CN109575510B - Preparation method of nanofiber mineral reinforced phenolic resin three-dimensional aerogel material - Google Patents
Preparation method of nanofiber mineral reinforced phenolic resin three-dimensional aerogel material Download PDFInfo
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Abstract
The invention relates to a preparation method of a three-dimensional structure phenolic resin aerogel material reinforced by nano clay mineral fibers. The method comprises the following steps: (1) activating the clay mineral fiber to obtain acid-activated nano clay mineral fiber; (2) preparing a three-dimensional composite material of the nano clay mineral fiber to obtain a three-dimensional fiber block composite gel material B; (3) and (3) after the three-dimensional fiber block composite gel material B is soaked in the component C solution, curing is carried out for 30-150min at 50-120 ℃, then soaking is carried out in an organic solvent, and vacuum freeze drying is carried out, so as to obtain the nano-clay mineral fiber reinforced three-dimensional structure phenolic resin aerogel material. The material obtained by the invention can be used for heat preservation and heat insulation of high-end equipment, or can be used as a catalyst carrier, an adsorbent of organic pollutants and the like.
Description
Technical Field
The invention relates to a preparation technology and application of a clay mineral fiber reinforced three-dimensional structure phenolic resin aerogel material, belonging to the field of material preparation.
Background
The aerogel is a light solid material with a nano-scale porous network structure, has the performances of low density, high specific surface area, high porosity, low thermal conductivity and the like, and is widely applied to heat preservation and insulation, catalytic carriers, supercapacitors, electrode materials, sewage treatment and the like. In recent years, with the national green energy-saving and environmental protection industryThe development of the aerogel materials with excellent heat insulation and preservation performance is increasing, and the aerogel materials have higher requirements on the performance, so that the aerogel materials not only have good mechanical properties, but also have certain elastic properties. Therefore, in order to meet the requirements of energy-saving and environment-friendly industries on the aerogel, the development of the phenolic resin composite aerogel with excellent mechanical properties and elasticity is imperative. Therefore, many people also develop related researches, such as ZL.105601854A, which discloses a three-dimensional felt fiber structure reinforced phenolic resin aerogel heat shielding material, and the obtained material has high strength and good dimensional stability, but the rigid structure causes the thermal conductivity coefficient of the aerogel to be greatly improved, and is not beneficial to heat preservation; ZL.102285775A discloses an organic aerogel heat insulation material reinforced by organic pre-oxidized fiber, the prepared aerogel has high strength and small heat conductivity coefficient, but the organic pre-oxidized fiber adopted by the aerogel heat insulation material is complex to prepare and has harm to the environment; ZL.104177644A discloses a preparation method of polyimide modified phenolic resin aerogel with excellent mechanical property, processability, insulativity and thermal insulation property, but the prepared aerogel material has poor high temperature resistance, so that the application of the aerogel material in high-end fields such as aerospace and the like is limited; CN106800630A discloses a flexible aerogel material and a preparation method thereof, but the preparation process is complex, the period is long, the requirement on equipment is high, and hydroxyacrylamide is toxic and smelly; CN 106189066A introduces a preparation method of a phenolic resin/silicon dioxide composite aerogel material, the material has excellent mechanical property and heat insulation and fire resistance, but the preparation process is complex, the energy consumption is high, and the large-scale popularization is difficult; yin et al describe a density of 0.312-0.356g/cm3The novel resin/silicon hybrid aerogel composite material with the compressive strength of 0.76-4.08MPa is also complex in preparation process and large in thermal conductivity coefficient of the prepared aerogel (synthetic and characterization of novel phenolic resin/silicone hybrid aerogel composites with improved properties).
The clay mineral, especially the clay mineral fiber with nanometer size structure, has excellent reinforcing and toughening functions. The material has the advantages of stable performance, heat resistance, flame retardance, large specific surface area, low heat conductivity coefficient, rich reserves, low price, wide sources and the like. In view of the excellent performance of the clay mineral, the invention adopts the nano-structure mineral fiber as the reinforcing functional material to improve the mechanical property of the phenolic aerogel material and develop the clay mineral fiber reinforced three-dimensional structure phenolic resin aerogel material with a light porous structure.
Disclosure of Invention
The invention aims to provide a preparation method of a phenolic resin aerogel material with a three-dimensional structure reinforced by nano-clay mineral fibers aiming at the defect of poor mechanical property of the traditional phenolic aerogel in the prior art. The method utilizes a three-dimensional structure clay mineral fiber gel material; the gel material is placed into a mixed reaction system containing phenolic compounds and aldehyde compounds, and the three-dimensional structure clay mineral porous hydrogel material coated by the phenolic resin is obtained through the preparation of vacuum impregnation and microwave heating of the phenolic resin. The material can be used for heat preservation and heat insulation of high-end equipment, or used as a catalyst carrier, an adsorbent of organic pollutants and the like.
The technical scheme of the invention is as follows:
a method for preparing a three-dimensional structure phenolic resin aerogel material reinforced by nano clay mineral fibers comprises the following steps:
(1) activation of clay mineral fibers: mixing clay mineral fiber with hydrochloric acid solution, soaking for 1-3 days, and vacuum filtering to obtain nano clay mineral fiber filter cake; washing, filtering, and drying at 60 deg.C for 8 hr; ball-milling and crushing, and sieving with a 250-350 mesh sieve to obtain acid activated nano clay mineral fibers;
wherein 150-250ml of hydrochloric acid solution with the concentration of 0.5-4mol/L is added into every 50g of clay mineral fiber; stirring for 1 hour by a stirrer before and after soaking respectively; the rotating speed of the stirrer is 1000 rpm;
(2) preparing a nano clay mineral fiber three-dimensional composite material: adding deionized water into the acid-activated nano clay mineral fiber prepared in the step (1), stirring for 2-3h, adding an organic thickener, continuously stirring for 30-90min in a constant-temperature water bath at 60-90 ℃ to form a hydrated gel A, placing a sample of the hydrated gel A in liquid nitrogen for freezing, and placing the sample in a vacuum freeze dryer for freeze drying for 3 days to obtain a three-dimensional fiber block composite gel material B;
wherein, 20-60ml deionized water is added into each g of acid activated nano clay mineral fiber; acid activated nanoclay mineral fiber: the mass ratio of the thickening agent is 1: 0.2-1; the rotating speed of the stirrer is 2000-4000 rpm;
(3) preparation of phenolic solution: stirring a phenolic compound, an aldehyde compound and deionized water for 30-60min, adding a catalyst, and continuously stirring for 3-10 min to obtain a solution C;
wherein, the phenolic compound: the molar ratio of the aldehyde compound is 1: 1.5-2.6; catalyst: the molar ratio of the phenolic compounds is 1: 100-1000; adding 0.475-1.365mol of phenolic compounds into every 1000ml of deionized water; the rotating speed of the stirrer is 3000 plus 6000 rpm;
(4) nano clay mineral fiber reinforced three-dimensional structure phenolic resin aerogel material: putting the three-dimensional fiber block composite gel material B obtained in the step (2) into an impregnation cylinder of a vacuum impregnation machine, adding the component C solution prepared in the step (3), sealing, vacuumizing, keeping the pressure in a vacuum impregnation container at 5-20kPa for 5-60min, opening a sealing cover, standing for 5-60min, taking out, putting into a reaction kettle, heating to 50-120 ℃ by microwave, adding the organic solvent into the organic solvent for soaking for 3-5 days after the gel is solidified for 30-150min, replacing the organic solvent every 24h, then carrying out vacuum freeze drying on the gel, and obtaining the nano-clay mineral fiber reinforced three-dimensional structure phenolic resin aerogel material after 3-5 days;
wherein, in the step (4): the mass ratio of the component C is 1: 1.2-1.8;
the nano clay mineral fiber in the step (1) is one or a mixture of two of sepiolite, attapulgite, brucite, halloysite or wollastonite which are purified and enriched and mineral fibers with equal mass.
The organic thickening agent in the step (2) is one or a mixture of two of starch, gelatin, polyvinyl alcohol or polyacrylic acid in equal mass,
the phenolic compound in the step (3) is one of resorcinol or hydroquinone or an equimolar mixture of the resorcinol and the hydroquinone,
the aldehyde compound in the step (3) is one of formaldehyde or furfural or an equimolar mixture of formaldehyde and furfural,
the catalyst in the step (3) is one or a mixture of two of sodium carbonate, sodium hydroxide or calcium hydroxide in equal molar ratio,
the organic solvent in the step (4) is one or a mixture of two solvents of absolute ethyl alcohol, acetone, normal hexane or normal heptane with equal volume.
The microwave heating equipment is a multipurpose microwave chemical synthesizer.
The vacuum freeze drying conditions in the steps (2) and (4) are that the temperature is-79 ℃ and the vacuum degree is 20 Pa.
The apparent density of the nano-clay mineral fiber composite three-dimensional structure phenolic resin aerogel material obtained by the preparation method is 0.10g/cm3-0.24g/cm3The heat conductivity coefficient is 0.012-0.034W/(m.K), and the compressive strength is 0.8MPa-2.5 MPa.
The invention has the beneficial effects that:
according to the invention, the nano-clay mineral fiber material with low price, environmental protection and abundant reserves is activated to obtain a well-dispersed fiber structure matrix material, so that the three-dimensional fiber block composite gel is prepared, the production cost is greatly reduced, and the abundant hydroxyl functional groups on the fiber provide an assembly point for the in-situ reaction of phenol and aldehyde solutions; the vacuum impregnation process is adopted, so that the phenol and aldehyde solution is quickly and fully compounded with the fiber block composite gel; the microwave crosslinking gel curing process greatly reduces the gel curing time and increases the crosslinking density of phenolic resin formed by the reaction of phenol and aldehyde; the three-dimensional fiber block composite aerogel and the phenolic resin aerogel have synergistic effect to form a pore structure in step distribution, and the pore structure can be regulated and controlled, so that the composite aerogel has the performances of low density, high strength and low heat conductivity coefficient.
The invention utilizes the light clay mineral fiber to prepare the three-dimensional fiber block composite gel material, and the phenolic resin aerogel material is reinforced by the three-dimensional fiber block composite gel material through vacuum impregnation and microwave heating preparation processes, so that the density and the gel curing time can be effectively reduced, the strength of the gel material is enhanced, and the heat conductivity coefficient is reduced. Taking example 4 as an example, the nano clay mineral fiber composite three-dimensional structure phenolic resin aerogel material prepared by the method has the density of 0.11g/cm3, the gel curing time of 90min, the compressive strength of 2.0MPa and the thermal conductivity of 0.015W/(m.K). The gel curing time was reduced by 94.5h and 70.5h, respectively, compared to the optimum values in zl.105601854a and zl.102285775a examples; the density value is reduced by 0.199g/cm3 and the thermal conductivity value is reduced by 0.015W/(m.K) compared with the optimum value in ZL.102285775A; compared with the optimal value in the literature of jinxiangyu (preparation and performance research of quartz fiber reinforced low-density phenolic composite material), the compressive strength value is improved by 1.37 MPa.
Drawings
FIG. 1 is an SEM photograph of a three-dimensional structure phenolic resin aerogel material obtained in example 7.
Detailed Description
Sepiolite, attapulgite, brucite, halloysite and wollastonite, which are all purified natural nano clay minerals, are powder with the corresponding mineral content of more than 90 percent, which is obtained by enriching sepiolite, attapulgite, brucite, halloysite and wollastonite which are natural minerals through centrifugal field gravity concentration in the step (1) of the following embodiment. (among them, natural mineral sepiolite was purchased from tengfa sepiolite development limited, natural mineral attapulgite was purchased from jiang su Chuan nanometer materials science and technology limited, brucite was purchased from luck mineral processing factory, linghou county, lan Yi Lu mineral processing factory, halloysite was purchased from nan Yi mineral processing factory, lingfeng mineral processing factory).
Example 1
Step 1: putting 50g of sepiolite into a 500ml stirring barrel, adding 150ml of hydrochloric acid solution with the concentration of 0.5mol/L, setting the rotation speed of a stirrer to be 1000rpm, stirring for 1h, continuing to stir at 1000rpm for 1h after soaking for 3 days, and carrying out vacuum filtration to obtain a nano clay mineral fiber filter cake; then returning the filter cake to the original stirring barrel, repeatedly washing for 4 times by using deionized water, adding 200ml of deionized water during each washing, uniformly stirring, carrying out suction filtration, finally putting the filter cake into a vacuum drying oven, and drying for 8 hours at 60 ℃; ball-milling, pulverizing, sieving with 250 mesh sieve, mixing, and packaging in a sealed bag to obtain acid-activated nanoclay mineral fiber;
step 2: adding 20g of the acid-activated nano sepiolite fibers prepared in the step (1) and 400mL of deionized water into a 2000mL stirring barrel, setting the rotating speed of the stirrer to be 2000rpm, stirring for 3h, adding 4g of a starch thickener, heating the stirring barrel in a constant-temperature water bath at the temperature of 60 ℃, keeping the rotating speed of the stirrer to be 2000rpm, continuously stirring for 90min to form a hydrated gel A, placing a sample of the hydrated gel A in liquid nitrogen (-196 ℃ for 2min), freezing the sample, and freeze-drying the sample in a vacuum freeze-drying machine (the temperature is-79 ℃ and the vacuum degree is 20Pa) for 3 days to obtain a three-dimensional fiber block composite gel material B;
and step 3: adding 104.5g (namely 0.95mol) of resorcinol, 42.75g (namely 1.425mol) of formaldehyde and 2000mL of deionized water into a 3000mL stirring barrel, stirring for 60min when the rotating speed of a stirrer is set to be 3000rpm to obtain a uniformly dispersed phenol-aldehyde mixed solution, adding 1.007g (namely 0.00950mol) of sodium carbonate catalyst, and continuously stirring for 10min at 3000rpm to obtain a uniformly mixed solution C;
and 4, step 4: and (3) putting 24g of the three-dimensional fiber block composite gel material B obtained in the step (2) into an impregnation cylinder of a vacuum impregnation machine, adding 763.2g of the component C solution prepared in the step (3), sealing, vacuumizing, keeping the pressure in the vacuum impregnation container at 5kPa for 5min, opening a sealing cover, standing for 5min, taking out, putting into a 3000ml reaction kettle, heating in a multipurpose microwave chemical synthesizer, heating to 50 ℃, keeping the temperature for 150min, crosslinking, solidifying the gel, adding 1000ml of acetone solvent, soaking and exchanging for 3 days, replacing acetone once every 24h, performing vacuum freeze drying (the temperature is-79 ℃, the vacuum degree is 20Pa) on the soaked and exchanged gel sample, and obtaining the nano-clay mineral fiber reinforced three-dimensional structure phenolic resin aerogel material after 3 days.
The performance test method comprises the following steps:
(1) the apparent density is measured by Archimedes drainage method, and the specific operation method comprises oven drying sample to be measured, and weighingDry weight m1(ii) a Then, placing the weighed sample in a drying container, vacuumizing for 30min, exhausting gas in the bottle and the air holes in the sample, injecting a proper amount of distilled water to enable the liquid level of the distilled water to be submerged over the surface of the sample, and continuously vacuumizing for 30min to saturate the sample; finally, the sample is taken out, and the weight m of the sample in the water is measured successively2And saturated wet weight m in air3. The bulk density was calculated according to the following formula.
Bulk density
(2) Mechanical property determination, cutting a sample into a cube of 20 multiplied by 20mm (length multiplied by width multiplied by height) by a sharp paper cutter, testing the mechanical property of the composite three-dimensional aerogel material by a CMT-6104 type electronic universal tensile testing machine, wherein the compression rate is 2mm/min, at least more than 12 samples are cut out from each group of samples, and after the test, the average value is taken as the strength value;
(3) the thermal conductivity of the samples was measured by cutting the samples into rectangular blocks of 40X 5mm (length X width X height) with a sharp paper cutter, measuring the thermal conductivity of the samples with a TC 3000E hot wire thermal conductivity meter, cutting out at least 4 samples per group of samples, measuring 3 data per sample, and taking the mean value as the thermal conductivity.
Through tests, the density of the nano clay mineral fiber reinforced three-dimensional structure phenolic resin aerogel material prepared in example 1 is 0.10g/cm3A compressive strength of 0.8MPa and a thermal conductivity of 0.012W/(m.K)
The performance index of the aerogel obtained in each of the following examples was measured in this manner, and the performance thereof is shown in Table 1.
Example 2
Step 1: putting 50g of attapulgite into a 500ml stirring barrel, adding 250ml of hydrochloric acid solution with the concentration of 4mol/L, setting the rotating speed of the stirrer to be 1000rpm, stirring for 1h, soaking for 1 day, then continuing stirring for 1h at 1000rpm, and carrying out vacuum filtration to obtain a nano clay mineral fiber filter cake; then returning the filter cake to the original stirring barrel, repeatedly washing with deionized water for 7 times, adding 200ml of deionized water during each washing, uniformly stirring, performing suction filtration, and finally putting the filter cake into a vacuum drying oven, and drying for 8 hours at 60 ℃; ball milling, crushing, sieving with 320 mesh sieve, mixing, and packing in sealed bag to obtain acid activated nanometer clay mineral fiber.
Step 2: adding 20g of the acid-activated nano attapulgite fiber prepared in the step (1) and 1200mL of deionized water into a 2000mL stirring barrel, setting the rotation speed of the stirrer to 4000rpm, stirring for 2h, adding 20g of gelatin thickener, heating the stirring barrel in a constant-temperature water bath at the temperature of 90 ℃, keeping the rotation speed of the stirrer to 4000rpm, continuously stirring for 30min to form a hydrated gel A, placing a sample of the hydrated gel A in liquid nitrogen (-196 ℃, freezing for 2min), and freeze-drying in a vacuum freeze-drying machine (the temperature is-79 ℃, and the vacuum degree is 20Pa) for 3 days to obtain a three-dimensional fiber block composite gel material B;
and step 3: adding 300.3g (namely 2.73mol) of hydroquinone, 212.94g (namely 7.098mol) of formaldehyde and 2000mL of deionized water into a 3000mL stirring barrel, stirring for 30min when the rotating speed of the stirrer is 6000rpm to obtain a uniformly dispersed phenol-aldehyde mixed solution, adding 0.109g (namely 0.00273mol) of sodium hydroxide catalyst, continuously stirring for 3min at 6000rpm to fully dissolve the catalyst and obtain a uniformly mixed solution C;
and 4, step 4: putting 40g of the three-dimensional fiber block composite gel material B obtained in the step (2) into an impregnation cylinder of a vacuum impregnation machine, adding 1488g of the component C solution prepared in the step (3), sealing, vacuumizing, keeping the pressure in the vacuum impregnation container at 20kPa for 60min, opening a sealing cover, standing for 60min, taking out, putting into a 3000ml reaction kettle, heating in a multipurpose microwave chemical synthesizer, heating to 120 ℃, keeping the temperature for 30min, crosslinking, solidifying the gel, adding 2000ml of n-hexane solvent, soaking and exchanging for 5 days, replacing the solvent every 24h, performing vacuum freeze drying (the temperature is-79 ℃, the vacuum degree is 20Pa) on the soaked and exchanged gel sample, and obtaining the nano-clay mineral fiber reinforced three-dimensional structure phenolic resin aerogel material after 5 days. The performance test method is shown in example 1, and the obtained performance data are shown in Table 1.
Example 3
Step 1: putting 50g brucite into a 500ml stirring barrel, adding 200ml hydrochloric acid solution with the concentration of 2mol/L, setting the rotation speed of a stirrer to be 1000rpm, stirring for 1h, soaking for 2 days, then continuing stirring for 1h at 1000rpm, and carrying out vacuum filtration to obtain a nano clay mineral fiber filter cake; then returning the filter cake to the original stirring barrel, repeatedly washing for 6 times by using deionized water, adding 200ml of deionized water during each washing, uniformly stirring, carrying out suction filtration, finally putting the filter cake into a vacuum drying oven, and drying for 8 hours at 60 ℃; ball milling, crushing, 280 mesh sieving, mixing and packing in sealed bag to obtain acid activated nanometer clay mineral fiber.
Step 2: adding 20g of the acid-activated nano brucite fiber prepared in the step (1) and 800mL of deionized water into a 2000mL stirring barrel, setting the rotating speed of the stirring machine to be 3000rpm, stirring for 2.5h, adding 8g of polyvinyl alcohol thickening agent, heating the stirring barrel in a constant-temperature water bath at the temperature of 80 ℃, keeping the rotating speed of the stirring machine to be 3000rpm, continuously stirring for 60min to form a hydrated gel A, placing the hydrated gel A sample in liquid nitrogen for (-196 ℃ for 2min), freezing, and freeze-drying in a vacuum freeze-drying machine (the temperature is-79 ℃ and the vacuum degree is 20Pa) for 3 days to obtain a three-dimensional fiber block composite gel material B;
and step 3: adding 104.5g (namely 0.95mol) of resorcinol, 182.4g (namely 1.90mol) of furfural and 2000mL of deionized water into a 3000mL stirring barrel, stirring for 45min when the rotating speed of the stirrer is set to 4500rpm to obtain a uniformly dispersed phenol-aldehyde mixed solution, adding 0.14g (namely 0.00189mol) of calcium hydroxide catalyst, continuously stirring for 5min at 4500rpm to fully dissolve the catalyst and obtain a uniformly mixed solution C;
and 4, step 4: and (3) putting 28g of the three-dimensional fiber block composite gel material B obtained in the step (2) into an impregnation cylinder of a vacuum impregnation machine, adding 1324.8g of the component C solution prepared in the step (3), sealing, vacuumizing, keeping the pressure in the vacuum impregnation container at 10kPa for 35min, opening a sealing cover, standing for 35min, taking out, putting into a 3000ml reaction kettle, heating in a multipurpose microwave chemical synthesizer, heating to 90 ℃, keeping the temperature for 60min, crosslinking, solidifying the gel, adding 1500ml of n-heptane solvent, soaking and exchanging for 4 days, replacing the solvent every 24h, performing vacuum freeze drying (the temperature is-79 ℃, the vacuum degree is 20Pa) on the soaked and exchanged gel sample, and obtaining the nano-clay mineral fiber reinforced three-dimensional structure phenolic resin aerogel material after 4 days. The performance test method is shown in example 1, and the obtained performance data are shown in Table 1.
Example 4
Step 1: putting 50g of halloysite into a 500ml stirring barrel, adding 180ml of hydrochloric acid solution with the concentration of 3mol/L, setting the rotation speed of a stirrer to be 1000rpm, stirring for 1h, soaking for 1.5 days, then continuing stirring for 1h at 1000rpm, and carrying out vacuum filtration to obtain a nano clay mineral fiber filter cake; then returning the filter cake to the original stirring barrel, repeatedly washing the filter cake for 7 times by using deionized water, adding 200ml of deionized water during each washing, uniformly stirring, carrying out suction filtration, and finally putting the filter cake into a vacuum drying oven, and drying for 8 hours at 60 ℃; ball milling, crushing, sieving with 300 mesh sieve, mixing, and packing in sealed bag to obtain acid activated nanometer clay mineral fiber.
Step 2: adding 20g of the acid-activated nano halloysite fiber prepared in the step (1) and 1000mL of deionized water into a 2000mL stirring barrel, setting the rotation speed of the stirrer to 3500rpm, stirring for 2h, adding 10g of polyacrylic acid thickener, heating the stirring barrel in a constant-temperature water bath at the temperature of 70 ℃, keeping the rotation speed of the stirrer to 3500rpm, continuously stirring for 70min to form a hydrated gel A, placing the hydrated gel A sample in liquid nitrogen (-196 ℃ for 2min), freezing, and freeze-drying in a vacuum freeze-drying machine (the temperature is-79 ℃ and the vacuum degree is 20Pa) for 3 days to obtain a three-dimensional fiber block composite gel material B;
and step 3: adding 52.25g (namely 0.475mol) of resorcinol, 52.25g (namely 0.475mol) of hydroquinone, 25.65g of formaldehyde (namely 0.855mol), 82.08g (namely 0.855mol) of furfural and 2000mL of deionized water into a 3000mL stirring barrel, stirring for 40min when the rotating speed of a stirrer is set to be 5000rpm to obtain a uniformly dispersed phenol-aldehyde mixed solution, adding 0.1696g (namely 0.0016mol) of sodium carbonate catalyst and 0.064g (namely 0.0016mol) of sodium hydroxide, and continuously stirring for 4min under the condition of 5000rpm to fully dissolve the catalyst and obtain a uniformly mixed solution C;
and 4, step 4: and (3) putting 30g of the three-dimensional fiber block composite gel material B obtained in the step (2) into an impregnation cylinder of a vacuum impregnator, adding 1751g of the component C solution prepared in the step (3), sealing, vacuumizing, keeping the pressure in the vacuum impregnation container at 8kPa for 20min, opening a sealing cover, standing for 20min, taking out, putting into a 3000ml reaction kettle, heating in a multipurpose microwave chemical synthesizer, heating to 80 ℃, keeping the temperature for 90min, crosslinking, solidifying the gel, adding 1000ml of acetone and 1000ml of n-hexane solvent, soaking and exchanging for 4 days, replacing the solvent every 24h, carrying out vacuum freeze drying (the temperature is-79 ℃ and the vacuum degree is 20Pa) on the soaked and exchanged gel sample, and obtaining the nano-clay mineral fiber reinforced three-dimensional structure phenolic resin aerogel material after 4 days. The performance test method is shown in example 1, and the obtained performance data are shown in Table 1.
Example 5
Step 1: putting 25g of sepiolite and 25g of attapulgite into a 500ml stirring barrel, adding 225ml of hydrochloric acid solution with the concentration of 4mol/L, setting the rotation speed of the stirrer to be 1000rpm, stirring for 1h, soaking for 1.8 days, then continuing stirring for 1h at 1000rpm, and carrying out vacuum filtration to obtain a nano clay mineral fiber filter cake; then returning the filter cake to the original stirring barrel, repeatedly washing with deionized water for 7 times, adding 200ml of deionized water during each washing, uniformly stirring, performing suction filtration, and finally putting the filter cake into a vacuum drying oven, and drying for 8 hours at 60 ℃; ball milling, crushing, sieving with 320 mesh sieve, mixing, and packing in sealed bag to obtain acid activated nanometer clay mineral fiber.
Step 2: adding 20g of the acid-activated nano-sepiolite and attapulgite mixed fiber prepared in the step (1) and 900mL of deionized water into a 2000mL stirring barrel, setting the rotation speed of the stirring machine to be 4000rpm, stirring for 2h, adding 6g of gelatin and 6g of polyvinyl alcohol thickener, heating the stirring barrel in a constant-temperature water bath at the temperature of 80 ℃, keeping the rotation speed of the stirring machine to be 4000rpm, continuously stirring for 60min to form a hydrated gel A, freezing the hydrated gel A sample in liquid nitrogen (-196 ℃, freezing for 2min), and freeze-drying in a vacuum freeze-drying machine (the temperature is-79 ℃ and the vacuum degree is 20Pa) for 3 days to obtain a three-dimensional fiber block composite gel material B;
and step 3: adding 180.4g (namely 1.64mol) of resorcinol, 108.2g (namely 3.607mol) of formaldehyde and 2000mL of deionized water into a 3000mL stirring barrel, stirring for 50min when the rotation speed of the stirrer is set to 3500rpm to obtain a uniformly dispersed phenol-aldehyde mixed solution, adding 0.578g (namely 0.00545mol) of sodium carbonate catalyst, continuously stirring for 8min under the condition of 3500rpm to fully dissolve the catalyst and obtain a uniformly mixed solution C;
and 4, step 4: and (3) putting 32g of the three-dimensional fiber block composite gel material B obtained in the step (2) into an impregnation cylinder of a vacuum impregnation machine, adding 1398g of the component C solution prepared in the step (3), sealing, vacuumizing, keeping the pressure in the vacuum impregnation container at 15kPa for 40min, opening a sealing cover, standing for 40min, taking out, putting into a 3000ml reaction kettle, heating in a multipurpose microwave chemical synthesizer, heating to 60 ℃, keeping the temperature for 120min, crosslinking, solidifying the gel, adding 1500ml of n-hexane solvent, soaking and exchanging for 3 days, replacing the solvent every 24h, performing vacuum freeze drying (the temperature is-79 ℃, the vacuum degree is 20Pa) on the soaked and exchanged gel sample, and obtaining the nano-clay mineral fiber reinforced three-dimensional structure phenolic resin aerogel material after 3 days. The performance test method is shown in example 1, and the obtained performance data are shown in Table 1.
Example 6
Step 1: putting 50g of wollastonite into a 500ml stirring barrel, adding 200ml of hydrochloric acid solution with the concentration of 1mol/L, setting the rotating speed of a stirrer to be 1000rpm, stirring for 1h, soaking for 2 days, then continuing stirring for 1h at 1000rpm, and carrying out vacuum filtration to obtain a nano clay mineral fiber filter cake; then returning the filter cake to the original stirring barrel, repeatedly washing for 5 times by using deionized water, adding 200ml of deionized water during each washing, uniformly stirring, carrying out suction filtration, finally putting the filter cake into a vacuum drying oven, and drying for 8 hours at 60 ℃; ball milling, crushing, sieving with 300 mesh sieve, mixing, and packing in sealed bag to obtain acid activated nanometer clay mineral fiber.
Step 2: adding 20g of the acid-activated nano wollastonite fiber prepared in the step (1) and 600mL of deionized water into a 2000mL stirring barrel, setting the rotating speed of the stirrer to 3500rpm, stirring for 2.5h, adding 8g of gelatin and 8g of polyacrylic acid thickener, heating the stirring barrel in a constant-temperature water bath at the temperature of 85 ℃, keeping the rotating speed of the stirrer to 3500rpm, continuously stirring for 50min to form a hydrated gel A, placing the hydrated gel A sample in liquid nitrogen for (-196 ℃ for 2min), freezing, and freeze-drying in a vacuum freeze-drying machine (the temperature is-79 ℃ and the vacuum degree is 20Pa) for 3 days to obtain a three-dimensional fiber block composite gel material B;
and step 3: adding 150.15g (namely 1.365mol) of resorcinol, 150.15g (namely 1.365mol) of hydroquinone, 196.56g (namely 6.552mol) of formaldehyde and 2000mL of deionized water into a 3000mL stirring barrel, stirring for 40min when the rotating speed of the stirrer is 6000rpm to obtain a uniformly dispersed phenol-aldehyde mixed solution, adding 0.241g (namely 0.00227mol) of sodium carbonate catalyst and 0.168g (namely 0.00227mol) of calcium hydroxide catalyst, and continuously stirring for 5min under the condition of 6000rpm to fully dissolve the catalysts and obtain a uniformly mixed solution C;
and 4, step 4: and (3) putting 36g of the three-dimensional fiber block composite gel material B obtained in the step (2) into an impregnation cylinder of a vacuum impregnation machine, adding 826.8g of the component C solution prepared in the step (3), sealing, vacuumizing, keeping the pressure in the vacuum impregnation container at 6kPa for 10min, opening a sealing cover, standing for 10min, taking out, putting into a 3000ml reaction kettle, heating in a multipurpose microwave chemical synthesizer, heating to 100 ℃, keeping the temperature for 40min, crosslinking, solidifying the gel, adding 500ml of acetone and 500ml of n-heptane solvent, soaking for exchange for 3 days, replacing the solvent every 24h, carrying out vacuum freeze drying (the temperature is-79 ℃ and the vacuum degree is 20Pa) on the soaked and exchanged gel sample, and obtaining the nano-clay mineral fiber reinforced three-dimensional structure phenolic resin aerogel material after 3 days. The performance test method is shown in example 1, and the obtained performance data are shown in Table 1.
Example 7
Step 1: putting 25g of halloysite and 25g of sepiolite into a 500ml stirring barrel, adding 150ml of hydrochloric acid solution with the concentration of 4mol/L, setting the rotation speed of the stirrer to be 1000rpm, stirring for 1h, soaking for 2 days, then continuing stirring for 1h at 1000rpm, and carrying out vacuum filtration to obtain a nano clay mineral fiber filter cake; then returning the filter cake to the original stirring barrel, repeatedly washing with deionized water for 7 times, adding 200ml of deionized water during each washing, uniformly stirring, performing suction filtration, and finally putting the filter cake into a vacuum drying oven, and drying for 8 hours at 60 ℃; ball milling, crushing, sieving with 250 mesh sieve, mixing, and packing in sealed bag to obtain acid activated nanometer clay mineral fiber.
Step 2: adding 20g of the acid-activated nano halloysite and sepiolite mixed fiber prepared in the step (1) and 1200mL of deionized water into a 2000mL stirring barrel, setting the rotation speed of the stirring machine to be 4000rpm, stirring for 2h, adding 6g of gelatin and 6g of starch thickener, heating the stirring barrel in a constant-temperature water bath at the temperature of 90 ℃, keeping the rotation speed of the stirring machine to be 4000rpm, continuously stirring for 40min to form a hydrated gel A, freezing the hydrated gel A sample in liquid nitrogen (-196 ℃ for 2min), and freeze-drying in a vacuum freeze-drying machine (the temperature is-79 ℃ and the vacuum degree is 20Pa) for 3 days to obtain a three-dimensional fiber block composite gel material B;
and step 3: adding 200.2g (namely 1.82mol) of resorcinol, 54.6g (namely 1.82mol) of formaldehyde, 174.72g (namely 1.82mol) of furfural and 2000mL of deionized water into a 3000mL stirring barrel, stirring for 50min when the rotation speed of a stirrer is 4000rpm to obtain a uniformly dispersed phenol-aldehyde mixed solution, adding 0.241g (namely 0.00227mol) of sodium hydroxide catalyst 0.0908g (namely 0.00227mol) of sodium carbonate catalyst, and continuously stirring for 7min under the condition of 4000rpm to fully dissolve the catalyst and obtain a uniformly mixed solution C;
and 4, step 4: and (3) putting 32g of the three-dimensional fiber block composite gel material B obtained in the step (2) into an impregnation cylinder of a vacuum impregnation machine, adding 1724.8g of the component C solution prepared in the step (3), sealing, vacuumizing, keeping the pressure in the vacuum impregnation container at 12kPa for 30min, opening a sealing cover, standing for 30min, taking out, putting into a 3000ml reaction kettle, heating in a multipurpose microwave chemical synthesizer, heating to 70 ℃, keeping the temperature for 110min, crosslinking, solidifying the gel, adding 2000ml of absolute ethyl alcohol solvent, soaking for 4 days, replacing the solvent every 24h, performing vacuum freeze drying (the temperature is-79 ℃, the vacuum degree is 20Pa) on the soaked and exchanged gel sample, and obtaining the nano-clay mineral fiber reinforced three-dimensional structure phenolic resin aerogel material after 4 days. The performance test method is shown in example 1, the obtained performance data are shown in Table 1, and the SEM spectrum is shown in FIG. 1.
From the figure, the pore size distribution of the aerogel is wide, mesoporous with the pore diameter of 2-50nm exists, and macroporous with the pore diameter of more than 50nm exists, so that the aerogel is a porous material with step distribution.
(1) The apparent density is measured by Archimedes drainage method, and the specific operation method comprises drying the sample to be measured, and weighing the dry weight m1(ii) a Then, placing the weighed sample in a drying container, vacuumizing for 30min, exhausting gas in the bottle and the air holes in the sample, injecting a proper amount of distilled water to enable the liquid level of the distilled water to be submerged over the surface of the sample, and continuously vacuumizing for 30min to saturate the sample; finally, the sample is taken out, and the weight m of the sample in the water is measured successively2And saturated wet weight m in air3. The bulk density was calculated according to the following formula.
Bulk density
(2) Mechanical property determination, cutting a sample into a cube of 20 multiplied by 20mm (length multiplied by width multiplied by height) by a sharp paper cutter, testing the mechanical property of the composite three-dimensional aerogel material by a CMT-6104 type electronic universal tensile testing machine, wherein the compression rate is 2mm/min, at least more than 12 samples are cut out from each group of samples, and after the test, the average value is taken as the strength value;
(3) the thermal conductivity of the samples was measured by cutting the samples into rectangular blocks of 40X 5mm (length X width X height) with a sharp paper cutter, measuring the thermal conductivity of the samples with a TC 3000E hot wire thermal conductivity meter, cutting out at least 4 samples per group of samples, measuring 3 data per sample, and taking the mean value as the thermal conductivity.
TABLE 1 Properties of the nanoclay mineral fiber-reinforced three-dimensional structure phenolic resin aerogel material obtained in the example
| Serial number | Apparent density (g/cm)3) | Compressive strength (MPa) | Thermal conductivity (W/(m.K)) |
| Example 1 | 0.10 | 0.8 | 0.012 |
| Example 2 | 0.23 | 2.4 | 0.029 |
| Example 3 | 0.14 | 1.5 | 0.018 |
| Example 4 | 0.11 | 2.0 | 0.015 |
| Example 5 | 0.15 | 1.6 | 0.021 |
| Example 6 | 0.24 | 2.5 | 0.034 |
| Example 7 | 0.19 | 1.8 | 0.025 |
In conclusion, the activated and dispersed nano clay mineral fiber and the organic thickening agent are used as raw materials, the raw materials are stirred and dispersed in a constant-temperature water bath to prepare uniform dispersion liquid, and then the uniform dispersion liquid is subjected to vacuum freeze drying to prepare the clay mineral fiber gel material with the three-dimensional structure; placing the gel material into a mixed reaction system containing a phenolic compound and an aldehyde compound, and obtaining a three-dimensional structure clay mineral porous hydrogel material coated by phenolic resin through vacuum impregnation, microwave heating, in-situ polymerization and gel curing; the porous hydrogel material is put into a beaker filled with an organic solvent to replace the water in the hydrogel material, reduce the surface tension of the solution and the shrinkage rate of a sample, and finally, the composite aerogel material with high strength and low heat conductivity coefficient is formed by vacuum freeze drying.
The invention is not the best known technology.
Claims (10)
1. A method for preparing a three-dimensional structure phenolic resin aerogel material reinforced by nano clay mineral fibers is characterized by comprising the following steps:
(1) activation of clay mineral fibers: mixing clay mineral fiber with hydrochloric acid solution, soaking for 1-3 days, and vacuum filtering to obtain nano clay mineral fiber filter cake; washing, filtering, and drying at 60 deg.C for 8 hr; ball-milling and crushing, and sieving with a 250-350 mesh sieve to obtain acid activated nano clay mineral fibers;
wherein 150-250ml of hydrochloric acid solution with the concentration of 0.5-4mol/L is added into every 50g of clay mineral fiber; stirring for 1 hour by a stirrer before and after soaking respectively;
(2) preparing a nano clay mineral fiber three-dimensional composite material: adding deionized water into the acid-activated nano clay mineral fiber prepared in the step (1), stirring for 2-3h, adding an organic thickener, continuously stirring for 30-90min in a constant-temperature water bath at 60-90 ℃ to form a hydrated gel A, placing a sample of the hydrated gel A in liquid nitrogen for freezing, and placing the sample in a vacuum freeze dryer for freeze drying for 3 days to obtain a three-dimensional fiber block composite gel material B;
wherein, 20-60ml deionized water is added into each g of acid activated nano clay mineral fiber; acid activated nanoclay mineral fiber: the mass ratio of the thickening agent is =1: 0.2-1;
(3) preparation of phenolic solution: stirring a phenolic compound, an aldehyde compound and deionized water for 30-60min, adding a catalyst, and continuously stirring for 3-10 min to obtain a solution C;
wherein, the phenolic compound: the molar ratio of the aldehyde compound is =1: 1.5-2.6; catalyst: the molar ratio of the phenolic compounds is =1: 100-1000; adding 0.475-1.365mol of phenolic compounds into every 1000ml of deionized water;
(4) nano clay mineral fiber reinforced three-dimensional structure phenolic resin aerogel material: putting the three-dimensional fiber block composite gel material B obtained in the step (2) into an impregnation cylinder of a vacuum impregnation machine, adding the component C solution prepared in the step (3), sealing, vacuumizing, keeping the pressure in a vacuum impregnation container at 5-20kPa for 5-60min, opening a sealing cover, standing for 5-60min, taking out, putting into a reaction kettle, heating to 50-120 ℃ by microwave, adding the organic solvent into the organic solvent for soaking for 3-5 days after the gel is solidified for 30-150min, replacing the organic solvent every 24h, then carrying out vacuum freeze drying on the gel, and obtaining the nano-clay mineral fiber reinforced three-dimensional structure phenolic resin aerogel material after 3-5 days;
wherein, in the step (2): the mass ratio of the component C is 1: 1.2-1.8;
the nano clay mineral fiber in the step (1) is one or a mixture of two of purified and enriched sepiolite, attapulgite, brucite, halloysite or wollastonite mineral fibers in equal mass.
2. The method for preparing the phenolic resin aerogel material with a three-dimensional structure reinforced by the nano-clay mineral fibers as claimed in claim 1, wherein the organic thickener in the step (2) is one or a mixture of two of starch, gelatin, polyvinyl alcohol and polyacrylic acid.
3. The method for preparing the phenolic resin aerogel material with three-dimensional structure reinforced by the nano-clay mineral fibers as claimed in claim 1, wherein the phenolic compound in the step (3) is one of resorcinol or hydroquinone or an equimolar mixture thereof.
4. The method for preparing a three-dimensional structure phenolic resin aerogel material reinforced by nanoclay mineral fibers as claimed in claim 1, wherein the aldehyde compound in step (3) is one of formaldehyde or furfural or an equimolar mixture thereof.
5. The method for preparing the phenolic resin aerogel material with three-dimensional structure reinforced by the nano-clay mineral fibers as claimed in claim 1, wherein the catalyst in the step (3) is one or two of sodium carbonate, sodium hydroxide or calcium hydroxide in equimolar mixture.
6. The method for preparing the three-dimensional structural phenolic resin aerogel material reinforced by nanoclay mineral fibers as claimed in claim 1, wherein the organic solvent in step (4) is one or two solvents of absolute ethyl alcohol, acetone, n-hexane or n-heptane in equal volume.
7. The method for preparing the three-dimensional structure phenolic resin aerogel material reinforced with nanoclay mineral fibers as recited in claim 1, wherein said microwave heating apparatus in step (4) is a multi-purpose microwave chemical synthesizer.
8. The method for preparing the phenolic resin aerogel material having a three-dimensional structure reinforced with nanoclay mineral fibers as claimed in claim 1, wherein the rotation speed of the stirrer in step (1) is 1000 rpm; the rotating speed of the stirrer in the step (2) is 2000-4000 rpm; the rotation speed of the stirrer in the step (3) is 3000-6000 rpm.
9. The method of claim 1, wherein the nanoclay mineral fiber-reinforced three-dimensional structure phenolic aerogel material has an apparent density of 0.10g/cm3-0.24 g/cm3The heat conductivity coefficient is 0.012-0.034W/(m.K), and the compressive strength is 0.8MPa-2.5 MPa.
10. The method for preparing the phenolic resin aerogel material with three-dimensional structure reinforced by nanoclay mineral fibers as claimed in claim 1, wherein the vacuum freeze-drying conditions in steps (2) and (4) are-79 ℃ and 20 Pa.
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