CN101585954A - Silicon dioxide hollow sphere/polymer composite heat insulating material and method for preparing same - Google Patents
Silicon dioxide hollow sphere/polymer composite heat insulating material and method for preparing same Download PDFInfo
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- CN101585954A CN101585954A CNA2008101122320A CN200810112232A CN101585954A CN 101585954 A CN101585954 A CN 101585954A CN A2008101122320 A CNA2008101122320 A CN A2008101122320A CN 200810112232 A CN200810112232 A CN 200810112232A CN 101585954 A CN101585954 A CN 101585954A
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- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000000084 colloidal system Substances 0.000 claims description 7
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- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
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- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229960004418 trolamine Drugs 0.000 description 4
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 4
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
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- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a silicon dioxide hollow sphere/polymer composite heat insulating material and a method for preparing the same. The composite material comprises a polymer substrate and submicron, agglomeration-free and monodisperse silicon dioxide hollow spheres evenly dispersed in the substrate, wherein the polymer substrate is a substrate of epoxy, polyurethane or polyethylene terephthalate; and for the submicron silicon dioxide hollow spheres, the hollow internal diameter is between 100 and 720nm, the thickness of the outer wall is between 50 and 100nm, and the weight of the submicron silicon dioxide hollow spheres is 1 to 35 percent of that of the polymer substrate. In the method, powder of the submicron, agglomeration-free and monodisperse silicon dioxide hollow sphere is prepared first; the powder is modified by the surface modifying technology; and finally, the modified powder is combined with the polymer taken as the substrate. The composite heat insulating material shows excellent heat insulating property, and the heat insulating property shows size-dependent characteristics in a rang of submicron. Moreover, because an organic foaming agent is not used in the preparation process, the composite heat insulating material is environment-friendly.
Description
Technical field
The present invention relates to a kind of silicon dioxide hollow sphere/polymer composite heat insulating material, and preparation method thereof.
Technical background
The dimension of material, pattern and structure are the important factors that influences the physical and chemical performance of material.For lagging material, have low density except selecting for use, the material of characteristic such as high-reflectivity, select for use porous materials on the structure be obtain low thermal conductivity can principal element.Common lagging material is porous material mostly, for example foamable polymer (moulding type polystyrene foamed (EPS), extrusion type polystyrene foamed (XPS), polyurethane foam, Resins, epoxy foam etc.) and inorganic mineral (asbestos, lime carbonate, clay, vermiculite, flyash, perlite etc.).Abundant porous duct has comprised the gas of lower thermal conductivity in these materials, has not only reduced the density of bulk material, also greatly reduces the thermal conductivity of material monolithic.
But also there are some problems in these existing lagging materials.For example, often there is the defective of size instability and poor heat stability in polystyrene foamed; Polyurethane foam is inflammable, and foaming process use freonll-11 whipping agent, brings environmental pollution easily; The easy moisture absorption of inorganic mineral, heat shock resistance and bad mechanical property, and the inorganic mineral thermal conductivity is higher, and effect of heat insulation is undesirable etc.Especially their all ubiquity contaminate environment or unfavorable defectives of effect of heat insulation have limited the range of application of these lagging materials, make these materials only can satisfy some to the less demanding occasion of heat-proof quality.
In addition,, also developed the NEW TYPE OF COMPOSITE lagging material, remedied the deficiency of different components, become a development trend of new energy-saving material research and development by the characteristic of compound differing materials in heat-insulating and energy-saving material field.For example in polymkeric substance or the fiber-like inorganic mineral enhanced aerosil, aerosil is to have " fractal " network structure of nanoparticle and the excellent heat insulation thermal insulation material of the nano-pore structure of a large amount of contained gass, but its bad mechanical strength, employing and polymkeric substance or fiber-like mineral compound way are carried out reinforcement, make mechanical property improve, but because the interpolation of some higher thermal conductivity material, the whole effect of heat insulation variation that causes composite heat-insulated material again, though promptly can improve partial properties by material is compound, but for matrix material, the introducing of out-phase is a cost to sacrifice other performance to the improvement of material property often.
Summary of the invention
The objective of the invention is to by reasonably designing the structure of each component in the matrix material, thereby obtain a kind ofly to have excellent heat insulation property and can satisfy the matrix material of application scenario other performance demands.
Another object of the present invention is to provide a kind of method of environment amenable this matrix material of preparation.
The invention provides a kind of silicon dioxide hollow sphere/polymer composite heat insulating material, it comprises a polymeric matrix, with the submicron, nothing reunion, the monodispersed silicon dioxide hollow sphere that are dispersed in this matrix, described polymeric matrix is the matrix of urethane, epoxy or polyethylene terephthalate, the inner hollow diameter of described submicron silicon dioxide hollow ball is 100～720nm, outer wall thickness is 50～100nm, and described submicron silicon dioxide hollow ball accounts for 1～35wt% of polymer-based carbon body weight.
The invention provides a kind of method for preparing above-mentioned silicon dioxide hollow sphere/polymer composite heat insulating material, comprise following step:
1) there is not reunion, the single dispersion, the preparation of submicron silicon dioxide hollow ball powder: by as at document 1: Wu Xiaofeng, Chen Yunfa, Wei Lianqi, Wang Qi process engineering journal, 2006, template synthetic technology described in 6 (Suppl.2) 285-289 based on precipitation kinetics control, 0.2～0.5g monodisperse polystyrene (PS) colloidal solid is dispersed in the mixing solutions of 94.5ml/5.5ml ethanol/water, behind supersound process 20～30min, drips the strong aqua of 0.65～2.3ml, after stirring, continue to drip tetraethyl orthosilicate (TEOS) 1.9～4.5ml, reaction 8～12h, afterwards, centrifugation goes out solid and with after the washing with alcohol three times, separates oven dry; Afterwards,, be warming up to 550～650 ℃ and be incubated 1～3h,, obtain the silicon dioxide hollow sphere powder to remove polystyrene colloid particle as template with 1～5 ℃/min heat-up rate;
The average particle size range of described monodisperse polystyrene (PS) colloidal solid is at 112～757nm;
2) modification of silicon-dioxide powdery:
With amine functions base silane coupling agent the silicon dioxide hollow sphere powder is carried out surface modification: the silicon dioxide hollow sphere powder that 0.5～1g step 1) is obtained joins in the 100ml acetone soln that contains 1～2g aminopropyl triethoxysilane coupling agent, behind ultrasonic 20～30min, stir 12h under the room temperature, separate and wash 2～3 times with acetone, vacuumizing and drying afterwards, identified as samples is designated as A after the modification;
Perhaps
With epoxide function base silane coupling agent the silicon dioxide hollow sphere powder is carried out surface modification: the silicon dioxide hollow sphere powder that 0.5～1g step 1) is obtained joins in the 100ml ethanolic soln of 1～2g epoxypropyl triethoxyl silane coupling agent, behind ultrasonic 20～30min, stir 12h under the room temperature, separate and wash 2～3 times with ethanol, vacuumizing and drying afterwards, identified as samples is designated as B after the modification;
3) preparation of silicon dioxide hollow sphere/polymer composite heat insulating material: will be in solvent as the polymer dissolution of matrix, add step 2 then) the silicon dioxide hollow sphere powder A or the B of the modification that obtains, after stirring following supersound process, pour mixed slurry in mould self-vulcanizing, in vacuum drying oven, solidify then, obtain silicon dioxide hollow sphere/polymer composite heat insulating material of the present invention after the demoulding.
In technical scheme of the present invention, the preparation of silicon dioxide hollow sphere/Resins, epoxy composite heat-insulated material is that 2～10g Resins, epoxy (E-42) is dissolved in 5～20ml acetone, then by 1～35% the amount that is equivalent to the Resins, epoxy quality, adding step 2) the silicon dioxide hollow sphere powder A of the modification that obtains, stir supersound process 20min down, afterwards, constantly stir and add 0.19～0.94g diethylenetriamine solidifying agent down, mixed slurry is poured in the stainless steel mould that has tetrafluoroethylene, behind the self-vulcanizing 24h, change vacuum drying oven over to, 130 ℃ solidify 5h down, obtain silicon dioxide hollow sphere of the present invention/Resins, epoxy composite heat-insulated material after the demoulding.
In technical scheme of the present invention, the preparation of silicon dioxide hollow sphere/urethane composite heat-insulated material is with 2～10g polyether glycol (Xylitol), 0.01～0.05g trolamine promotor mixing and stirring, 1～35% amount according to the polyether glycol quality adds step 2) the silicon dioxide hollow sphere powder A of the modification that obtains, stir supersound process 20min down, afterwards, constantly stir and add 5～15g isocyanate curing agent down, the powerful stirring adds 0.001～0.005g dibutyl tin dilaurate catalyst down, mixed slurry is poured into the stainless steel mould that has tetrafluoroethylene, behind the self-vulcanizing 24h, obtain silicon dioxide hollow sphere of the present invention/urethane composite heat-insulated material after the demoulding.
In technical scheme of the present invention, the preparation of silicon dioxide hollow sphere/polyethylene terephthalate composite heat-insulated material is that polyethylene terephthalate 2～10g is dissolved in 5～20ml phenol-tetrachloromethane mixing solutions, then by 1～35% the amount that is equivalent to the polyethylene terephthalate quality, adding step 2) the silicon dioxide hollow sphere powder B of the modification that obtains, stir supersound process 20min down, afterwards, mixed slurry is poured in the stainless steel mould that has tetrafluoroethylene, behind the drying at room temperature 48h, change vacuum drying oven over to and vacuumize drying, obtain silicon dioxide hollow sphere of the present invention/polyethylene terephthalate composite heat-insulated material after the demoulding.
The present invention is submicron (100～720nm) cavity and the uniform nano level ball wall that is closed with air by adopting on nothing reunion, single dispersion, the submicron silicon dioxide hollow ball structure, its ball wall outside surface is through silane coupler modified, with avidity and its dispersiveness in polystyrene resin that strengthens inorganics and organic resin, with the reunion of reduction hollow ball particle in resin, and then reduce the intergranular series connection thermal conductance of hollow ball.Silicon dioxide hollow sphere with different cavity size surface graft modifications 1～35% is dispersed in the common resin by weight percentage then.Be closed with air and mutual isolated submicron " cell " in a large number owing to be scattered here and there in the resin matrix, its inwall has suppressed the confining gas transmission of heat by convection effectively, therefore such composite heat-insulated material shows excellent heat-proof quality, and along with the cavity size that is dispersed in the silicon dioxide hollow sphere in the resin matrix changes, its heat-proof quality shows the characteristic that size relies in sub-micrometer range.Compare traditional polymer foaming material, the present invention can design the structural parameter of composite heat-insulated material in advance, to meet the application scenario requirement; And in preparation process, avoid using organic blowing agent, thereby this composite heat-insulated material environmental friendliness.
Embodiment
Embodiment 1
Reference is at document 1: Wu Xiaofeng, Chen Yunfa, Wei Lianqi, Wang Qi process engineering journal, the template synthetic technology preparation nothing based on precipitation kinetics control described in 2006,6 (Suppl.2) 285-289 is reunited, list disperses, submicron silicon dioxide hollow ball powder.(average particle size range is dispersed in the mixing solutions of 94.5ml/5.5ml ethanol/water 112～757nm), behind the supersound process 25min, drips the strong aqua of 1.3ml with 0.3g monodisperse polystyrene (PS) colloidal solid, after stirring, continue to drip tetraethyl orthosilicate (TEOS) 2.5ml, reaction 10h, afterwards, centrifugation goes out solid, again be scattered in the mixing solutions of 94.5ml/5.5ml ethanol/water, repeat above-mentioned precipitation process, after the centrifugation, after washing with alcohol three times, separate oven dry; Afterwards, with 3 ℃/min heat-up rate, be warming up to 600 ℃ and be incubated 2h, to remove the polystyrene colloid particle as template, obtain the silicon dioxide hollow sphere powder, its mean inside diameter is 120nm.
Adopt process for modifying surface, the above-mentioned silicon dioxide hollow sphere powder of 0.8g is joined in the 100ml acetone that contains 1.5g aminopropyl three ethoxy silane (silane coupling agent) ultrasonic 25min; After stirring 12h under the room temperature, isolate, solid and with acetone washing 3 times, vacuumizing and drying, obtaining mean diameter is the silicon dioxide hollow sphere powder A of amido modification 120nm, surperficial.
8g Resins, epoxy (E-42) is dissolved in the 12ml acetone, then by 0 (in contrast) that is equivalent to the Resins, epoxy quality, 3wt%, 10wt%, the amount of 22wt% and 34wt%, adding step 2) the silicon dioxide hollow sphere powder A of the modification that obtains, stir supersound process 20min down, afterwards, constantly stir and add 0.82g diethylenetriamine solidifying agent down, mixed slurry is poured in the stainless steel mould that has tetrafluoroethylene of 5mm * 5mm * 2mm size, behind the self-vulcanizing 24h, change vacuum drying oven over to, 130 ℃ solidify 5h down, obtain silicon dioxide hollow sphere of the present invention/Resins, epoxy composite heat-insulated material S-EP-120nm after the demoulding.
The S-EP-120nm series of samples is carried out heat-proof quality to be detected.Among the present invention, (PPMS-9 USA) carries out material compound heat-insulation Performance Detection, and the scanning temperature range is 298K～358K at Physical Property Measurement System.The thermal performance test result of different samples (S, representative sample, the cavity mean diameter of digitized representation hollow particle) is as shown in table 1.
Thermal conductivity under the different epoxy based composite heat insulation of the table 1 material sample room temperature
| 0％ | 3％ | 10％ | 22％ | 34％ | |
| S-EP-120nm (W/K.m) | 0.1950 | 0.1502 | 0.178 | 0.243 | 0.336 |
| S-EP-442nm (W/K.m) | 0.1950 | 0.0821 | 0.0921 | 0.0944 | 0.2011 |
| S-EP-719nm (W/K.m) | 0.1950 | 0.0926 | 0.1022 | 0.1231 | 0.1548 |
Embodiment 2
With the 8g Xylitol, 0.03g trolamine (promotor) mixing and stirring, according to 0 (in contrast) of polyether glycol quality, 5wt%, 15wt%, the amount of 25wt% and 35wt%, the silicon dioxide hollow sphere powder A that adds the modification that makes among the embodiment 1, stir supersound process 20min down, afterwards, constantly stir and add 10g isocyanic ester (solidifying agent) down, stir and add 0.0028g dibutyl tin dilaurate (catalyzer) down, mixed slurry is poured into the stainless steel mould that has tetrafluoroethylene of 5mm * 5mm * 2mm size, behind the self-vulcanizing 24h, obtain silicon dioxide hollow sphere of the present invention/urethane composite heat-insulated material S-PU-120nm after the demoulding.
The S-PU-120nm series of samples is carried out heat-proof quality to be detected.Among the present invention, (PPMS-9 USA) carries out material compound heat-insulation Performance Detection, and the scanning temperature range is 298K～358K at Physical Property Measurement System.The thermal performance test result of different samples (S, representative sample, the cavity mean diameter of digitized representation hollow particle) is as shown in table 2.
Thermal conductivity under the different polyurethane-base composite heat-insulated material of the table 2 sample room temperature
| 0％ | 5％ | 15％ | 25％ | 35％ | |
| S-PU-120nm (W/K.m) | 0.7325 | 0.1076 | 0.0902 | 0.1364 | 0.3561 |
| S-PU-442nm (W/K.m) | 0.7325 | 0.0436 | 0.0516 | 0.0952 | 0.275 |
| S-PU-719nm (W/K.m) | 0.7325 | 0.0742 | 0.0843 | 0.1106 | -- |
Embodiment 3
Adopt process for modifying surface, the silicon dioxide hollow sphere powder that makes among the 0.8g embodiment 1 is joined in the 100ml ethanolic soln of 1.5g epoxypropyl triethoxyl silane coupling agent, behind the ultrasonic 25min, stir 12h under the room temperature, separate and wash 3 times with ethanol, vacuumizing and drying afterwards, obtaining mean diameter is the silicon dioxide hollow sphere powder B of epoxy group(ing) modification 719nm, surperficial.
Polyethylene terephthalate 8g is dissolved in 15ml phenol-tetrachloromethane mixing solutions, then by 0 (in contrast) that is equivalent to the polyethylene terephthalate quality, 4wt%, 12wt%, the amount of 28wt% and 32wt%, the silicon dioxide hollow sphere powder B that adds modification, stir supersound process 20min down, afterwards, mixed slurry is poured in the stainless steel mould that has tetrafluoroethylene of 5mm * 5mm * 2mm size, behind the drying at room temperature 48h, change vacuum drying oven over to and vacuumize drying, obtain silicon dioxide hollow sphere of the present invention/polyethylene terephthalate composite heat-insulated material S-PET-120nm after the demoulding.
Thermal conductivity under the different polyethylene terephthalate based composite heat insulation of the table 3 material room temperature
| 0％ | 4％ | 12％ | 28％ | 32％ | |
| S-PET-120nm (W/K.m) | 0.2316 | 0.1760 | 0.1942 | 0.2427 | 0.3652 |
| S-PET-442nm (W/K.m) | 0.2316 | 0.0762 | 0.08541 | 0.1437 | 0.2874 |
| S-PET-719nm (W/K.m) | 0.2316 | 0.0884 | 0.09254 | 0.1673 | 0.2568 |
The S-PET-120nm series of samples is carried out heat-proof quality to be detected.Among the present invention, (PPMS-9 USA) carries out material compound heat-insulation Performance Detection, and the scanning temperature range is 298K～358K at Physical Property Measurement System.The thermal performance test result of different samples (S, representative sample, the cavity mean diameter of digitized representation hollow particle) is as shown in table 3.
Embodiment 4
Be similar to the method among the embodiment 1, (average particle size range is dispersed in the mixing solutions of 94.5ml/5.5ml ethanol/water 112～757nm) with 0.5g monodisperse polystyrene (PS) colloidal solid, behind the supersound process 20min, drip the strong aqua of 2.3ml, after stirring, continue to drip tetraethyl orthosilicate (TEOS) 4.5ml, reaction 8h, afterwards, centrifugation goes out solid, is scattered in again in the mixing solutions of 94.5ml/5.5ml ethanol/water, repeat above-mentioned precipitation process, after the centrifugation, and, separate oven dry with after the washing with alcohol three times; Afterwards, with 1 ℃/min heat-up rate, be warming up to 550 ℃ and be incubated 3h, to remove the polystyrene colloid particle as template, obtain the silicon dioxide hollow sphere powder, its mean inside diameter is 442nm.
Adopt process for modifying surface, the above-mentioned silicon dioxide hollow sphere powder of 1g is joined in the 100ml acetone soln that contains 2g aminopropyl triethoxysilane (silane coupling agent) ultrasonic 25min; Isolate after stirring 12h under the room temperature, solid is also used absolute ethanol washing 3 times, vacuumizing and drying, and obtaining mean diameter is the silicon dioxide hollow sphere powder A of amido modification 442nm, surperficial.
10g Resins, epoxy (E-42) is dissolved in the 20ml acetone, then by 0 (in contrast) that is equivalent to the Resins, epoxy quality, 3wt%, 10wt%, the amount of 22wt% and 34wt%, the silicon dioxide hollow sphere powder A that adds modification, stir supersound process 20min down, afterwards, constantly stir and add 0.94g diethylenetriamine solidifying agent down, mixed slurry is poured in the stainless steel mould that has tetrafluoroethylene of 5mm * 5mm * 2mm size, behind the self-vulcanizing 24h, change vacuum drying oven over to, 130 ℃ solidify 5h down, obtain silicon dioxide hollow sphere of the present invention/Resins, epoxy composite heat-insulated material S-EP-442nm after the demoulding.
The S-EP-442nm series of samples is carried out heat-proof quality detect, the results are shown in table 1.
Embodiment 5
Be similar to the method among the embodiment 2, with the 10g Xylitol, 0.05g trolamine (promotor) mixing and stirring, according to 0 (in contrast) of polyether glycol quality, 5wt%, 15wt%, the amount of 25wt% and 35wt%, the silicon dioxide hollow sphere powder A that adds the modification that makes among the embodiment 4, stir supersound process 20min down, afterwards, constantly stir and add 15g isocyanic ester (solidifying agent) down, stir and add 0.005g dibutyl tin dilaurate (catalyzer) down, mixed slurry is poured into the stainless steel mould that has tetrafluoroethylene of 5mm * 5mm * 2mm size, behind the self-vulcanizing 24h, obtain silicon dioxide hollow sphere of the present invention/urethane composite heat-insulated material S-PU-442nm after the demoulding.
The S-PU-442nm series of samples is carried out heat-proof quality detect, the results are shown in table 2.
Embodiment 6
Be similar to the method among the embodiment 3, adopt process for modifying surface, the silicon dioxide hollow sphere powder that makes among the 1g embodiment 4 is joined in the 100ml ethanolic soln of 2g epoxypropyl triethoxyl silane coupling agent, behind the ultrasonic 25min, stir 12h under the room temperature, separate and wash 3 times with ethanol, vacuumizing and drying afterwards, obtaining mean diameter is the silicon dioxide hollow sphere powder B of epoxy group(ing) modification 442nm, surperficial.
Polyethylene terephthalate 10g is dissolved in 20ml phenol-tetrachloromethane mixing solutions, then by 0 (in contrast) that is equivalent to the polyethylene terephthalate quality, 4wt%, 12wt%, the amount of 28wt% and 32wt%, the silicon dioxide hollow sphere powder B that adds modification, stir supersound process 20min down, afterwards, mixed slurry is poured in the stainless steel mould that has tetrafluoroethylene of 5mm * 5mm * 2mm size, behind the drying at room temperature 48h, change vacuum drying oven over to and vacuumize drying, obtain silicon dioxide hollow sphere of the present invention/polyethylene terephthalate composite heat-insulated material S-PET-442nm after the demoulding.
The S-PET-442nm series of samples is carried out heat-proof quality detect, the results are shown in table 3.
Embodiment 7
Be similar to the method among the embodiment 1, (average particle size range is dispersed in the mixing solutions of 94.5ml/5.5ml ethanol/water 112～757nm) with 0.2g monodisperse polystyrene (PS) colloidal solid, behind the supersound process 20min, drip the strong aqua of 0.65ml, after stirring, continue to drip tetraethyl orthosilicate (TEOS) 1.9ml, reaction 12h, afterwards, centrifugation goes out solid, is scattered in again in the mixing solutions of 94.5ml/5.5ml ethanol/water, repeat above-mentioned precipitation process, after the centrifugation, and, separate oven dry with after the washing with alcohol three times; Afterwards, with 1 ℃/min heat-up rate, be warming up to 650 ℃ and be incubated 1h, to remove the polystyrene colloid particle as template, obtain the silicon dioxide hollow sphere powder, its mean inside diameter is 719nm.
Adopt process for modifying surface, the above-mentioned silicon dioxide hollow sphere powder of 0.5g is joined in the 100ml acetone soln that contains 1g aminopropyl triethoxysilane (silane coupling agent) ultrasonic 25min; Isolate after stirring 12h under the room temperature, solid is also used absolute ethanol washing 3 times, vacuumizing and drying, and obtaining mean diameter is the silicon dioxide hollow sphere powder A of amido modification 719nm, surperficial.
2g Resins, epoxy (E-42) is dissolved in the 5ml acetone, then by 0 (in contrast) that is equivalent to the Resins, epoxy quality, 3wt%, 10wt%, the amount of 22wt% and 34wt%, the silicon dioxide hollow sphere powder A that adds modification, stir supersound process 20min down, afterwards, constantly stir and add 0.19g diethylenetriamine solidifying agent down, mixed slurry is poured in the stainless steel mould that has tetrafluoroethylene of 5mm * 5mm * 2mm size, behind the self-vulcanizing 24h, change vacuum drying oven over to, 130 ℃ solidify 5h down, obtain silicon dioxide hollow sphere of the present invention/Resins, epoxy composite heat-insulated material S-EP-719nm after the demoulding.
The S-EP-719nm series of samples is carried out heat-proof quality detect, the results are shown in table 1.
Embodiment 8
Be similar to the method among the embodiment 2, with the 2g Xylitol, 0.01g trolamine (promotor) mixing and stirring, according to 0 (in contrast) of polyether glycol quality, 5wt%, 15wt%, the amount of 25wt% and 35wt%, the silicon dioxide hollow sphere powder A that adds the modification that makes among the embodiment 7, stir supersound process 20min down, afterwards, constantly stir and add 5g isocyanic ester (solidifying agent) down, stir and add 0.001g dibutyl tin dilaurate (catalyzer) down, mixed slurry is poured into the stainless steel mould that has tetrafluoroethylene of 5mm * 5mm * 2mm size, behind the self-vulcanizing 24h, obtain silicon dioxide hollow sphere of the present invention/urethane composite heat-insulated material S-PU-719nm after the demoulding.
The S-PU-719nm series of samples is carried out heat-proof quality detect, the results are shown in table 2.
Embodiment 9
Be similar to the method among the embodiment 3, adopt process for modifying surface, the silicon dioxide hollow sphere powder that makes among the 0.5g embodiment 7 is joined in the 100ml ethanolic soln of 1g epoxypropyl triethoxyl silane coupling agent, behind the ultrasonic 25min, stir 12h under the room temperature, separate and wash 3 times with ethanol, vacuumizing and drying afterwards, obtaining mean diameter is the silicon dioxide hollow sphere powder B of epoxy group(ing) modification 719nm, surperficial.
Polyethylene terephthalate 2g is dissolved in 5ml phenol-tetrachloromethane mixing solutions, then by 0 (in contrast) that is equivalent to the polyethylene terephthalate quality, 4wt%, 12wt%, the amount of 28wt% and 32wt%, the silicon dioxide hollow sphere powder B that adds modification, stir supersound process 20min down, afterwards, mixed slurry is poured in the stainless steel mould that has tetrafluoroethylene of 5mm * 5mm * 2mm size, behind the drying at room temperature 48h, change vacuum drying oven over to and vacuumize drying, obtain silicon dioxide hollow sphere of the present invention/polyethylene terephthalate composite heat-insulated material S-PET-719nm after the demoulding.
The S-PET-719nm series of samples is carried out heat-proof quality detect, the results are shown in table 3.
From table 1～3, different as can be seen sample (S, representative samples; EP, epoxy composite material; PU represents compound polyurethane material; The PET polyethylene terephthalate is represented the cavity mean diameter of digitized representation hollow particle) the thermal performance test result.Table 1 shows the increase along with inoganic solids content, the thermal conductivity of epoxy matrix composite is along with silicon dioxide hollow sphere content increases, the trend that a reduction is arranged earlier, when solid content reaches 3%, the thermal conductivity of matrix material reaches Schwellenwert, when solids content greater than 3% the time, different samples (different cavity size) thermal conductivity presents increase in various degree again along with the increase of solid content.At the filler solid content is 3% o'clock, and the submicron silicon dioxide hollow ball of different samples/PS matrix material is showed excellent heat-proof quality, and its thermal conductivity is at 0.0821～0.1502W/K.m.Wherein, to sample S-EP-442nm, minimum thermal conductivity reaches 0.0821W/K.m.The sample result that comparison sheet 1 thermal conductivity is minimum (solid content 3%), can find, along with cavity size reduces, thermal conductivity of composite materials reduces earlier, when cavity size reaches 442nm, its thermal conductivity reaches 0.0821W/K.m, and subsequently, thermal conductivity reduces along with the cavity size of silicon dioxide hollow sphere and increases.This depends in solids content one fixs, be dispersed in hollow ball number and dispersion state in the resin system, because the number of hollow ball is in sub-micrometer range, increase along with reducing of cavity size, so, in certain limit, the numbers of particles increase causes particle series connection effect to offset size to reduce restraining effect to gaseous exchange, as can be seen from Table 1, in sub-micrometer range, when cavity size was reduced to 442nm from 719nm, cavity size played a major role to its gas inside convection current restraining effect.Along with the further reduction of cavity size, numbers of particles increases, and series connection increases between the particle, and the thermal conductivity of matrix material obviously increases, and therefore, in this scope, the matrix material thermal conductivity coefficient shows certain size-dependent.Similarly, to urethane composite heat-insulated material and polyethylene terephthalate based composite heat insulation material (as table 2, shown in 3), thermal conductivity shows and the epoxy composite material similar trend with the increase of solids content.When both reach a certain amount of at silicon dioxide hollow sphere content, obtain minimum thermal conductivity, be respectively 5% and 4%.These results show, in the different polymer materialss, when adding a spot of submicron silicon dioxide hollow ball, different polymer matrix composites show excellent heat-proof quality.
Claims (8)
1, a kind of silicon dioxide hollow sphere/polymer composite heat insulating material, it comprises a polymeric matrix, with the submicron, nothing reunion, the monodispersed silicon dioxide hollow sphere that are dispersed in this matrix, described polymeric matrix is the matrix of epoxy, urethane or polyethylene terephthalate, the inner hollow diameter of described submicron silicon dioxide hollow ball is 100～720nm, outer wall thickness is 50～100nm, and described submicron silicon dioxide hollow ball accounts for 1～35wt% of polymer-based carbon body weight.
2, a kind of method for preparing silicon dioxide hollow sphere/polymer composite heat insulating material comprises following step:
1) do not have to reunite, singly disperse, the preparation of submicron silicon dioxide hollow ball powder: with 0.2～0.5g monodisperse polystyrene colloid particles dispersed in the mixing solutions of 94.5ml/5.5ml ethanol/water, after the supersound process, drip the strong aqua of 0.65～2.3ml, after stirring, continue to drip tetraethyl orthosilicate 1.9～4.5ml, after the reaction, centrifugation goes out solid and with after the washing with alcohol, separates oven dry; Afterwards,, be warming up to 550～650 ℃ and be incubated 1～3h,, obtain the silicon dioxide hollow sphere powder to remove polystyrene colloid particle as template with 1～5 ℃/min heat-up rate;
Described monodisperse polystyrene colloid particulate average particle size range is at 112～757nm;
2) modification of silicon-dioxide powdery:
With amine functions base silane coupling agent the silicon dioxide hollow sphere powder is carried out surface modification: the silicon dioxide hollow sphere powder that 0.5～1g step 1) is obtained joins in the 100ml acetone soln that contains 1～2g aminopropyl triethoxysilane coupling agent, after ultrasonic, stir 12h under the room temperature, separate and wash 2～3 times with acetone, vacuumizing and drying afterwards, identified as samples is designated as A after the modification;
Perhaps
With epoxide function base silane coupling agent the silicon dioxide hollow sphere powder is carried out surface modification: the silicon dioxide hollow sphere powder that 0.5～1g step 1) is obtained joins in the 100ml ethanolic soln of 1～2g epoxypropyl triethoxyl silane coupling agent, after ultrasonic, stir 12h under the room temperature, separate and wash 2～3 times with ethanol, vacuumizing and drying afterwards, identified as samples is designated as B after the modification;
3) preparation of silicon dioxide hollow sphere/polymer composite heat insulating material: will be in solvent as the polymer dissolution of matrix, add step 2 then) the silicon dioxide hollow sphere powder A or the B of the modification that obtains, after stirring following supersound process, pour mixed slurry in mould self-vulcanizing, in vacuum drying oven, solidify then, obtain required silicon dioxide hollow sphere/polymer composite heat insulating material after the demoulding.
3, the method for preparing silicon dioxide hollow sphere/polymer composite heat insulating material according to claim 2 is characterized in that: the supersound process time of described step 1) is 20～30min.
4, the method for preparing silicon dioxide hollow sphere/polymer composite heat insulating material according to claim 2 is characterized in that: the reaction times that described step 1) drips behind the tetraethyl orthosilicate is 8～12h.
5, the method for preparing silicon dioxide hollow sphere/polymer composite heat insulating material according to claim 2 is characterized in that: ultrasonic time described step 2) is 20～30min.
6, the method for preparing silicon dioxide hollow sphere/polymer composite heat insulating material according to claim 2, it is characterized in that: described step 3) is for to be dissolved into 2～10g Resins, epoxy in 5～20ml acetone, then by 1～35% the amount that is equivalent to the Resins, epoxy quality, adding step 2) the silicon dioxide hollow sphere powder A of the modification that obtains, after stirring following supersound process, constantly stir and add 0.19～0.94g solidifying agent down, mixed slurry is poured in the mould, after the self-vulcanizing, change vacuum drying oven over to, 130 ℃ solidify 5h, the demoulding down.
7, the method for preparing silicon dioxide hollow sphere/polymer composite heat insulating material according to claim 2, it is characterized in that: described step 3) is with 2～10g polyether glycol, 0.01～0.05g promotor mixing and stirring, 1～35% amount according to the polyether glycol quality adds step 2) the silicon dioxide hollow sphere powder A of the modification that obtains, after stirring following supersound process, constantly stir and add 5～15g solidifying agent down, the powerful stirring adds 0.001～0.005g catalyzer down, pour mixed slurry into mould, after the self-vulcanizing, the demoulding.
8, the method for preparing silicon dioxide hollow sphere/polymer composite heat insulating material according to claim 2, it is characterized in that: described step 3) is for to be dissolved into polyethylene terephthalate 2～10g in 5～20ml phenol-tetrachloromethane mixing solutions, then by 1～35% the amount that is equivalent to the polyethylene terephthalate quality, adding step 2) the silicon dioxide hollow sphere powder B of the modification that obtains, after stirring following supersound process, mixed slurry is poured in the mould, behind the drying at room temperature 48h, change vacuum drying oven over to and vacuumize drying, the demoulding.
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Granted publication date: 20110504 |