WO2022257291A1 - Thermally conductive pbt material having bicontinuous phase three-dimensional network structure - Google Patents

Thermally conductive pbt material having bicontinuous phase three-dimensional network structure Download PDF

Info

Publication number
WO2022257291A1
WO2022257291A1 PCT/CN2021/118378 CN2021118378W WO2022257291A1 WO 2022257291 A1 WO2022257291 A1 WO 2022257291A1 CN 2021118378 W CN2021118378 W CN 2021118378W WO 2022257291 A1 WO2022257291 A1 WO 2022257291A1
Authority
WO
WIPO (PCT)
Prior art keywords
pbt
dimensional network
network structure
thermally conductive
temperature
Prior art date
Application number
PCT/CN2021/118378
Other languages
French (fr)
Chinese (zh)
Inventor
陈登龙
吴惠民
吴丹丹
柯俊沐
吴健健
Original Assignee
福建师范大学泉港石化研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 福建师范大学泉港石化研究院 filed Critical 福建师范大学泉港石化研究院
Publication of WO2022257291A1 publication Critical patent/WO2022257291A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B30/00—Compositions for artificial stone, not containing binders
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular

Definitions

  • the invention relates to a thermally conductive material, more specifically to a thermally conductive PBT material with a dual continuous phase three-dimensional network structure.
  • Thermally conductive polymer materials have many advantages, such as low material density, good stability, low price, low electrical conductivity, easy production and molding, and flexible product design. In the selection of many component materials, thermally conductive polymer materials are increasingly replacing metal materials, and the research on thermally conductive polymer materials presents a vibrant scene.
  • thermally conductive polymer materials are filled, and this material has some defects, that is, when the content of thermally conductive fillers is low, the thermal conductivity of thermally conductive plastics is poor, which cannot meet the requirements of actual use, and the content of thermally conductive fillers is high. , the thermal conductivity is good, but the thermally conductive high polymer material will have problems such as a significant decrease in mechanical properties and processing difficulties. Therefore, reducing the amount of thermally conductive filler used and preparing thermally conductive polymer materials has become a popular research direction.
  • thermally conductive material can achieve high thermal conductivity with low addition of thermally conductive components.
  • the object of the present invention is to provide a thermally conductive PBT material with a dual continuous phase three-dimensional network structure.
  • the thermally conductive material has a special three-dimensional network structure and is easy to form a complete thermally conductive material in the resin material
  • the channel has the advantages of less addition ratio, good thermal conductivity, and no damage to the original mechanical properties of the material.
  • a dual-continuous phase three-dimensional network structure heat-conducting PBT material characterized in that, in parts by weight, 70-100 parts of resin, 15-25 parts of heat-conducting material, 5-15 parts of toughening agent, and 4-8 parts of compatibilizer 0.5-1.5 parts of lubricant, 0.1-0.3 parts of antioxidant, prepared by high mixing, plasticizing and granulating;
  • the preparation method comprises the following steps:
  • step (3) Add the premixed material obtained in step (2) to a twin-screw extruder to extrude and granulate to obtain a dual-continuous-phase three-dimensional network structure heat-conducting PBT material; control the working parameters of the twin-screw extruder as follows: The temperature of the first zone is 130-150°C, the temperature of the second zone is 150-200°C, the temperature of the third zone is 200-250°C, the temperature of the fourth zone is 200-250°C, the temperature of the fifth zone is 200-230°C, and the temperature of the die head is 180 -220°C, the feeding speed is 50-100r/min, and the screw speed is 200-250r/min.
  • thermally conductive material is a three-dimensional network structure thermally conductive material.
  • thermally conductive material with a three-dimensional network structure is prepared according to the following steps:
  • the treated graphite whiskers in S1 have a diameter of 0.2-2 ⁇ m and a length of ⁇ 50 ⁇ m.
  • the coupling agent described in S2 is at least one of titanate coupling agent, aluminate coupling agent and silane coupling agent, and the solvent is at least one of ethanol, methanol and acetone,
  • the radial dimension of the flaky alumina is 5-50 ⁇ m, the thickness is 100-500 nm, and the average particle size of the AlN is ⁇ 1 ⁇ m.
  • the mesh size of the mesh in S3 is ⁇ 500 mesh.
  • the resin is a PBT/PP composite material with a bicontinuous phase structure
  • the toughening agent is at least one of acrylate high rubber powder, POE, ethylene methyl acrylate copolymer elastomer (EMA)
  • the compatibilizer is at least one of POE-g-MAH and SEBS-g-MAH, and the grafting rate is ⁇ 1.5%
  • the lubricant is at least one of MBS and stearic acid
  • the antioxidant is a mixture of 168 and 1010 in a mass ratio of 1:1-2.
  • the PBT/PP composite material with a bicontinuous phase structure is prepared according to the following steps. First, the two materials of PP and PBT are respectively weighed according to a mass ratio of 5:5 and added to a high-speed mixer for thorough mixing, and then put into the opposite direction Engaging parallel twin-screw extruders are melt-extruded and granulated to obtain the PBT/PP composite material with a bicontinuous phase structure; wherein, the screw speed is set at 300-500r/min, and the barrel temperature is set at From the beginning of the section to the end of the machine head, it is 180-200°C, 200-220°C, 200-220°C, 210-230°C, 190-210°C, 190-200°C.
  • the thermally conductive material has a special three-dimensional network structure, and it is easy to form a complete heat conduction channel in the PBT material. It has a small addition ratio, good thermal conductivity, and does not damage the original material. There are advantages such as mechanical properties.
  • the prepared heat-conducting PBT material has the advantages of balanced mechanical properties, good molding and processing performance, and high use value.
  • the raw materials are widely sourced, non-toxic, simple in processing, low in cost, and have broad market prospects.
  • step (3) Add the premixed material obtained in step (2) to a twin-screw extruder to extrude and granulate to obtain a dual-continuous-phase three-dimensional network structure heat-conducting PBT material; control the working parameters of the twin-screw extruder as follows: The temperature of the first zone is 145°C, the temperature of the second zone is 180°C, the temperature of the third zone is 215°C, the temperature of the fourth zone is 230°C, the temperature of the fifth zone is 215°C, the temperature of the die head is 210°C, and the feeding speed is 90r/min. The screw speed is 210r/min;
  • the preparation steps of the PBT/PP composite material with a double continuous phase structure are as follows: Weigh PP and PBT according to the mass ratio of 5:5, add them to a high-speed mixer and mix them thoroughly, and put them into a parallel twin-screw extruder with parallel meshing in different directions. Exit machine melt extrusion granulation. A PBT/PP composite material with a dual continuous phase structure was obtained, the screw speed was set at 450r/min, and the barrel temperature was set from the beginning of the feeding section to the end of the machine head in order of 190°C, 215°C, 220°C, and 225°C , 205°C, 195°C.
  • the heat-conducting material involved is a three-dimensional network structure heat-conducting material, and its preparation method is as follows:
  • step (3) Add the premixed material obtained in step (2) to a twin-screw extruder to extrude and granulate to obtain a dual-continuous-phase three-dimensional network structure heat-conducting PBT material; control the working parameters of the twin-screw extruder as follows: The temperature of the first zone is 130°C, the temperature of the second zone is 150°C, the temperature of the third zone is 200°C, the temperature of the fourth zone is 200°C, the temperature of the fifth zone is 200°C, the temperature of the die head is 180°C, and the feeding speed is 50r/min. The screw speed is 200r/min;
  • the preparation steps of the PBT/PP composite material with a double continuous phase structure are as follows: Weigh PP and PBT according to the mass ratio of 5:5, add them to a high-speed mixer and mix them thoroughly, and put them into a parallel twin-screw extruder with parallel meshing in different directions. Exit machine melt extrusion granulation.
  • the PBT/PP composite material with double continuous phase structure was obtained, the screw speed was set at 300 r/min, and the temperature of the barrel was set from the beginning of the feeding section to the end of the machine head in order of 180°C, 200°C, 200°C, 210°C °C, 190 °C, 190 °C.
  • the heat-conducting material involved is a three-dimensional network structure heat-conducting material, and its preparation method is as follows:
  • the preparation method comprises the following steps:
  • step (3) Add the premixed material obtained in step (2) to a twin-screw extruder to extrude and granulate to obtain a dual-continuous-phase three-dimensional network structure heat-conducting PBT material; control the working parameters of the twin-screw extruder as follows: The temperature of the first zone is 140°C, the temperature of the second zone is 170°C, the temperature of the third zone is 220°C, the temperature of the fourth zone is 230°C, the temperature of the fifth zone is 210°C, the temperature of the die head is 200°C, and the feeding speed is 80r/min. The screw speed is 220r/min;
  • the preparation steps of the PBT/PP composite material with a double continuous phase structure are as follows: Weigh PP and PBT according to the mass ratio of 5:5, add them to a high-speed mixer and mix them thoroughly, and put them into a parallel twin-screw extruder with parallel meshing in different directions. Exit machine melt extrusion granulation. A PBT/PP composite material with a double continuous phase structure was obtained, the screw speed was set at 400r/min, and the barrel temperature was set from the beginning of the feeding section to the end of the machine head in order of 190°C, 210°C, 210°C, and 220°C , 200°C, 200°C.
  • the heat-conducting material involved is a three-dimensional network structure heat-conducting material, and its preparation method is as follows:
  • EMA ethylene methyl acrylate copolymer elastomer
  • step (3) Add the premixed material obtained in step (2) to a twin-screw extruder to extrude and granulate to obtain a dual-continuous-phase three-dimensional network structure heat-conducting PBT material; control the working parameters of the twin-screw extruder as follows: The temperature of the first zone is 150°C, the temperature of the second zone is 200°C, the temperature of the third zone is 250°C, the temperature of the fourth zone is 250°C, the temperature of the fifth zone is 230°C, the temperature of the die head is 220°C, and the feeding speed is 100r/min. The screw speed is 250r/min;
  • the preparation steps of the PBT/PP composite material with a double continuous phase structure are as follows: Weigh PP and PBT according to the mass ratio of 5:5, add them to a high-speed mixer and mix them thoroughly, and put them into a parallel twin-screw extruder with parallel meshing in different directions. Exit machine melt extrusion granulation. A PBT/PP composite material with a double continuous phase structure was obtained, the screw speed was set at 500r/min, and the barrel temperature was set from the beginning of the feeding section to the end of the machine head in order of 200°C, 220°C, 220°C, and 230°C , 210°C, 200°C.
  • the heat-conducting material involved is a three-dimensional network structure heat-conducting material, and its preparation method is as follows:
  • S3 block epoxy resin is pulverized with a pulverizer, and screened with a 1000-mesh screen to finally obtain phenolic resin powder, the graphite whiskers prepared by S1 and the silane coupling agent surface-treated flake aluminum oxide prepared by S2 and Add AlN material and epoxy resin powder into water at a mass ratio of 1:1:12, ultrasonically oscillate and stir for 3 hours to disperse evenly, filter and put in a drying oven for 48 hours at 100°C, and heat up to 300°C after drying. After solidification, the temperature is raised to 900°C in a carbonization furnace under the protection of nitrogen atmosphere for carbonization to obtain a three-dimensional network structure heat-conducting material.
  • step (3) Add the premixed material obtained in step (2) to a twin-screw extruder to extrude and granulate to obtain a dual-continuous-phase three-dimensional network structure heat-conducting PBT material; control the working parameters of the twin-screw extruder as follows: The temperature of the first zone is 145°C, the temperature of the second zone is 180°C, the temperature of the third zone is 215°C, the temperature of the fourth zone is 230°C, the temperature of the fifth zone is 215°C, the temperature of the die head is 210°C, and the feeding speed is 90r/min. The screw speed is 210r/min;
  • the preparation steps of the PBT/PP composite material with a double continuous phase structure are as follows: Weigh PP and PBT according to the mass ratio of 5:5, add them to a high-speed mixer and mix them thoroughly, and put them into a parallel twin-screw extruder with parallel meshing in different directions. Exit machine melt extrusion granulation. A PBT/PP composite material with a dual continuous phase structure was obtained, the screw speed was set at 450r/min, and the barrel temperature was set from the beginning of the feeding section to the end of the machine head in order of 190°C, 215°C, 220°C, and 225°C , 205°C, 195°C.
  • the heat-conducting material involved is a three-dimensional network structure heat-conducting material, and its preparation method is as follows:
  • This comparative example involves providing a dual-continuous-phase heat-conducting PBT material and its preparation method. Its formulation and preparation method are basically the same as in Example 4, the only difference is that the flaky alumina and AlN are directly treated with a coupling agent. The material is used as a heat-conducting material instead of using a three-dimensional network structure heat-conducting material as a heat-conducting material.
  • This comparative example involves providing a dual-continuous-phase heat-conducting PBT material and its preparation method. Its formulation and preparation method are basically the same as in Example 4, the only difference being that a single PBT resin is directly used as the matrix resin instead of a The PBT/PP composite material with double continuous phase structure is used as the matrix resin.
  • Embodiment one to embodiment four comparative example one to the product obtained by comparative example two are subjected to performance test, and its tensile strength is tested according to national standard GB/T1040-2006; Thermal conductivity is tested according to GB/T3399-1982, and the results are shown in Table 1
  • the double-continuous-phase three-dimensional network structure heat-conducting PBT material prepared by the present invention has a special three-dimensional network structure, and it is easy to form a complete heat-conducting channel in the PBT material. It has good performance and does not destroy the original mechanical properties of the material.
  • the PBT/PP composite material with a dual-continuous phase structure is used as the matrix resin.
  • the dual-continuous phase resin It is more conducive to the dispersion of heat-conducting materials in the matrix resin, and the prepared heat-conducting PBT material has the advantages of better balance of mechanical properties, good molding and processing performance, and high use value.
  • Comparative Example 1 uses directly surface-treated flake alumina and AlN materials as heat-conducting materials, instead of using three-dimensional network structure heat-conducting materials as heat-conducting materials.
  • Comparative Example 2 directly uses a single PBT resin as the matrix resin instead of using a PBT/PP composite material with a dual continuous phase structure as the matrix resin.
  • the thermal conductivity of Comparative Example 1 and Comparative Example 2 is inferior to that of Examples 1 to 4.
  • Embodiment 4 has the best overall performance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Disclosed is a thermally conductive PBT material having a bicontinuous phase three-dimensional network structure. The thermally conductive material has a special three-dimensional network structure, can easily form a complete heat conduction channel in a PBT material, and has the advantages of low proportion of additives, good thermal conduction performance and no damage to the original mechanical properties of the material, and the like. Meanwhile, a PBT/PP composite material having the bicontinuous phase structure is used as a matrix resin. Compared with a traditional preparation method of a filler-type thermally conductive PBT material, the adoption of bicontinuous phase resin facilitates dispersion of the thermally conductive material in the matrix resin, and the prepared thermally conductive PBT material has the advantages of uniform mechanical properties, good formation processability and high use value. Moreover, the raw material is widely available and non-toxic, and has a simple processing method, a low cost and a broad market prospect.

Description

一种双连续相立体网络结构导热PBT材料A thermally conductive PBT material with dual continuous phase three-dimensional network structure 技术领域technical field
本发明涉及导热材料，更具体的说是涉及一种双连续相立体网络结构导热PBT材料。The invention relates to a thermally conductive material, more specifically to a thermally conductive PBT material with a dual continuous phase three-dimensional network structure.
背景技术Background technique
随着电子电气技术的高速发展，现代电子设备均朝着质量轻、体积小、使用方便的方向发展。单位体积的电子原件产生的热量越来越多，如果想要这些设备能够正常的工作，能否迅速的散掉产生的热量成为了影响的关键因素。导热高聚物材料具有很多的优点，如材料密度小、稳定性好、价格低廉、导电性低、易于生产成型、产品设计灵活等。在很多元件材料的选择上，导热高聚物材料正越来越多的代替了金属材料，导热高聚物材料的研究呈现了生机勃勃的景象。然而，现在普遍使用的导热高聚物材料是填充型的，这种材料存在着一些缺陷，即导热填料含量较低时导热塑料的导热性能差，不能满足实际使用的要求，导热填料含量较高时，导热性能好，但是导热高聚物材料会出现力学性能显著下降、加工困难等问题。因此，降低了导热填料的使用量，制备导热高聚物材料成为了热门的研究方向。With the rapid development of electronic and electrical technology, modern electronic equipment is developing in the direction of light weight, small size and convenient use. Electronic components per unit volume generate more and more heat. If you want these devices to work normally, whether you can quickly dissipate the generated heat has become a key factor. Thermally conductive polymer materials have many advantages, such as low material density, good stability, low price, low electrical conductivity, easy production and molding, and flexible product design. In the selection of many component materials, thermally conductive polymer materials are increasingly replacing metal materials, and the research on thermally conductive polymer materials presents a vibrant scene. However, the commonly used thermally conductive polymer materials are filled, and this material has some defects, that is, when the content of thermally conductive fillers is low, the thermal conductivity of thermally conductive plastics is poor, which cannot meet the requirements of actual use, and the content of thermally conductive fillers is high. , the thermal conductivity is good, but the thermally conductive high polymer material will have problems such as a significant decrease in mechanical properties and processing difficulties. Therefore, reducing the amount of thermally conductive filler used and preparing thermally conductive polymer materials has become a popular research direction.
技术问题technical problem
如何从结构入手设计导热组分的协同复合，从而使导热材料达到导热组分在低添加量下具有高导热性能。How to design the synergistic composite of thermally conductive components from the structure, so that the thermally conductive material can achieve high thermal conductivity with low addition of thermally conductive components.
技术解决方案technical solution
为了克服现有技术中存在的缺点和不足，本发明的目的在于提供一种双连续相立体网络结构导热PBT材料，该导热材料具有特殊的三维网状结构，容易在树脂材料中形成完整的导热通道，具有添加比例少，导热性能好，不破坏材料原有机械性能等优点。In order to overcome the shortcomings and deficiencies in the prior art, the object of the present invention is to provide a thermally conductive PBT material with a dual continuous phase three-dimensional network structure. The thermally conductive material has a special three-dimensional network structure and is easy to form a complete thermally conductive material in the resin material The channel has the advantages of less addition ratio, good thermal conductivity, and no damage to the original mechanical properties of the material.
本发明是通过以下技术方案实现的：The present invention is achieved through the following technical solutions:
一种双连续相立体网络结构导热PBT材料，其特征在于，按重量份数计，取树脂70-100份、导热材料15-25份、增韧剂5-15份、相容剂4-8份、润滑剂0.5-1.5份，抗氧化剂0.1-0.3份，经高混、塑化造粒制备而成；A dual-continuous phase three-dimensional network structure heat-conducting PBT material, characterized in that, in parts by weight, 70-100 parts of resin, 15-25 parts of heat-conducting material, 5-15 parts of toughening agent, and 4-8 parts of compatibilizer 0.5-1.5 parts of lubricant, 0.1-0.3 parts of antioxidant, prepared by high mixing, plasticizing and granulating;
制备方法包括下列步骤：The preparation method comprises the following steps:
（1）按照配比称取树脂、导热材料、增韧剂、相容剂、润滑剂、抗氧化剂，备用；(1) Weigh the resin, thermal conductive material, toughening agent, compatibilizer, lubricant, antioxidant according to the proportion, and set aside;
（2）依次将树脂、导热材料、增韧剂、相容剂、润滑剂、抗氧化剂加入高速混合机内，以250-400rpm/min的转速常温搅拌1h，得到预混料；(2) Add resin, thermal conductive material, toughening agent, compatibilizer, lubricant, and antioxidant into the high-speed mixer in sequence, and stir at room temperature at a speed of 250-400rpm/min for 1 hour to obtain a premix;
（3）将步骤（2）所得的预混料加入到双螺杆挤出机中挤出造粒，得到双连续相立体网络结构导热PBT材料；控制所述双螺杆挤出机的工作参数如下：一区温度为130-150℃，二区温度为150-200℃，三区温度为200-250℃，四区温度为200-250℃，五区温度为200-230℃，模头温度为180-220℃，喂料速度为50-100r/min，螺杆转速为200-250r/min。(3) Add the premixed material obtained in step (2) to a twin-screw extruder to extrude and granulate to obtain a dual-continuous-phase three-dimensional network structure heat-conducting PBT material; control the working parameters of the twin-screw extruder as follows: The temperature of the first zone is 130-150°C, the temperature of the second zone is 150-200°C, the temperature of the third zone is 200-250°C, the temperature of the fourth zone is 200-250°C, the temperature of the fifth zone is 200-230°C, and the temperature of the die head is 180 -220°C, the feeding speed is 50-100r/min, and the screw speed is 200-250r/min.
进一步地，所述导热材料为立体网络结构导热材料。Further, the thermally conductive material is a three-dimensional network structure thermally conductive material.
进一步地，所述立体网络结构导热材料按照如下步骤制备得到：Further, the thermally conductive material with a three-dimensional network structure is prepared according to the following steps:
S1、首先用去离子水配制10wt%的双氧水溶液，然后石墨晶须完全浸入双氧水溶液中，放入微波炉里进行辐射处理，处理时间120s，将反应处理后的样品用去离子水清洗后在干燥炉中干燥，备用得到处理后石墨晶须；S1. First prepare 10wt% hydrogen peroxide solution with deionized water, then completely immerse the graphite whiskers in the hydrogen peroxide solution, put it in a microwave oven for radiation treatment, and the treatment time is 120s. After the reaction treatment, the sample is washed with deionized water and dried Dried in the oven, ready for use to obtain the treated graphite whiskers;
S2、将偶联剂按照质量比是1-3：1加入到溶剂中进行稀释，混合搅拌8-12h，在烧杯中使两种液体混合为均一的液体，将质量比1：3的片状氧化铝和AlN粉末加入混合液体中，不断搅拌均匀，制得偶联剂表面处理片状氧化铝和AlN材料；S2. Add the coupling agent to the solvent according to the mass ratio of 1-3:1 to dilute, mix and stir for 8-12 hours, mix the two liquids into a uniform liquid in a beaker, and dilute the flakes with a mass ratio of 1:3 Alumina and AlN powders are added to the mixed liquid and stirred continuously to obtain flaky alumina and AlN materials with coupling agent surface treatment;
S3、将块状环氧树脂用粉碎机粉碎，并用网筛进行筛选最终得到酚醛树脂粉末，将S1中的处理后石墨晶须和S2制得的偶联剂表面处理片状氧化铝和AlN材料与环氧树脂粉末以1：1：1-2的质量比加入水中，超声振荡并搅拌2-3h使其分散均匀，过滤后放入干燥箱中80-100℃下干燥36-48h，样品干燥后升温至200-300℃进行固化，最后炭化炉中氮气气氛保护下升温至600-900℃进行炭化制得立体网络结构导热材料。S3. Pulverize the bulk epoxy resin with a pulverizer, and screen it with a mesh screen to finally obtain the phenolic resin powder, and treat the treated graphite whiskers in S1 and the coupling agent surface-treated flake aluminum oxide and AlN materials prepared in S2. Add epoxy resin powder to water at a mass ratio of 1:1:1-2, ultrasonically oscillate and stir for 2-3 hours to disperse evenly, filter and put in a drying oven for 36-48 hours at 80-100°C to dry the sample Afterwards, the temperature is raised to 200-300°C for curing, and finally the temperature is raised to 600-900°C for carbonization in a carbonization furnace under the protection of a nitrogen atmosphere to obtain a three-dimensional network structure heat-conducting material.
进一步地，S1中所述处理后石墨晶须，直径0.2-2μm，长度≥50μm。Further, the treated graphite whiskers in S1 have a diameter of 0.2-2 μm and a length of ≥50 μm.
进一步地，S2中所述偶联剂为钛酸酯偶联剂、铝酸酯偶联剂和硅烷偶联剂中的至少一种，所述溶剂为乙醇、甲醇和丙酮中的至少一种，所述片状氧化铝径向尺度为5-50μm，厚度为100-500 nm，所述AlN平均粒径≤1μm。Further, the coupling agent described in S2 is at least one of titanate coupling agent, aluminate coupling agent and silane coupling agent, and the solvent is at least one of ethanol, methanol and acetone, The radial dimension of the flaky alumina is 5-50 μm, the thickness is 100-500 nm, and the average particle size of the AlN is ≤1 μm.
进一步地，S3中所述网筛目数≥500目。Further, the mesh size of the mesh in S3 is ≥500 mesh.
进一步地，所述树脂为具有双连续相形态结构的PBT/PP复合材料；所述增韧剂为丙烯酸酯高胶粉、POE、乙烯丙烯酸甲酯共聚物弹性体(EMA)中的至少一种；所述相容剂为相容剂为POE-g-MAH、SEBS-g-MAH中至少一种，接枝率≥1.5%；所述润滑剂为MBS、硬脂酸中的至少一种；所述抗氧化剂为168和1010按照1：1-2的质量比组成的混合物。Further, the resin is a PBT/PP composite material with a bicontinuous phase structure; the toughening agent is at least one of acrylate high rubber powder, POE, ethylene methyl acrylate copolymer elastomer (EMA) The compatibilizer is at least one of POE-g-MAH and SEBS-g-MAH, and the grafting rate is ≥ 1.5%; the lubricant is at least one of MBS and stearic acid; The antioxidant is a mixture of 168 and 1010 in a mass ratio of 1:1-2.
进一步地，所述具有双连续相形态结构的PBT/PP复合材料按照如下步骤进行制备，首先按照质量比5：5分别称取PP和PBT两种材料加入高速混合机充分混合，然后投入异向啮合平行双螺杆挤出机熔融挤出造粒，制得所述具有双连续相形态结构的PBT/PP复合材料；其中，螺杆转速设定为300-500r/min，机筒温度设定是加料段开始到机头结束依次为180-200℃，200-220℃，200-220℃，210-230℃，190-210℃，190-200℃。Further, the PBT/PP composite material with a bicontinuous phase structure is prepared according to the following steps. First, the two materials of PP and PBT are respectively weighed according to a mass ratio of 5:5 and added to a high-speed mixer for thorough mixing, and then put into the opposite direction Engaging parallel twin-screw extruders are melt-extruded and granulated to obtain the PBT/PP composite material with a bicontinuous phase structure; wherein, the screw speed is set at 300-500r/min, and the barrel temperature is set at From the beginning of the section to the end of the machine head, it is 180-200°C, 200-220°C, 200-220°C, 210-230°C, 190-210°C, 190-200°C.
有益效果Beneficial effect
本发明具有如下的有益效果：The present invention has following beneficial effect:
1、制备一种双连续相立体网络结构导热PBT材料，该导热材料具有特殊的立体网络结构结构，容易在PBT材料中形成完整的导热通道，具有添加比例少，导热性能好，不破坏材料原有机械性能等优点。1. Prepare a thermally conductive PBT material with a dual continuous phase three-dimensional network structure. The thermally conductive material has a special three-dimensional network structure, and it is easy to form a complete heat conduction channel in the PBT material. It has a small addition ratio, good thermal conductivity, and does not damage the original material. There are advantages such as mechanical properties.
2、采用具有双连续相形态结构的PBT/PP复合材料作为基体树脂，相较于传统的填充型导热PBT材料的制备方法，采用双连续相树脂更有利于导热材料在基体树脂中的分散，制得的导热PBT材料具有机械性能均衡、成型加工性能好，使用价值高等优点。2. Using PBT/PP composite material with dual continuous phase structure as the matrix resin, compared with the traditional preparation method of filled thermally conductive PBT material, the use of dual continuous phase resin is more conducive to the dispersion of thermally conductive materials in the matrix resin, The prepared heat-conducting PBT material has the advantages of balanced mechanical properties, good molding and processing performance, and high use value.
3、采用原料来源广泛，无毒害性，加工方法简单，成本低，具有广阔的市场前景。3. The raw materials are widely sourced, non-toxic, simple in processing, low in cost, and have broad market prospects.
本发明的最佳实施方式BEST MODE FOR CARRYING OUT THE INVENTION
一种双连续相立体网络结构导热PBT材料，按重量份数计，取具有双连续相形态结构的PBT/PP复合材料90份；导热材料23份；POE12份；SEBS-g-MAH5.5份；硬脂酸1.2份；抗氧化剂（168：1010=1：2）0.25份；经高混、塑化造粒制备而成。A thermally conductive PBT material with a dual continuous phase three-dimensional network structure. In parts by weight, 90 parts of a PBT/PP composite material with a dual continuous phase structure; 23 parts of a thermal conductive material; 12 parts of POE; 5.5 parts of SEBS-g-MAH ; 1.2 parts of stearic acid; 0.25 parts of antioxidant (168:1010=1:2); prepared by high-mixing and plasticizing granulation.
其制备方法包括下列步骤：Its preparation method comprises the following steps:
（1）按照配比称取树脂、导热材料、增韧剂、相容剂、润滑剂、抗氧化剂，备用；(1) Weigh the resin, thermal conductive material, toughening agent, compatibilizer, lubricant, antioxidant according to the proportion, and set aside;
（2）依次将树脂、导热材料、增韧剂、相容剂、润滑剂、抗氧化剂加入高速混合机内，以350rpm/min的转速常温搅拌1h，得到预混料；(2) Add resin, thermal conductive material, toughening agent, compatibilizer, lubricant, and antioxidant into the high-speed mixer in sequence, and stir at room temperature at a speed of 350rpm/min for 1 hour to obtain a premix;
（3）将步骤（2）所得的预混料加入到双螺杆挤出机中挤出造粒，得到双连续相立体网络结构导热PBT材料；控制所述双螺杆挤出机的工作参数如下：一区温度为145℃，二区温度为180℃，三区温度为215℃，四区温度为230℃，五区温度为215℃，模头温度为210℃，喂料速度为90r/min，螺杆转速为210r/min；(3) Add the premixed material obtained in step (2) to a twin-screw extruder to extrude and granulate to obtain a dual-continuous-phase three-dimensional network structure heat-conducting PBT material; control the working parameters of the twin-screw extruder as follows: The temperature of the first zone is 145°C, the temperature of the second zone is 180°C, the temperature of the third zone is 215°C, the temperature of the fourth zone is 230°C, the temperature of the fifth zone is 215°C, the temperature of the die head is 210°C, and the feeding speed is 90r/min. The screw speed is 210r/min;
其中涉及到的具有双连续相形态结构的PBT/PP复合材料制备步骤如下：按照质量比5：5分别称取PP和PBT两种材料加入高速混合机充分混合，投入异向啮合平行双螺杆挤出机熔融挤出造粒。制得具有双连续相形态结构的PBT/PP复合材料，螺杆转速设定为450r/min，机筒温度设定是加料段开始到机头结束依次为190℃，215℃，220℃，225℃，205℃，195℃。The preparation steps of the PBT/PP composite material with a double continuous phase structure are as follows: Weigh PP and PBT according to the mass ratio of 5:5, add them to a high-speed mixer and mix them thoroughly, and put them into a parallel twin-screw extruder with parallel meshing in different directions. Exit machine melt extrusion granulation. A PBT/PP composite material with a dual continuous phase structure was obtained, the screw speed was set at 450r/min, and the barrel temperature was set from the beginning of the feeding section to the end of the machine head in order of 190°C, 215°C, 220°C, and 225°C , 205°C, 195°C.
其中涉及的导热材料为立体网络结构导热材料，其制备方法如下：The heat-conducting material involved is a three-dimensional network structure heat-conducting material, and its preparation method is as follows:
S1、首先用去离子水配制10wt%的双氧水溶液，然后石墨晶须完全浸入双氧水溶液中，放入微波炉里进行辐射处理，处理时间120s，将反应处理后的样品用去离子水清洗后在干燥炉中干燥、备用；S1. First prepare 10wt% hydrogen peroxide solution with deionized water, then completely immerse the graphite whiskers in the hydrogen peroxide solution, put it in a microwave oven for radiation treatment, and the treatment time is 120s. After the reaction treatment, the sample is washed with deionized water and dried Dry in the oven, ready for use;
S2、将铝酸酯偶联剂按照质量比是1：1加入到乙醇中进行稀释，混合搅拌10h，在烧杯中使两种液体混合为均一的液体，将质量比1：3的片状氧化铝和AlN粉末加入混合液体中，不断搅拌均匀，制得铝酸酯偶联剂表面处理片状氧化铝和AlN材料；S2. Dilute the aluminate coupling agent into ethanol at a mass ratio of 1:1, mix and stir for 10 hours, mix the two liquids into a uniform liquid in a beaker, and oxidize the flakes with a mass ratio of 1:3 Aluminum and AlN powders are added to the mixed liquid and stirred continuously to obtain aluminum oxide coupling agent surface-treated flaky alumina and AlN materials;
S3、将块状环氧树脂用粉碎机粉碎，并用800目网筛进行筛选最终得到酚醛树脂粉末，将S1制得的石墨晶须和S2制得的偶联剂表面处理片状氧化铝和AlN材料与环氧树脂粉末以1：1：2的质量比加入水中，超声振荡并搅拌2.5h使其分散均匀，过滤后放入干燥箱中80℃下干燥40h，样品干燥后升温至280℃进行固化，最后炭化炉中氮气气氛保护下升温至800℃进行炭化制得立体网络结构导热材料。S3. Pulverize the bulk epoxy resin with a pulverizer, and screen it with a 800-mesh screen to finally obtain phenolic resin powder. Surface-treat the graphite whiskers prepared in S1 and the coupling agent prepared in S2 with flaky alumina and AlN Materials and epoxy resin powder were added to water at a mass ratio of 1:1:2, ultrasonically oscillated and stirred for 2.5 hours to disperse evenly, filtered and placed in a drying oven for 40 hours at 80°C, and the sample was dried and then heated to 280°C for After solidification, the temperature is raised to 800°C in a carbonization furnace under the protection of nitrogen atmosphere for carbonization to obtain a three-dimensional network structure heat-conducting material.
本发明的实施方式Embodiments of the present invention
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。The present invention will be described in detail below in conjunction with specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention. These all belong to the protection scope of the present invention.
实施例一Embodiment one
一种双连续相立体网络结构导热PBT材料，按重量份数计，取具有双连续相形态结构的PBT/PP复合材料70份、导热材料15份、丙烯酸酯高胶粉5份、POE-g-MAH 4份、MBS 0.5份、抗氧化剂(168：1010=1：1)0.1份，经高混、塑化造粒制备而成。A thermally conductive PBT material with a dual continuous phase three-dimensional network structure. In parts by weight, 70 parts of a PBT/PP composite material with a dual continuous phase morphological structure, 15 parts of a thermal conductive material, 5 parts of acrylate high rubber powder, and POE-g -MAH 4 parts, MBS 0.5 parts, antioxidant (168:1010=1:1) 0.1 parts, prepared by high mixing, plasticizing and granulating.
其制备方法包括下列步骤：Its preparation method comprises the following steps:
（1）按照配比称取树脂、导热材料、增韧剂、相容剂、润滑剂、抗氧化剂，备用；(1) Weigh the resin, thermal conductive material, toughening agent, compatibilizer, lubricant, antioxidant according to the proportion, and set aside;
（2）依次将树脂、导热材料、增韧剂、相容剂、润滑剂、抗氧化剂加入高速混合机内，以250rpm/min的转速常温搅拌1h，得到预混料；(2) Add resin, thermal conductive material, toughening agent, compatibilizer, lubricant, and antioxidant into the high-speed mixer in sequence, and stir at room temperature for 1 hour at a speed of 250rpm/min to obtain a premix;
（3）将步骤（2）所得的预混料加入到双螺杆挤出机中挤出造粒，得到双连续相立体网络结构导热PBT材料；控制所述双螺杆挤出机的工作参数如下：一区温度为130℃，二区温度为150℃，三区温度为200℃，四区温度为200℃，五区温度为200℃，模头温度为180℃，喂料速度为50r/min，螺杆转速为200r/min；(3) Add the premixed material obtained in step (2) to a twin-screw extruder to extrude and granulate to obtain a dual-continuous-phase three-dimensional network structure heat-conducting PBT material; control the working parameters of the twin-screw extruder as follows: The temperature of the first zone is 130°C, the temperature of the second zone is 150°C, the temperature of the third zone is 200°C, the temperature of the fourth zone is 200°C, the temperature of the fifth zone is 200°C, the temperature of the die head is 180°C, and the feeding speed is 50r/min. The screw speed is 200r/min;
其中涉及到的具有双连续相形态结构的PBT/PP复合材料制备步骤如下：按照质量比5：5分别称取PP和PBT两种材料加入高速混合机充分混合，投入异向啮合平行双螺杆挤出机熔融挤出造粒。制得具有双连续相形态结构的PBT/PP复合材料，螺杆转速设定为300 r/min，机筒温度设定是加料段开始到机头结束依次为180℃，200℃，200℃，210℃，190℃，190℃。The preparation steps of the PBT/PP composite material with a double continuous phase structure are as follows: Weigh PP and PBT according to the mass ratio of 5:5, add them to a high-speed mixer and mix them thoroughly, and put them into a parallel twin-screw extruder with parallel meshing in different directions. Exit machine melt extrusion granulation. The PBT/PP composite material with double continuous phase structure was obtained, the screw speed was set at 300 r/min, and the temperature of the barrel was set from the beginning of the feeding section to the end of the machine head in order of 180°C, 200°C, 200°C, 210°C °C, 190 °C, 190 °C.
其中涉及的导热材料为立体网络结构导热材料，其制备方法如下：The heat-conducting material involved is a three-dimensional network structure heat-conducting material, and its preparation method is as follows:
S1、首先用去离子水配制10wt%的双氧水溶液，然后石墨晶须完全浸入双氧水溶液中，放入微波炉里进行辐射处理，处理时间120s，将反应处理后的样品用去离子水清洗后在干燥炉中干燥、备用；S1. First prepare 10wt% hydrogen peroxide solution with deionized water, then completely immerse the graphite whiskers in the hydrogen peroxide solution, put it in a microwave oven for radiation treatment, and the treatment time is 120s. After the reaction treatment, the sample is washed with deionized water and dried Dry in the oven, ready for use;
S2、将钛酸酯偶联剂按照质量比是1：1加入到乙醇中进行稀释，混合搅拌8h，在烧杯中使两种液体混合为均一的液体，将质量比1：3的片状氧化铝和AlN粉末加入混合液体中，不断搅拌均匀，制得钛酸酯偶联剂表面处理片状氧化铝和AlN材料；S2. Dilute the titanate coupling agent into ethanol at a mass ratio of 1:1, mix and stir for 8 hours, mix the two liquids into a uniform liquid in a beaker, and oxidize the flakes with a mass ratio of 1:3 Aluminum and AlN powders are added to the mixed liquid, and continuously stirred evenly to prepare flaky aluminum oxide and AlN materials with titanate coupling agent surface treatment;
S3、将块状环氧树脂用粉碎机粉碎，并用500目网筛进行筛选最终得到酚醛树脂粉末，将S1制得的石墨晶须和S2制得的偶联剂表面处理片状氧化铝和AlN材料与环氧树脂粉末以1：1：1-2的质量比加入水中，超声振荡并搅拌2-3h使其分散均匀，过滤后放入干燥箱中80-100℃下干燥36-48h，样品干燥后升温至200-300℃进行固化，最后炭化炉中氮气气氛保护下升温至600-900℃进行炭化制得立体网络结构导热材料。S3. Pulverize the bulk epoxy resin with a pulverizer, and sieve it with a 500-mesh sieve to finally obtain the phenolic resin powder. Surface-treat the graphite whiskers prepared in S1 and the coupling agent prepared in S2 with flaky alumina and AlN The material and epoxy resin powder are added to water at a mass ratio of 1:1:1-2, ultrasonically oscillated and stirred for 2-3 hours to disperse evenly, then filtered and placed in a drying oven for 36-48 hours at 80-100°C. Samples After drying, the temperature is raised to 200-300°C for curing, and finally the temperature is raised to 600-900°C for carbonization in a carbonization furnace under the protection of a nitrogen atmosphere to obtain a three-dimensional network structure heat-conducting material.
实施例二Embodiment two
一种双连续相立体网络结构导热PBT材料由下列重量份的原料，按重量份数计，取具有双连续相形态结构的PBT/PP复合材料80份、导热材料20份、POE10份、SEBS-g-MAH6份、硬脂酸1份、抗氧化剂（168：1010=1：2）0.2份，经高混、塑化造粒制备而成。A thermally conductive PBT material with a dual continuous phase three-dimensional network structure consists of the following raw materials in parts by weight, 80 parts of a PBT/PP composite material with a dual continuous phase structure, 20 parts of a thermal conductive material, 10 parts of POE, SEBS- 6 parts of g-MAH, 1 part of stearic acid, 0.2 parts of antioxidant (168:1010=1:2), prepared by high mixing and plasticizing granulation.
制备方法包括下列步骤：The preparation method comprises the following steps:
（1）按照配比称取树脂、导热材料、增韧剂、相容剂、润滑剂、抗氧化剂，备用；(1) Weigh the resin, thermal conductive material, toughening agent, compatibilizer, lubricant, antioxidant according to the proportion, and set aside;
（2）依次将树脂、导热材料、增韧剂、相容剂、润滑剂、抗氧化剂加入高速混合机内，以300rpm/min的转速常温搅拌1h，得到预混料；(2) Add resin, thermal conductive material, toughening agent, compatibilizer, lubricant, and antioxidant into the high-speed mixer in sequence, and stir at room temperature at a speed of 300rpm/min for 1 hour to obtain a premix;
（3）将步骤（2）所得的预混料加入到双螺杆挤出机中挤出造粒，得到双连续相立体网络结构导热PBT材料；控制所述双螺杆挤出机的工作参数如下：一区温度为140℃，二区温度为170℃，三区温度为220℃，四区温度为230℃，五区温度为210℃，模头温度为200℃，喂料速度为80r/min，螺杆转速为220r/min；(3) Add the premixed material obtained in step (2) to a twin-screw extruder to extrude and granulate to obtain a dual-continuous-phase three-dimensional network structure heat-conducting PBT material; control the working parameters of the twin-screw extruder as follows: The temperature of the first zone is 140°C, the temperature of the second zone is 170°C, the temperature of the third zone is 220°C, the temperature of the fourth zone is 230°C, the temperature of the fifth zone is 210°C, the temperature of the die head is 200°C, and the feeding speed is 80r/min. The screw speed is 220r/min;
其中涉及到的具有双连续相形态结构的PBT/PP复合材料制备步骤如下：按照质量比5：5分别称取PP和PBT两种材料加入高速混合机充分混合，投入异向啮合平行双螺杆挤出机熔融挤出造粒。制得具有双连续相形态结构的PBT/PP复合材料，螺杆转速设定为400r/min，机筒温度设定是加料段开始到机头结束依次为190℃，210℃，210℃，220℃，200℃，200℃。The preparation steps of the PBT/PP composite material with a double continuous phase structure are as follows: Weigh PP and PBT according to the mass ratio of 5:5, add them to a high-speed mixer and mix them thoroughly, and put them into a parallel twin-screw extruder with parallel meshing in different directions. Exit machine melt extrusion granulation. A PBT/PP composite material with a double continuous phase structure was obtained, the screw speed was set at 400r/min, and the barrel temperature was set from the beginning of the feeding section to the end of the machine head in order of 190°C, 210°C, 210°C, and 220°C , 200°C, 200°C.
其中涉及的导热材料为立体网络结构导热材料，其制备方法如下：The heat-conducting material involved is a three-dimensional network structure heat-conducting material, and its preparation method is as follows:
S1、首先用去离子水配制10wt%的双氧水溶液，然后石墨晶须完全浸入双氧水溶液中，放入微波炉里进行辐射处理，处理时间120s，将反应处理后的样品用去离子水清洗后在干燥炉中干燥、备用；S1. First prepare 10wt% hydrogen peroxide solution with deionized water, then completely immerse the graphite whiskers in the hydrogen peroxide solution, put it in a microwave oven for radiation treatment, and the treatment time is 120s. After the reaction treatment, the sample is washed with deionized water and dried Dry in the oven, ready for use;
S2、将铝酸酯偶联剂按照质量比是2：1加入到甲醇中进行稀释，混合搅拌12h，在烧杯中使两种液体混合为均一的液体，将质量比1：3的片状氧化铝和AlN粉末加入混合液体中，不断搅拌均匀，制得铝酸酯偶联剂表面处理片状氧化铝和AlN材料；S2. Dilute the aluminate coupling agent into methanol at a mass ratio of 2:1, mix and stir for 12 hours, mix the two liquids into a uniform liquid in a beaker, and oxidize the flakes with a mass ratio of 1:3 Aluminum and AlN powders are added to the mixed liquid and stirred continuously to obtain aluminum oxide coupling agent surface-treated flaky alumina and AlN materials;
S3、将块状环氧树脂用粉碎机粉碎，并用800目网筛进行筛选最终得到酚醛树脂粉末，将S1制得的石墨晶须和S2制得的铝酸酯偶联剂表面处理片状氧化铝和AlN材料与环氧树脂粉末以1：1：2的质量比加入水中，超声振荡并搅拌2.5h使其分散均匀，过滤后放入干燥箱中90℃下干燥40h，样品干燥后升温至250℃进行固化，最后炭化炉中氮气气氛保护下升温至700℃进行炭化制得立体网络结构导热材料。S3. Pulverize the bulk epoxy resin with a pulverizer, and sieve it with a 800-mesh screen to finally obtain the phenolic resin powder, and oxidize the graphite whiskers prepared in S1 and the aluminate coupling agent prepared in S2 in sheet form Aluminum and AlN materials and epoxy resin powder are added to water at a mass ratio of 1:1:2, ultrasonically oscillated and stirred for 2.5 hours to make them uniformly dispersed, filtered and placed in a drying oven for 40 hours at 90°C, and the sample is dried and then heated to Curing is carried out at 250°C, and finally the temperature is raised to 700°C in a carbonization furnace under the protection of nitrogen atmosphere for carbonization to obtain a three-dimensional network structure heat-conducting material.
实施例三Embodiment three
一种双连续相立体网络结构导热PBT材料，按重量份数计，取具有双连续相形态结构的PBT/PP复合材料100份、导热材料25份、乙烯丙烯酸甲酯共聚物弹性体(EMA)15份、POE-g-MAH 8份、MBS1.5份、抗氧化剂（168：1010=1：1）0.3份，经高混、塑化造粒制备而成。A kind of bicontinuous three-dimensional network structure heat conduction PBT material, by weight, take 100 parts of PBT/PP composite material with bicontinuous phase morphology structure, 25 parts of heat conduction materials, ethylene methyl acrylate copolymer elastomer (EMA) 15 parts, POE-g-MAH 8 parts, MBS 1.5 parts, antioxidant (168:1010=1:1) 0.3 parts, prepared by high mixing, plasticizing and granulating.
其制备方法包括下列步骤：Its preparation method comprises the following steps:
（1）按照配比称取树脂、导热材料、增韧剂、相容剂、润滑剂、抗氧化剂，备用；(1) Weigh the resin, thermal conductive material, toughening agent, compatibilizer, lubricant, antioxidant according to the proportion, and set aside;
（2）依次将树脂、导热材料、增韧剂、相容剂、润滑剂、抗氧化剂加入高速混合机内，以400rpm/min的转速常温搅拌1h，得到预混料；(2) Add resin, heat-conducting material, toughening agent, compatibilizer, lubricant, and antioxidant into the high-speed mixer in sequence, and stir at room temperature at a speed of 400rpm/min for 1 hour to obtain a premix;
（3）将步骤（2）所得的预混料加入到双螺杆挤出机中挤出造粒，得到双连续相立体网络结构导热PBT材料；控制所述双螺杆挤出机的工作参数如下：一区温度为150℃，二区温度为200℃，三区温度为250℃，四区温度为250℃，五区温度为230℃，模头温度为220℃，喂料速度为100r/min，螺杆转速为250r/min；(3) Add the premixed material obtained in step (2) to a twin-screw extruder to extrude and granulate to obtain a dual-continuous-phase three-dimensional network structure heat-conducting PBT material; control the working parameters of the twin-screw extruder as follows: The temperature of the first zone is 150°C, the temperature of the second zone is 200°C, the temperature of the third zone is 250°C, the temperature of the fourth zone is 250°C, the temperature of the fifth zone is 230°C, the temperature of the die head is 220°C, and the feeding speed is 100r/min. The screw speed is 250r/min;
其中涉及到的具有双连续相形态结构的PBT/PP复合材料制备步骤如下：按照质量比5：5分别称取PP和PBT两种材料加入高速混合机充分混合，投入异向啮合平行双螺杆挤出机熔融挤出造粒。制得具有双连续相形态结构的PBT/PP复合材料，螺杆转速设定为500r/min，机筒温度设定是加料段开始到机头结束依次为200℃，220℃，220℃，230℃，210℃，200℃。The preparation steps of the PBT/PP composite material with a double continuous phase structure are as follows: Weigh PP and PBT according to the mass ratio of 5:5, add them to a high-speed mixer and mix them thoroughly, and put them into a parallel twin-screw extruder with parallel meshing in different directions. Exit machine melt extrusion granulation. A PBT/PP composite material with a double continuous phase structure was obtained, the screw speed was set at 500r/min, and the barrel temperature was set from the beginning of the feeding section to the end of the machine head in order of 200°C, 220°C, 220°C, and 230°C , 210°C, 200°C.
其中涉及的导热材料为立体网络结构导热材料，其制备方法如下：The heat-conducting material involved is a three-dimensional network structure heat-conducting material, and its preparation method is as follows:
S1、首先用去离子水配制10wt%的双氧水溶液，然后石墨晶须完全浸入双氧水溶液中，放入微波炉里进行辐射处理，处理时间120s，将反应处理后的样品用去离子水清洗后在干燥炉中干燥、备用；S1. First prepare 10wt% hydrogen peroxide solution with deionized water, then completely immerse the graphite whiskers in the hydrogen peroxide solution, put it in a microwave oven for radiation treatment, and the treatment time is 120s. After the reaction treatment, the sample is washed with deionized water and dried Dry in the oven, ready for use;
S2、将硅烷偶联剂按照质量比是3：1加入到丙酮中进行稀释，混合搅拌12h，在烧杯中使两种液体混合为均一的液体，将质量比1：3的片状氧化铝和AlN粉末加入混合液体中，不断搅拌均匀，制得硅烷偶联剂表面处理片状氧化铝和AlN材料；S2. Dilute the silane coupling agent into acetone according to the mass ratio of 3:1, mix and stir for 12 hours, mix the two liquids into a uniform liquid in a beaker, and mix the flaky alumina and the mass ratio of 1:3 Add AlN powder into the mixed liquid and stir continuously to obtain silane coupling agent surface-treated flaky alumina and AlN materials;
S3、将块状环氧树脂用粉碎机粉碎，并用1000目网筛进行筛选最终得到酚醛树脂粉末，将S1制得的石墨晶须和S2制得的硅烷偶联剂表面处理片状氧化铝和AlN材料与环氧树脂粉末以1：1：12的质量比加入水中，超声振荡并搅拌3h使其分散均匀，过滤后放入干燥箱中100℃下干燥48h，样品干燥后升温至300℃进行固化，最后炭化炉中氮气气氛保护下升温至900℃进行炭化制得立体网络结构导热材料。S3, block epoxy resin is pulverized with a pulverizer, and screened with a 1000-mesh screen to finally obtain phenolic resin powder, the graphite whiskers prepared by S1 and the silane coupling agent surface-treated flake aluminum oxide prepared by S2 and Add AlN material and epoxy resin powder into water at a mass ratio of 1:1:12, ultrasonically oscillate and stir for 3 hours to disperse evenly, filter and put in a drying oven for 48 hours at 100°C, and heat up to 300°C after drying. After solidification, the temperature is raised to 900°C in a carbonization furnace under the protection of nitrogen atmosphere for carbonization to obtain a three-dimensional network structure heat-conducting material.
实施例四Embodiment four
一种双连续相立体网络结构导热PBT材料，按重量份数计，取具有双连续相形态结构的PBT/PP复合材料90份；导热材料23份；POE12份；SEBS-g-MAH5.5份；硬脂酸1.2份；抗氧化剂（168：1010=1：2）0.25份；经高混、塑化造粒制备而成。A thermally conductive PBT material with a dual continuous phase three-dimensional network structure. In parts by weight, 90 parts of a PBT/PP composite material with a dual continuous phase structure; 23 parts of a thermal conductive material; 12 parts of POE; 5.5 parts of SEBS-g-MAH ; 1.2 parts of stearic acid; 0.25 parts of antioxidant (168:1010=1:2); prepared by high-mixing and plasticizing granulation.
其制备方法包括下列步骤：Its preparation method comprises the following steps:
（1）按照配比称取树脂、导热材料、增韧剂、相容剂、润滑剂、抗氧化剂，备用；(1) Weigh the resin, thermal conductive material, toughening agent, compatibilizer, lubricant, antioxidant according to the proportion, and set aside;
（2）依次将树脂、导热材料、增韧剂、相容剂、润滑剂、抗氧化剂加入高速混合机内，以350rpm/min的转速常温搅拌1h，得到预混料；(2) Add resin, thermal conductive material, toughening agent, compatibilizer, lubricant, and antioxidant into the high-speed mixer in sequence, and stir at room temperature at a speed of 350rpm/min for 1 hour to obtain a premix;
（3）将步骤（2）所得的预混料加入到双螺杆挤出机中挤出造粒，得到双连续相立体网络结构导热PBT材料；控制所述双螺杆挤出机的工作参数如下：一区温度为145℃，二区温度为180℃，三区温度为215℃，四区温度为230℃，五区温度为215℃，模头温度为210℃，喂料速度为90r/min，螺杆转速为210r/min；(3) Add the premixed material obtained in step (2) to a twin-screw extruder to extrude and granulate to obtain a dual-continuous-phase three-dimensional network structure heat-conducting PBT material; control the working parameters of the twin-screw extruder as follows: The temperature of the first zone is 145°C, the temperature of the second zone is 180°C, the temperature of the third zone is 215°C, the temperature of the fourth zone is 230°C, the temperature of the fifth zone is 215°C, the temperature of the die head is 210°C, and the feeding speed is 90r/min. The screw speed is 210r/min;
其中涉及到的具有双连续相形态结构的PBT/PP复合材料制备步骤如下：按照质量比5：5分别称取PP和PBT两种材料加入高速混合机充分混合，投入异向啮合平行双螺杆挤出机熔融挤出造粒。制得具有双连续相形态结构的PBT/PP复合材料，螺杆转速设定为450r/min，机筒温度设定是加料段开始到机头结束依次为190℃，215℃，220℃，225℃，205℃，195℃。The preparation steps of the PBT/PP composite material with a double continuous phase structure are as follows: Weigh PP and PBT according to the mass ratio of 5:5, add them to a high-speed mixer and mix them thoroughly, and put them into a parallel twin-screw extruder with parallel meshing in different directions. Exit machine melt extrusion granulation. A PBT/PP composite material with a dual continuous phase structure was obtained, the screw speed was set at 450r/min, and the barrel temperature was set from the beginning of the feeding section to the end of the machine head in order of 190°C, 215°C, 220°C, and 225°C , 205°C, 195°C.
其中涉及的导热材料为立体网络结构导热材料，其制备方法如下：The heat-conducting material involved is a three-dimensional network structure heat-conducting material, and its preparation method is as follows:
S1、首先用去离子水配制10wt%的双氧水溶液，然后石墨晶须完全浸入双氧水溶液中，放入微波炉里进行辐射处理，处理时间120s，将反应处理后的样品用去离子水清洗后在干燥炉中干燥、备用；S1. First prepare 10wt% hydrogen peroxide solution with deionized water, then completely immerse the graphite whiskers in the hydrogen peroxide solution, put it in a microwave oven for radiation treatment, and the treatment time is 120s. After the reaction treatment, the sample is washed with deionized water and dried Dry in the oven, ready for use;
S2、将铝酸酯偶联剂按照质量比是1：1加入到乙醇中进行稀释，混合搅拌10h，在烧杯中使两种液体混合为均一的液体，将质量比1：3的片状氧化铝和AlN粉末加入混合液体中，不断搅拌均匀，制得铝酸酯偶联剂表面处理片状氧化铝和AlN材料；S2. Dilute the aluminate coupling agent into ethanol at a mass ratio of 1:1, mix and stir for 10 hours, mix the two liquids into a uniform liquid in a beaker, and oxidize the flakes with a mass ratio of 1:3 Aluminum and AlN powders are added to the mixed liquid and stirred continuously to obtain aluminum oxide coupling agent surface-treated flaky alumina and AlN materials;
S3、将块状环氧树脂用粉碎机粉碎，并用800目网筛进行筛选最终得到酚醛树脂粉末，将S1制得的石墨晶须和S2制得的偶联剂表面处理片状氧化铝和AlN材料与环氧树脂粉末以1：1：2的质量比加入水中，超声振荡并搅拌2.5h使其分散均匀，过滤后放入干燥箱中80℃下干燥40h，样品干燥后升温至280℃进行固化，最后炭化炉中氮气气氛保护下升温至800℃进行炭化制得立体网络结构导热材料。S3. Pulverize the bulk epoxy resin with a pulverizer, and screen it with a 800-mesh screen to finally obtain phenolic resin powder. Surface-treat the graphite whiskers prepared in S1 and the coupling agent prepared in S2 with flaky alumina and AlN Materials and epoxy resin powder were added to water at a mass ratio of 1:1:2, ultrasonically oscillated and stirred for 2.5 hours to disperse evenly, filtered and placed in a drying oven for 40 hours at 80°C, and the sample was dried and then heated to 280°C for After solidification, the temperature is raised to 800°C in a carbonization furnace under the protection of nitrogen atmosphere for carbonization to obtain a three-dimensional network structure heat-conducting material.
对比例：Comparative example:
对比例一Comparative example one
本对比例涉及提供了一种双连续相导热PBT材料及其制备方法，其配方和制备方法与实施例四基本一致，不同之处仅在于，直接采用偶联剂表面处理片状氧化铝和AlN材料作为导热材料，而非采用立体网络结构导热材料作为导热材料。This comparative example involves providing a dual-continuous-phase heat-conducting PBT material and its preparation method. Its formulation and preparation method are basically the same as in Example 4, the only difference is that the flaky alumina and AlN are directly treated with a coupling agent. The material is used as a heat-conducting material instead of using a three-dimensional network structure heat-conducting material as a heat-conducting material.
对比例二Comparative example two
本对比例涉及提供了一种双连续相导热PBT材料及其制备方法，其配方和制备方法与实施例四基本一致，不同之处仅在于，直接采用单一PBT树脂作为基体树脂，而非采用具有双连续相形态结构的PBT/PP复合材料作为基体树脂。This comparative example involves providing a dual-continuous-phase heat-conducting PBT material and its preparation method. Its formulation and preparation method are basically the same as in Example 4, the only difference being that a single PBT resin is directly used as the matrix resin instead of a The PBT/PP composite material with double continuous phase structure is used as the matrix resin.
将实施例一至实施例四，对比例一至对比例二所得到的产品进行性能测试，其拉伸强度按照国标GB/T1040-2006进行测试；导热系数按照GB/T3399-1982进行测试，其结果见表1Embodiment one to embodiment four, comparative example one to the product obtained by comparative example two are subjected to performance test, and its tensile strength is tested according to national standard GB/T1040-2006; Thermal conductivity is tested according to GB/T3399-1982, and the results are shown in Table 1
 the
 the
Figure 925091dest_path_image001
Figure 925091dest_path_image001
由表1性能测试结果可见：It can be seen from the performance test results in Table 1:
1、从实施例一至实施例四可以看出：本发明制备双连续相立体网络结构导热PBT材料具有特殊的立体网络结构结构，容易在PBT材料中形成完整的导热通道，具有添加比例少，导热性能好，不破坏材料原有机械性能等优点，同时采用具有双连续相形态结构的PBT/PP复合材料作为基体树脂，相较于传统的填充型导热PBT材料的制备方法，采用双连续相树脂更有利于导热材料在基体树脂中的分散，制得的导热PBT材料具有较佳的机械性能均衡、成型加工性能好，使用价值高等优点。1. From Example 1 to Example 4, it can be seen that the double-continuous-phase three-dimensional network structure heat-conducting PBT material prepared by the present invention has a special three-dimensional network structure, and it is easy to form a complete heat-conducting channel in the PBT material. It has good performance and does not destroy the original mechanical properties of the material. At the same time, the PBT/PP composite material with a dual-continuous phase structure is used as the matrix resin. Compared with the traditional preparation method of filled thermally conductive PBT materials, the dual-continuous phase resin It is more conducive to the dispersion of heat-conducting materials in the matrix resin, and the prepared heat-conducting PBT material has the advantages of better balance of mechanical properties, good molding and processing performance, and high use value.
2、在对比例一、二中，对比例一采用直接采用偶联剂表面处理片状氧化铝和AlN材料作为导热材料，而非采用立体网络结构导热材料作为导热材料。对比例二直接采用单一PBT树脂作为基体树脂，而非采用具有双连续相形态结构的PBT/PP复合材料作为基体树脂，对比例一和对比例二的导热性能劣于实施例一至实施例四，实施例四综合性能最优。2. In Comparative Examples 1 and 2, Comparative Example 1 uses directly surface-treated flake alumina and AlN materials as heat-conducting materials, instead of using three-dimensional network structure heat-conducting materials as heat-conducting materials. Comparative Example 2 directly uses a single PBT resin as the matrix resin instead of using a PBT/PP composite material with a dual continuous phase structure as the matrix resin. The thermal conductivity of Comparative Example 1 and Comparative Example 2 is inferior to that of Examples 1 to 4. Embodiment 4 has the best overall performance.
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。Specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art may make various changes or modifications within the scope of the claims, which do not affect the essence of the present invention.

Claims (8)

  1. 一种双连续相立体网络结构导热PBT材料，其特征在于，按重量份数计，取树脂70-100份、导热材料15-25份、增韧剂5-15份、相容剂4-8份、润滑剂0.5-1.5份，抗氧化剂0.1-0.3份，经高混、塑化造粒制备而成；A dual-continuous phase three-dimensional network structure heat-conducting PBT material, characterized in that, in parts by weight, 70-100 parts of resin, 15-25 parts of heat-conducting material, 5-15 parts of toughening agent, and 4-8 parts of compatibilizer 0.5-1.5 parts of lubricant, 0.1-0.3 parts of antioxidant, prepared by high mixing, plasticizing and granulating;
    制备方法包括下列步骤：The preparation method comprises the following steps:
    （1）按照配比称取树脂、导热材料、增韧剂、相容剂、润滑剂、抗氧化剂，备用；(1) Weigh the resin, thermal conductive material, toughening agent, compatibilizer, lubricant, antioxidant according to the proportion, and set aside;
    （2）依次将树脂、导热材料、增韧剂、相容剂、润滑剂、抗氧化剂加入高速混合机内，以250-400rpm/min的转速常温搅拌1h，得到预混料；(2) Add resin, thermal conductive material, toughening agent, compatibilizer, lubricant, and antioxidant into the high-speed mixer in sequence, and stir at room temperature at a speed of 250-400rpm/min for 1 hour to obtain a premix;
    （3）将步骤（2）所得的预混料加入到双螺杆挤出机中挤出造粒，得到双连续相立体网络结构导热PBT材料；控制所述双螺杆挤出机的工作参数如下：一区温度为130-150℃，二区温度为150-200℃，三区温度为200-250℃，四区温度为200-250℃，五区温度为200-230℃，模头温度为180-220℃，喂料速度为50-100r/min，螺杆转速为200-250r/min。(3) Add the premixed material obtained in step (2) to a twin-screw extruder to extrude and granulate to obtain a dual-continuous-phase three-dimensional network structure heat-conducting PBT material; control the working parameters of the twin-screw extruder as follows: The temperature of the first zone is 130-150°C, the temperature of the second zone is 150-200°C, the temperature of the third zone is 200-250°C, the temperature of the fourth zone is 200-250°C, the temperature of the fifth zone is 200-230°C, and the temperature of the die head is 180 -220°C, the feeding speed is 50-100r/min, and the screw speed is 200-250r/min.
  2. 根据权利要求1所述的一种双连续相立体网络结构导热PBT材料，其特征在于，所述导热材料为立体网络结构导热材料。The thermally conductive PBT material with a dual continuous phase three-dimensional network structure according to claim 1, wherein the thermally conductive material is a three-dimensional network structure thermally conductive material.
  3. 根据权利要求2所述的一种双连续相立体网络结构导热PBT材料，其特征在于，所述立体网络结构导热材料按照如下步骤制备得到：A dual-continuous phase three-dimensional network structure heat-conducting PBT material according to claim 2, wherein the three-dimensional network structure heat-conducting material is prepared according to the following steps:
    S1、首先用去离子水配制10wt%的双氧水溶液，然后石墨晶须完全浸入双氧水溶液中，放入微波炉里进行辐射处理，处理时间120s，将反应处理后的样品用去离子水清洗后在干燥炉中干燥，备用得到处理后石墨晶须；S1. First prepare 10wt% hydrogen peroxide solution with deionized water, then completely immerse the graphite whiskers in the hydrogen peroxide solution, put it in a microwave oven for radiation treatment, and the treatment time is 120s. After the reaction treatment, the sample is washed with deionized water and dried Dried in the oven, ready for use to obtain the treated graphite whiskers;
    S2、将偶联剂按照质量比是1-3：1加入到溶剂中进行稀释，混合搅拌8-12h，在烧杯中使两种液体混合为均一的液体，将质量比1：3的片状氧化铝和AlN粉末加入混合液体中，不断搅拌均匀，制得偶联剂表面处理片状氧化铝和AlN材料；S2. Add the coupling agent to the solvent according to the mass ratio of 1-3:1 to dilute, mix and stir for 8-12 hours, mix the two liquids into a uniform liquid in a beaker, and dilute the flakes with a mass ratio of 1:3 Alumina and AlN powders are added to the mixed liquid and stirred continuously to obtain flaky alumina and AlN materials with coupling agent surface treatment;
    S3、将块状环氧树脂用粉碎机粉碎，并用网筛进行筛选最终得到酚醛树脂粉末，将S1中的处理后石墨晶须和S2制得的偶联剂表面处理片状氧化铝和AlN材料与环氧树脂粉末以1：1：1-2的质量比加入水中，超声振荡并搅拌2-3h使其分散均匀，过滤后放入干燥箱中80-100℃下干燥36-48h，样品干燥后升温至200-300℃进行固化，最后炭化炉中氮气气氛保护下升温至600-900℃进行炭化制得立体网络结构导热材料。S3. Pulverize the bulk epoxy resin with a pulverizer, and screen it with a mesh screen to finally obtain the phenolic resin powder, and treat the treated graphite whiskers in S1 and the coupling agent surface-treated flake aluminum oxide and AlN materials prepared in S2. Add epoxy resin powder to water at a mass ratio of 1:1:1-2, ultrasonically oscillate and stir for 2-3 hours to disperse evenly, filter and put in a drying oven for 36-48 hours at 80-100°C to dry the sample Afterwards, the temperature is raised to 200-300°C for curing, and finally the temperature is raised to 600-900°C for carbonization in a carbonization furnace under the protection of a nitrogen atmosphere to obtain a three-dimensional network structure heat-conducting material.
  4. 根据权利要求3所述的一种双连续相立体网络结构导热PBT材料，其特征在于，S1中所述处理后石墨晶须，直径0.2-2μm，长度≥50μm。The thermally conductive PBT material with a bicontinuous phase three-dimensional network structure according to claim 3, characterized in that the graphite whiskers after treatment in S1 have a diameter of 0.2-2 μm and a length of ≥50 μm.
  5. 根据权利要求3所述的一种双连续相立体网络结构导热PBT材料，其特征在于，S2中所述偶联剂为钛酸酯偶联剂、铝酸酯偶联剂和硅烷偶联剂中的至少一种，所述溶剂为乙醇、甲醇和丙酮中的至少一种，所述片状氧化铝径向尺度为5-50μm，厚度为100-500nm，所述AlN平均粒径≤1μm。The thermally conductive PBT material with a dual continuous phase three-dimensional network structure according to claim 3, wherein the coupling agent described in S2 is a titanate coupling agent, an aluminate coupling agent and a silane coupling agent The solvent is at least one of ethanol, methanol and acetone, the radial dimension of the flaky alumina is 5-50 μm, the thickness is 100-500 nm, and the average particle size of the AlN is ≤1 μm.
  6. 根据权利要求3所述的一种双连续相立体网络结构导热PBT材料，其特征在于，S3中所述网筛目数≥500目。The heat-conducting PBT material with a dual-continuous phase three-dimensional network structure according to claim 3, wherein the mesh size of the mesh in S3 is ≥500 mesh.
  7. 根据权利要求1所述的一种双连续相立体网络结构导热PBT材料，其特征在于，所述树脂为具有双连续相形态结构的PBT/PP复合材料；所述增韧剂为丙烯酸酯高胶粉、POE、乙烯丙烯酸甲酯共聚物弹性体(EMA)中的至少一种；所述相容剂为相容剂为POE-g-MAH、SEBS-g-MAH中至少一种，接枝率≥1.5%；所述润滑剂为MBS、硬脂酸中的至少一种；所述抗氧化剂为168和1010按照1：1-2的质量比组成的混合物。The heat-conducting PBT material with a bicontinuous three-dimensional network structure according to claim 1, wherein the resin is a PBT/PP composite material with a bicontinuous phase structure; the toughening agent is acrylate high glue At least one of powder, POE, ethylene methyl acrylate copolymer elastomer (EMA); the compatibilizer is at least one of POE-g-MAH, SEBS-g-MAH, and the grafting rate ≥1.5%; the lubricant is at least one of MBS and stearic acid; the antioxidant is a mixture of 168 and 1010 in a mass ratio of 1:1-2.
  8. 根据权利要求7所述的一种双连续相立体网络结构导热PBT材料，其特征在于，所述具有双连续相形态结构的PBT/PP复合材料按照如下步骤进行制备，首先按照质量比5：5分别称取PP和PBT两种材料加入高速混合机充分混合，然后投入异向啮合平行双螺杆挤出机熔融挤出造粒，制得所述具有双连续相形态结构的PBT/PP复合材料；其中，螺杆转速设定为300-500r/min，机筒温度设定是加料段开始到机头结束依次为180-200℃，200-220℃，200-220℃，210-230℃，190-210℃，190-200℃。A thermally conductive PBT material with a bicontinuous phase three-dimensional network structure according to claim 7, wherein the PBT/PP composite material having a bicontinuous phase morphology structure is prepared according to the following steps, firstly according to a mass ratio of 5:5 Respectively weigh PP and PBT two kinds of materials and add them into a high-speed mixer to fully mix them, and then put them into a counter-meshing parallel twin-screw extruder for melt extrusion and granulation to obtain the PBT/PP composite material with a dual continuous phase structure; Among them, the screw speed is set to 300-500r/min, and the temperature of the barrel is set from the beginning of the feeding section to the end of the machine head in order of 180-200°C, 200-220°C, 200-220°C, 210-230°C, 190- 210°C, 190-200°C.
PCT/CN2021/118378 2021-06-08 2021-09-15 Thermally conductive pbt material having bicontinuous phase three-dimensional network structure WO2022257291A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110635830.1 2021-06-08
CN202110635830.1A CN113292062A (en) 2021-06-08 2021-06-08 Heat-conducting PBT (polybutylene terephthalate) material with bicontinuous-phase three-dimensional network structure

Publications (1)

Publication Number Publication Date
WO2022257291A1 true WO2022257291A1 (en) 2022-12-15

Family

ID=77327456

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/118378 WO2022257291A1 (en) 2021-06-08 2021-09-15 Thermally conductive pbt material having bicontinuous phase three-dimensional network structure

Country Status (2)

Country Link
CN (1) CN113292062A (en)
WO (1) WO2022257291A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113292062A (en) * 2021-06-08 2021-08-24 福建师范大学泉港石化研究院 Heat-conducting PBT (polybutylene terephthalate) material with bicontinuous-phase three-dimensional network structure

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102719099A (en) * 2012-06-08 2012-10-10 金发科技股份有限公司 Thermal conductive molding compound and preparation method thereof
CN104559147A (en) * 2014-12-16 2015-04-29 惠州力王佐信科技有限公司 Anti-dripping smoke-suppression-type environment-friendly heat-conducting material and preparation method thereof
CN112724597A (en) * 2020-12-23 2021-04-30 江苏科化新材料科技有限公司 Nano-whisker modified epoxy resin composition
CN113292062A (en) * 2021-06-08 2021-08-24 福建师范大学泉港石化研究院 Heat-conducting PBT (polybutylene terephthalate) material with bicontinuous-phase three-dimensional network structure

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105504707B (en) * 2016-02-24 2018-04-06 江苏美奥新材料有限公司 A kind of PBT plastic of heat conduction toughening flame-proof enhancing and preparation method thereof
CN108148361B (en) * 2017-12-29 2020-06-30 江阴济化新材料有限公司 Heat-conducting PBT material and preparation method and application thereof
CN112358686B (en) * 2020-11-13 2023-05-16 福建和盛塑业有限公司 MPP special material containing three-dimensional reticular structure heat conduction material and preparation method of power cable sheath tube of MPP special material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102719099A (en) * 2012-06-08 2012-10-10 金发科技股份有限公司 Thermal conductive molding compound and preparation method thereof
CN104559147A (en) * 2014-12-16 2015-04-29 惠州力王佐信科技有限公司 Anti-dripping smoke-suppression-type environment-friendly heat-conducting material and preparation method thereof
CN112724597A (en) * 2020-12-23 2021-04-30 江苏科化新材料科技有限公司 Nano-whisker modified epoxy resin composition
CN113292062A (en) * 2021-06-08 2021-08-24 福建师范大学泉港石化研究院 Heat-conducting PBT (polybutylene terephthalate) material with bicontinuous-phase three-dimensional network structure

Also Published As

Publication number Publication date
CN113292062A (en) 2021-08-24

Similar Documents

Publication Publication Date Title
CN108250747B (en) Thermoplastic polyetherimide insulating and heat-conducting composite material and preparation method thereof
CN103602060A (en) Heat-conducting, wear-resistant and insulated nylon 6 composite material and preparation method thereof
CN103862589B (en) A kind of melt blending prepares the method for polyamide-based heat-conductive composite material
CN108929487A (en) A kind of thermally conductive electromagnetic shielding polypropylene composite material and preparation method
CN105400192A (en) Nylon blended polypropylene powder for selective laser sintering and preparation method thereof
CN102093692A (en) Polycarbonate (PC)/ acrylonitrile butadiene styrene (ABS) conductive alloy material and preparation method and use thereof
CN106675008A (en) High-heat conducting nylon 6 composite material and preparation method thereof
WO2022257291A1 (en) Thermally conductive pbt material having bicontinuous phase three-dimensional network structure
CN108929536A (en) A kind of heat conductive electronic equipment graphene/polyamide compoiste material and preparation method
CN114957855B (en) Wave-absorbing heat-conducting thermoplastic composite material and preparation method thereof
CN112080067A (en) High-filling filler modified polyolefin composite material and preparation method and application thereof
CN102936410B (en) A kind of in-situ polymerization prepares the method for polyamide-based heat-conductive composite material
CN105017765A (en) Basic magnesium sulfate whisker/PA610T composite material and preparation method thereof
WO2023103273A1 (en) Liquid crystalline polymer composite material for rapid injection molding and preparation method therefor, and injection molding screw for rapid injection molding
CN111534075B (en) Thermoplastic heat-conducting composite material and preparation method thereof
CN112358686B (en) MPP special material containing three-dimensional reticular structure heat conduction material and preparation method of power cable sheath tube of MPP special material
CN112223578B (en) Method for preparing high-toughness strontium ferrite/PPS injection molding granules through in-situ polymerization
CN112280301B (en) Low-dielectric-constant polyphenylene sulfide composite material and preparation process thereof
CN106987049A (en) A kind of functional agglomerate of reinforced polypropylene tensile strength
CN113388242A (en) Novel PME plastic
CN112745661B (en) Material with high dielectric constant under high-frequency electric field and suitable for reflow soldering and LDS (laser direct structuring) and preparation method thereof
CN112480615A (en) Carbon fiber/PET composite material and preparation method and application thereof
CN105462069A (en) Functionalized boron nitride nanosheet/polypropylene composite material and preparation method thereof
CN116178836B (en) Special microwave modified calcite powder for polypropylene and preparation method thereof
CN111253746A (en) Electrical insulation thermoplastic resin composition and preparation method and application thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21944791

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21944791

Country of ref document: EP

Kind code of ref document: A1