Flame-retardant and heat-conducting epoxy composite material as well as preparation method and application thereof
By adding pipylin formaldehyde and modified thermal conductive particles to the epoxy resin curing system, combined with amine aldehyde contraction reactions, prepare the dual -epoxy composite materials with flame retardant and thermal conductivity The problem of difficulty in balance realizes the high heat guidance, good insulation and mechanical properties of materials.
Patent Information
- Application Number
- CN202411690780.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-25
- Publication Date
- 2025-01-24
AI Technical Summary
Existing thermal conductivity and flame retardant epoxy composite materials are difficult to achieve a balance between thermal conductivity and insulation properties, and at the same time lack good mechanical properties.
By adding pheasitin formaldehyde and modified thermal particle fillers to the epoxy resin curing system, combined with high -activated amine aldo contraction reactions, prepare epoxy composite materials with flame retardant and thermal conductivity.
It has realized the both the high -heat guidance, good insulation and mechanical properties of materials, and has a wide range of prospects, especially in the field of high -end multi -functional composite materials.
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Figure CN119350803A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the field of polymer materials, and in particular to a flame retardant and heat conductive epoxy composite material and a preparation method and application thereof. Background Art
[0002] Epoxy composites are widely used in daily life fields such as adhesives, coatings and plastic molds. However, with the increasing awareness of fire prevention, more and more application fields of epoxy composites require high heat dissipation, and the research on flame retardant and thermal conductive epoxy composites is imminent.
[0003] In the field of thermal conductive epoxy composite materials, the heat dissipation performance of the material is generally improved by adding thermal conductive fillers, and the improvement in heat dissipation performance is proportional to the amount of filler used. In the field of flame retardant epoxy composite materials, the fire resistance of the material is generally improved by adding flame retardant fillers, and the increase in flame retardancy is also proportional to the amount of filler used. Therefore, it is difficult to achieve a balance between thermal conductivity and insulation performance. Therefore, there is a need for an energy-saving epoxy composite material that has both thermal conductivity and insulation performance and good mechanical properties. Summary of the invention
[0004] In view of the above-mentioned deficiencies and problems in the prior art, an object of the present invention is to provide an epoxy composite material with good thermal conductivity, insulation and mechanical properties.
[0005] Another object of the present invention is to provide a method for preparing the epoxy composite material.
[0006] Another object of the present invention is to provide application of the epoxy composite material.
[0007] In order to achieve the above invention objectives, the present invention provides a flame retardant and thermally conductive epoxy composite material, which includes the following components: epoxy resin, terephthalaldehyde, amine curing agent, modified thermally conductive particle filler and diluent.
[0008] In a preferred embodiment, the epoxy composite material according to the present invention comprises, by weight, 30-50 parts of epoxy resin, 10-20 parts of terephthalaldehyde, 2-10 parts of amine curing agent, 35-75 parts of modified thermal conductive particle filler and 10-30 parts of diluent.
[0009] In a preferred embodiment, the epoxy resin is at least one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, novolac epoxy resin, and alicyclic epoxy resin.
[0010] In a preferred embodiment, the amine curing agent is at least one or more of dicyandiamide, aliphatic amine, alicyclic amine, polyether amine and aromatic amine. The aliphatic amine is preferably diethylenetriamine, but not limited thereto. The alicyclic amine is preferably isophoronediamine, but not limited thereto. The aromatic amine is preferably meta-xylylenediamine, but not limited thereto.
[0011] In a preferred embodiment, the diluent is at least one or more of acetone, butanone, toluene, dichloromethane, N,N-dimethylformamide and N,N-dimethylacetamide.
[0012] In a preferred embodiment, the modified thermally conductive particle filler is a thermally conductive particle filler treated with a silane coupling agent or a titanate coupling agent. Specifically, the modified thermally conductive particle filler is preferably obtained by grafting organic functional groups on the surface of the thermally conductive powder through a dry modification process.
[0013] In a preferred embodiment, the thermally conductive particles are at least one or more of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, aluminum hydroxide or artificial diamond.
[0014] In another aspect, the present invention provides a method for preparing the flame retardant and thermally conductive epoxy composite material, the method comprising the following steps:
[0015] (1) weighing epoxy resin, terephthalaldehyde, amine curing agent, modified thermal conductive particle filler and diluent, stirring and mixing them evenly and degassing to obtain an epoxy resin composite solution;
[0016] (2) pouring the epoxy resin composite solution into a mold, pre-curing at 30-90° C. (preferably 50-90° C.) for 0.5-1 hour (preferably 1 hour) to volatilize the diluent, and then curing at 130-180° C. (preferably 150° C.) for 6-12 hours (preferably 12 hours) to obtain the epoxy composite material.
[0017] In another aspect, the present invention provides use of the flame retardant and thermally conductive epoxy composite material in preparing electronic packaging materials.
[0018] Compared with the prior art, the present invention utilizes a highly active amine-aldehyde condensation reaction to prepare an intrinsic flame retardant network, and only requires adding an organic substance containing a benzaldehyde structure to the existing epoxy resin amine curing system, and the process is simple. A large amount of thermal conductive powder can be added to the above network to prepare a composite material with both flame retardancy and high thermal conductivity, which has broad application prospects in the field of high-end multifunctional composite materials. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 3 is a SEM morphology picture of the epoxy composite material according to the preferred embodiment 1 of the present invention.
[0020] Figure 2 This is a schematic diagram of the intrinsic flame retardancy of phenylimide. DETAILED DESCRIPTION
[0021] In order to facilitate the understanding of the present invention, the present invention will be described more fully below with reference to relevant embodiments. Preferred embodiments of the present invention are given in the embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.
[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.
[0023] The reagents used in the following examples, unless otherwise specified, can be obtained from commercial channels; the methods used in the following examples, unless otherwise specified, can be implemented by conventional methods.
[0024] Example 1
[0025] An epoxy composite material, the preparation steps of which are as follows:
[0026] Step 1: Take 30 parts of epoxy resin E51, 10 parts of terephthalaldehyde, 2 parts of dicyandiamide, 50 parts of KH-560 modified boron nitride filler and 10 parts of acetone according to weight parts, stir and mix them evenly with a stirrer and degas to obtain an epoxy resin composite solution;
[0027] Step 2: Pour the epoxy resin composite solution into a mold, pre-cure at 30° C. for 0.5 hours to volatilize the diluent, and then cure at 130° C. for 12 hours to obtain an epoxy composite material.
[0028] The preparation method of the KH-560 modified boron nitride filler is as follows: add boron nitride powder to KH-560, heat and stir at 90°C for 1 hour, filter and dry to obtain the filler. The amount of KH-560 used is 1% of the powder mass.
[0029] Example 2
[0030] An epoxy composite material, the preparation steps of which are as follows:
[0031] Step 1: Take 50 parts of epoxy resin E44, 20 parts of terephthalaldehyde, 10 parts of diethylenetriamine (fatty amine), 75 parts of KH-560 modified boron nitride filler and 20 parts of N,N-dimethylformamide according to weight parts, stir and mix them evenly with a stirrer and degas to obtain an epoxy resin composite solution;
[0032] Step 2: Pour the epoxy resin composite solution into a mold, pre-cure at 90° C. for 1 hour to volatilize the diluent, and then cure at 180° C. for 6 hours to obtain an epoxy composite material.
[0033] The preparation method of the KH-560 modified boron nitride filler is as follows: add boron nitride powder to KH-560, heat and stir at 90°C for 1 hour, filter and dry to obtain the filler. The amount of KH-560 used is 1% of the powder mass.
[0034] Example 3
[0035] An epoxy composite material, the preparation steps of which are as follows:
[0036] Step 1: Take 50 parts of epoxy resin E51, 20 parts of terephthalaldehyde, 8 parts of isophorone diamine (alicyclic amine), 50 parts of KH-560 modified aluminum nitride filler and 30 parts of toluene according to weight parts, stir and mix them evenly with a stirrer and degas to obtain an epoxy resin composite solution;
[0037] Step 2: Pour the epoxy resin composite solution into a mold, pre-cure at 60° C. for 1 hour to volatilize the diluent, and then cure at 180° C. for 12 hours to obtain an epoxy composite material.
[0038] The preparation method of the aluminum nitride filler modified by KH-560 is as follows: aluminum nitride powder is added to KH-560, heated and stirred at 90°C for 1 hour, and then filtered and dried. The amount of KH-560 used is 1% of the powder mass.
[0039] Example 4
[0040] An epoxy composite material, the preparation steps of which are as follows:
[0041] Step 1: Take 40 parts of alicyclic epoxy resin (3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexylmethyl ester), 20 parts of terephthalaldehyde, 6 parts of meta-phenylenediamine (aromatic amine), 50 parts of KH-560 modified silicon nitride filler and 20 parts of N,N-dimethylformamide according to weight parts, stir and mix evenly with a stirrer and degas, to obtain an epoxy resin composite solution;
[0042] Step 2: Pour the epoxy resin composite solution into a mold, pre-cure at 90° C. for 1 hour to volatilize the diluent, and then cure at 130° C. for 8 hours to obtain an epoxy composite material.
[0043] The preparation method of the KH-560 modified silicon nitride filler is as follows: add silicon nitride powder to KH-560, heat and stir at 90°C for 1 hour, filter and dry to obtain the filler. The amount of KH-560 used is 1% of the powder mass.
[0044] Example 5
[0045] An epoxy composite material, the preparation steps of which are as follows:
[0046] Step 1: Take 30 parts of bisphenol F epoxy resin (DGEBS), 20 parts of terephthalaldehyde, 4 parts of dicyandiamide, 35 parts of KH-560 modified alumina filler and 20 parts of N,N-dimethylformamide according to weight parts, stir and mix them evenly with a stirrer and degas to obtain an epoxy resin composite solution;
[0047] Step 2: Pour the epoxy resin composite solution into a mold, pre-cure at 60° C. for 0.5 hour to volatilize the diluent, and then cure at 130° C. for 6 hours to obtain an epoxy composite material.
[0048] The preparation method of the KH-560 modified alumina filler is as follows: add alumina powder to KH-560, heat and stir at 90°C for 1 hour, filter and dry to obtain the filler. The amount of KH-560 used is 1% of the mass of the powder.
[0049] Comparative Example 1
[0050] An epoxy composite material, the preparation steps of which are as follows:
[0051] Step 1: Take 50 parts of epoxy E51, 5 parts of dicyandiamide, 50 parts of KH-560 modified boron nitride filler and 20 parts of N,N-dimethylformamide according to weight parts, stir and mix them evenly with a stirrer and degas to obtain an epoxy resin composite solution;
[0052] Step 2: Pour the epoxy resin composite solution into a mold, pre-cure at 50° C. for 1 hour to volatilize the diluent, and then cure at 150° C. for 6 hours to obtain an epoxy composite material.
[0053] The preparation method of the KH-560 modified boron nitride filler is as follows: add boron nitride powder to KH-560, heat and stir at 90°C for 1 hour, filter and dry to obtain the filler. The amount of KH-560 used is 1% of the powder mass.
[0054] Comparative Example 2
[0055] An epoxy composite material, the preparation steps of which are as follows:
[0056] Step 1: Take 50 parts of epoxy E51, 10 parts of terephthalaldehyde, 5 parts of dicyandiamide, 50 parts of unmodified boron nitride filler and 20 parts of N,N-dimethylformamide according to weight parts, use a stirrer to mix evenly and degas to obtain an epoxy resin composite solution.
[0057] Step 2: Pour the epoxy resin composite solution into a mold, pre-cure at 50° C. for 1 hour to volatilize the diluent, and then cure at 150° C. for 6 hours to obtain an epoxy composite material.
[0058] Comparative Example 3
[0059] An epoxy composite material, the preparation method of which comprises the following steps:
[0060] Step 1: Take 50 parts of epoxy E51, 10 parts of terephthalaldehyde, 5 parts of methyltetrahydrophthalic anhydride, 50 parts of unmodified boron nitride filler and 20 parts of acetone according to weight parts, stir and mix them evenly with a stirrer and degas to obtain an epoxy resin composite solution;
[0061] Step 2: Pour the epoxy resin composite solution into a mold, pre-cure at 90° C. for 1 hour to volatilize the diluent, and then cure at 150° C. for 6 hours to obtain an epoxy composite material.
[0062] Performance Test:
[0063] Thermal conductivity: The thermal diffusion coefficient of the implementation case and the comparison case was tested using the DXF 900 laser scattering thermal conductivity meter from TA, USA.
[0064] Dielectric strength: Chroma 19073 was used to test the dielectric strength of the implementation case and the comparison case.
[0065] Glass transition temperature: The different samples were studied and analyzed using a DSC 25 differential scanning calorimeter from TA Instruments, USA.
[0066] Mechanical properties: The samples were tested using the UTM 5000 universal testing machine from Shenzhen Sansi Company. Based on ASTM D638-03, each sample was tested five times.
[0067] Limiting Oxygen Index Test (LOI): The limiting oxygen index test is carried out in accordance with ASTM D2863 standard. LOI indicates the minimum oxygen concentration in a mixture of oxygen and nitrogen that can just sustain the combustion of the material.
[0068] Vertical combustion: Burn the test sample with a Bunsen burner for 10±0.5 seconds, then remove the Bunsen burner at a speed of 300mm / s and record the first spontaneous combustion time (t1). After the spontaneous combustion stops, immediately carry out the second combustion, and after burning for 10±0.5 seconds, remove the Bunsen burner and record the second spontaneous combustion time (t2).
[0069] Morphology analysis: The surface morphology of the gold-plated samples was observed using an EVO18 scanning electron microscope produced by Carl Zeiss, Germany.
[0070] Figure 1 The SEM morphology of the sample prepared in Example 1 is shown. Figure 1 It can be seen that boron nitride is densely arranged inside the resin network to form a good thermal conductivity path, thereby achieving high thermal conductivity.
[0071] The test results are shown in Table 1.
[0072] Table 1. Performance comparison of examples and comparative examples
[0073]
[0074] The present invention introduces terephthalaldehyde into the existing epoxy resin curing system without changing the existing epoxy resin curing process, and has good application prospects. From the test results in Table 1, it can be seen that the prepared composite material has both flame retardant and thermal conductive properties. Figure 2 As shown, the phenylimide bonds condense into rings at high temperatures to form a dense carbon layer, thereby achieving a physical barrier effect and preventing further combustion of the material.
[0075] Comparing the limiting oxygen index (LOI) and vertical combustion of Example 1 and Comparative Example 1, it can be seen that the limiting oxygen index of the composite material without adding terephthalaldehyde is lower, and the vertical combustion t1 and t2 time are longer, indicating that the phenylimide structure can play an intrinsic flame retardant role. By adding the modified thermally conductive particles, the thermal conductivity of the composite material can be efficiently improved. It can be seen from the thermal conductivity of Example 1 and Comparative Example 2 that the modified thermally conductive particle filler increases the interfacial wettability with the resin, thereby showing higher thermal conductivity. By comparing Example 1 and Comparative Example 3, it can be seen that the anhydride curing agent cannot react with terephthalaldehyde, so the composite material obtained by curing has a lower limiting oxygen index and a longer vertical combustion t1 and t2 time.
[0076] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
[0077] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.
Claims
1. A flame retardant and thermally conductive epoxy composite material, characterized in that The invention comprises the following components: epoxy resin, terephthalaldehyde, amine curing agent, modified thermal conductive particle filler and diluent.
2. The epoxy composite material according to claim 1, characterized in that: The epoxy composite material comprises, by weight, 30-50 parts of epoxy resin, 10-20 parts of terephthalaldehyde, 2-10 parts of amine curing agent, 35-75 parts of modified thermal conductive particle filler and 10-30 parts of diluent.
3. The epoxy composite material according to claim 1, characterized in that: The epoxy resin is at least one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, novolac epoxy resin, and alicyclic epoxy resin.
4. The epoxy composite material according to claim 1, characterized in that: The amine curing agent is at least one or more of dicyandiamide, aliphatic amine, alicyclic amine, polyether amine and aromatic amine.
5. The epoxy composite material according to claim 1, characterized in that: The diluent is at least one or more of acetone, butanone, toluene, dichloromethane, N,N-dimethylformamide and N,N-dimethylacetamide.
6. The epoxy composite material according to claim 1, characterized in that: The modified thermally conductive particle filler is a thermally conductive particle filler modified by a silane coupling agent or a titanate coupling agent.
7. The epoxy composite material according to claim 6, characterized in that: The thermally conductive particles are at least one or more of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, aluminum hydroxide or artificial diamond.
8. The epoxy composite material according to claim 6, characterized in that: Organic functional groups are grafted onto the surface of the thermally conductive powder through a dry modification process to obtain the modified thermally conductive particle filler.
9. A method for preparing the epoxy composite material according to any one of claims 1 to 8, characterized in that The following steps are involved: (1) weighing epoxy resin, terephthalaldehyde, amine curing agent, modified thermal conductive particle filler and diluent, stirring and mixing them evenly and degassing to obtain an epoxy resin composite solution; (2) pouring the epoxy resin composite solution into a mold, pre-curing at 30-90° C. for 0.5-1 hour to volatilize the diluent, and then curing at 130-180° C. for 6-12 hours to obtain the epoxy composite material.
10. Use of the epoxy composite material according to any one of claims 1 to 8 in preparing electronic packaging materials.