CN109575510A - A kind of preparation method of nanofiber mineral enhancing phenolic resin three-dimensional aerogel material - Google Patents

A kind of preparation method of nanofiber mineral enhancing phenolic resin three-dimensional aerogel material Download PDF

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CN109575510A
CN109575510A CN201811515703.2A CN201811515703A CN109575510A CN 109575510 A CN109575510 A CN 109575510A CN 201811515703 A CN201811515703 A CN 201811515703A CN 109575510 A CN109575510 A CN 109575510A
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mineral fibres
nanoclay
phenolic resin
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dimensional structure
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CN109575510B (en
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汤庆国
王鹏飞
王磊
张悦
梁金生
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Hebei University of Technology
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/048—Elimination of a frozen liquid phase
    • C08J2201/0482—Elimination of a frozen liquid phase the liquid phase being organic
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    • C08J2205/026—Aerogel, i.e. a supercritically dried gel
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    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08J2361/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
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Abstract

The present invention is a kind of preparation method of three-dimensional structure phenolic resin airsetting material using the enhancing of nanoclay mineral fibres.This method comprises the following steps: (1) clay mineral fiber activation, obtains acid activation nanoclay mineral fibres；(2) preparation of nanoclay mineral fibres three-dimensional composite material obtains three-dimensional fiber block composite gel material B；(3) after three-dimensional fiber block composite gel material B being impregnated C component solution, through 50-120 DEG C, solidify 30-150min, then impregnate in organic solvent, vacuum freeze drying obtains the three-dimensional structure phenolic resin aerogel material of nanoclay mineral fibres enhancing.The material that the present invention obtains can be used for the insulation of high-end devices, or as catalyst carrier, the adsorbent etc. of organic pollutant.

Description

A kind of preparation method of nanofiber mineral enhancing phenolic resin three-dimensional aerogel material
Technical field
The present invention relates to a kind of technology of preparing of clay mineral fiber reinforcement three-dimensional structure phenolic resin aerogel material and Using belonging to field of material preparation.
Background technique
Aeroge is a kind of lightweight solid material with nanometer porous network structure, has low-density, high-ratio surface The performances such as product, high porosity and low heat conductivity, are widely used in insulation, catalytic carrier, supercapacitor, electrode material and dirt Water process etc..In recent years, with the continuous development of national green energy conservation and environmental protection industry, the gas with excellent thermal insulation thermal insulation property The dosage of gel rubber material is continuously increased, and has higher requirement to its performance thereupon, does not require nothing more than it with good power Learn performance, it is also necessary to which it is with certain elastic property.Therefore, in order to meet the requirement of energy conservation and environmental protection industry to aeroge, It is a kind of imperative with excellent mechanical performance and the phenolic resin composite aerogel of elasticity to develop.For this purpose, many people also open up Correlative study is opened, as ZL.105601854A has invented a kind of three-dimensional fiber felt structure enhancing phenolic resin aerogel heat shielding Material is covered, obtains intensity height, good stability of the dimension, but this rigid structure causes aeroge thermal coefficient to greatly improve, it is unfavorable In heat preservation；ZL.102285775A has invented a kind of organic-aerogel heat-insulating material of organosilicon prepolymer oxygen silk fiber enhancing, and airsetting is made Glue intensity is high, thermal coefficient is small, but its organosilicon prepolymer oxygen silk fiber used prepares complicated and there is harm to environment； ZL.104177644A has invented the polyimide modified phenol of a kind of mechanical performance, processing performance, insulating properties and excellent thermal insulation performance The preparation method of urea formaldehyde aeroge, but the high temperature resistance of the aerogel material prepared is poor, limits its aerospace etc. The application of high-end field；CN106800630A discloses a kind of flexible aerogel material and preparation method thereof, but its preparation process It is complicated, the period is long, the high requirements on the equipment, and hydroxyacrylamide is toxic taste；CN 106189066A describes a kind of phenolic aldehyde Resin/silicon dioxide composite aerogel material preparation method, the material have excellent mechanical property and heat-insulating, fire-preventing performance, But its preparation process is complicated, energy consumption is high, it is difficult to which scale is promoted；Yin etc. describes a kind of density 0.312-0.356g/cm3, resistance to compression The new type resin of intensity 0.76-4.08MPa/silicon hybridization aerogel composite is equally that preparation process is more complex, and gas is made Gel thermal coefficient (Synthesis and characterization of novel phenolic resin/ bigger than normal silicone hybrid aerogel composites with enhancedthermal,mechanical andablative properties)。
The clay mineral fiber of clay mineral, especially nano-scale structure has enhancing, toughening functions well.Its property Can stabilization, heat-proof combustion-resistant, large specific surface area and thermal coefficient it is low, and rich reserves, it is cheap, from a wealth of sources the advantages that. In view of the performance that clay mineral is excellent, the present invention does enhancing functional material using nanostructure mineral fibres, to improve phenolic aldehyde gas The mechanical property of gel rubber material develops the clay mineral fiber reinforcement three-dimensional structure phenolic resin aerogel of light porous structure Material.
Summary of the invention
It is an object of the present invention to the disadvantages poor for phenolic aldehyde aeroge itself mechanical property traditional in current techniques, provide A kind of preparation method using nanoclay mineral fibres enhancing three-dimensional structure phenolic resin aerogel material.This method utilizes three Tie up structure clay mineral fibres gel rubber material；The gel rubber material is placed into containing with the mixed of phenolic compound and aldehyde compound It closes in reaction system, by the preparation of vacuum impregnation and the microwave heating of phenolic resin, obtains the three-dimensional knot of phenolic resin cladding Structure clay mineral porous hydrogel material.The material can be used for the insulation of high-end devices, or as catalyst carrier, organic The adsorbent etc. of pollutant.
The technical solution of the present invention is as follows:
A kind of preparation method of the three-dimensional structure phenolic resin airsetting material using the enhancing of nanoclay mineral fibres, including Following steps:
(1) it clay mineral fiber activation: after clay mineral fiber is mixed with hydrochloric acid solution, impregnates 1-3 days, then vacuum It filters, obtains nanoclay mineral fibres filter cake；It is filtered after washing, it is 8 hours dry at 60 DEG C；Ball mill grinding crosses 250~350 Mesh obtains acid activation nanoclay mineral fibres；
Wherein, the hydrochloric acid solution that 150-250ml concentration is 0.5-4mol/L is added in every 50g clay mineral fiber；Before immersion It is respectively stirred 1 hour with blender afterwards；Blender revolving speed 1000rpm；
(2) preparation of nanoclay mineral fibres three-dimensional composite material: to acid activation nanoclay mine made from step (1) Deionized water is added in fibres, and after stirring 2-3h, organic thickening agent is added, and under 60-90 DEG C of water bath with thermostatic control, continues to stir 30- After 90min, hydrated gel body A is formed, hydrated gel body A sample is placed in liquid nitrogen after freezing, is put into vacuum freeze drier Middle freeze-drying 3 days, obtains three-dimensional fiber block composite gel material B；
Wherein, 20-60ml deionized water is added in every g acid activation nanoclay mineral fibres；Acid activation nanoclay mineral Fiber: the mass ratio of thickener is=1:0.2-1；Blender revolving speed is 2000-4000rpm；
(3) preparation of novolac solution: after phenolic compound and aldehyde compound and deionized water stirring 30-60min, add Enter catalyst, continues 3~10min of stirring, obtain solution C；
Wherein, phenolic compound: the molar ratio of aldehyde compound is=1:1.5-2.6；Catalyst: phenolic compound rubs You are than being=1:100~1000；0.475-1.365mol phenolic compound is added in every 1000ml deionized water；Blender revolving speed is 3000-6000rpm；
(4) the three-dimensional structure phenolic resin airsetting material of nanoclay mineral fibres enhancing: the three-dimensional that step (2) are obtained Fibre agglomerates composite gel material B is put into the dip tank of vacuum impregnation machine, close after C component solution made from step (3) is added Envelope, vacuumizes, and vacuum impregnation container inner pressure is 5-20kPa, dip time 5-60min, opens sealing cover, time of repose 5- After 60min, taking-up is placed in reaction kettle, and microwave heating is to 50-120 DEG C, and after gel solidification 30-150min, organic solvent is added Gel during which per organic solvent of replacement for 24 hours, then is carried out vacuum freeze drying, is received after 3-5 days by middle immersion 3-5 days The rice fibre-reinforced three-dimensional structure phenolic resin aerogel material of clay mineral；
Wherein, the mass ratio of A:C component is 1:1.2-1.8 in the step (4)；
Nanoclay mineral fibres in the step (1) is sepiolite, the attapulgite, water magnesium after purification enrichment Stone, galapectite or wollastonite, one of mineral fibres or the mixture for waiting the quality such as two kinds.
Organic thickening agent in the step (2) is one or both of starch, gelatin, polyvinyl alcohol or polyacrylic acid Equal mass mixings object,
Phenolic compound in the step (3) is one of resorcinol or hydroquinone or the mixing of their equimolars Object,
Aldehyde compound in the step (3) be one of formaldehyde or furfural or their equimolar mixtures,
Catalyst in the step (3) be sodium carbonate, sodium hydroxide or calcium hydroxide one kind or wait two kinds of equimolars Mixture,
Organic solvent in the step (4) is one or two kinds of solvents of dehydrated alcohol, acetone, n-hexane or normal heptane Isometric mixture.
The equipment of the microwave heating is multipurpose microwave chemosynthesis instrument.
Vacuum freeze drying condition in the step (2) and (4) is that temperature is -79 DEG C, vacuum degree 20Pa.
The nanoclay mineral fibres complex three-dimensional structures phenolic resin aerogel that preparation method according to the present invention obtains Material apparent density is 0.10g/cm3-0.24g/cm3, thermal coefficient is 0.012-0.034W/ (mK), and compression strength is 0.8MPa-2.5MPa。
The invention has the benefit that
The present invention is by activating cheap, environmentally protective and rich reserves nanoclay mineral fibrous materials Processing obtains a kind of well dispersed fibre structure basis material, prepares three-dimensional fiber block plural gel with this, substantially reduce Production cost, and hydroxy functional group abundant on fiber, for phenol, aldehyde solution reaction in-situ provide group and decorate；Using vacuum Impregnation technology, makes phenol, aldehyde solution quickly and sufficient and fibre agglomerates plural gel is compound；And microwave cross-linked gel solidifies work Skill greatly reduces the gel solidification time, and increases the crosslink density of phenol, aldehyde reaction formation phenolic resin；Three-dimensional fiber Synergistic effect between block composite aerogel and phenolic resin aerogel forms the pore structure and pore structure of terraced distribution It is controllable, make it have the performance that density is small, intensity is high, thermal coefficient is low.
The present invention prepares three-dimensional fiber block composite gel material using soft clay mineral fibres, and passes through vacuum impregnation Enhance phenolic resin aerogel material with it with microwave heating technique, can effectively reduce density and gel solidification time, Enhance its intensity and reduces thermal coefficient.The nanoclay mineral fibres complex three-dimensional structures phenolic aldehyde tree prepared using this method Rouge aerogel material, by taking embodiment 4 as an example, density 0.11g/cm3, gel solidification time are 90min, compression strength is 2.0MPa and thermal coefficient are 0.015W/ (mK).Compared in ZL.105601854A and ZL.102285775A embodiment Optimal value, gel solidification time reduce 94.5h and 70.5h respectively；Compared to optimal in ZL.102285775A embodiment Value, density value reduce 0.199g/cm3, and thermal conductivity value reduces 0.015W/ (mK)；Compared to Jin Xiangyu, (quartz fibre increases The preparation of strong low-density phenolic composite and performance study) optimal value in document, compression strength values improve 1.37MPa.
Detailed description of the invention
Fig. 1 is the SEM spectrum of three-dimensional structure phenolic resin aerogel material obtained in embodiment 7.
Specific embodiment
Sepiolite, attapulgite, shepardite, galapectite and wollastonite described in following embodiment step (1), are to mention Pure natural nanoclay mineral, refer to using natural minerals sepiolite, attapulgite, shepardite, galapectite and wollastonite, through from The purification mineral obtained after psychological field gravity separation enrichment, the content of corresponding mineral reach 90% or more powder.(wherein, naturally Mineral sepiolite buys Yu Tengfa sepiolite development corporation, Ltd., the purchase of natural minerals attapulgite in nine river nano material of Jiangsu Science and Technology Ltd., shepardite purchase are in Lingshou County Lan Xiang mineral products processing factory, galapectite purchase in Lingshou County south sunlight mineral products Processing factory, chrysotile buy Yu Ruifeng mineral products processing factory).
Embodiment 1
Step 1: 50g sepiolite being put into the agitator of 500ml, it is molten that the hydrochloric acid that 150ml concentration is 0.5mol/L is added Liquid, setting blender revolving speed 1000rpm stir 1h, are further continued for stirring 1h with 1000rpm after impregnating 3 days, vacuum filtration is received Rice clay mineral fiber filter cake；Then filter cake is returned into former agitator, is washed repeatedly with deionized water 4 times, when washing each time The deionized water of 200ml is added, and filters after mixing evenly, finally filter cake is put into vacuum oven, dry 8 is small at 60 DEG C Shi Hou；250 meshes are crossed in ball mill grinding, are mixed, and be fitted into spare in hermetic bag, are obtained acid activation nanoclay mineral fibres；
Step 2: 20g acid activation nanometer sepiolite fibre and 400mL deionized water made from step (1) being taken to be added to In 2000mL agitator, setting blender revolving speed is 2000rpm, after stirring 3h, 4g starch thickener is added, and agitator is set It is heated in the water bath with thermostatic control that temperature is 60 DEG C, being kept stirring machine revolving speed is 2000rpm, continues after stirring 90min, forms aquation Hydrated gel body A sample is placed in liquid nitrogen (- 196 DEG C, 2min) freezings, is put into vacuum freeze drier (temperature by gelinite A It is -79 DEG C, vacuum degree 20Pa) middle freeze-drying 3 days, obtain three-dimensional fiber block composite gel material B；
Step 3: by going for 104.5g (i.e. 0.95mol) resorcinol, 42.75g (i.e. 1.425mol) formaldehyde and 2000ml Ionized water is added in 3000mL agitator, when setting blender revolving speed is 3000rpm, is stirred 60min, is obtained finely dispersed Phenol, aldehyde mixed solution are added sodium carbonate catalyst 1.007g (i.e. 0.00950mol), and continuation is stirred under conditions of 3000rpm 10min obtains uniformly mixed solution C；
Step 4: the 24g three-dimensional fiber block composite gel material B that step (2) obtain is put into the dipping of vacuum impregnation machine In cylinder, after C component solution made from 763.2g step (3) is added, sealing is vacuumized, and vacuum impregnation container inner pressure is 5kPa, Dip time is 5min, opening sealing cover, and after time of repose 5min, taking-up is placed in 3000ml reaction kettle, and it is micro- to be put into multipurpose It is heated in wave chemical synthesis instrument, is warming up to 50 DEG C, soaking time 150min, be allowed to be crosslinked, after gel solidification, 1000ml third is added Ketone solvent impregnates exchange 3 days, and per an acetone is replaced for 24 hours, the gel sample after impregnating exchange carries out vacuum freeze drying (temperature It is -79 DEG C, vacuum degree 20Pa), the three-dimensional structure phenolic resin aerogel material of nanoclay mineral fibres enhancing is obtained after 3 days Material.
Its performance test methods is as follows:
(1) apparent density measurement is measured using Archimedes drainage, and concrete operation method is to dry sample to be tested, Weigh its dry weight m1；Then, the sample after weighing is put in drying receptacle and vacuumizes 30min, it will be in bottle and sample interior is shown Gas in stomata empties, and is then poured into suitable distilled water, the liquid level of distilled water is made not have specimen surface, continue to vacuumize 30min is saturated sample；Sample is finally taken out, its weight m in water is successively measured2With aerial saturation weight in wet base m3。 According to following formula, bulk density is calculated.
Bulk density
(2) sample is cut into the vertical of 20 × 20 × 20mm (length × width × height) with sharp paper knife by mechanics performance determining Cube, with the mechanical property of CMT-6104 type electronic universal tension tester test complex three-dimensional structures aerogel material, compression Rate is 2mm/min, and every group of sample is at least cut out 12 or more samples, and after test, taking its average value is its intensity value；
(3) sample is cut into the cuboid of 40 × 40 × 5mm (length × width × height) by thermal coefficient with sharp paper knife, With the thermal coefficient of TC 3000E heat-pole method thermal conductivity factor instrument measurement sample, every group of sample is at least cut out 4 or more samples, Each sample measures 3 data, and taking its mean value is its thermal coefficient.
By testing, the three-dimensional structure phenolic resin aerogel material of the enhancing of nanoclay mineral fibres made from embodiment 1 Material density is 0.10g/cm3, compressive strength is 0.8MPa and thermal coefficient is 0.012W/ (mK)
The performance indicator of aeroge obtained by following embodiment presses such method test, and performance is as shown in table 1.
Embodiment 2
Step 1: 50g attapulgite being put into the agitator of 500ml, it is molten that the hydrochloric acid that 250ml concentration is 4mol/L is added Liquid, setting blender revolving speed 1000rpm stirs 1h, after impregnating 1 day, is further continued for stirring 1h with 1000rpm, vacuum filtration is received Rice clay mineral fiber filter cake；Then filter cake is returned into former agitator, is washed repeatedly with deionized water 7 times, when washing each time The deionized water of 200ml is added, and filters after mixing evenly, finally filter cake is put into vacuum oven, dry 8 is small at 60 DEG C Shi Hou；320 meshes are crossed in ball mill grinding, are mixed, and be fitted into spare in hermetic bag, are obtained acid activation nanoclay mineral fibres.
Step 2: 20g acid activation nano-attapulgite mineral wool and 1200mL deionized water made from step (1) being taken to be added to In 2000mL agitator, setting blender revolving speed is 4000rpm, after stirring 2h, 20g gelatin thickener is added, and by agitator It is placed in water bath with thermostatic control at a temperature of 90 °C and heats, being kept stirring machine revolving speed is 4000rpm, continues after stirring 30min, forms water Change gelinite A, hydrated gel body A sample is placed in liquid nitrogen (- 196 DEG C, 2min) freezings, is put into vacuum freeze drier (temperature Degree is -79 DEG C, vacuum degree 20Pa) middle freeze-drying 3 days, obtain three-dimensional fiber block composite gel material B；
Step 3: by going for 300.3g (i.e. 2.73mol) hydroquinone, 212.94g (i.e. 7.098mol) formaldehyde and 2000ml Ionized water is added in 3000mL agitator, when setting blender revolving speed is 6000rpm, is stirred 30min, is obtained finely dispersed Phenol, aldehyde mixed solution are added sodium hydroxide catalyst 0.109g (i.e. 0.00273mol), and continuation is stirred under conditions of 6000rpm 3min is mixed, dissolves catalyst sufficiently, and obtains uniformly mixed solution C；
Step 4: the 40g three-dimensional fiber block composite gel material B that step (2) obtain is put into the dipping of vacuum impregnation machine In cylinder, after C component solution made from 1488g step (3) is added, sealing is vacuumized, and vacuum impregnation container inner pressure is 20kPa, Dip time is 60min, opening sealing cover, and after time of repose 60min, taking-up is placed in 3000ml reaction kettle, is put into multipurpose It is heated in microwave chemosynthesis instrument, is warming up to 120 DEG C, soaking time 30min, be allowed to be crosslinked, after gel solidification, 2000ml is added N-hexane solvent soaking exchanges 5 days, and per a solvent is replaced for 24 hours, the gel sample after impregnating exchange carries out vacuum freeze drying (temperature is -79 DEG C, vacuum degree 20Pa), obtains the three-dimensional structure phenolic resin gas of nanoclay mineral fibres enhancing after 5 days Gel rubber material.Its performance test methods is shown in that embodiment 1, gained performance data are shown in Table 1.
Embodiment 3
Step 1: 50g shepardite is put into the agitator of 500ml, the hydrochloric acid solution that 200ml concentration is 2mol/L is added, Blender revolving speed 1000rpm is set and stirs 1h, after impregnating 2 days, is further continued for stirring 1h with 1000rpm, vacuum filtration obtains nanometer Clay mineral fiber filter cake；Then filter cake is returned into former agitator, is washed with deionized water 6 times, is added when washing each time repeatedly Enter the deionized water of 200ml, and filter after mixing evenly, finally filter cake is put into vacuum oven, it is 8 hours dry at 60 DEG C Afterwards；280 meshes are crossed in ball mill grinding, are mixed, and be fitted into spare in hermetic bag, are obtained acid activation nanoclay mineral fibres.
Step 2: 20g acid activation nanometer brucite fiber and 800mL deionized water made from step (1) being taken to be added to In 2000mL agitator, setting blender revolving speed is 3000rpm, after stirring 2.5h, 8g polyvinyl alcohol thickeners is added, and will stir It mixes bucket and is placed in temperature to heat in 80 DEG C of water bath with thermostatic control, being kept stirring machine revolving speed is 3000rpm, is continued after stirring 60min, shape At hydrated gel body A, hydrated gel body A sample is placed in liquid nitrogen (- 196 DEG C, 2min) freezings, is put into vacuum freeze drier Freeze-drying 3 days in (temperature is -79 DEG C, vacuum degree 20Pa), three-dimensional fiber block composite gel material B is obtained；
Step 3: by 104.5g (i.e. 0.95mol) resorcinol, 182.4g (i.e. 1.90mol) furfural and 2000ml go from Sub- water is added in 3000mL agitator, when setting blender revolving speed is 4500rpm, is stirred 45min, is obtained finely dispersed Phenol, aldehyde mixed solution are added calcium hydroxide catalyst 0.14g (i.e. 0.00189mol), and continuation is stirred under conditions of 4500rpm 5min dissolves catalyst sufficiently, and obtains uniformly mixed solution C；
Step 4: the 28g three-dimensional fiber block composite gel material B that step (2) obtain is put into the dipping of vacuum impregnation machine In cylinder, after C component solution made from 1324.8g step (3) is added, sealing is vacuumized, vacuum impregnation container inner pressure is 10kPa, dip time 35min open sealing cover, and after time of repose 35min, taking-up is placed in 3000ml reaction kettle, are put into It is heated in multipurpose microwave chemosynthesis instrument, is warming up to 90 DEG C, soaking time 60min, be allowed to be crosslinked, after gel solidification, be added 1500ml normal heptane solvent impregnates exchange 4 days, and per a solvent is replaced for 24 hours, it is cold that the gel sample after impregnating exchange carries out vacuum Dry (temperature is -79 DEG C, vacuum degree 20Pa) is lyophilized, the three-dimensional structure phenolic aldehyde of nanoclay mineral fibres enhancing is obtained after 4 days Resin aerogel material.Its performance test methods is shown in that embodiment 1, gained performance data are shown in Table 1.
Embodiment 4
Step 1: 50g galapectite is put into the agitator of 500ml, the hydrochloric acid solution that 180ml concentration is 3mol/L is added, Blender revolving speed 1000rpm is set and stirs 1h, after impregnating 1.5 days, is further continued for stirring 1h with 1000rpm, vacuum filtration is received Rice clay mineral fiber filter cake；Then filter cake is returned into former agitator, filter cake is washed 7 times with deionized water repeatedly, each time The deionized water of 200ml is added when washing, and filters after mixing evenly, finally filter cake is put into vacuum oven, at 60 DEG C After 8 hours dry；300 meshes are crossed in ball mill grinding, are mixed, and be fitted into spare in hermetic bag, are obtained acid activation nanoclay mineral Fiber.
Step 2: 20g acid activation nanometer galapectite fiber and 1000mL deionized water made from step (1) being taken to be added to In 2000mL agitator, setting blender revolving speed is 3500rpm, after stirring 2h, 10g Polyacrylate thickeners is added, and will stir It mixes bucket and is placed in temperature to heat in 70 DEG C of water bath with thermostatic control, being kept stirring machine revolving speed is 3500rpm, is continued after stirring 70min, shape At hydrated gel body A, hydrated gel body A sample is placed in liquid nitrogen (- 196 DEG C, 2min) freezings, is put into vacuum freeze drier Freeze-drying 3 days in (temperature is -79 DEG C, vacuum degree 20Pa), three-dimensional fiber block composite gel material B is obtained；
Step 3: by 52.25g (i.e. 0.475mol) resorcinol, 52.25g (i.e. 0.475mol) hydroquinone, 25.65g Formaldehyde (i.e. 0.855mol), 82.08g (i.e. 0.855mol) furfural and 2000ml deionized water are added in 3000mL agitator, When setting blender revolving speed is 5000rpm, 40min is stirred, obtains finely dispersed phenol, aldehyde mixed solution, sodium carbonate is added and urges Agent 0.1696g (i.e. 0.0016mol) and 0.064g (i.e. 0.0016mol) sodium hydroxide, continuation are stirred under conditions of 5000rpm 4min is mixed, dissolves catalyst sufficiently, and obtains uniformly mixed solution C；
Step 4: the 30g three-dimensional fiber block composite gel material B that step (2) obtain is put into the dipping of vacuum impregnation machine In cylinder, after C component solution made from 1751g step (3) is added, sealing is vacuumized, and vacuum impregnation container inner pressure is 8kPa, Dip time is 20min, opening sealing cover, and after time of repose 20min, taking-up is placed in 3000ml reaction kettle, is put into multipurpose It is heated in microwave chemosynthesis instrument, is warming up to 80 DEG C, soaking time 90min, be allowed to be crosslinked, after gel solidification, 1000ml is added Acetone and 1000ml n-hexane solvent soaking exchange 4 days, and per a solvent is replaced for 24 hours, the gel sample after impregnating exchange is carried out Vacuum freeze drying (temperature is -79 DEG C, vacuum degree 20Pa), obtains the three-dimensional knot of nanoclay mineral fibres enhancing after 4 days Structure phenolic resin aerogel material.Its performance test methods is shown in that embodiment 1, gained performance data are shown in Table 1.
Embodiment 5
Step 1: 25g sepiolite and 25g attapulgite being put into the agitator of 500ml, 225ml concentration, which is added, is The hydrochloric acid solution of 4mol/L, setting blender revolving speed 1000rpm are stirred 1h, after impregnating 1.8 days, are further continued for being stirred with 1000rpm 1h, vacuum filtration obtain nanoclay mineral fibres filter cake；Then filter cake is returned into former agitator, is washed repeatedly with deionized water 7 times, the deionized water of 200ml is added when washing each time, and filters after mixing evenly, filter cake is finally put into vacuum oven In, after 8 hours dry at 60 DEG C；320 meshes are crossed in ball mill grinding, are mixed, and be fitted into spare in hermetic bag, are obtained acid activation and receive Rice clay mineral fiber.
Step 2: taking going for 20g acid activation nanometer sepiolite and attapulgite composite fibre made from step (1) and 900mL Ionized water is added in 2000mL agitator, and setting blender revolving speed is 4000rpm, after stirring 2h, 6g gelatin is added and 6g is poly- Vinyl alcohol thickener, and agitator is placed in the water bath with thermostatic control that temperature is 80 DEG C and is heated, the machine revolving speed of being kept stirring is 4000rpm continues after stirring 60min, forms hydrated gel body A, hydrated gel body A sample is placed in liquid nitrogen (- 196 DEG C, It 2min) freezes, is put into vacuum freeze drier (temperature is -79 DEG C, vacuum degree 20Pa) freeze-drying 3 days, obtains three-dimensional Fibre agglomerates composite gel material B；
Step 3: by 180.4g (i.e. 1.64mol) resorcinol, 108.2g (i.e. 3.607mol) formaldehyde and 2000ml go from Sub- water is added in 3000mL agitator, when setting blender revolving speed is 3500rpm, is stirred 50min, is obtained finely dispersed Phenol, aldehyde mixed solution are added sodium carbonate catalyst 0.578g (i.e. 0.00545mol), and continuation is stirred under conditions of 3500rpm 8min dissolves catalyst sufficiently, and obtains uniformly mixed solution C；
Step 4: the 32g three-dimensional fiber block composite gel material B that step (2) obtain is put into the dipping of vacuum impregnation machine In cylinder, after C component solution made from 1398g step (3) is added, sealing is vacuumized, and vacuum impregnation container inner pressure is 15kPa, Dip time is 40min, opening sealing cover, and after time of repose 40min, taking-up is placed in 3000ml reaction kettle, is put into multipurpose It is heated in microwave chemosynthesis instrument, is warming up to 60 DEG C, soaking time 120min, be allowed to be crosslinked, after gel solidification, 1500ml is added N-hexane solvent soaking exchanges 3 days, and per a solvent is replaced for 24 hours, the gel sample after impregnating exchange carries out vacuum freeze drying (temperature is -79 DEG C, vacuum degree 20Pa), obtains the three-dimensional structure phenolic resin gas of nanoclay mineral fibres enhancing after 3 days Gel rubber material.Its performance test methods is shown in that embodiment 1, gained performance data are shown in Table 1.
Embodiment 6
Step 1: 50g wollastonite is put into the agitator of 500ml, the hydrochloric acid solution that 200ml concentration is 1mol/L is added, Blender revolving speed 1000rpm is set and stirs 1h, after impregnating 2 days, is further continued for stirring 1h with 1000rpm, vacuum filtration obtains nanometer Clay mineral fiber filter cake；Then filter cake is returned into former agitator, is washed with deionized water 5 times, is added when washing each time repeatedly Enter the deionized water of 200ml, and filter after mixing evenly, finally filter cake is put into vacuum oven, it is 8 hours dry at 60 DEG C Afterwards；300 meshes are crossed in ball mill grinding, are mixed, and be fitted into spare in hermetic bag, are obtained acid activation nanoclay mineral fibres.
Step 2: 20g acid activation nanometer wollastonite fibre and 600mL deionized water made from step (1) being taken to be added to In 2000mL agitator, setting blender revolving speed is 3500rpm, and after stirring 2.5h, 8g gelatin and the thickening of 8g polyacrylic acid is added Agent, and agitator is placed in the water bath with thermostatic control that temperature is 85 DEG C and is heated, being kept stirring machine revolving speed is 3500rpm, continues to stir After 50min, hydrated gel body A is formed, hydrated gel body A sample is placed in liquid nitrogen (- 196 DEG C, 2min) freezings, is put into vacuum Freeze-drying 3 days in freeze drier (temperature is -79 DEG C, vacuum degree 20Pa), three-dimensional fiber block plural gel material is obtained Expect B；
Step 3: by 150.15g (i.e. 1.365mol) resorcinol, 150.15g (i.e. 1.365mol) hydroquinone, 196.56g (i.e. 6.552mol) formaldehyde and 2000ml deionized water are added in 3000mL agitator, and setting blender revolving speed is When 6000rpm, 40min is stirred, obtains finely dispersed phenol, aldehyde mixed solution, sodium carbonate catalyst 0.241g is added (i.e. 0.00227mol) stirred under conditions of 6000rpm with calcium hydroxide catalyst 0.168g (i.e. 0.00227mol), continuation 5min dissolves catalyst sufficiently, and obtains uniformly mixed solution C；
Step 4: the 36g three-dimensional fiber block composite gel material B that step (2) obtain is put into the dipping of vacuum impregnation machine In cylinder, after C component solution made from 826.8g step (3) is added, sealing is vacuumized, and vacuum impregnation container inner pressure is 6kPa, Dip time is 10min, opening sealing cover, and after time of repose 10min, taking-up is placed in 3000ml reaction kettle, is put into multipurpose It is heated in microwave chemosynthesis instrument, is warming up to 100 DEG C, soaking time 40min, be allowed to be crosslinked, after gel solidification, 500ml is added Acetone and 500ml normal heptane solvent impregnate exchange 3 days, and per a solvent is replaced for 24 hours, the gel sample after impregnating exchange carries out true Vacuum freecing-dry (temperature is -79 DEG C, vacuum degree 20Pa), obtains the three-dimensional structure of nanoclay mineral fibres enhancing after 3 days Phenolic resin aerogel material.Its performance test methods is shown in that embodiment 1, gained performance data are shown in Table 1.
Embodiment 7
Step 1: 25g galapectite and 25g sepiolite being put into the agitator of 500ml, addition 150ml concentration is 4mol/L Hydrochloric acid solution, setting blender revolving speed 1000rpm stir 1h, impregnate 2 days after, be further continued for 1000rpm stir 1h, vacuum take out Filter obtains nanoclay mineral fibres filter cake；Then filter cake is returned into former agitator, is washed repeatedly with deionized water 7 times, it is each The deionized water of 200ml is added when secondary washing, and filters after mixing evenly, finally filter cake is put into vacuum oven, 60 DEG C After lower drying 8 hours；250 meshes are crossed in ball mill grinding, are mixed, and be fitted into spare in hermetic bag, are obtained acid activation nanoclay mine Fibres.
Step 2: take 20g acid activation nanometer galapectite and sepiolite composite fibre and 1200mL made from step (1) go from Sub- water is added in 2000mL agitator, and setting blender revolving speed is 4000rpm, and after stirring 2h, 6g gelatin and 6g starch is added Thickener, and agitator is placed in water bath with thermostatic control at a temperature of 90 °C and is heated, being kept stirring machine revolving speed is 4000rpm, is continued After stirring 40min, hydrated gel body A is formed, hydrated gel body A sample is placed in liquid nitrogen (- 196 DEG C, 2min) freezings, is put into Freeze-drying 3 days in vacuum freeze drier (temperature is -79 DEG C, vacuum degree 20Pa), it is compound solidifying to obtain three-dimensional fiber block Glue material B；
Step 3: (i.e. by 200.2g (i.e. 1.82mol) resorcinol, 54.6g (i.e. 1.82mol) formaldehyde, 174.72g 1.82mol) furfural and 2000ml deionized water are added in 3000mL agitator, when setting blender revolving speed is 4000rpm, are stirred 50min is mixed, finely dispersed phenol, aldehyde mixed solution are obtained, sodium carbonate catalyst 0.241g (i.e. 0.00227mol) hydrogen-oxygen is added Change sodium catalyst 0.0908g (i.e. 0.00227mol), continuation stirs 7min under conditions of 4000rpm, keeps catalyst sufficiently molten Solution, and obtain uniformly mixed solution C；
Step 4: the 32g three-dimensional fiber block composite gel material B that step (2) obtain is put into the dipping of vacuum impregnation machine In cylinder, after C component solution made from 1724.8g step (3) is added, sealing is vacuumized, vacuum impregnation container inner pressure is 12kPa, dip time 30min open sealing cover, and after time of repose 30min, taking-up is placed in 3000ml reaction kettle, are put into more It is heated in purposes microwave chemosynthesis instrument, is warming up to 70 DEG C, soaking time 110min, be allowed to be crosslinked, after gel solidification, be added 2000ml anhydrous ethanol solvent impregnates exchange 4 days, and per a solvent is replaced for 24 hours, the gel sample after impregnating exchange carries out vacuum Freeze-drying (temperature is -79 DEG C, vacuum degree 20Pa), obtains the three-dimensional structure phenol of nanoclay mineral fibres enhancing after 4 days Urea formaldehyde aerogel material.Its performance test methods is shown in that embodiment 1, gained performance data are shown in Table 1, and SEM spectrum is shown in Fig. 1.
From the figure we can see that the pore-size distribution of aeroge is wider, there are the mesoporous of bore dia 2-50nm, deposit simultaneously It is greater than 50nm macropore in bore dia, is a kind of porous material of terraced distribution.
(1) apparent density measurement is measured using Archimedes drainage, and concrete operation method is to dry sample to be tested, Weigh its dry weight m1；Then, the sample after weighing is put in drying receptacle and vacuumizes 30min, it will be in bottle and sample interior is shown Gas in stomata empties, and is then poured into suitable distilled water, the liquid level of distilled water is made not have specimen surface, continue to vacuumize 30min is saturated sample；Sample is finally taken out, its weight m in water is successively measured2With aerial saturation weight in wet base m3。 According to following formula, bulk density is calculated.
Bulk density
(2) sample is cut into the vertical of 20 × 20 × 20mm (length × width × height) with sharp paper knife by mechanics performance determining Cube, with the mechanical property of CMT-6104 type electronic universal tension tester test complex three-dimensional structures aerogel material, compression Rate is 2mm/min, and every group of sample is at least cut out 12 or more samples, and after test, taking its average value is its intensity value；
(3) sample is cut into the cuboid of 40 × 40 × 5mm (length × width × height) by thermal coefficient with sharp paper knife, With the thermal coefficient of TC 3000E heat-pole method thermal conductivity factor instrument measurement sample, every group of sample is at least cut out 4 or more samples, Each sample measures 3 data, and taking its mean value is its thermal coefficient.
The three-dimensional structure phenolic resin airsetting material property of the enhancing of nanoclay mineral fibres obtained in 1 embodiment of table
Serial number Apparent density (g/cm3) Compression strength (MPa) Thermal coefficient (W/ (mK))
Embodiment 1 0.10 0.8 0.012
Embodiment 2 0.23 2.4 0.029
Embodiment 3 0.14 1.5 0.018
Embodiment 4 0.11 2.0 0.015
Embodiment 5 0.15 1.6 0.021
Embodiment 6 0.24 2.5 0.034
Embodiment 7 0.19 1.8 0.025
In conclusion the present invention is raw material using the nanoclay mineral fibres and organic thickening agent of activated dispersion, In water bath with thermostatic control, dispersion is stirred to raw material, uniform dispersion is made, then through vacuum freeze drying, it is viscous to prepare three-dimensional structure Native mineral fibres gel rubber material；The gel rubber material is placed into containing with the hybrid reaction body of phenolic compound and aldehyde compound In system, by vacuum impregnation, microwave heating, in-situ polymerization and gel solidification, the three-dimensional structure clay of phenolic resin cladding is obtained Mineral porous hydrogel material；This porous hydrogel material is put into the beaker for filling organic solvent, to displace water-setting Moisture in glue material reduces solution surface tension and sample shrinking percentage, most forms intensity height through vacuum freeze drying afterwards, leads The low aerogel composite of hot coefficient.
Unaccomplished matter of the present invention is well-known technique.

Claims (10)

1. a kind of preparation method of the three-dimensional structure phenolic resin airsetting material using the enhancing of nanoclay mineral fibres, feature For this method comprises the following steps:
(1) it clay mineral fiber activation: after clay mineral fiber is mixed with hydrochloric acid solution, impregnates 1-3 days, then vacuum is taken out Filter, obtains nanoclay mineral fibres filter cake；It is filtered after washing, it is 8 hours dry at 60 DEG C；250~350 mesh are crossed in ball mill grinding Sieve, obtains acid activation nanoclay mineral fibres；
Wherein, the hydrochloric acid solution that 150-250ml concentration is 0.5-4mol/L is added in every 50g clay mineral fiber；It is each to impregnate front and back It is stirred 1 hour with blender；
(2) preparation of nanoclay mineral fibres three-dimensional composite material: to the fibre of acid activation nanoclay mineral made from step (1) Deionized water is added in dimension, and after stirring 2-3h, organic thickening agent is added, and under 60-90 DEG C of water bath with thermostatic control, continues to stir 30-90min Afterwards, hydrated gel body A is formed, hydrated gel body A sample is placed in liquid nitrogen after freezing, is put into vacuum freeze drier and freezes It is 3 days dry, obtain three-dimensional fiber block composite gel material B；
Wherein, 20-60 ml deionized water is added in every g acid activation nanoclay mineral fibres；Acid activation nanoclay mineral are fine Dimension: the mass ratio of thickener is=1:0.2-1；
(3) preparation of novolac solution: after phenolic compound, aldehyde compound and deionized water are stirred 30-60min, addition is urged Agent continues 3~10min of stirring, obtains solution C；
Wherein, phenolic compound: the molar ratio of aldehyde compound is=1:1.5-2.6；Catalyst: the molar ratio of phenolic compound For=1:100~1000；0.475-1.365mol phenolic compound is added in every 1000ml deionized water；
(4) the three-dimensional structure phenolic resin airsetting material of nanoclay mineral fibres enhancing: the three-dimensional fiber that step (2) are obtained Block composite gel material B is put into the dip tank of vacuum impregnation machine, after C component solution made from step (3) is added, sealing, It vacuumizes, vacuum impregnation container inner pressure is 5-20kPa, dip time 5-60min, opens sealing cover, time of repose 5- After 60min, taking-up is placed in reaction kettle, and microwave heating is to 50-120 DEG C, and after gel solidification 30-150min, organic solvent is added Gel during which per organic solvent of replacement for 24 hours, then is carried out vacuum freeze drying, is received after 3-5 days by middle immersion 3-5 days The rice fibre-reinforced three-dimensional structure phenolic resin aerogel material of clay mineral；
Wherein, the mass ratio of A:C component is 1:1.2-1.8 in the step (4)；
Nanoclay mineral fibres in the step (1) be sepiolite after purification enrichment, attapulgite, shepardite, Galapectite or wollastonite, one of mineral fibres or the mixture for waiting the quality such as two kinds.
2. utilizing the system of the three-dimensional structure phenolic resin airsetting material of nanoclay mineral fibres enhancing as described in claim 1 Preparation Method, it is characterized in that the organic thickening agent in the step (2) is one in starch, gelatin, polyvinyl alcohol or polyacrylic acid Kind or two kinds of equal mass mixings objects.
3. utilizing the system of the three-dimensional structure phenolic resin airsetting material of nanoclay mineral fibres enhancing as described in claim 1 Preparation Method, it is characterized in that the phenolic compound in the step (3) be one of resorcinol or hydroquinone or they etc. Molar mixture.
4. utilizing the system of the three-dimensional structure phenolic resin airsetting material of nanoclay mineral fibres enhancing as described in claim 1 Preparation Method, it is characterized in that the aldehyde compound in the step (3) is to be that one of formaldehyde or furfural or their equimolars are mixed Close object.
5. utilizing the system of the three-dimensional structure phenolic resin airsetting material of nanoclay mineral fibres enhancing as described in claim 1 Preparation Method, it is characterized in that catalyst in the step (3) be sodium carbonate, sodium hydroxide or calcium hydroxide one kind or wait two kinds Equimolar mixture.
6. utilizing the system of the three-dimensional structure phenolic resin airsetting material of nanoclay mineral fibres enhancing as described in claim 1 Preparation Method, it is characterized in that organic solvent in the step (4) be dehydrated alcohol, acetone, n-hexane or normal heptane one kind or Two kinds of isometric mixtures of solvent.
7. utilizing the system of the three-dimensional structure phenolic resin airsetting material of nanoclay mineral fibres enhancing as described in claim 1 Preparation Method, it is characterized in that the equipment of microwave heating described in step (4) is multipurpose microwave chemosynthesis instrument.
8. utilizing the system of the three-dimensional structure phenolic resin airsetting material of nanoclay mineral fibres enhancing as described in claim 1 Preparation Method, it is characterized in that the blender revolving speed 1000rpm in step (1)；Blender revolving speed in step (2) is 2000- 4000rpm；Blender revolving speed in step (3) is 3000-6000rpm.
9. utilizing the system of the three-dimensional structure phenolic resin airsetting material of nanoclay mineral fibres enhancing as described in claim 1 Preparation Method, it is characterized in that nanoclay mineral fibres complex three-dimensional structures phenolic resin aerogel material ground apparent density For 0.10g/cm3-0.24g/cm3, thermal coefficient is 0.012-0.034W/ (mK), compression strength 0.8MPa-2.5MPa.
10. utilizing the three-dimensional structure phenolic resin airsetting material of nanoclay mineral fibres enhancing as described in claim 1 Preparation method, it is characterized in that it is -79 DEG C that the vacuum freeze drying condition in the step (2) and (4), which is temperature, vacuum degree For 20Pa.
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