CN108129797A - The preparation method of nanoporous Zeolite modifying makrolon foamed thermal insulating in a kind of vacuum heat-insulating plate composite core material - Google Patents

The preparation method of nanoporous Zeolite modifying makrolon foamed thermal insulating in a kind of vacuum heat-insulating plate composite core material Download PDF

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CN108129797A
CN108129797A CN201711438935.8A CN201711438935A CN108129797A CN 108129797 A CN108129797 A CN 108129797A CN 201711438935 A CN201711438935 A CN 201711438935A CN 108129797 A CN108129797 A CN 108129797A
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fiber
nanometer
core material
makrolon
zeolite
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魏亮
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Ningbo Hi Tech Zone Xia Yuan Technology Co Ltd
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Ningbo Hi Tech Zone Xia Yuan Technology Co Ltd
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Abstract

The invention discloses a kind of preparation method of nanoporous Zeolite modifying makrolon foamed thermal insulating in vacuum heat-insulating plate composite core material, the composite core material is by nanometer Bi2Te3Modified cyanurotriamide formal fiber, nanoporous Zeolite modifying makrolon foamed thermal insulating and fiber aerogel composite press (10 12)：(5‑6)：What the weight ratio of (2 4) was combined.The present invention screens inorganic nano particle modified organic fiber flexibility heat-insulating material, improves the anti-brittleness of core material；By carrying out efficient combination with Inorganic whisker expanded material, the thermal conductivity factor and density of core material further reduced, it is ensured that composite core material has preferable heat-insulating property.

Description

The poly- carbonic acid of nanoporous Zeolite modifying in a kind of vacuum heat-insulating plate composite core material The preparation method of ester foaming heat-insulating material
The application is divisional application, original bill Patent No.：201610290809.1 the applying date is on April 27th, 2016, hair It is bright entitled：A kind of vacuum heat-insulating plate composite core material and preparation method.
Technical field
The present invention relates to vacuum heat-insulating plate fields, and in particular to a kind of vacuum heat-insulating plate composite core material and preparation side Method is suitable for the thermal insulation material of refrigerator, refrigerator.
Background technology
With the gradual enhancing that people realize energy-saving and emission-reduction, the development and application to new energy, new technology, new material Propose new requirement.At present, in the insulated cabinet of refrigerator, as heat-insulating material, other than foamed thermal insulating, have The vacuum heat insulation materials of high thermal insulation have been more and more widely used.
Vacuum heat-insulating plate is as a kind of novel thermal insulation material, and thermal conductivity factor is low, thickness is thin, therefore in refrigerator, cold The fields such as library, Medical heat-preserving box reduce energy consumption, improve economy, and vacuum heat-insulating plate has huge development potentiality.It is exhausted in vacuum In hot plate, the selection of core material is extremely important.At present, most commonly used core material have porous silica aerogel, silica xerogel, White carbon, calcined silica, since these materials have porous structure so that it is extensive with relatively low thermal conductivity factor Using.
Chinese patent CN103032653A discloses a kind of vacuum heat-insulating plate composite core material and preparation method, big in patent Amount has used gas phase SiO2Composite core material vacuum heat insulation plate is prepared for inorganic material such as glass fibres, thermal conductivity factor is 0.0038W/(m·K).But due to largely using inorganic SiO2Material causes the brittleness of core material larger, in extrusion forming process In, these inorganic powder materials can be extracted when vacuumizing, and so as to influence the leakproofness of vacuum heat-insulating plate, reduce its heat insulating ability Energy.
Therefore, how to select that there is the excellent flexibility heat-insulating material of relatively low thermal conductivity coefficient to have a very important significance.
Invention content
In order to solve the problems, such as that vacuum heat-insulating plate exists in the prior art, the invention discloses one kind to have low thermal conductivity coefficient With the vacuum heat-insulating plate composite core material and preparation method of the crisp ability of highly resistance.
To achieve the above objectives, the technical solution adopted by the present invention is：
A kind of vacuum heat-insulating plate composite core material, the composite core material are by nanometer Bi2Te3Modified melamine Amine formal fiber, nanoporous Zeolite modifying makrolon foamed thermal insulating and fiber-aerogel composite press (10- 12)：(5-6)：What the weight ratio of (2-4) was combined.
Preferably, the nanometer Bi2Te3Nanometer Bi in modified cyanurotriamide formal fiber2Te3Shared mass fraction is 8-10%.
Preferably, quality shared by nanoporous zeolite in the nanoporous Zeolite modifying makrolon foamed thermal insulating Number is 5-8%.
Preferably, the density of the composite core material is less than 0.35g/cm3, the small 0.02W/ of thermal conductivity factor (mK).
As a kind of preferred embodiment, the nanometer Bi2Te3Modified cyanurotriamide formal fiber is by such as lower section What method was prepared：
(1) bismuth chloride, tellurium powder, potassium hydroxide, sodium borohydride are dissolved in N-N- dimethylformamides, by the solution of gained Carry out the hydro-thermal reaction 20-28h at 110-160 DEG C, cooled to room temperature after hydro-thermal reaction, after filtered, washing, 10-15h is dried in vacuo at 75-85 DEG C and obtains a nanometer Bi2Te3；Wherein, the substance of bismuth chloride, tellurium powder, potassium hydroxide, sodium borohydride The ratio between amount be 2:3:(0.4-0.6):The amount ratio of (0.3-0.5), bismuth chloride and the substance of N-N- dimethylformamides is 1:5；
(2) by formaldehyde, nanometer Bi2Te325- is stirred with the rate of 300-500r/min at 35-45 DEG C with stabilizer After 35min, 75 DEG C are warming up to, adds in melamine, and it is 10.0 to adjust pH value with triethanolamine, improves mixing speed extremely Its pH is adjusted to 7.0 after 600r/min reactions 2h, is uniformly mixed and obtains stoste, using dry spinning to nanometer Bi2Te3Modified three Poly cyanamid formal fiber；Wherein, formaldehyde, nanometer Bi2Te3, melamine and stabilizer mass ratio be 0.4:(0.08- 0.1):0.6:0.01。
Preferably, during dry spinning, concentration of dope 15-25%, spinneret hole count be 800-1200 holes, orifice diameter For 0.05-0.07mm, spinning speed 250-350m/min.
A kind of preferred preparation method of the nanoporous Zeolite modifying makrolon foamed thermal insulating is：
(1) tetrapropyl amine aqueous solution and ethyl orthosilicate are added sequentially in water, at ambient temperature 300-500r/min Speed stirring 22-26h after, add in aluminium isopropoxide, then with continue under the velocity conditions of 500-700r/min stir 20-28h obtain To the colloidal sol containing silicon and aluminium, ethyl orthosilicate, tetraethyl amine, water, aluminium isopropoxide in the sol system containing silicon and aluminium The ratio between the amount of substance be 1:(0.3-0.35):(17.5-18.5):(0.003-0.004)；By the colloidal sol containing silicon and aluminium successively Carry out microwave radiation technology aging reaction, the segmentation hydrothermal crystallizing reaction of 48h, after the completion of crystallization, gained crystallization product through vacuum filtration, Washing, 105-115 DEG C of drying 10h obtain the molecular sieve of Nano zeolite that grain size is 80-100nm；Wherein, segmentation hydrothermal crystallizing reaction It is divided to two sections, 78-82 DEG C of first segment hydrothermal crystallizing temperature, crystallization time 85-95min；Second segment hydrothermal crystallizing temperature 118-122 DEG C, crystallization time 25-35min；
(2) ethyl alcohol and water are pressed 1:1 volume ratio is mixed to get alcohol solution, with the hydrochloric acid of 1mol/L by alcohol solution PH value is adjusted to 5.0, and to obtain mixed solution spare；Molecular sieve of Nano zeolite is added in the mixed solution, is then transferred to With 15-25min is handled in 45-55 DEG C of water-bath of ultrasonic wave and stirring, the wherein power of ultrasonic wave is 10W, the rotating speed of stirring For 400r/min, γ-(methacryloxypropyl) propyl trimethoxy silicane continuation is then added dropwise and stirs under the same conditions 2h, then after being filtered, washed, dried, grinding, modified nano-zeolite molecular sieve is obtained, wherein, molecular sieve of Nano zeolite and second The mass volume ratio of alcohol is 0.08-0.12g/mL, molecular sieve of Nano zeolite and γ-(methacryloxypropyl) propyl trimethoxy silicon The mass ratio of alkane is 9-11:1；
(3) makrolon of 10-15h dry at 115-125 DEG C is added in mixing machine, in 248-252 DEG C of stirring After melting 25-35min, addition modified nano-zeolite molecular sieve continues stirring melting mixing 1h and obtains melt blended material, will melt Blend is put into 25 DEG C of autoclave, with the CO of 45-50MPa2Rapid release after saturation punching press 30h, the melting after saturation Blend is put into glycerol bath the 40-60s that foams, then is placed in ice-water bath and cools down the 2min acquisition poly- carbonic acid of nanoporous Zeolite modifying Ester foaming heat-insulating material.
Preferably, what the fiber-aerogel composite can be prepared via a method which：
(1) ethyl orthosilicate and absolute ethyl alcohol are pressed 1:6 volume ratio in 38-42 DEG C of water-bath, 350-450r/min's Speed is stirred 50-70min, and the dilute hydrochloric acid of 0.2mol/L is added dropwise in whipping process, continues to stir 30min after the completion, Standing is fully hydrolyzed it for 24 hours；Then stir 25-35min under the speed of 500-700r/min, and during stirring by N,N-Dimethylformamide, distilled water and ammonium hydroxide are added dropwise to, obtains dilute salt of Ludox, wherein ethyl orthosilicate, 0.2mol/L Acid, N,N-dimethylformamide, distilled water and ammonium hydroxide volume ratio be 5:10:1:5:2；
(2) it between fibrofelt is sandwiched in stainless steel plate according to original thickness, is put into rustless steel container, vacuumizes, utilize air Pressure and using bottom filling by Ludox impregnated fiber from the bottom up, be sealed fiber/colloidal sol complex, treat further old Change；
(3) fiber/colloidal sol complex is put into autoclave, seals, protected under the conditions of 240-250 DEG C, 6-7Mpa Ethyl alcohol is released after warm 1.5-2.5h, you can fibre-reinforced aerogel flexible composite is made.
Preferably, the stabilizer is polyvinyl alcohol.
The invention discloses the preparation method of the composite core material, specially：By the nanometer Bi of corresponding parts by weight2Te3 Modified cyanurotriamide formal fiber, nanoporous Zeolite modifying makrolon foamed thermal insulating and fiber-aeroge are compound Material is filled into the bag film of a side opening, and bag film sealing is placed in die forming machine after filling, makes filling Material is uniformly distributed in bag film, and filler material is press-formed under the briquetting pressure of 48-52MPa, is finally unloaded Die pressure, demoulding obtain molding core material.
Compared with prior art, the present invention it has the following advantages that：It is flexible absolutely to screen inorganic nano particle modified organic fiber Hot material improves the anti-brittleness of core material；By carrying out efficient combination with inorganic-organic hybrid expanded material, further Reduce the thermal conductivity factor and density of core material, it is ensured that composite core material has preferable heat-insulating property.
Specific embodiment
It is described below to disclose the present invention so that those skilled in the art can realize the present invention.It is excellent in being described below Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.
Embodiment 1
A kind of vacuum heat-insulating plate composite core material is by nanometer Bi2Te3Modified cyanurotriamide formal fiber, nanometer Porous zeolite modified polycarbonate foamed thermal insulating and fiber-aerogel composite press 5:3:2 weight ratio is filled into one In the bag film of side opening, bag film sealing is placed in die forming machine after filling, packing material is made uniformly to divide It is distributed in bag film, filler material is press-formed under the briquetting pressure of 50MPa, finally unload die pressure, demould To molding core material.
Wherein, the nanometer Bi2Te3Modified cyanurotriamide formal fiber is prepared via a method which：
(1) bismuth chloride and tellurium powder, potassium hydroxide, sodium borohydride are dissolved in N-N- dimethylformamides, by the molten of gained Liquid carries out the hydro-thermal reaction 28h at 110 DEG C, cooled to room temperature after hydro-thermal reaction, after filtered, washing, at 80 DEG C Lower vacuum drying 12h obtains a nanometer Bi2Te3；Wherein, the ratio between amount of substance of bismuth chloride, tellurium powder, potassium hydroxide, sodium borohydride is 2:3:0.4:0.5, the amount ratio of the substance of bismuth chloride and N-N- dimethylformamides is 1:5；
(2) by formaldehyde, nanometer Bi2Te3After 30min being stirred with polyvinyl alcohol at 40 DEG C with the rate of 400r/min, heating To 75 DEG C, the melamine of 12.6g is added in, and it is 10.0 to adjust pH value with triethanolamine, improves mixing speed to 600r/min Its pH is adjusted to 7.0 after reaction 2h, is uniformly mixed and obtains stoste, use dry spinning (concentration of dope 20%, spinneret hole count For 1000 holes, orifice diameter 0.06mm, spinning speed 300m/min) to nanometer Bi2Te3Modified cyanurotriamide formal Fiber；Wherein, formaldehyde, nanometer Bi2Te3, melamine and polyvinyl alcohol mass ratio be 0.4:0.08:0.6:0.01；Wherein receive Rice Bi2Te3Shared mass fraction is 8%.
The preparation method of the nanoporous Zeolite modifying makrolon foamed thermal insulating is：
(1) tetrapropyl amine aqueous solution and ethyl orthosilicate are added sequentially in water, at ambient temperature the speed of 400r/min After degree stirring 22h, aluminium isopropoxide is added in, then obtain containing silicon and aluminium to continue to stir 28h under the velocity conditions of 600r/min Colloidal sol, the ratio between amount of substance of ethyl orthosilicate, tetraethyl amine, water, aluminium isopropoxide in the sol system containing silicon and aluminium It is 1:0.3:18.5:0.004；Microwave radiation technology aging reaction, the segmentation hydro-thermal that colloidal sol containing silicon and aluminium is carried out to 48h successively are brilliant Change reaction, after the completion of crystallization, gained crystallization product is through being filtered by vacuum, washing, to obtain grain size be 80-85nm's to 110 DEG C of drying 10h Molecular sieve of Nano zeolite；Wherein, the reaction of segmentation hydrothermal crystallizing is divided to two sections, 80 DEG C of first segment hydrothermal crystallizing temperature, crystallization time 90min；120 DEG C of second segment hydrothermal crystallizing temperature, crystallization time 30min；
(2) ethyl alcohol and water are pressed 1:1 volume ratio is mixed to get alcohol solution, with the hydrochloric acid of 1mol/L by alcohol solution PH value is adjusted to 5.0, and to obtain mixed solution spare；Molecular sieve of Nano zeolite is added in the mixed solution, is then transferred to With 20min is handled in 50 DEG C of water-baths of ultrasonic wave and stirring, the wherein power of ultrasonic wave is 10W, and the rotating speed of stirring is 400r/ Then min is added dropwise γ-(methacryloxypropyl) propyl trimethoxy silicane and continues to stir 2h under the same conditions, then into Row is filtered, is washed, is dry, after grinding, obtains modified nano-zeolite molecular sieve, wherein, the matter of molecular sieve of Nano zeolite and ethyl alcohol Amount volume ratio is 0.1g/mL, and the mass ratio of molecular sieve of Nano zeolite and γ-(methacryloxypropyl) propyl trimethoxy silicane is 10:1；
(3) makrolon of 12h dry at 120 DEG C is added in mixing machine, after 250 DEG C of stirring melting 30min, Addition modified nano-zeolite molecular sieve continues stirring melting mixing 1h and obtains melt blended material, and melt blended material is put into 25 DEG C In autoclave, with the CO of 45MPa2Rapid release after saturation punching press 30h, the melt blended material after saturation is put into glycerol bath and sent out 60s is steeped, then is placed in ice-water bath and cools down 2min acquisition nanoporous Zeolite modifying makrolon foamed thermal insulatings, nanoporous Mass fraction shared by zeolite is 5%.
Fiber-the aerogel composite is prepared via a method which：
(1) ethyl orthosilicate and absolute ethyl alcohol are pressed 1:6 volume ratio is in 40 DEG C of water-baths, the speed stirring of 400r/min 1h is mixed, the dilute hydrochloric acid of 0.2mol/L is added dropwise in whipping process, continues to stir 30min after the completion, standing makes it fully for 24 hours Hydrolysis；Then 30min is stirred under the speed of 600r/min, and N is added dropwise during stirring, N- dimethyl formyls Amine, distilled water and ammonium hydroxide, obtain Ludox, wherein ethyl orthosilicate, the dilute hydrochloric acid of 0.2mol/L, n,N-Dimethylformamide, The volume ratio of distilled water and ammonium hydroxide is 5:10:1:5:2；
(2) it between fibrofelt is sandwiched in stainless steel plate according to original thickness, is put into rustless steel container, vacuumizes, utilize air Pressure and using bottom filling by Ludox impregnated fiber from the bottom up, be sealed fiber/colloidal sol complex, treat further old Change；
(3) fiber/colloidal sol complex is put into autoclave, sealed, after heat preservation 2h under the conditions of 250 DEG C, 6Mpa Ethyl alcohol is released, you can fibre-reinforced aerogel flexible composite is made.
Embodiment 2
A kind of vacuum heat-insulating plate composite core material is by nanometer Bi2Te3Modified cyanurotriamide formal fiber, nanometer Porous zeolite modified polycarbonate foamed thermal insulating and fiber-aerogel composite press 11:5:4 weight ratio is filled into one In the bag film of side opening, bag film sealing is placed in die forming machine after filling, packing material is made uniformly to divide It is distributed in bag film, filler material is press-formed under the briquetting pressure of 52MPa, finally unload die pressure, demould To molding core material.
Wherein, the nanometer Bi2Te3Modified cyanurotriamide formal fiber is prepared via a method which：
(1) bismuth chloride, tellurium powder, potassium hydroxide, sodium borohydride are dissolved in N-N- dimethylformamides, by the solution of gained The hydro-thermal reaction 26h at 130 DEG C is carried out, cooled to room temperature after hydro-thermal reaction, after filtered, washing, at 75 DEG C Vacuum drying 15h obtains a nanometer Bi2Te3；Wherein, the ratio between amount of substance of bismuth chloride, tellurium powder, potassium hydroxide, sodium borohydride is 2: 3:0.5:0.4, the amount ratio of the substance of bismuth chloride and N-N- dimethylformamides is 1:5；
(2) by formaldehyde, nanometer Bi2Te3After 25min being stirred with polyvinyl alcohol at 35 DEG C with the rate of 500r/min, heating To 75 DEG C, the melamine of 12.6g is added in, and it is 10.0 to adjust pH value with triethanolamine, improves mixing speed to 600r/min Its pH is adjusted to 7.0 after reaction 2h, is uniformly mixed and obtains stoste, use dry spinning (concentration of dope 15%, spinneret hole count For 1200 holes, orifice diameter 0.05mm, spinning speed 350m/min) to nanometer Bi2Te3Modified cyanurotriamide formal Fiber；Wherein, formaldehyde, nanometer Bi2Te3, melamine and polyvinyl alcohol mass ratio be 0.4:0.09:0.6:0.01；Wherein receive Rice Bi2Te3Shared mass fraction is 9%.
The preparation method of the nanoporous Zeolite modifying makrolon foamed thermal insulating is：
(1) tetrapropyl amine aqueous solution and ethyl orthosilicate are added sequentially in water, at ambient temperature with 300r/min's After speed stirring 26h, aluminium isopropoxide is added in, then obtain containing silicon and aluminium to continue to stir 28h under the velocity conditions of 500r/min Colloidal sol, ethyl orthosilicate in the sol system containing silicon and aluminium, tetraethyl amine, water, aluminium isopropoxide substance amount it Than being 1:0.32:18:0.003；Colloidal sol containing silicon and aluminium is carried out to microwave radiation technology aging reaction, the segmentation hydro-thermal of 48h successively Crystallization, after the completion of crystallization, gained crystallization product is through being filtered by vacuum, washing, 105 DEG C of drying 10h obtain grain size as 85-90nm Molecular sieve of Nano zeolite；Wherein, the reaction of segmentation hydrothermal crystallizing is divided to two sections, 78 DEG C of first segment hydrothermal crystallizing temperature, crystallization time 95min；118 DEG C of second segment hydrothermal crystallizing temperature, crystallization time 35min；
(2) ethyl alcohol and water are pressed 1:1 volume ratio is mixed to get alcohol solution, with the hydrochloric acid of 1mol/L by alcohol solution PH value is adjusted to 5.0, and to obtain mixed solution spare；Molecular sieve of Nano zeolite is added in the mixed solution, is then transferred to With 25min is handled in 45 DEG C of water-baths of ultrasonic wave and stirring, the wherein power of ultrasonic wave is 10W, and the rotating speed of stirring is 400r/ Then min is added dropwise γ-(methacryloxypropyl) propyl trimethoxy silicane and continues to stir 2h under the same conditions, then into Row is filtered, is washed, is dry, after grinding, obtains modified nano-zeolite molecular sieve, wherein, the matter of molecular sieve of Nano zeolite and ethyl alcohol Amount volume ratio is the mass ratio of 0.08g/mL, molecular sieve of Nano zeolite and γ-(methacryloxypropyl) propyl trimethoxy silicane It is 9:1；
(3) makrolon of 15h dry at 115 DEG C is added in mixing machine, after 248 DEG C of stirring melting 35min, Addition modified nano-zeolite molecular sieve continues stirring melting mixing 1h and obtains melt blended material, and melt blended material is put into 25 DEG C In autoclave, with the CO of 46MPa2Rapid release after saturation punching press 30h, the melt blended material after saturation is put into glycerol bath and sent out 40s is steeped, then is placed in ice-water bath and cools down 2min acquisition nanoporous Zeolite modifying makrolon foamed thermal insulatings, nanoporous Mass fraction shared by zeolite is 5.5%.
Fiber-the aerogel composite is prepared via a method which：
(1) ethyl orthosilicate and absolute ethyl alcohol are pressed 1:6 volume ratio is in 38 DEG C of water-baths, the speed stirring of 350r/min 70min is mixed, the dilute hydrochloric acid of 0.2mol/L is added dropwise in whipping process, continues to stir 30min after the completion, standing makes it for 24 hours It is fully hydrolyzed；Then 35min is stirred under the speed of 500r/min, and N is added dropwise during stirring, N- dimethyl methyls Amide, distilled water and ammonium hydroxide obtain Ludox, wherein ethyl orthosilicate, the dilute hydrochloric acid of 0.2mol/L, N, N- dimethyl formyls The volume ratio of amine, distilled water and ammonium hydroxide is 5:10:1:5:2；
(2) it between fibrofelt is sandwiched in stainless steel plate according to original thickness, is put into rustless steel container, vacuumizes, utilize air Pressure and using bottom filling by Ludox impregnated fiber from the bottom up, be sealed fiber/colloidal sol complex, treat further old Change；
(3) fiber/colloidal sol complex is put into autoclave, seals, kept the temperature under the conditions of 246 DEG C, 6.5Mpa Ethyl alcohol is released after 2.2h, you can fibre-reinforced aerogel flexible composite is made.
Embodiment 3
A kind of vacuum heat-insulating plate composite core material is by nanometer Bi2Te3Modified cyanurotriamide formal fiber, nanometer Porous zeolite modified polycarbonate foamed thermal insulating and fiber-aerogel composite press 11:6:3 weight ratio is filled into one In the bag film of side opening, bag film sealing is placed in die forming machine after filling, packing material is made uniformly to divide It is distributed in bag film, filler material is press-formed under the briquetting pressure of 48MPa, finally unload die pressure, demould To molding core material.
Wherein, the nanometer Bi2Te3Modified cyanurotriamide formal fiber is prepared via a method which：
(1) bismuth chloride, tellurium powder, potassium hydroxide, sodium borohydride are dissolved in N-N- dimethylformamides, by the solution of gained Carry out at 140 DEG C hydro-thermal reaction for 24 hours, cooled to room temperature after hydro-thermal reaction, it is filtered, washing after, at 85 DEG C Vacuum drying 10h obtains a nanometer Bi2Te3；Wherein, the ratio between amount of substance of bismuth chloride, tellurium powder, potassium hydroxide, sodium borohydride is 2: 3:0.5:0.5, the amount ratio of the substance of bismuth chloride and N-N- dimethylformamides is 1:5；
(2) by formaldehyde, nanometer Bi2Te3After 25min being stirred with polyvinyl alcohol at 45 DEG C with the rate of 300r/min, heating To 75 DEG C, the melamine of 12.6g is added in, and it is 10.0 to adjust pH value with triethanolamine, improves mixing speed to 600r/min Its pH is adjusted to 7.0 after reaction 2h, is uniformly mixed and obtains stoste, use dry spinning (concentration of dope 25%, spinneret hole count For 800 holes, orifice diameter 0.07mm, spinning speed 250m/min) to nanometer Bi2Te3Modified cyanurotriamide formal is fine Dimension；Wherein, formaldehyde, nanometer Bi2Te3, melamine and polyvinyl alcohol mass ratio be 0.4:0.08:0.6:0.01；Wherein nanometer Bi2Te3Shared mass fraction is 9%.
The preparation method of the nanoporous Zeolite modifying makrolon foamed thermal insulating is：
(1) tetrapropyl amine aqueous solution and ethyl orthosilicate are added sequentially in water, at ambient temperature with 500r/min's After speed stirring 22h, aluminium isopropoxide is added in, then obtain containing silicon and aluminium to continue to stir 20h under the velocity conditions of 700r/min Colloidal sol, ethyl orthosilicate in the sol system containing silicon and aluminium, tetraethyl amine, water, aluminium isopropoxide substance amount it Than being 1:0.34:18:0.004；Colloidal sol containing silicon and aluminium is carried out to microwave radiation technology aging reaction, the segmentation hydro-thermal of 48h successively Crystallization, after the completion of crystallization, gained crystallization product is through being filtered by vacuum, washing, 115 DEG C of drying 10h obtain grain size as 90-95nm Molecular sieve of Nano zeolite；Wherein, the reaction of segmentation hydrothermal crystallizing is divided to two sections, 82 DEG C of first segment hydrothermal crystallizing temperature, crystallization time 85min；122 DEG C of second segment hydrothermal crystallizing temperature, crystallization time 25min；
(2) ethyl alcohol and water are pressed 1:1 volume ratio is mixed to get alcohol solution, with the hydrochloric acid of 1mol/L by alcohol solution PH value is adjusted to 5.0, and to obtain mixed solution spare；Molecular sieve of Nano zeolite is added in the mixed solution, is then transferred to With 15min is handled in 55 DEG C of water-baths of ultrasonic wave and stirring, the wherein power of ultrasonic wave is 10W, and the rotating speed of stirring is 400r/ Then min is added dropwise γ-(methacryloxypropyl) propyl trimethoxy silicane and continues to stir 2h under the same conditions, then into Row is filtered, is washed, is dry, after grinding, obtains modified nano-zeolite molecular sieve, wherein, the matter of molecular sieve of Nano zeolite and ethyl alcohol Amount volume ratio is the mass ratio of 0.12g/mL, molecular sieve of Nano zeolite and γ-(methacryloxypropyl) propyl trimethoxy silicane It is 11:1；
(3) makrolon of 10h dry at 125 DEG C is added in mixing machine, after 252 DEG C of stirring melting 25min, Addition modified nano-zeolite molecular sieve continues stirring melting mixing 1h and obtains melt blended material, and melt blended material is put into 25 DEG C In autoclave, with the CO of 50MPa2Rapid release after saturation punching press 30h, the melt blended material after saturation is put into glycerol bath and sent out 60s is steeped, then is placed in ice-water bath and cools down 2min acquisition nanoporous Zeolite modifying makrolon foamed thermal insulatings, nanoporous Mass fraction shared by zeolite is 6%.
Fiber-the aerogel composite is prepared via a method which：
(1) ethyl orthosilicate and absolute ethyl alcohol are pressed 1:6 volume ratio is in 42 DEG C of water-baths, the speed stirring of 450r/min 50min is mixed, the dilute hydrochloric acid of 0.2mol/L is added dropwise in whipping process, continues to stir 30min after the completion, standing makes it for 24 hours It is fully hydrolyzed；Then 25min is stirred under the speed of 700r/min, and N is added dropwise during stirring, N- dimethyl methyls Amide, distilled water and ammonium hydroxide obtain Ludox, wherein ethyl orthosilicate, the dilute hydrochloric acid of 0.2mol/L, N, N- dimethyl formyls The volume ratio of amine, distilled water and ammonium hydroxide is 5:10:1:5:2；
(2) it between fibrofelt is sandwiched in stainless steel plate according to original thickness, is put into rustless steel container, vacuumizes, utilize air Pressure and using bottom filling by Ludox impregnated fiber from the bottom up, be sealed fiber/colloidal sol complex, treat further old Change；
(3) fiber/colloidal sol complex is put into autoclave, seals, kept the temperature under the conditions of 243 DEG C, 6.5Mpa Ethyl alcohol is released after 1.8h, you can fibre-reinforced aerogel flexible composite is made.
Embodiment 4
A kind of vacuum heat-insulating plate composite core material is by nanometer Bi2Te3Modified cyanurotriamide formal fiber, nanometer Porous zeolite modified polycarbonate foamed thermal insulating and fiber-aerogel composite press 12:6:2 weight ratio is filled into one In the bag film of side opening, bag film sealing is placed in die forming machine after filling, packing material is made uniformly to divide It is distributed in bag film, filler material is press-formed under the briquetting pressure of 51MPa, finally unload die pressure, demould To molding core material.
Wherein, the nanometer Bi2Te3Modified cyanurotriamide formal fiber is prepared via a method which：
(1) bismuth chloride, tellurium powder, potassium hydroxide, sodium borohydride are dissolved in N-N- dimethylformamides, by the solution of gained The hydro-thermal reaction 20h at 160 DEG C is carried out, cooled to room temperature after hydro-thermal reaction, after filtered, washing, at 82 DEG C Vacuum drying 13h obtains a nanometer Bi2Te3；Wherein, the ratio between amount of substance of bismuth chloride, tellurium powder, potassium hydroxide, sodium borohydride is 2: 3:0.6:0.3, the amount ratio of the substance of bismuth chloride and N-N- dimethylformamides is 1:5；
(2) by formaldehyde, nanometer Bi2Te3After 30min being stirred with polyvinyl alcohol at 42 DEG C with the rate of 400r/min, heating To 75 DEG C, the melamine of 12.6g is added in, and it is 10.0 to adjust pH value with triethanolamine, improves mixing speed to 600r/min Its pH is adjusted to 7.0 after reaction 2h, is uniformly mixed and obtains stoste, use dry spinning (concentration of dope 18%, spinneret hole count For 1100 holes, orifice diameter 0.06mm, spinning speed 320m/min) to nanometer Bi2Te3Modified cyanurotriamide formal Fiber；Wherein, formaldehyde, nanometer Bi2Te3, melamine and polyvinyl alcohol mass ratio be 0.4:0.1:0.6:0.01；Wherein receive Rice Bi2Te3Shared mass fraction is 10%.
The preparation method of the nanoporous Zeolite modifying makrolon foamed thermal insulating is：
(1) tetrapropyl amine aqueous solution and ethyl orthosilicate are added sequentially in water, at ambient temperature with 350r/min's After speed stirring 25h, aluminium isopropoxide is added in, then obtain containing silicon and aluminium to continue to stir 23h under the velocity conditions of 650r/min Colloidal sol, ethyl orthosilicate in the sol system containing silicon and aluminium, tetraethyl amine, water, aluminium isopropoxide substance amount it Than being 1:0.35:17.5:0.003；Colloidal sol containing silicon and aluminium is carried out to microwave radiation technology aging reaction, the segmentation water of 48h successively Thermal crystallisation reacts, and after the completion of crystallization, gained crystallization product is through being filtered by vacuum, washing, 112 DEG C of drying 10h obtain grain size as 95- The molecular sieve of Nano zeolite of 100nm；Wherein, the reaction of segmentation hydrothermal crystallizing is divided to two sections, 81 DEG C of first segment hydrothermal crystallizing temperature, crystallization Time 92min；121 DEG C of second segment hydrothermal crystallizing temperature, crystallization time 28min；
(2) ethyl alcohol and water are pressed 1:1 volume ratio is mixed to get alcohol solution, with the hydrochloric acid of 1mol/L by alcohol solution PH value is adjusted to 5.0, and to obtain mixed solution spare；Molecular sieve of Nano zeolite is added in the mixed solution, is then transferred to With 18min is handled in 52 DEG C of water-baths of ultrasonic wave and stirring, the wherein power of ultrasonic wave is 10W, and the rotating speed of stirring is 400r/ Then min is added dropwise γ-(methacryloxypropyl) propyl trimethoxy silicane and continues to stir 2h under the same conditions, then into Row is filtered, is washed, is dry, after grinding, obtains modified nano-zeolite molecular sieve, wherein, the matter of molecular sieve of Nano zeolite and ethyl alcohol Amount volume ratio is the mass ratio of 0.09g/mL, molecular sieve of Nano zeolite and γ-(methacryloxypropyl) propyl trimethoxy silicane It is 10:1；
(3) makrolon of 13h dry at 118 DEG C is added in mixing machine, after 251 DEG C of stirring melting 28min, Addition modified nano-zeolite molecular sieve continues stirring melting mixing 1h and obtains melt blended material, and melt blended material is put into 25 DEG C In autoclave, with the CO of 48MPa2Rapid release after saturation punching press 30h, the melt blended material after saturation is put into glycerol bath and sent out 55s is steeped, then is placed in ice-water bath and cools down 2min acquisition nanoporous Zeolite modifying makrolon foamed thermal insulatings, nanoporous Mass fraction shared by zeolite is 8%.
Fiber-the aerogel composite is prepared via a method which：
(1) ethyl orthosilicate and absolute ethyl alcohol are pressed 1:6 volume ratio is in 41 DEG C of water-baths, the speed stirring of 420r/min 65min is mixed, the dilute hydrochloric acid of 0.2mol/L is added dropwise in whipping process, continues to stir 30min after the completion, standing makes it for 24 hours It is fully hydrolyzed；Then 28min is stirred under the speed of 650r/min, and N is added dropwise during stirring, N- dimethyl methyls Amide, distilled water and ammonium hydroxide obtain Ludox, wherein ethyl orthosilicate, the dilute hydrochloric acid of 0.2mol/L, N, N- dimethyl formyls The volume ratio of amine, distilled water and ammonium hydroxide is 5:10:1:5:2；
(2) it between fibrofelt is sandwiched in stainless steel plate according to original thickness, is put into rustless steel container, vacuumizes, utilize air Pressure and using bottom filling by Ludox impregnated fiber from the bottom up, be sealed fiber/colloidal sol complex, treat further old Change；
(3) fiber/colloidal sol complex is put into autoclave, seals, 2.5h is kept the temperature under the conditions of 240 DEG C, 7Mpa Ethyl alcohol is released afterwards, you can fibre-reinforced aerogel flexible composite is made.
QB/T 2081-1995, GB/T10295-2008, GB/T 30022-2013 standards is respectively adopted to core material The indexs such as density, thermal conductivity factor, tensile strength are measured, and test result is as shown in table 1：
Basic principle, main feature and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and Improvement is both fallen in the range of claimed invention.The present invention claims protection domain by appended claims and its Equivalent defines.

Claims (5)

1. a kind of system of nanoporous Zeolite modifying makrolon foamed thermal insulating in vacuum heat-insulating plate composite core material Preparation Method, it is characterised in that：The nanoporous Zeolite modifying makrolon foamed thermal insulating is to be prepared via a method which It forms：
(1) tetrapropyl amine aqueous solution and ethyl orthosilicate are added sequentially in water, at ambient temperature with 300-500r/min's After speed stirring 22-26h, aluminium isopropoxide is added in, then stirring 20-28h is continued with the speed of 500-700r/min and is obtained containing silicon With the colloidal sol of aluminium, ethyl orthosilicate in the sol system containing silicon and aluminium, tetraethyl amine, water, aluminium isopropoxide substance The ratio between amount is 1:(0.3-0.35):(17.5-18.5):(0.003-0.004)；Colloidal sol containing silicon and aluminium is subjected to 48h successively Microwave radiation technology aging reaction, segmentation hydrothermal crystallizing reaction, after the completion of crystallization, gained crystallization product through being filtered by vacuum, washing, 105-115 DEG C of drying 10h obtains the molecular sieve of Nano zeolite that grain size is 80-100nm；Wherein, the reaction of segmentation hydrothermal crystallizing is divided to two Section, 78-82 DEG C of first segment hydrothermal crystallizing temperature, crystallization time 85-95min；118-122 DEG C of second segment hydrothermal crystallizing temperature, it is brilliant Change time 25-35min；
(2) ethyl alcohol and water are pressed 1:1 volume ratio is mixed to get alcohol solution, with the hydrochloric acid of 1mol/L by the pH value of alcohol solution Being adjusted to 5.0, to obtain mixed solution spare；Molecular sieve of Nano zeolite is added in the mixed solution, be then transferred to 15-25min is handled in 45-55 DEG C of water-bath of ultrasonic wave and stirring, the wherein power of ultrasonic wave is 10W, and the rotating speed of stirring is Then 400r/min is added dropwise γ-(methacryloxypropyl) propyl trimethoxy silicane continuation and stirs 2h under the same conditions, After being filtered, washed again, dried, grinding, modified nano-zeolite molecular sieve is obtained, wherein, molecular sieve of Nano zeolite and ethyl alcohol Mass volume ratio for 0.08-0.12g/mL, molecular sieve of Nano zeolite and γ-(methacryloxypropyl) propyl trimethoxy silicane Mass ratio be 9-11:1；
(3) makrolon of 10-15h dry at 115-125 DEG C is added in mixing machine, in 248-252 DEG C of stirring melting After 25-35min, addition modified nano-zeolite molecular sieve continues stirring melting mixing 1h and obtains melt blended material, by melt blending Object is put into 25 DEG C of autoclave, with the CO of 45-50MPa2Rapid release after saturation punching press 30h, the melt blending after saturation Object is put into glycerol bath the 40-60s that foams, then is placed in ice-water bath and cools down 2min acquisition nanoporous Zeolite modifying makrolon hairs Steep heat-insulating material.
2. preparation method as described in claim 1, it is characterised in that：The vacuum heat-insulating plate is by nanometer with composite core material Bi2Te3Modified cyanurotriamide formal fiber, nanoporous Zeolite modifying makrolon foamed thermal insulating and fiber-aeroge Composite material presses (10-12)：(5-6)：What the weight ratio of (2-4) was combined；
Wherein, the nanometer Bi2Te3Nanometer Bi in modified cyanurotriamide formal fiber2Te3Shared mass fraction is 8-10%； Mass fraction shared by nanoporous zeolite is 5-8% in the nanoporous Zeolite modifying makrolon foamed thermal insulating；Institute The density for stating composite core material is less than 0.35g/cm3, thermal conductivity factor is less than 0.02W/ (mK).
3. preparation method as claimed in claim 2, it is characterised in that：The preparation side of the vacuum heat-insulating plate composite core material Method is, by the nanometer Bi of corresponding parts by weight2Te3Modified cyanurotriamide formal fiber, nanoporous Zeolite modifying makrolon hair Bubble heat-insulating material and fiber-aerogel composite are filled into the bag film of a side opening, and bag film is sealed after filling Mouth is placed in die forming machine, and packing material is made uniformly to be distributed in bag film, right under the briquetting pressure of 48-52MPa Filler material is press-formed, and finally unloads die pressure, demoulding obtains molding core material.
4. preparation method as claimed in claim 3, which is characterized in that the fiber-aerogel composite is by such as lower section What method was prepared：
(1) ethyl orthosilicate and absolute ethyl alcohol are pressed 1:6 volume ratio is in 38-42 DEG C of water-bath, the speed of 350-450r/min 50-70min is stirred, the dilute hydrochloric acid of 0.2mol/L is added dropwise in whipping process, continues to stir 30min after the completion, stand It is fully hydrolyzed it for 24 hours；Then 25-35min is stirred under the speed of 500-700r/min, and is added dropwise during stirring Enter n,N-Dimethylformamide, distilled water and ammonium hydroxide, obtain Ludox, wherein ethyl orthosilicate, the dilute hydrochloric acid of 0.2mol/L, N, The volume ratio of dinethylformamide, distilled water and ammonium hydroxide is 5:10:1:5:2；
(2) it between fibrofelt is sandwiched in stainless steel plate according to original thickness, is put into rustless steel container, vacuumizes, utilize atmospheric pressure And Ludox impregnated fiber from the bottom up is sealed fiber/colloidal sol complex, treats further aging using bottom filling；
(3) fiber/colloidal sol complex is put into autoclave, seals, kept the temperature under the conditions of 240-250 DEG C, 6-7Mpa Ethyl alcohol is released after 1.5-2.5h, you can fibre-reinforced aerogel flexible composite is made.
5. preparation method as claimed in claim 3, it is characterised in that：The nanometer Bi2Te3Modified cyanurotriamide formal fiber It is prepared via a method which：
(1) bismuth chloride, tellurium powder, potassium hydroxide, sodium borohydride are dissolved in N-N- dimethylformamides, the solution of gained is existed Hydro-thermal reaction 20-28h is carried out at 110-160 DEG C, cooled to room temperature after hydro-thermal reaction, after filtered, washing, 10-15h is dried in vacuo at 75-85 DEG C and obtains a nanometer Bi2Te3；Wherein, the substance of bismuth chloride, tellurium powder, potassium hydroxide, sodium borohydride The ratio between amount be 2:3:(0.4-0.6):The amount ratio of (0.3-0.5), bismuth chloride and the substance of N-N- dimethylformamides is 1:5；
(2) by formaldehyde, nanometer Bi2Te3After 25-35min being stirred with stabilizer at 35-45 DEG C with the rate of 300-500r/min, 75 DEG C are warming up to, melamine is added in, and it is 10.0 to adjust pH value with triethanolamine, improves mixing speed to 600r/min reactions Its pH is adjusted to 7.0 after 2h, is uniformly mixed and obtains stoste, using dry spinning to nanometer Bi2Te3Modified cyanurotriamide formal Fiber；Wherein, formaldehyde, nanometer Bi2Te3, melamine and stabilizer mass ratio 0.4:(0.08-0.1):0.6:0.01.
CN201711438935.8A 2016-04-27 2016-04-27 The preparation method of nanoporous Zeolite modifying makrolon foamed thermal insulating in a kind of vacuum heat-insulating plate composite core material Withdrawn CN108129797A (en)

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