in X; Polymeric amide aerogel heat-insulating material structure prepared by TPC, IPC, pPDA and TAB tetra-kinds of material copolymerizations is such as formula shown in XI; Polymeric amide aerogel heat-insulating material structure prepared by TPC, IPC, pPDA and BTC tetra-kinds of material copolymerizations is such as formula shown in XII; Polymeric amide aerogel heat-insulating material structure prepared by TPC, ODA and OAPS tri-kinds of material copolymerizations is such as formula shown in XIII; Polymeric amide aerogel heat-insulating material structure prepared by IPC, ODA and OAPS tri-kinds of material copolymerizations is such as formula shown in XIV; Polymeric amide aerogel heat-insulating material structure prepared by TPC, IPC, ODA and OAPS tetra-kinds of material copolymerizations is such as formula shown in XV; Polymeric amide aerogel heat-insulating material structure prepared by TPC, pPDA and OAPS tri-kinds of material copolymerizations is such as formula shown in XVI; Polymeric amide aerogel heat-insulating material structure prepared by IPC, pPDA and OAPS tri-kinds of material copolymerizations is such as formula shown in XVII; Polymeric amide aerogel heat-insulating material structure prepared by TPC, IPC, pPDA and OAPS tetra-kinds of material copolymerizations is such as formula shown in XVIII.The density of low-k polymeric amide aerogel heat-insulating material is 0.2 ~ 0.6gcm
-3, specific inductivity is 1.21 ~ 1.60, and thermal conductivity is 0.045 ~ 0.065W/mK.
In its Chinese style XIII ~ formula XVIII, X is
N, m are the integer of 1 ~ 120, specifically can be the integer of 15 ~ 25,25 ~ 35 or 40 ~ 60, and preferably 25.
The preparation method of low-k polymeric amide aerogel heat-insulating material of the present invention comprises the following steps:
The first step, is dissolved in intensive polar solvent under nitrogen protection by aromatic diamine, is joined by aromatic diacid chlorides in above-mentioned solution, stirs under nitrogen atmosphere, obtains the polymeric amide colloidal sol of clear.Wherein when taking polyamine as linking agent, the mol ratio of aromatic diacid chlorides and aromatic diamine is (1.00 ~ 1.10): 1.00, when with polynary acyl chlorides for linking agent time, the mol ratio of aromatic diacid chlorides and aromatic diamine is (0.91 ~ 1.00): 1.00;
Described intensive polar solvent is dry N-methylpyrrolidone (1-methyl-2-pyrrolidinone, be called for short NMP), anhydrous N, dinethylformamide (N, N-dimethylformamide, be called for short DMF), anhydrous N, any one in N-N,N-DIMETHYLACETAMIDE (dimethylacetamide, be called for short DMAc);
Second step, polyamine or polynary acyl chlorides is added as linking agent in the polymeric amide colloidal sol of described the first step gained, obtain cross-linking type polymeric amide colloidal sol, under nitrogen atmosphere, stirring reaction was poured in mould after 10 ~ 60 minutes, leave standstill and within 10 ~ 60 minutes, treat that its gel obtains polyamide gels, the polyamide gels obtained is carried out solvent exchange three times after aging 12 ~ 48 hours in the anhydrous intensive polar solvent described in the first step, obtains the polyamide gels with three-dimensional net structure after solvent exchange; If linking agent is polyamine, then polyamine is (0.017 ~ 0.033) with the mol ratio of the aromatic diamine added: 1.000; Linking agent is polynary acyl chlorides, then polynary acyl chlorides is (0.017 ~ 0.033) with the mol ratio of the aromatic diamine added: 1.000;
The solvent that described solvent exchange uses is anhydrous methanol, any one in dehydrated alcohol, anhydrous isopropyl alcohol, anhydrous propanone, preferred dehydrated alcohol;
3rd step, carries out CO by the polyamide gels after the solvent exchange of described second step gained
2supercritical fluid drying process: CO
2supercritical fluid drying condition be with any one in dehydrated alcohol, anhydrous isopropyl alcohol or anhydrous propanone for drying medium, polyamide gels is put into CO
2in supercritical drying equipment, be heated to 35 ~ 85 DEG C, be filled with CO
2to 9 ~ 20MPa, pressurize carried out CO after 0.5 ~ 3 hour
2supercritical fluid drying 4 ~ 24 hours, then can obtain low-k polymeric amide aerogel heat-insulating material with the speed slow releasing pressure of 40 ~ 70kPa/min.
Adopt the present invention can reach following beneficial effect:
Low-k polymeric amide aerogel heat-insulating material of the present invention is made up of aromatic diacid chlorides, aromatic diamine and the polyamine shown in formula I ~ formula XVIII or polynary acyl chlorides structure fragment, and the polymeric amide aerogel heat-insulating material of this structure has lower specific inductivity and thermal conductivity.The present invention is based on sol-gel technique, with aromatic diacid chlorides, aromatic diamine and linking agent (polyamine or polynary acyl chlorides) for raw material prepares polyamide gels, through CO
2supercritical fluid drying process obtains low-k polymeric amide aerogel heat-insulating material.
Therefore the present invention has following advantage:
(1) the polymeric amide aerogel heat-insulating material adopting the inventive method to prepare has lower specific inductivity, by second step in implementation step and the 3rd step, namely by sol-gel method and supercritical drying process, the polymeric amide aerogel heat-insulating material prepared has lower specific inductivity.This is because sol-gel method and supercritical drying process make material have nano-pore structure, significantly can reduce the specific inductivity of material.The specific inductivity of polymeric amide aerogel material is 1.20 ~ 1.60, has lower specific inductivity (if polymide dielectric constant is about 3.4) than other macromolecular materials, is more conducive to expanding its application in electron device.
(2) the low-k polymeric amide aerogel heat-insulating material density adopting the inventive method to prepare is low, thermal conductivity is low, and heat-proof quality is good.By the 3rd step CO
2polymeric amide aerogel heat-insulating material density prepared by supercritical fluid drying technique is low, and aperture is little, has good iris action to solid heat transfer and gas heat-transfer.The polymeric amide aerogel heat-insulating material density that the present invention obtains is 0.2 ~ 0.6gcm
-3, thermal conductivity is 0.045 ~ 0.065W/mK.
(3) the inventive method preparation technology is simple, and raw material is easy to get, and (polymeric amide aerogel cost is about 2000 yuan/kg to advantage of lower cost, and polyimide aerogels cost is about 4500 yuan/kg), lower to environmental requirement, whole technical process is consuming time short, is applicable to suitability for industrialized production.
Embodiment
Be below that the invention will be further described in conjunction with the embodiments, but these embodiments must not be used for explaining limiting the scope of the invention.
Embodiment 1
The first step, by 4,4 '-diaminodiphenyl oxide (ODA) is dissolved in dry N-methylpyrrolidone (NMP) under nitrogen protection, p-phthaloyl chloride (TPC) is joined in above-mentioned solution, stir under nitrogen atmosphere, form the polymeric amide colloidal sol of clear, wherein the mol ratio of TPC and ODA is 0.95:1.00;
Second step, adds linking agent 1,3 in the colloidal sol of described the first step gained, 5-benzene three formyl chloride (BTC), obtains the polymeric amide colloidal sol be cross-linked, stirring reaction 20 minutes under nitrogen atmosphere, colloidal sol is poured in mould, leave standstill and within 30 minutes, treat the polyamide gels that its gel obtains.The polyamide gels obtained is carried out solvent exchange after aging 24 hours in anhydrous NMP, obtains the polyamide gels after solvent exchange.Wherein the mol ratio of BTC and ODA is 0.022:1.000, solvent exchange is the mixing solutions of anhydrous NMP and dehydrated alcohol, the mixing solutions of the anhydrous NMP and dehydrated alcohol that use volume ratio to be respectively 3:1 and 1:3 is replaced once respectively, finally uses dehydrated alcohol displacement once;
3rd step, carries out CO by the polyamide gels after solvent exchange
2supercritical fluid drying process, CO
2supercritical fluid drying condition is drying medium with dehydrated alcohol, polyamide gels put into supercritical drying equipment, is heated to 55 DEG C, is filled with CO
2to 15MPa, pressurize carried out CO after 1 hour
2supercritical fluid drying 8 hours, then can obtain low-k polymeric amide aerogel heat-insulating material with 50kPa/min speed slow releasing pressure.Hydrophobicity polymeric amide aerogel heat-insulating material density prepared by this example is 0.31gcm
-3, when 25 DEG C, thermal conductivity is 0.046W/mK, and specific inductivity is 1.25.
Embodiment 2
The first step, by 4,4 '-diaminodiphenyl oxide (ODA) is dissolved in anhydrous N under nitrogen protection, in dinethylformamide (DMF), p-phthaloyl chloride (TPC) is joined in above-mentioned solution, stir under nitrogen atmosphere, form the polymeric amide colloidal sol of clear, wherein the mol ratio of TPC and ODA is 0.95:1.00;
Second step, adds linking agent 1,3 in the colloidal sol of described the first step gained, 5-benzene three formyl chloride (BTC), obtains the polymeric amide colloidal sol be cross-linked, stirring reaction 20 minutes under nitrogen atmosphere, colloidal sol is poured in mould, leave standstill and within 30 minutes, treat the polyamide gels that its gel obtains.The polyamide gels obtained is carried out solvent exchange after aging 24 hours in dry DMF, obtains the polyamide gels after solvent exchange.Wherein the mol ratio of BTC and ODA is 0.022:1.000, solvent exchange is the mixing solutions of dry DMF and dehydrated alcohol, the mixing solutions of the dry DMF and dehydrated alcohol that use volume ratio to be respectively 3:1 and 1:3 is replaced once respectively, finally uses dehydrated alcohol displacement once;
3rd step, carries out CO by the polyamide gels after solvent exchange
2supercritical fluid drying process, CO
2supercritical fluid drying condition is drying medium with dehydrated alcohol, polyamide gels put into supercritical drying equipment, is heated to 55 DEG C, is filled with CO
2to 15MPa, pressurize carried out CO after 1 hour
2supercritical fluid drying 8 hours, then can obtain low-k polymeric amide aerogel heat-insulating material with 50kPa/min speed slow releasing pressure.Hydrophobicity polymeric amide aerogel heat-insulating material density prepared by this example is 0.32gcm
-3, when 25 DEG C, thermal conductivity is 0.045W/mK, and specific inductivity is 1.27.
Embodiment 3
The first step, by 4,4 '-diaminodiphenyl oxide (ODA) is dissolved in anhydrous N under nitrogen protection, in N-N,N-DIMETHYLACETAMIDE (DMAc), p-phthaloyl chloride (TPC) is joined in above-mentioned solution, stir under nitrogen atmosphere, form the polymeric amide colloidal sol of clear, wherein the mol ratio of TPC and ODA is 0.95:1.00;
Second step, adds linking agent 1,3 in the colloidal sol of described the first step gained, 5-benzene three formyl chloride (BTC), obtains the polymeric amide colloidal sol be cross-linked, stirring reaction 20 minutes under nitrogen atmosphere, colloidal sol is poured in mould, leave standstill and within 30 minutes, treat the polyamide gels that its gel obtains.The polyamide gels obtained is carried out solvent exchange after aging 24 hours in anhydrous DMAc, obtains the polyamide gels after solvent exchange.Wherein the mol ratio of BTC and ODA is 0.022:1.000, solvent exchange is the mixing solutions of anhydrous DMAc and dehydrated alcohol, the mixing solutions of the anhydrous DMAc and dehydrated alcohol that use volume ratio to be respectively 3:1 and 1:3 is replaced once respectively, finally uses dehydrated alcohol displacement once;
3rd step, carries out CO by the polyamide gels after solvent exchange
2supercritical fluid drying process, CO
2supercritical fluid drying condition is drying medium with dehydrated alcohol, polyamide gels put into supercritical drying equipment, is heated to 55 DEG C, is filled with CO
2to 15MPa, pressurize carried out CO after 1 hour
2supercritical fluid drying 8 hours, then can obtain low-k polymeric amide aerogel heat-insulating material with 50kPa/min speed slow releasing pressure.Hydrophobicity polymeric amide aerogel heat-insulating material density prepared by this example is 0.33gcm
-3, when 25 DEG C, thermal conductivity is 0.046W/mK, and specific inductivity is 1.26.
Embodiment 2,3 is the intensive polar solvent only changed in reaction system with the difference of embodiment 1, prepares the thermal conductivity of resulting materials between 0.045 ~ 0.046W/mK, and specific inductivity is between 1.25 ~ 1.27, and result difference is very little.Visible, the change of intensive polar solvent does not affect prepared material property.
Embodiment 4
The first step, by 4,4 '-diaminodiphenyl oxide (ODA) is dissolved in dry N-methylpyrrolidone (NMP) under nitrogen protection, p-phthaloyl chloride (TPC) is joined in above-mentioned solution, stir under nitrogen atmosphere, form the polymeric amide colloidal sol of clear, wherein the mol ratio of TPC and ODA is 1.05:1.00;
Second step, linking agent 1 is added in the colloidal sol of described the first step gained, 3,5-tri-(4-amino-benzene oxygen) benzene (TAB), obtain the polymeric amide colloidal sol be cross-linked, under nitrogen atmosphere, stirring reaction 20 minutes, pours into colloidal sol in mould, leaves standstill and within 30 minutes, treats the polyamide gels that its gel obtains.The polyamide gels obtained is carried out solvent exchange after aging 24 hours in anhydrous NMP, obtains the polyamide gels after solvent exchange.Wherein the mol ratio of TAB and ODA is 0.022:1.000, solvent exchange is the mixing solutions of anhydrous NMP and dehydrated alcohol, the mixing solutions of the anhydrous NMP and dehydrated alcohol that use volume ratio to be respectively 3:1 and 1:3 is replaced once respectively, finally uses dehydrated alcohol displacement once;
3rd step, carries out CO by the polyamide gels after solvent exchange
2supercritical fluid drying process, CO
2supercritical fluid drying condition is drying medium with dehydrated alcohol, polyamide gels put into supercritical drying equipment, is heated to 55 DEG C, is filled with CO
2to 15MPa, pressurize carried out CO after 1 hour
2supercritical fluid drying 8 hours, then can obtain low-k polymeric amide aerogel heat-insulating material with 50kPa/min speed slow releasing pressure.Hydrophobicity polymeric amide aerogel heat-insulating material density prepared by this example is 0.32gcm
-3, when 25 DEG C, thermal conductivity is 0.045W/mK, and specific inductivity is 1.29.
Embodiment 5
The first step, by 4,4 '-diaminodiphenyl oxide (ODA) is dissolved in dry N-methylpyrrolidone (NMP) under nitrogen protection, p-phthaloyl chloride (TPC) is joined in above-mentioned solution, stir under nitrogen atmosphere, form the polymeric amide colloidal sol of clear, wherein the mol ratio of TPC and ODA is 1.05:1.00;
Second step, linking agent eight (aminophenyl) polysilsesquioxane (OAPS) is added in the colloidal sol of described the first step gained, obtain the polymeric amide colloidal sol be cross-linked, stirring reaction 20 minutes under nitrogen atmosphere, colloidal sol is poured in mould, leave standstill and within 30 minutes, treat the polyamide gels that its gel obtains.The polyamide gels obtained is carried out solvent exchange after aging 24 hours in anhydrous NMP, obtains the polyamide gels after solvent exchange.Wherein the mol ratio of OAPS and ODA is 0.022:1.000, solvent exchange is the mixing solutions of anhydrous NMP and dehydrated alcohol, the mixing solutions of the anhydrous NMP and dehydrated alcohol that use volume ratio to be respectively 3:1 and 1:3 is replaced once respectively, finally uses dehydrated alcohol displacement once;
3rd step, carries out CO by the polyamide gels after solvent exchange
2supercritical fluid drying process, CO
2supercritical fluid drying condition is drying medium with dehydrated alcohol, polyamide gels put into supercritical drying equipment, is heated to 55 DEG C, is filled with CO
2to 15MPa, pressurize carried out CO after 1 hour
2supercritical fluid drying 8 hours, then can obtain low-k polymeric amide aerogel heat-insulating material with 50kPa/min speed slow releasing pressure.Hydrophobicity polymeric amide aerogel heat-insulating material density prepared by this example is 0.35gcm
-3, when 25 DEG C, thermal conductivity is 0.045W/mK, and specific inductivity is 1.30.
Embodiment 5 is the polyamine linking agents only changed in reaction system with the difference of embodiment 4, and the thermal conductivity preparing resulting materials is 0.045W/mK, and specific inductivity is between 1.29 ~ 1.30, and result difference is very little.Visible, the selection of polyamine linking agent does not affect prepared material property.
Embodiment 6 ~ 275
The intensive polar solvent main purpose that the first step adds is dissolving 4,4 '-diaminodiphenyl oxide (ODA), as the solvent of reaction system, as can be seen from embodiment 1 ~ 3, the selection of intensive polar solvent does not affect (recording the subtle change of thermal conductivity and specific inductivity within the scope of test error) polymeric amide aerogel heat-insulating material performance; The linking agent that second step adds is to obtain the polyamide gels be cross-linked, and as can be seen from embodiment 4 ~ 5, the performance of selection on polymeric amide aerogel of linking agent polyamine does not affect, from raw material sources and cost consideration, and the preferred TAB of linking agent polyamine; Solvent exchange process is the solvent NMP in order to replace with dehydrated alcohol in polyamide gels, and NMP can be replaced into dehydrated alcohol 3 times by solvent exchange; 3rd step CO
2being warming up to 35 ~ 85 DEG C in supercritical drying process with pressurising power to 9 ~ 20MPa is to reach CO
2above-critical state (7.4MPa, 31 DEG C), the length of time of drying is determined depending on material size and thickness, can not extracting liquid in supercritical drying process is completely dry, and the dwell time reaches overcritical balance to allow in still, the speed of speed of finally exitting has no significant effect material property.Therefore, above condition all on polymeric amide aerogel heat-insulating material performance without impact, as long as select in the scope described in summary of the invention, all can prepare the polymeric amide aerogel heat-insulating material that performance difference is little.And the kind of the mainly diacid chloride that polymeric amide aerogel heat-insulating material performance is had an impact, diamines, linking agent and consumption, therefore the processing parameter that adopts of embodiment 6 ~ 275 is as shown in table 1, and the experimental technique parameter do not arranged in table is identical with embodiment 1.
Table 1 polymeric amide aerogel material preparation technology parameter and material property parameter
Note: the chemical name that in table, reagent is write a Chinese character in simplified form.P-phthaloyl chloride (TPC), m-phthaloyl chloride (IPC), 4,4 '-diaminodiphenyl oxide (ODA), Ursol D (pPDA), 1,3,5-benzene three formyl chloride (BTC), 1,3,5-tri-(4-amino-benzene oxygen) benzene (TAB), eight (aminophenyl) polysilsesquioxane (OAPS).In table, each reactant molar ratio is for benchmark with the mole number of diamines.
Claims (13)
1. a low-k polymeric amide aerogel heat-insulating material, it is characterized in that low-k polymeric amide aerogel heat-insulating material is for raw material with aromatic diacid chlorides and aromatic diamine, polyamine or polynary acyl chlorides are linking agent, adopt the process of sol-gel to prepare the polyamide gels with three-dimensional net structure, polyamide gels is through CO
2obtain after supercritical drying;
Described aromatic diacid chlorides is the mixture of p-phthaloyl chloride TPC or m-phthaloyl chloride IPC or TPC and IPC;
Described aromatic diamine is 4,4 '-diaminodiphenyl oxide ODA or Ursol D pPDA;
Described polyamine is 1,3,5-tri-(4-amino-benzene oxygen) benzene TAB or eight (aminophenyl) polysilsesquioxane OAPS; Polynary acyl chlorides is 1,3,5-benzene three formyl chloride BTC; Polymeric amide aerogel heat-insulating material structure prepared by TPC, ODA and BTC tri-kinds of material copolymerizations is such as formula shown in I; Polymeric amide aerogel heat-insulating material structure prepared by TPC, ODA and TAB tri-kinds of material copolymerizations is such as formula shown in II; Polymeric amide aerogel heat-insulating material structure prepared by IPC, ODA and BTC tri-kinds of material copolymerizations is as shown in formula III; Polymeric amide aerogel heat-insulating material structure prepared by IPC, ODA and TAB tri-kinds of material copolymerizations is such as formula shown in IV; Polymeric amide aerogel heat-insulating material structure prepared by TPC, pPDA and TAB tri-kinds of material copolymerizations is such as formula shown in V; Polymeric amide aerogel heat-insulating material structure prepared by TPC, pPDA and BTC tri-kinds of material copolymerizations is such as formula shown in VI; Polymeric amide aerogel heat-insulating material structure prepared by IPC, pPDA and TAB tri-kinds of material copolymerizations is such as formula shown in VII; Polymeric amide aerogel heat-insulating material structure prepared by IPC, pPDA and BTC tri-kinds of material copolymerizations is such as formula shown in VIII; Polymeric amide aerogel heat-insulating material structure prepared by TPC, IPC, ODA and BTC tetra-kinds of material copolymerizations is such as formula shown in IX; Polymeric amide aerogel heat-insulating material structure prepared by TPC, IPC, ODA and TAB tetra-kinds of material copolymerizations is such as formula shown in X; Polymeric amide aerogel heat-insulating material structure prepared by TPC, IPC, pPDA and TAB tetra-kinds of material copolymerizations is such as formula shown in XI; Polymeric amide aerogel heat-insulating material structure prepared by TPC, IPC, pPDA and BTC tetra-kinds of material copolymerizations is such as formula shown in XII; Polymeric amide aerogel heat-insulating material structure prepared by TPC, ODA and OAPS tri-kinds of material copolymerizations is such as formula shown in XIII; Polymeric amide aerogel heat-insulating material structure prepared by IPC, ODA and OAPS tri-kinds of material copolymerizations is such as formula shown in XIV; Polymeric amide aerogel heat-insulating material structure prepared by TPC, IPC, ODA and OAPS tetra-kinds of material copolymerizations is such as formula shown in XV; Polymeric amide aerogel heat-insulating material structure prepared by TPC, pPDA and OAPS tri-kinds of material copolymerizations is such as formula shown in XVI; Polymeric amide aerogel heat-insulating material structure prepared by IPC, pPDA and OAPS tri-kinds of material copolymerizations is such as formula shown in XVII; Polymeric amide aerogel heat-insulating material structure prepared by TPC, IPC, pPDA and OAPS tetra-kinds of material copolymerizations is such as formula shown in XVIII;
In its Chinese style XIII ~ formula XVIII, X is
N, m are the integer of 1 ~ 120, specifically can be the integer of 15 ~ 25,25 ~ 35 or 40 ~ 60, and preferably 25.
2. a kind of low-k polymeric amide aerogel heat-insulating material as claimed in claim 1, when it is characterized in that described aromatic diacid chlorides is the mixture of TPC and IPC, the mole number of TPC accounts for 5% ~ 95% of TPC and IPC total mole number.
3. a kind of low-k polymeric amide aerogel heat-insulating material as claimed in claim 1, is characterized in that described polyamine is TAB.
4. a kind of low-k polymeric amide aerogel heat-insulating material as claimed in claim 1, it is characterized in that when taking polyamine as linking agent, the mol ratio of aromatic diacid chlorides, aromatic diamine is (1.00 ~ 1.10): 1.00, polyamine with institute add aromatic diamine mol ratio be (0.017 ~ 0.033): 1.000.
5. a kind of low-k polymeric amide aerogel heat-insulating material as claimed in claim 1, it is characterized in that when with polynary acyl chlorides for linking agent time, the mol ratio of aromatic diacid chlorides, aromatic diamine is (0.90 ~ 1.00): 1.00, and polynary acyl chlorides is (0.017 ~ 0.033) with the mol ratio of the aromatic diamine added: 1.000.
6. a kind of low-k polymeric amide aerogel heat-insulating material as claimed in claim 1, is characterized in that n, m are the integer of 15 ~ 25,25 ~ 35 or 40 ~ 60.
7. a kind of low-k polymeric amide aerogel heat-insulating material as claimed in claim 1, is characterized in that n, m are 25.
8. prepare a method for low-k polymeric amide aerogel heat-insulating material as claimed in claim 1, it is characterized in that comprising the following steps:
The first step, is dissolved in intensive polar solvent under nitrogen protection by aromatic diamine, is joined by aromatic diacid chlorides in above-mentioned solution, stirs under nitrogen atmosphere, obtains the polymeric amide colloidal sol of clear; Wherein when taking polyamine as linking agent, the mol ratio of aromatic diacid chlorides and aromatic diamine is (1.00 ~ 1.10): 1.00, when with polynary acyl chlorides for linking agent time, the mol ratio of aromatic diacid chlorides and aromatic diamine is (0.91 ~ 1.00): 1.00;
Second step, polyamine or polynary acyl chlorides is added as linking agent in the polymeric amide colloidal sol of the first step gained, obtain cross-linking type polymeric amide colloidal sol, pour into after stirring reaction in mould under nitrogen atmosphere, leave standstill and treat that its gel obtains polyamide gels, carry out solvent exchange three times after the polyamide gels obtained is aging in the anhydrous intensive polar solvent described in the first step, obtain the polyamide gels with three-dimensional net structure after solvent exchange; If linking agent is polyamine, then polyamine is (0.017 ~ 0.033) with the mol ratio of the aromatic diamine added: 1.000; Linking agent is polynary acyl chlorides, then polynary acyl chlorides is (0.017 ~ 0.033) with the mol ratio of the aromatic diamine added: 1.000;
3rd step, carries out CO by the polyamide gels after the solvent exchange of second step gained
2supercritical fluid drying process obtains low-k polymeric amide aerogel heat-insulating material.
9. prepare the method for low-k polymeric amide aerogel heat-insulating material as claimed in claim 1 as claimed in claim 8, it is characterized in that described intensive polar solvent is dry N-methylpyrrolidone NMP, anhydrous N, any one in dinethylformamide DMF, anhydrous N,N-dimethylacetamide DMAc.
10. prepare the method for low-k polymeric amide aerogel heat-insulating material as claimed in claim 1 as claimed in claim 8, it is characterized in that stirring reaction duration is 10 ~ 60 minutes under nitrogen atmosphere described in second step, standing duration is 10 ~ 60 minutes, and aging duration is 12 ~ 48 hours.
11. methods preparing low-k polymeric amide aerogel heat-insulating material as claimed in claim 1 as claimed in claim 8, is characterized in that the solvent that solvent exchange described in second step uses is anhydrous methanol, any one in dehydrated alcohol, anhydrous isopropyl alcohol, anhydrous propanone.
12. methods preparing low-k polymeric amide aerogel heat-insulating material as claimed in claim 1 as claimed in claim 11, is characterized in that the solvent that described solvent exchange uses is dehydrated alcohol.
13. methods preparing low-k polymeric amide aerogel heat-insulating material as claimed in claim 1 as claimed in claim 8, is characterized in that the 3rd step CO
2supercritical fluid drying condition be with any one in dehydrated alcohol, anhydrous isopropyl alcohol or anhydrous propanone for drying medium, polyamide gels is put into CO
2in supercritical drying equipment, be heated to 35 ~ 85 DEG C, be filled with CO
2to 9 ~ 20MPa, pressurize carried out CO after 0.5 ~ 3 hour
2supercritical fluid drying 4 ~ 24 hours, then with the speed slow releasing pressure of 40 ~ 70kPa/min.
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