CN115873374A - Melamine formaldehyde resin/dodecanol composite material with high thermal conductivity and high toughness and preparation method thereof - Google Patents
Melamine formaldehyde resin/dodecanol composite material with high thermal conductivity and high toughness and preparation method thereof Download PDFInfo
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- CN115873374A CN115873374A CN202211314942.8A CN202211314942A CN115873374A CN 115873374 A CN115873374 A CN 115873374A CN 202211314942 A CN202211314942 A CN 202211314942A CN 115873374 A CN115873374 A CN 115873374A
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- formaldehyde resin
- dodecanol
- melamine formaldehyde
- melamine
- silicon nitride
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- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 30
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 21
- 239000011162 core material Substances 0.000 claims abstract description 19
- -1 silicon nitride modified melamine formaldehyde Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 4
- 239000012948 isocyanate Substances 0.000 claims abstract 2
- 238000010438 heat treatment Methods 0.000 claims description 45
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical class N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 33
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000839 emulsion Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 17
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 12
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000004945 emulsification Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 229920002866 paraformaldehyde Polymers 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 7
- 239000008098 formaldehyde solution Substances 0.000 claims 3
- 239000002904 solvent Substances 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 8
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000004005 microsphere Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 20
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 20
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- RVHPJLCXULJZOU-UHFFFAOYSA-N furan-2,5-dione;sodium;styrene Chemical compound [Na].O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 RVHPJLCXULJZOU-UHFFFAOYSA-N 0.000 description 10
- 239000011257 shell material Substances 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- 238000004146 energy storage Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005336 cracking Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000012782 phase change material Substances 0.000 description 5
- 239000011232 storage material Substances 0.000 description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 4
- 239000004640 Melamine resin Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003094 microcapsule Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
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- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
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Abstract
The invention discloses a melamine formaldehyde resin/dodecanol composite material with high thermal conductivity and high toughness and a preparation method thereof. Lauryl alcohol is selected as a core material, silicon nitride modified melamine formaldehyde resin is selected as an outer wall, and the lauryl alcohol and the silicon nitride modified melamine formaldehyde resin are subjected to in-situ polymerization reaction under the action of an emulsifier to form a structure of silicon nitride modified melamine coated lauryl alcohol. Meanwhile, the tri-isocyanate is added in the synthesis process of the melamine formaldehyde resin, so that the toughness of the melamine formaldehyde resin is improved, and the impact strength of the surface of the microsphere is improved. The composite material has high phase change latent heat, good heat conductivity, good thermal stability and strong impact resistance to the environment.
Description
Technical Field
The invention relates to the field of energy storage materials, in particular to a melamine formaldehyde resin/dodecanol composite material with high thermal conductivity and high toughness and a preparation method thereof.
Background
Thermal energy storage is an important branch in energy science and technology, and is an effective means for improving energy utilization rate. There are many ways of storing energy thermally, and phase change energy storage is one of them. When the phase change energy storage material is changed in phase state, the phase change energy storage material can absorb the heat of the environment and emit the heat when needed, so that the purpose of controlling the temperature of the surrounding environment is achieved.
There are many kinds of phase change materials, and polyols are widely used as one of them. The polyalcohol has a highly symmetrical lamellar core structure, molecules on the same layer are connected by Van der Waals force, hydrogen bonds are formed among layers by OH, when the solid-solid phase transition temperature is reached, a low-symmetrical isotropic face core structure is formed, meanwhile, the hydrogen bonds are broken, the phase transition from a crystalline state to an amorphous state is generated, hydrogen bond energy is released, and if the temperature is continuously increased, the polyalcohol reaches a melting point and becomes liquid. The melting point of the dodecanol is 24 ℃, which is close to room temperature, so that the dodecanol can be more easily applied in practical situations, and is cheap, thereby being an ideal solar energy storage material.
The phase-change material is used as an energy storage carrier, can relieve the problem of energy shortage, but can volatilize when the phase state changes. In order to improve the stability and facilitate transportation and storage, the invention coats the outer wall of the phase-change material. The melamine formaldehyde resin (MF) has good compatibility with organic phase change materials, has the characteristics of colorless transparency after curing, stability in boiling water, high temperature resistance, self-extinguishing property, arc resistance and the like, has wide sources and low price, and is suitable for being used as an outer wall.
However, melamine formaldehyde resins also have certain limitations. It is known that the thermal conductivity of the organic shell material is always significantly lower than that of the inorganic material. Thus, having an organic natureThe phase change material of the housing has a low thermal conductivity, which results in a slow heat release and heat absorption rate. There are generally two ways to increase the thermal properties of the organic shell material, one of which is to increase the thermal conductivity of the core material. Another is to improve the thermal properties of the polymeric housing material by adding high thermal conductivity additives. Heretofore, highly thermally conductive inorganic materials including inorganic particles and carbon-based materials have been used as additives to form composite shell structures, such as graphene, carbon nanotubes, siO 2 、SiC、Ti 4 O 7 And so on. Thus, the organic-inorganic hybrid shell exhibits better thermal and mechanical properties than conventional shell materials. On the other hand, due to the fact that a large number of triazine ring structures are contained in melamine resin, the molecular flexibility is poor, the macroscopic expression is that the resin is large in brittleness and insufficient in toughness, the melamine resin serving as a thin shell on the surface of the microsphere is very easy to break when being impacted by external force, and long-term storage and use of the microcapsule are not facilitated. Therefore, the invention aims to improve the flexibility of the melamine formaldehyde resin wall material, improve the impact strength of the melamine formaldehyde resin wall material and enhance the heat conduction efficiency.
Disclosure of Invention
The invention provides a melamine formaldehyde resin/dodecanol composite material with high thermal conductivity and high toughness and a preparation method thereof. The composite material has the advantages of good heat conductivity, good outer wall flexibility, strong impact resistance, stable appearance, good dodecanol coating rate and high phase change latent heat, and is a good energy storage material.
A preparation method of a melamine formaldehyde resin/dodecanol phase-change material with high thermal conductivity and high toughness comprises the following steps:
1) Modified Si 3 N 4 The preparation of (1): weighing 10g of silicon nitride and 10g of KH-550, ultrasonically mixing for 15min, adding 60mL of ethanol and oxalic acid to adjust the pH =4.5-5.5, heating to 80 ℃, stirring at 600rpm for 2h, filtering, washing and freeze-drying.
2) Emulsification of the core material: adding 120mL of deionized water into a 400mL polytetrafluoroethylene beaker, adding an emulsifier, stirring for 15min at the rotating speed of 600rpm, then adjusting the pH to 3.5, adjusting the rotating speed to 3000rpm, slowly dropwise adding 8g of dodecanol, heating to 50 ℃, and stirring for 1.5h to obtain dodecanol emulsion.
3) The preparation of the melamine-formaldehyde resin solution comprises the steps of adding 50mL of distilled water into a three-neck flask with a reflux condenser pipe, adjusting the pH value to 8.5 by using alkali, adding 3.7g of paraformaldehyde, heating to 70 ℃, adding 2.6g of melamine after the solution is clarified, adding a certain amount of triisocyanate after the addition is finished and reacting for 1 hour, and continuing to react for 1 hour.
4) Preparation of modified melamine formaldehyde resin solution: adding a certain amount of modified silicon nitride powder into the resin solution obtained in the step 3), and continuing to react for 1 hour.
5) Heating the dodecanol emulsion to 80 ℃, heating while dropping the modified melamine formaldehyde resin solution prepared in the step 4), reacting for 3 hours after dropping, cooling to room temperature, performing suction filtration, and drying to obtain the melamine formaldehyde resin/dodecanol composite material.
In the step 2), the emulsifier is dodecanol =1g, and the emulsifier can be OP-10, tween-80 or a styrene maleic anhydride solution. The styrene maleic anhydride solution needs to be prepared by self, and the preparation method comprises the following steps: 45mL of a 3wt% sodium hydroxide solution was added with 5g of styrene maleic anhydride sodium salt, stirred at 80 ℃ for 3 hours, and cooled to room temperature for later use.
In step 2), substances for adjusting the pH are citric acid, sulfuric acid and acetic acid.
In step 3), the substances used for adjusting the pH are: triethanolamine, sodium hydroxide and triethylamine.
In step 3), melamine was added in three portions, each with a time interval of ten minutes, according to 3.
In the step 3), the mass of the triisocyanate added is 40-60% of the mass of the melamine.
In step 4), the modified silicon nitride is added in a mass of about 0.2 to 0.6g.
The principle of the invention is as follows: the coating of the dodecanol by the melamine formaldehyde resin is realized by an in-situ polymerization method. The method selects water as a dispersion medium, and the core material particles are immersed in the monomer to obtain monodisperse polymer particles. The modified melamine formaldehyde resin solution is mixed with core dodecanol, which is pre-dispersed to the desired size, and controlled deposition and precipitation of polymer occurs at the interface by a change in pH.
In the melamine resin forming process, preformed polymer molecules are linked and polymerized into macromolecules by methylene or methylene ether bonds and are gradually cured and formed, triazine rings with larger steric hindrance are directly connected with the methylene, and the molecules are mutually staggered and connected in the crosslinking process, so that the molecules have poor flexibility, and the melamine resin shows the characteristics of outer softness and inner stiffness. The triisocyanate of the present invention is a flexible molecule having a plurality of reactive sites bonded to the hydroxyl and amino groups of a plurality of triazine rings. The triazine ring is connected with flexible molecules, so that the flexibility of the resin molecules is enhanced, and the crosslinking density is reduced.
The inorganic silicon nitride particle has the in-plane thermal conductivity coefficient of 18.42W/m.K, and is widely used in polymer, metal and ceramic composite materials to improve the thermal conductivity of the composite materials. However, there are very serious boundary problems between the inorganic silicon nitride particles and the organic shell layer, which prevent the effective combination of silicon nitride and the melamine formaldehyde resin shell layer. In order to eliminate the surface boundary effect, the silicon nitride is connected by adopting the silane coupling agent, and the surface of the silicon nitride is pre-modified. The modified silicon nitride has better compatibility with the melamine formaldehyde resin shell layer than unmodified silicon nitride.
The invention has the beneficial effects that:
1. the thermal conductivity of the silicon nitride is 18.42W/m.K, compared with melamine formaldehyde resin, the thermal conductivity is greatly improved, the thermal expansion coefficient is low, the stability is good, and the improvement of energy transmission is greatly facilitated.
2. KH-550 is utilized to react with nano Si 3 N 4 And (3) modifying, and removing water among molecules in a freeze-drying mode after modification, so that the spatial morphology is ensured. Meanwhile, the modified silicon nitride has better compatibility with organic polymers.
3. The triisocyanate is added, and a flexible chain segment is introduced into the resin to reduce the crosslinking density of a rigid structure and increase the flexibility of the resin.
4. By adding melamine in portions, the content of free formaldehyde in the melamine formaldehyde resin can be reduced.
Drawings
FIG. 1 is a scanned graph of a high thermal conductivity and high toughness melamine formaldehyde resin/dodecanol composite material prepared in example 1;
FIG. 2 is a scanned image of a melamine formaldehyde resin/dodecanol composite prepared in comparative example 1;
fig. 3 is an infrared image of the silicon nitride modified melamine-formaldehyde resin, dodecanol, high thermal conductivity and high toughness melamine-formaldehyde resin/dodecanol composite material in example 1.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Example 1
(1) Modified Si 3 N 4 The preparation of (1): weighing 10g of silicon nitride and 10g of KH-550, ultrasonically mixing for 15min, adding 60mL of ethanol and oxalic acid to adjust the pH =4.5, stirring at 80 ℃ and 600rpm for 2h, filtering, washing and freeze-drying.
(2) Preparation of styrene maleic anhydride solution (emulsifier): 45mL of a 3wt% sodium hydroxide solution was added to 5g of styrene maleic anhydride sodium salt, stirred at 80 ℃ for 3h, and cooled to room temperature for use.
(3) Emulsification of the core material: adding 120mL of deionized water into a 400mL polytetrafluoroethylene beaker, adding an emulsifier (styrene maleic anhydride solution), and stirring for 15min at the rotating speed of 600 rpm; adjusting the pH value to 3.5, adjusting the rotating speed to 3000rpm, slowly dripping 8g of dodecanol, heating to 50 ℃, and stirring for 1.5h to obtain dodecanol emulsion.
(4) Preparation of melamine formaldehyde resin solution: adding 50mL of distilled water into a three-neck flask with a reflux condenser pipe, adjusting the pH value to 8.5 by using alkali, adding 3.7g of paraformaldehyde, heating to 70 ℃, adding 2.6g of melamine after the solution is clarified, adding 1.25g of triisocyanate after the solution is reacted for 1 hour, and continuing the reaction for 1 hour.
(5) 0.2g of modified silicon nitride was added to the resin solution obtained in step (4), and the mixture was stirred for 1 hour.
(6) And (4) transferring the lauryl alcohol-containing emulsion prepared in the step (3) into a new three-neck flask, heating to 80 ℃, simultaneously heating, dripping the modified melamine formaldehyde resin solution prepared in the step (5), reacting for 3 hours, cooling to room temperature, performing suction filtration, and drying to obtain the melamine formaldehyde resin/lauryl alcohol composite material with high thermal conductivity and high toughness.
Example 2
(1) Modified Si 3 N 4 The preparation of (1): weighing 10g of silicon nitride and 10g of KH-550, ultrasonically mixing for 15min, adding 60mL of ethanol and oxalic acid to adjust the pH to be 4.5, stirring at 80 ℃ and 600rpm for 2h, filtering, washing and freeze-drying.
(2) Preparation of styrene maleic anhydride solution: 45mL of a 3wt% sodium hydroxide solution was added to 5g of styrene maleic anhydride sodium salt, stirred at 80 ℃ for 3h, and cooled to room temperature for use.
(3) Emulsification of the core material: adding 120mL of deionized water into a 400mL polytetrafluoroethylene beaker, adding an emulsifier (styrene maleic anhydride solution), and stirring for 15min at the rotating speed of 600 rpm; adjusting the pH value to 3.5, adjusting the rotating speed to 3000rpm, slowly dripping 8g of dodecanol, heating to 50 ℃, and stirring for 1.5h to obtain dodecanol emulsion.
(4) The preparation of the melamine formaldehyde resin solution comprises the steps of adding 50mL of distilled water into a three-neck flask provided with a reflux condenser tube, adjusting the pH value to 8.5 by using alkali, adding 3.7g of paraformaldehyde, heating to 70 ℃, adding 2.6g of melamine after the solution is clarified, reacting for 1 hour after the addition is finished, adding 1.25g of triisocyanate, and continuing the reaction for 1 hour.
(5) 0.4g of modified silicon nitride was added to the resin solution obtained in step (4), and the mixture was stirred for 1 hour.
(6) And (3) transferring the lauryl alcohol-containing emulsion prepared in the step (3) into a new three-neck flask, heating to 80 ℃, dripping the modified melamine formaldehyde resin solution prepared in the step (5) while heating, reacting for 3 hours, cooling to room temperature, performing suction filtration, and drying to obtain the melamine formaldehyde resin/lauryl alcohol composite material with high heat conductivity and high toughness.
Example 3
(1) Modified Si 3 N 4 The preparation of (1): weighing 10g of silicon nitride and 10g of KH-550, ultrasonically mixing for 15min, adding 60mL of ethanol and oxalic acid to adjust the pH to be 4.5, stirring at 80 ℃ and 600rpm for 2h, filtering, washing and freeze-drying.
(2) Preparation of styrene maleic anhydride solution: 45mL of a 3wt% sodium hydroxide solution was added with 5g of styrene maleic anhydride sodium salt, stirred at 80 ℃ for 3 hours, and cooled to room temperature for later use.
(3) Emulsification of the core material: adding 120mL of deionized water into a 400mL polytetrafluoroethylene beaker, adding an emulsifier (styrene maleic anhydride solution), and stirring for 15min at the rotating speed of 600 rpm; adjusting the pH value to 3.5, adjusting the rotating speed to 3000rpm, slowly dripping 8g of dodecanol, heating to 50 ℃, and stirring for 1.5h to obtain dodecanol emulsion.
(4) The preparation of the melamine formaldehyde resin solution comprises the steps of adding 50mL of distilled water into a three-neck flask provided with a reflux condenser tube, adjusting the pH value to 8.5 by using alkali, adding 3.7g of paraformaldehyde, heating to 70 ℃, adding 2.6g of melamine after the solution is clarified, reacting for 1 hour after the addition is finished, adding 1.25g of triisocyanate, and continuing the reaction for 1 hour.
(5) 0.6g of modified silicon nitride was added to the resin solution obtained in step (4), and the mixture was stirred for 1 hour.
(6) And (4) transferring the lauryl alcohol-containing emulsion prepared in the step (3) into a new three-neck flask, heating to 80 ℃, simultaneously heating, dripping the modified melamine formaldehyde resin solution prepared in the step (5), reacting for 3 hours, cooling to room temperature, performing suction filtration, and drying to obtain the melamine formaldehyde resin/lauryl alcohol composite material with high thermal conductivity and high toughness.
Example 4
(1) Modified Si 3 N 4 The preparation of (1): weighing 10g of silicon nitride and 10g of KH-550, ultrasonically mixing for 15min, adding 60mL of ethanol and oxalic acid to adjust the pH to be 4.5, stirring at 80 ℃ and 600rpm for 2h, filtering, washing and freeze-drying.
(2) Preparation of styrene maleic anhydride solution (emulsifier): 45mL of a 3wt% sodium hydroxide solution was added to 5g of styrene maleic anhydride sodium salt, stirred at 80 ℃ for 3h, and cooled to room temperature for use.
(3) Emulsification of the core material: adding 120mL of deionized water into a 400mL polytetrafluoroethylene beaker, adding an emulsifier (styrene maleic anhydride solution), and stirring for 15min at the rotating speed of 600 rpm; adjusting the pH value to 3.5, adjusting the rotating speed to 3000rpm, slowly dripping 8g of dodecanol, heating to 50 ℃, and stirring for 1.5h to obtain dodecanol emulsion.
(4) The preparation of the melamine-formaldehyde resin solution comprises the steps of adding 50mL of distilled water into a three-neck flask with a reflux condenser tube, adjusting the pH value to 8.5 by using alkali, adding 3.7g of paraformaldehyde, heating to 70 ℃, adding 2.6g of melamine after the solution is clarified, adding 1.25g of triisocyanate after the addition is finished and reacting for 1 hour, and continuing to react for 1 hour.
(5) 0.8g of modified silicon nitride was added to the resin solution obtained in step (4), and the mixture was stirred for 1 hour.
(6) And (3) transferring the lauryl alcohol-containing emulsion prepared in the step (3) into a new three-neck flask, heating to 80 ℃, dripping the modified melamine formaldehyde resin solution prepared in the step (5) while heating, reacting for 3 hours, cooling to room temperature, performing suction filtration, and drying to obtain the melamine formaldehyde resin/lauryl alcohol composite material with high heat conductivity and high toughness.
Example 5
(1) Modified Si 3 N 4 The preparation of (1): weighing 10g of silicon nitride and 10g of KH-550, ultrasonically mixing for 15min, adding 60mL of ethanol and oxalic acid to adjust the pH to be 4.5, stirring at 80 ℃ and 600rpm for 2h, filtering, washing and freeze-drying.
(2) Preparation of styrene maleic anhydride solution (emulsifier): 45mL of a 3wt% sodium hydroxide solution was added with 5g of styrene maleic anhydride sodium salt, stirred at 80 ℃ for 3 hours, and cooled to room temperature for later use.
(3) Emulsification of the core material: adding 120mL of deionized water into a 400mL polytetrafluoroethylene beaker, adding an emulsifier (styrene maleic anhydride solution), and stirring for 15min at the rotating speed of 600 rpm; adjusting the pH value to 3.5, adjusting the rotating speed to 3000rpm, slowly dripping 8g of dodecanol, heating to 50 ℃, and stirring for 1.5h to obtain dodecanol emulsion.
(4) Preparation of melamine formaldehyde resin solution: adding 50mL of distilled water into a three-neck flask with a reflux condenser pipe, adjusting the pH value to 8.5 by using alkali, adding 3.7g of paraformaldehyde, heating to 70 ℃, adding 2.6g of melamine after the solution is clarified, adding 0.8g of triisocyanate after the solution is reacted for 1 hour, and continuing the reaction for 1 hour.
(5) 0.2g of modified silicon nitride was added to the resin solution obtained in step (4), and the mixture was stirred for 1 hour.
(6) And (3) transferring the lauryl alcohol-containing emulsion prepared in the step (3) into a new three-neck flask, heating to 80 ℃, dripping the modified melamine formaldehyde resin solution prepared in the step (5) while heating, reacting for 3 hours, cooling to room temperature, performing suction filtration, and drying to obtain the melamine formaldehyde resin/lauryl alcohol composite material with high heat conductivity and high toughness.
Example 6
(1) Modified Si 3 N 4 The preparation of (1): weighing 10g of silicon nitride and 10g of KH-550, ultrasonically mixing for 15min, adding 60mL of ethanol and oxalic acid to adjust the pH =4.5, stirring at 80 ℃ and 600rpm for 2h, filtering, washing and freeze-drying.
(2) Preparation of styrene maleic anhydride solution (emulsifier): 45mL of a 3wt% sodium hydroxide solution was added to 5g of styrene maleic anhydride sodium salt, stirred at 80 ℃ for 3h, and cooled to room temperature for use.
(3) Emulsification of the core material: adding 120mL of deionized water into a 400mL polytetrafluoroethylene beaker, adding an emulsifier (styrene maleic anhydride solution), and stirring for 15min at the rotating speed of 600 rpm; adjusting the pH value to 3.5, adjusting the rotating speed to 3000rpm, slowly dripping 8g of dodecanol, heating to 50 ℃, and stirring for 1.5h to obtain dodecanol emulsion.
(4) Preparation of melamine formaldehyde resin solution: adding 50mL of distilled water into a three-neck flask with a reflux condenser pipe, adjusting the pH value to 8.5 by using alkali, adding 3.7g of paraformaldehyde, heating to 70 ℃, adding 2.6g of melamine after the solution is clarified, adding 0.4g of triisocyanate after the solution is reacted for 1 hour, and continuing the reaction for 1 hour.
(5) 0.2g of modified silicon nitride was added to the resin solution obtained in step (4), and the mixture was stirred for 1 hour.
(6) And (3) transferring the lauryl alcohol-containing emulsion prepared in the step (3) into a new three-neck flask, heating to 80 ℃, dripping the modified melamine formaldehyde resin solution prepared in the step (5) while heating, reacting for 3 hours, cooling to room temperature, performing suction filtration, and drying to obtain the melamine formaldehyde resin/lauryl alcohol composite material with high heat conductivity and high toughness.
Comparative example 1 (comparison with example 1, without addition of modified silicon nitride)
(1) Preparation of styrene maleic anhydride solution (emulsifier): 45mL of a 3wt% sodium hydroxide solution was added to 5g of styrene maleic anhydride sodium salt, stirred at 80 ℃ for 3h, and cooled to room temperature for use.
(2) Emulsification of the core material: adding 120mL of deionized water into a 400mL polytetrafluoroethylene beaker, adding an emulsifier (styrene maleic anhydride solution), and stirring for 15min at the rotating speed of 600 rpm; adjusting the pH value to 3.5, adjusting the rotating speed to 3000rpm, slowly dripping 8g of dodecanol, heating to 50 ℃, and stirring for 1.5h to obtain dodecanol emulsion.
(3) The preparation of the melamine-formaldehyde resin solution comprises the steps of adding 50mL of distilled water into a three-neck flask with a reflux condenser tube, adjusting the pH value to 8.5 by using alkali, adding 3.7g of paraformaldehyde, heating to 70 ℃, adding 2.6g of melamine after the solution is clarified, adding 1.25g of triisocyanate after the reaction is finished and reacting for 1 hour, and continuing stirring for 1 hour.
(4) And (3) transferring the lauryl alcohol-containing emulsion prepared in the step (2) into a new three-neck flask, heating to 80 ℃, dripping the melamine formaldehyde resin solution prepared in the step (3) while heating, reacting for 3 hours, cooling to room temperature, filtering, and drying.
Comparative example 2 (comparison with example 1, without triisocyanate)
(1) Modified Si 3 N 4 The preparation of (1): weighing 10g of silicon nitride and 10g of KH-550, ultrasonically mixing for 15min, adding 60mL of ethanol and oxalic acid to adjust the pH to be 4.5, stirring at 80 ℃ and 600rpm for 2h, filtering, washing and freeze-drying.
(2) Preparation of styrene maleic anhydride solution (emulsifier): 45mL of a 3wt% sodium hydroxide solution was added to 5g of styrene maleic anhydride sodium salt, stirred at 80 ℃ for 3h, and cooled to room temperature for use.
(3) Emulsification of the core material: adding 120mL of deionized water into a 400mL polytetrafluoroethylene beaker, adding an emulsifier (styrene maleic anhydride solution), and stirring for 15min at the rotating speed of 600 rpm; adjusting the pH value to 3.5, adjusting the rotating speed to 3000rpm, slowly dripping 8g of dodecanol, heating to 50 ℃, and stirring for 1.5h to obtain dodecanol emulsion.
(4) The preparation of the melamine formaldehyde resin solution comprises the steps of adding 50mL of distilled water into a three-neck flask with a reflux condenser pipe, adjusting the pH value to 8.5 by using alkali, adding 3.7g of paraformaldehyde, heating to 70 ℃, adding 2.6g of melamine after the solution is clarified, and continuing to react for 1 hour after the addition is finished.
(5) 0.2g of modified silicon nitride was added to the resin solution obtained in step (4), and the mixture was stirred for 1 hour.
(6) And (4) transferring the lauryl alcohol-containing emulsion prepared in the step (3) into a new three-neck flask, heating to 80 ℃, dripping the modified melamine formaldehyde resin solution prepared in the step (5) while heating, reacting for 3 hours, cooling to room temperature, performing suction filtration, and drying.
Comparative example 3 (addition of unmodified silicon nitride compared with example 1)
(1) Preparation of styrene maleic anhydride solution (emulsifier): 45mL of a 3wt% sodium hydroxide solution was added to 5g of styrene maleic anhydride sodium salt, stirred at 80 ℃ for 3h, and cooled to room temperature for use.
(2) Emulsification of the core material: adding 120mL of deionized water into a 400mL polytetrafluoroethylene beaker, adding an emulsifier (styrene maleic anhydride solution), and stirring for 15min at the rotating speed of 600 rpm; adjusting the pH value to 3.5, adjusting the rotating speed to 3000rpm, slowly dripping 8g of dodecanol, heating to 50 ℃, and stirring for 1.5h to obtain dodecanol emulsion.
(3) Preparation of melamine formaldehyde resin solution: adding 50mL of distilled water into a three-neck flask with a reflux condenser pipe, adjusting the pH value to 8.5 by using alkali, adding 3.7g of paraformaldehyde, heating to 70 ℃, adding 2.6g of melamine after the solution is clarified, adding 0.8g of triisocyanate after the solution is reacted for 1 hour, and continuing the reaction for 1 hour.
(4) 0.2g of silicon nitride was added to the resin solution obtained in step (3), and the mixture was stirred for 1 hour.
(5) And (3) transferring the lauryl alcohol-containing emulsion prepared in the step (2) into a new three-neck flask, heating to 80 ℃, dripping the modified melamine formaldehyde resin solution prepared in the step (4) while heating, reacting for 3 hours, cooling to room temperature, performing suction filtration, and drying.
And a differential scanning calorimeter is used for measuring the thermal properties of the melamine formaldehyde resin/dodecanol composite material with high thermal conductivity and high toughness and pure dodecanol. The endothermic enthalpy change of the material can be obtained by measuring at a temperature of 20 ℃ to 70 ℃ and a temperature rise rate of 10 ℃/min in a nitrogen atmosphere. In the high-thermal-conductivity high-toughness melamine formaldehyde resin/dodecanol composite material, the coating rate omega (%) of dodecanol can be estimated according to the formula (1):
ω=ΔH the obtained powder is /ΔH Dodecanol *100% （1）
The mechanical strength of the melamine formaldehyde resin/dodecanol composite is described by the cracking rate. Generally, high toughness corresponds to low crack rates. To test the cracking rate, an amount of powder was dispersed in distilled water and the suspension was mechanically sheared at 5000 rpm for 10 min. The suspension was then filtered and washed twice with ethanol and three times with petroleum ether. Finally, the product was dried at room temperature. The cracking rate (N%) can be estimated according to the formula (2):
N=(W 0 -W t )*ω/W o *100% (2)
wherein, W o Is the weight of the microcapsules before shearing (g), W t Is the mass (g) of the microcapsules after shearing, and ω is the coating rate of dodecanol in the powder.
Table 1: lauryl alcohol content and cracking rate tables for examples 1, 5, 6 and comparative example 2
From table 1 it can be derived that the dodecanol content is substantially unchanged, but the cracking rate of the triisocyanate-modified powder is significantly lower than that of the unmodified microcapsules, and the cracking rate decreases with increasing amount of triisocyanate added. Indicating that certain amounts of triisocyanate can increase the flexibility of the melamine, thereby reducing the cracking rate.
Table 2: relational tables between silicon nitride addition amounts and thermal conductivities of examples 1 to 4 and comparative examples 1 and 3
As can be seen from Table 2, with the increase of the addition amount of silicon nitride, the heat conductivity coefficient of the composite material increases, and the heat conduction effect of the composite material is better. Meanwhile, after the unmodified silicon nitride is added, although the thermal conductivity coefficient is improved to a certain extent, the effect is not as good as that after the modification, the reason is that the boundary effect of the unmodified inorganic silicon nitride powder and the organic resin is obvious, and the silicon nitride cannot grow on the melamine-formaldehyde resin well, so that the improvement of the overall performance of the composite material is limited.
Fig. 1 shows that the melamine-formaldehyde resin/dodecanol composite material with high thermal conductivity and high toughness prepared in example 1 is spherical, and the surface of the sphere is provided with small spheres, namely nano silicon nitride, which indicates that the silicon nitride reacts with the melamine-formaldehyde resin to form a product to coat dodecanol.
Fig. 2 shows that the melamine formaldehyde resin/dodecanol material prepared in comparative example 1 has smooth spherical outer wall, and is also observed to have partial spherical rupture and hollow structure in the middle, thus proving that the melamine formaldehyde resin serves as the outer wall and the dodecanol is coated inside to have a core-shell structure.
Fig. 3 shows the silicon nitride modified melamine-formaldehyde resin, dodecanol, high thermal conductivity and high toughness melamine-formaldehyde resin/dodecanol composite material of example 1. Dodecanol is 3300 cm -1 Has a broad peak, and is O-H stretching vibration, 2900 cm -1 The strong peak appeared to be CH 2 Stretching vibration of key, 1050cm -1 O-H stretching vibration of primary alcohol. Silicon nitride modified melamine formaldehyde resinLipid concentrations of about 2923 and 1606 cm -1 The strong peak detected is caused by NH stretching and bending vibration; 3300 cm of -1 The strong and wide absorption peak nearby is generated by the superposition of the absorption peaks of stretching vibration of O-H and N-H, 1560 cm -1 And 1500 cm -1 Two strong absorption peaks appear, which are related to C = N stretching vibration on the aromatic ring and N-H shear bending vibration, and the C-N stretching vibration absorption peak appears in 1350 cm -1 To (3). Characteristic absorption bands of the core material dodecanol and the silicon nitride modified melamine formaldehyde resin appear in the curve of the high-thermal-conductivity high-toughness melamine formaldehyde resin/dodecanol composite material, and the fact that the core material dodecanol is coated by the silicon nitride modified melamine-formaldehyde resin is indicated.
The above description is only a preferred embodiment of the present invention, and all the equivalent changes and modifications made according to the claims of the present invention should be covered by the present invention.
Claims (5)
1. A preparation method of a melamine formaldehyde resin/dodecanol composite material with high thermal conductivity and high toughness is characterized by comprising the following steps:
1) Emulsification of the core material: adding 120mL of deionized water into a 400mL polytetrafluoroethylene beaker, adding an emulsifier, stirring for 15min at the rotating speed of 600rpm, then adjusting the pH to 3.5, adjusting the rotating speed to 3000rpm, slowly dropwise adding dodecanol, heating to 50 ℃, and stirring for 1.5h to obtain dodecanol emulsion;
2) Preparation of melamine formaldehyde solution: adding 50mL of distilled water into a three-neck flask with a reflux condenser, adjusting the pH value to 8.5 by using alkali, adding 3.7g of paraformaldehyde, heating to 70 ℃, adding 2.6g of melamine after the solution is clarified, reacting for 1h, adding a certain amount of triisocyanate, and continuously stirring for 1h to obtain a melamine-formaldehyde solution;
3) Preparation of modified melamine formaldehyde resin solution: adding a certain amount of modified silicon nitride powder into the melamine formaldehyde solution, and continuously reacting for 1h;
4) Heating the dodecanol emulsion to 80 ℃, heating while dripping the modified melamine formaldehyde resin solution prepared in the step 3), reacting for 3 hours, cooling to room temperature, filtering, and drying to obtain the melamine formaldehyde resin/dodecanol composite material.
2. The process according to claim 1, wherein the melamine is added in step 2) in three portions according to 3.
3. The preparation method according to claim 1, wherein the modified silicon nitride is modified with KH-550, and the preparation method comprises the following steps: weighing 10g of silicon nitride and 10g of KH-550, ultrasonically mixing for 15min, adding 60mL of ethanol solvent, adjusting the pH value by oxalic acid to be 4.5-5.5, stirring for 2h at 80 ℃ and 600rpm, filtering, washing and freeze-drying.
4. The method of claim 1, wherein the amount of the tri-isocyanate added in step 2) is 40 to 60% by mass of the melamine.
5. The method according to claim 1, wherein the modified silicon nitride is added in step 3) in an amount of 0.2g to 0.8g by mass.
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| CN101555401A (en) * | 2008-04-10 | 2009-10-14 | 中国科学院化学研究所 | Microcapsule of organic phase change energy storage material and preparation method thereof |
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