CN102633464B - Method for preparing SiO2 aerogel heat insulating composite through adhesive slip casting - Google Patents

Method for preparing SiO2 aerogel heat insulating composite through adhesive slip casting Download PDF

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CN102633464B
CN102633464B CN 201210125214 CN201210125214A CN102633464B CN 102633464 B CN102633464 B CN 102633464B CN 201210125214 CN201210125214 CN 201210125214 CN 201210125214 A CN201210125214 A CN 201210125214A CN 102633464 B CN102633464 B CN 102633464B
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preparation
silicon
phenolic resin
composite material
aerogel
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CN102633464A (en
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史铁钧
张明
文听雷
陈苏峰
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Hefei University of Technology
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Hefei University of Technology
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Abstract

The invention discloses a method for preparing a SiO2 aerogel heat insulating composite through adhesive slip casting,.The method comprises the following steps of: firstly, drying at normal temperature and normal pressure by taking tetraethoxysilane and methyltriethoxysilane as a co-precursor, absolute ethyl alcohol as a reaction solvent and DMF (Dimethyl Formamide) as a drying chemical control additive to obtain a mesoporous nanometer SiO2 aerogel material with uniform pore diameter distribution; then, carrying out flexibility modification by utilizing a polyurethane elastomer to prepare modified phenolic resin glue serving as an adhesive; and preparing the SiO2 aerogel heat insulating composite by using a slip casting method. The mechanical property of the aerogel is improved, and therefore, the SiO2 aerogel material has favorable toughness and mechanical property while playing a heat insulating role.

Description

The sizing agent injection forming prepares the method for silicon dioxide aerogel heat-insulating composite material
One, technical field
The present invention relates to a kind of preparation method of silicon dioxide silica aerogel composite material, specifically the sizing agent injection forming prepares the method for silicon dioxide aerogel heat-insulating composite material.
Two, background technology
Silicon-dioxide (SiO 2) aerogel is a kind of continuous three-dimensional net structure that is formed by the mutual polymerization of nanometer scale particle, be full of the light porous amorphous material of high dispersive of air dielectric in hole, and have that specific surface area is large, porosity is high, density is low, specific refractory power and the characteristics such as thermal conductivity is low, have a wide range of applications in various fields such as the anti-resistance of sound, thermal isolation, catalytic carrier, aerospace.
Aerogel as the lightest in the world solid material, is the minimum solid-state material of thermal conductivity of generally acknowledging at present.Simultaneously, aerosil also has higher use temperature, even still has porous network structure preferably under 900 ℃ of high temperature, but pure SiO 2Aerogel intensity is low, poor toughness, can not be used for the heat insulating engineering as independent block materials.In order to improve its intensity and toughness, in recent years, more research is concerned about and improves SiO 2On the mechanical property and use properties of aerogel material, and obtained more progress.
At present about using various filamentary material doping preparation SiO 2The existing many reports of the method for aerogel composite.Use tetraethoxy to be the silicon source, the soda acid two-step approach prepares SiO 2Aerogel simultaneously take aramid fiber as framework material, is prepared the SiO with certain toughness and mechanical property 2The aerogel composite heat-insulated material.But with used filamentary material the same as the method for toughening material in the past, micron order cavity in fiber preform can't be filled fully by aerogel, cause filamentary material and aerogel in conjunction with undertighten, after drying, both minute defections larger (CN 101823867A).More investigator adopts the block SiO of supercritical fluid drying technique preparation 2Aerogel heat-insulating material uses Union carbide A-162 to be precursor, and methyl alcohol is solvent, after acid-base catalyzed reaction, prepares the block SiO with superior elasticity through supercritical fluid drying technique 2Aerogel.Although this drying means can be prepared more stable product of quality, but supercritical drying process need high-tension apparatus, it is very harsh that condition is controlled requirement, thereby the preparation cost of aerogel is expensive, limited the large-scale promotion application (CN 102225769A) of Monolithic aerogel.
Three, summary of the invention
The present invention aims to provide a kind of method that sizing agent injection forming prepares silicon dioxide aerogel heat-insulating composite material, and technical problem to be solved is to provide the block heat-insulation composite material of aerosil that a kind of method that is suitable for suitability for industrialized production prepares even aperture distribution, mechanical property excellence.
The present invention is total to precursor by the soda acid two-step catalysis, adopts sol-gel method to prepare the SiO that pore size meets the mesoporous nano material requirements and is evenly distributed 2Aerogel, then the method by casting makes SiO 2Aerogel and modified phenolic resin adhesive are compound, prepare the SiO with good mechanical properties 2Aerogel heat-proof composite material.
Sizing agent injection forming of the present invention prepares the method for silicon dioxide aerogel heat-insulating composite material, comprise the preparation of silicon-dioxide alcogel, the preparation of aerosil, the preparation of modified phenolic resin adhesive and each unit process of preparation of heat-insulation composite material, it is characterized in that:
The preparation of described silicon-dioxide alcogel is to add deionized water, dehydrated alcohol and N in the solution of silicon source, N '-dimethyl formamide (DMF), rear dropping acid catalyst adjust pH 3-4 stirs, under room temperature catalytic hydrolysis 20-24 hour, drip again alkaline catalysts adjust pH 6-7, stir and standing after obtain the silicon-dioxide alcogel, described silicon source solution is that tetraethoxy and Union carbide A-162 are mixed to get; Wherein the mol ratio of tetraethoxy, Union carbide A-162, deionized water, dehydrated alcohol and DMF is 1: (0.3-0.6): (6-10): (15-18): (0.3-0.5); The mixing solutions that the silicon-dioxide alcogel that obtains is placed in tetraethoxy and dehydrated alcohol made its network structure complete in 40-60 ℃ of ageing 48-72 hour, and in mixing solutions, the volume ratio of tetraethoxy and dehydrated alcohol is 15-25: 85-75;
Described acid catalyst is selected from hydrochloric acid, nitric acid, citric acid or oxalic acid;
Described alkaline catalysts is selected from ammoniacal liquor or sodium hydroxide;
The preparation of described aerosil is to add normal hexane to carry out solvent exchange 3-5 time in silicon-dioxide alcogel after the ageing, then be placed in hexane solution impregnation 40-50 hour of the trimethylchlorosilane of 5-20vt% (concentration expressed in percentage by volume), classification drying subsequently obtains the aerosil powder;
The preparation of described modified phenolic resin adhesive is take acetone as solvent, the urethane of sizing agent thermoset phenolic resin and toughner-NCO end-blocking is mixed, obtained modified phenolic resin adhesive in 10-15 hour in 60-80 ℃ of reaction, the quality of the urethane of wherein-NCO end-blocking is the 10-40% of resol quality;
The preparation of described heat-insulation composite material be the modified phenolic resin adhesive for preparing be slurry, described slurry is poured into the surface of the aerosil powder of preparation, make slurry substantially cover the surface of aerosil powder, then carry out impregnation by action of gravity, the fully rear classification drying of impregnation obtains silicon dioxide aerogel heat-insulating composite material; The quality of described aerosil powder is the 85-90% of described aerogel heat-proof composite material quality.
In the preparation process of described aerosil, the drying temperature of classification drying is respectively 30 ℃, 60 ℃, 80 ℃, 100 ℃ and 120 ℃, and every grade of temperature is distinguished dry 4-6 hour.
In the preparation process of described heat-insulation composite material, the drying temperature of classification drying is respectively 60 ℃, 80 ℃, 100 ℃ and 130 ℃, and every grade of temperature is distinguished dry 2-3 hour.
Described thermoset phenolic resin is selected from 2127 types or 2130 type thermoset phenolic resins.
The urethane number-average molecular weight of described-NCO end-blocking is 3000-6000.
Compared with prior art, beneficial effect of the present invention is embodied in:
1, the present invention adopts two kinds of tetraethoxy and Union carbide A-162s silicon source as precursors altogether, adds simultaneously DMF and controls additive as chemical seasoning, the SiO that the suitable ratio of regulating each reactant prepares 2The aerogel powder aperture is little, and specific surface is large, and is evenly distributed, and meets the requirement of lagging material.
2, the present invention carries out toughening modifying to sizing agent, thus make matrix material after moulding except keeping good heat-proof quality, also possess good mechanical property and mechanical property, make material possess good globality and obdurability; In addition, polyurethane toughened dose that adopts in the present invention itself just has lower thermal conductivity, and the most important feature of heat-reactive phenolic resin glue has high thermal resistance exactly, even at very high temperature, also can keep globality and the dimensional stability of its structure.
3, preparation method of the present invention is simple, and security is good, and strongthener is easy to get, and cost is low.
Four, description of drawings
Fig. 1 is the SiO that the present invention prepares 2The scanning electron microscope of aerogel powder (SEM) figure.The prepared aerogel of constant pressure and dry is a kind of porous nanometer material of contiguous network structure as can be seen from Figure 1, has more uniform nanoporous network structure, and pore size distribution mainly concentrates on 20-30nm at 2-50nm.
Fig. 2 is the SiO that the present invention prepares 2The photo of aerogel heat-proof block composite material.
Fig. 3 is the SiO that the present invention prepares 2The aerogel heat-proof block composite material is measured conduction process temperature situation over time.As can be seen from Figure 3 in a short period of time, the rising temperature just is tending towards constant.
Five, embodiment
The present invention will be further described by reference to the accompanying drawings by the following examples.
The thermoset phenolic resin that the present embodiment uses is the 2130 type heat-reactive phenolic resins that the HeFei University of Technology chemical plant produces; Urethane be molecular weight be 6000-NCO end-sealed type urethane.
Embodiment 1:
1, the preparation of silicon-dioxide alcogel
10.38g tetraethoxy, 5.34g Union carbide A-162,5.40g deionized water, 34.5g dehydrated alcohol and 1.83gDMF (mol ratio is 1: 0.6: 6: 15: 0.5) are mixed and stir, adding the salt acid for adjusting pH value is 3.5, stirred catalytic hydrolysis reaction 24 hours under room temperature, then adding ammoniacal liquor to regulate the pH value is 6.5, the standing SiO that obtains after continuation stirring 10min 2Alcogel.With the SiO that obtains 2Alcogel is placed in the mixing solutions (volume ratio 20: 80) of tetraethoxy and dehydrated alcohol in 50 ℃ of ageings 50 hours.
2, the preparation of aerosil
SiO after the ageing 2Add normal hexane to carry out exchange of solvent in alcogel, 1 day once, exchange three times, with impregnation in the hexane solution of the trimethylchlorosilane that is placed on 10vt% 48 hours, obtained respectively nano level SiO after taking-up in dry 4 hours under 30 ℃, 60 ℃, 80 ℃, 100 ℃ and 120 ℃ 2Aerogel powder.
As shown in Figure 1, the SiO that obtains 2The microscopic aperture size of aerogel powder is at 20-30nm, and is evenly distributed closely, meets as the lagging material aperture less than (~60nm) the requirement of gas molecule mean free path.
3, the preparation of modified phenolic resin adhesive
At first thermoset phenolic resin is carried out drying treatment, then be dissolved in acetone, add thermoset phenolic resin quality 40%-urethane (according to a conventional method being prepared at 7: 24 with mol ratio by monomer PPG1000 and monomer I PDI) of NCO end-blocking and stirring, 80 ℃ of lower water-bath back flow reaction obtained modified phenolic resin adhesive in 15 hours.
4, the preparation of heat-insulation composite material
Take the modified phenolic resin adhesive of step 3 preparation as slurry, be poured into SiO 2The surface of aerogel powder covers it substantially, then relies on action of gravity to carry out impregnation, impregnation fully after under 60 ℃, 80 ℃, 100 ℃ and 130 ℃ dry 2 hours respectively, obtain SiO 2Aerogel heat-proof composite material, SiO 2The quality of aerogel powder is SiO 287% of aerogel heat-proof composite material quality.
The SiO that the present embodiment is prepared 2The density of aerogel heat-proof composite material is 0.351g/cm 3, measuring its thermal conductivity under room temperature is 0.085W/mK, the room temperature compressive strength is 1.8MPa.
Embodiment 2:
The present embodiment preparation method is with embodiment 1, and different is that in step 1, the Union carbide A-162 addition is 4.46g, and the addition of deionized water is 7.20g; In step 2, the volumetric concentration of the hexane solution of trimethylchlorosilane is 5vt%; In step 3-quality of the urethane of NCO end-blocking is 30% of the resol quality of anhydrating, 13 hours reaction times.

Claims (3)

1. the sizing agent injection forming prepares the method for silicon dioxide aerogel heat-insulating composite material, comprise the preparation of silicon-dioxide alcogel, the preparation of aerosil, the preparation of modified phenolic resin adhesive and each unit process of preparation of heat-insulation composite material, it is characterized in that:
The preparation of described silicon-dioxide alcogel is to add deionized water, dehydrated alcohol and DMF in the solution of silicon source, rear dropping acid catalyst adjust pH 3-4 stirs, under room temperature catalytic hydrolysis 20-24 hour, drip again alkaline catalysts adjust pH 6-7, stir and standing after obtain the silicon-dioxide alcogel, described silicon source solution is that tetraethoxy and Union carbide A-162 are mixed to get; Wherein the mol ratio of tetraethoxy, Union carbide A-162, deionized water, dehydrated alcohol and DMF is 1:(0.3-0.6): (6-10): (15-18): (0.3-0.5); The silicon-dioxide alcogel that obtains is placed in the mixing solutions of tetraethoxy and dehydrated alcohol in 40-60 ℃ of ageing 48-72 hour, in mixing solutions, the volume ratio of tetraethoxy and dehydrated alcohol is 15-25:85-75;
Described acid catalyst is selected from hydrochloric acid, nitric acid, citric acid or oxalic acid;
Described alkaline catalysts is selected from ammoniacal liquor or sodium hydroxide;
The preparation of described aerosil is to add normal hexane to carry out solvent exchange 3-5 time in silicon-dioxide alcogel after the ageing, then be placed in hexane solution impregnation 40-50 hour of the trimethylchlorosilane of 5-20vt%, classification drying subsequently obtains the aerosil powder;
The preparation of described modified phenolic resin adhesive is take acetone as solvent, the urethane of sizing agent thermoset phenolic resin and toughner-NCO end-blocking is mixed, obtained modified phenolic resin adhesive in 10-15 hour in 60-80 ℃ of reaction, the quality of the urethane of wherein-NCO end-blocking is the 10-40% of resol quality;
Described thermoset phenolic resin is selected from 2127 types or 2130 type thermoset phenolic resins;
The urethane number-average molecular weight of described-NCO end-blocking is 3000-6000;
The preparation of described heat-insulation composite material be the modified phenolic resin adhesive for preparing be slurry, described slurry is poured in the aerosil powder of preparation, carry out impregnation by action of gravity, the fully rear classification drying of impregnation obtains silicon dioxide aerogel heat-insulating composite material; The quality of described aerosil powder is the 85-90% of described aerogel heat-proof composite material quality.
2. preparation method according to claim 1, it is characterized in that: in the preparation process of described aerosil, the drying temperature of classification drying is respectively 30 ℃, 60 ℃, 80 ℃, 100 ℃ and 120 ℃, every grade of temperature dry 4-6 hour respectively.
3. preparation method according to claim 1, it is characterized in that: in the preparation process of described heat-insulation composite material, the drying temperature of classification drying is respectively 60 ℃, 80 ℃, 100 ℃ and 130 ℃, every grade of temperature dry 2-3 hour respectively.
CN 201210125214 2012-04-26 2012-04-26 Method for preparing SiO2 aerogel heat insulating composite through adhesive slip casting Expired - Fee Related CN102633464B (en)

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CN105295298A (en) * 2014-06-27 2016-02-03 李永前 Clumpy hydrophobic phenolic resin/silicon dioxide compounded aerogel and preparation method thereof
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CN102351494A (en) * 2011-07-20 2012-02-15 厦门大学 Method for preparing foam material reinforced silica aerogel composite material

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