WO2022156832A2 - 高绝缘性的低温电子封装材料的制备方法 - Google Patents

高绝缘性的低温电子封装材料的制备方法 Download PDF

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WO2022156832A2
WO2022156832A2 PCT/CN2022/089223 CN2022089223W WO2022156832A2 WO 2022156832 A2 WO2022156832 A2 WO 2022156832A2 CN 2022089223 W CN2022089223 W CN 2022089223W WO 2022156832 A2 WO2022156832 A2 WO 2022156832A2
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epoxy resin
electronic packaging
packaging material
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boron nitride
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PCT/CN2022/089223
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WO2022156832A3 (zh
WO2022156832A9 (zh
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刘溧
黄骏
吴欢
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江苏拜富科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron

Definitions

  • the invention relates to the field of electronic packaging materials, in particular to a preparation method of a high-insulation low-temperature electronic packaging material.
  • the function of electronic packaging is to protect microelectronic devices (IC).
  • IC microelectronic devices
  • the most important performance indicators as packaging materials are thermal conductivity and thermal expansion coefficient.
  • the heat generated by highly integrated ICs must be released in time to prevent overheating. working under the state, affecting its life and performance;
  • the coefficient of thermal expansion (CTE) of the packaging material should be as consistent as possible with the chip and carrier.
  • CTE coefficient of thermal expansion
  • the rapid development of electronic packaging technology has promoted the development of packaging materials, that is, from the past mainly metal and ceramic packaging to plastic packaging. Due to its relatively cheap price, simple molding process, and suitable for mass production, Reliability is comparable to ceramic packaging and many other advantages, which have accounted for more than 95% of the entire packaging material, and epoxy resin molding compound is the most widely used in plastic packaging.
  • Epoxy resin has excellent heat resistance, electrical insulation, adhesion, dielectric properties, mechanical properties, small shrinkage, chemical resistance, and good processability and operability after adding curing agent. .
  • the object of the present invention is to provide a method for preparing a low-temperature electronic packaging material with high insulation: by adding modified epoxy resin and modified boron nitride into a high-speed mixer and mixing, a mixture is obtained, The 4,4'-diaminodiphenyl sulfone is added to the mixture, stirred until dissolved, and then cured to obtain the high-insulation low-temperature electronic packaging material, which solves the high temperature resistance and thermal conductivity of the existing plastic electronic packaging materials. The performance is still poor, a problem that has limited the development of plastic electronic packaging materials.
  • a preparation method of a high-insulation low-temperature electronic packaging material comprising the following steps:
  • Step 1 Weigh 100-150 parts of modified epoxy resin, 5-25 parts of modified boron nitride and 10-15 parts of 4,4'-diaminodiphenyl sulfone according to parts by weight, for subsequent use;
  • Step 2 adding the modified epoxy resin and the modified boron nitride into the high-speed mixer, and mixing for 4-6h under the condition of a stirring speed of 1200-2500r/min to obtain a mixture;
  • Step 3 Add 4,4'-diaminodiphenylsulfone to the mixture, then heat up to 130-140°C and stir until 4,4'-diaminodiphenylsulfone is completely dissolved, then vacuumize for 3-4h, Curing at 130-140 DEG C for 1-2 hours, and curing at 200-210 DEG C for 1-2 hours to obtain the high-insulation low-temperature electronic packaging material.
  • the preparation method of the modified epoxy resin is as follows:
  • the dosage ratio of the saturated sodium carbonate solution and diphenyldichlorosilane in step S11 is 10-20 mL:5-8 mL.
  • the epoxy resin in step S12 is epoxy resin E-44
  • the dosage ratio of the epoxy resin, dehydrated alcohol, intermediate 1 and dibutyltin dilaurate is 10g : 50-100 mL: 0.5-1.0 g: 0.01-0.15 g.
  • the mass ratio of the intermediate 2, DOPO and triphenylphosphine in step S13 is 100-200:1-5:0.01-0.05.
  • the preparation method of the modified boron nitride is as follows:
  • the mass fraction of the concentrated sulfuric acid in step S21 is 95-98%
  • the mass fraction of the concentrated nitric acid is 65-68%
  • the concentrated sulfuric acid, concentrated nitric acid and cubic boron nitride powder The dosage ratio is 30mL:10mL:1-5g.
  • the silane coupling agent in step S22 is silane coupling agent KH-560, and the dosage ratio of the silane coupling agent, the ethanol solution and the pretreated boron nitride is 2-5g:50 -70mL:1-3g, the mass fraction of the ethanol solution is 90%.
  • the modified epoxy resin and the modified boron nitride are added into a high-speed mixer and mixed to obtain a mixture, and 4,4'-diaminodiphenyl The sulfone is added to the mixture, stirred until dissolved, and then cured to obtain the high-insulation low-temperature electronic packaging material;
  • the preparation method uses modified epoxy resin as the main material, and the epoxy resin has excellent heat resistance, electrical Insulation, adhesion, dielectric, mechanical properties, small shrinkage, chemical resistance, good processability and operability after adding curing agent, suitable for electronic packaging materials, modified
  • modified The epoxy resin has higher heat resistance, so as to avoid the adverse effect of heat released by electronic components on the performance of electronic packaging materials.
  • the thermal conductivity of epoxy resin can be effectively improved, so as to facilitate the integration of electronic components.
  • the released heat can be quickly dissipated, so that the electronic packaging material still has high insulation performance under high temperature conditions, which can meet the needs of the development of electronic packaging.
  • a modified epoxy resin was also prepared, which was hydrolyzed by diphenyldichlorosilane to form intermediate 1, and then the hydroxyl group on intermediate 1 reacted with the hydroxyl group on epoxy resin to introduce silicon element and benzene ring to obtain intermediate 2, and then some epoxy groups on intermediate 2 react with DOPO, thereby introducing organophosphorus and benzene ring to obtain the modified epoxy resin, and the introduced benzene ring has good stability , the introduced silicon and phosphorus elements have higher bond energy, which can improve the thermal stability of the epoxy resin, thereby maintaining the high stability of the epoxy resin.
  • Hexagonal boron nitride has high thermal conductivity, good mechanical properties, and strong oxidation resistance. It also has strong neutron absorption capacity and good mechanical properties. It has high electrical insulating properties, high thermal conductivity and high insulating properties, so it is suitable for modifying epoxy resins, but the surface of hexagonal boron nitride has unsaturated bonds and dangling bonds, which will cause agglomeration and lead to its It is not easy to disperse in epoxy resin, which affects the performance of epoxy resin.
  • the cubic boron nitride powder is acidified by concentrated sulfuric acid and concentrated nitric acid, so as to introduce hydroxyl or carboxyl groups to the surface of the cubic boron nitride powder, and then hydrolyzed by silane coupling agent to form After silanol, it is then dehydrated and condensed into oligosiloxane, thereby improving the dispersibility of boron nitride powder in epoxy resin and avoiding its agglomeration, thereby improving the thermal conductivity of epoxy resin without reducing its insulating performance. the goal of.
  • the present embodiment is a preparation method of a modified epoxy resin, comprising the following steps:
  • the present embodiment is a preparation method of a modified epoxy resin, comprising the following steps:
  • the present embodiment is a preparation method of modified boron nitride, comprising the following steps:
  • the present embodiment is a preparation method of a high-insulation low-temperature electronic packaging material, comprising the following steps:
  • Step 1 Weigh 100 parts of modified epoxy resin from Example 1, 5 parts of modified boron nitride and 10 parts of 4,4'-diaminodiphenyl sulfone from Example 3 according to parts by weight ,spare;
  • Step 2 adding the modified epoxy resin and the modified boron nitride into the high-speed mixer, and mixing for 4 hours under the condition of a stirring speed of 1200 r/min to obtain a mixture;
  • Step 3 Add 4,4'-diaminodiphenylsulfone to the mixture, then heat up to 130 °C and stir until 4,4'-diaminodiphenylsulfone is completely dissolved, then vacuumize for 3 hours, and then solidify at 130 °C 1h, and curing at 200° C. for 1h to obtain the high-insulation low-temperature electronic packaging material.
  • the present embodiment is a preparation method of a high-insulation low-temperature electronic packaging material, comprising the following steps:
  • Step 1 Weigh 150 parts by weight of modified epoxy resin from Example 2, 25 parts of modified boron nitride and 15 parts of 4,4'-diaminodiphenylsulfone from Example 3 ,spare;
  • Step 2 adding the modified epoxy resin and the modified boron nitride into the high-speed mixer, and mixing for 6 hours at a stirring rate of 2500 r/min to obtain a mixture;
  • Step 3 Add 4,4'-diaminodiphenylsulfone to the mixture, then heat up to 140 °C and stir until 4,4'-diaminodiphenylsulfone is completely dissolved, then vacuumize for 4 hours, and then solidify at 140 °C 2h, and curing at 210° C. for 2h to obtain the high-insulation low-temperature electronic packaging material.
  • Comparative Example 1 The difference between Comparative Example 1 and Example 5 is that epoxy resin E-44 is used instead of modified epoxy resin, and modified boron nitride is not added.
  • Comparative Example 2 The difference between Comparative Example 2 and Example 5 is that epoxy resin E-44 was used instead of the modified epoxy resin.
  • the high-insulation low-temperature electronic packaging material exhibits high insulation and high thermal conductivity under the action of modified epoxy resin and modified boron nitride
  • the modified epoxy resin E-44 has higher high temperature resistance, and can still maintain a high resistivity in a high temperature environment, thereby achieving high insulation performance
  • the addition of modified boron nitride can significantly improve the thermal conductivity of epoxy resin E-44, and at the same time improve a certain heat resistance.
  • description with reference to the terms “one embodiment,” “example,” “specific example,” etc. means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one aspect of the present invention. in one embodiment or example.
  • schematic representations of the above terms do not necessarily refer to the same embodiment or example.
  • the particular features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Power Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

本发明公开了高绝缘性的低温电子封装材料的制备方法，涉及电子封装材料领域，通过将改性环氧树脂、改性氮化硼加入至高速混合机中混合，得到混合料，将4，4'-二氨基二苯砜加入至混合料中，搅拌至溶解，之后固化，得到该高绝缘性的低温电子封装材料；该制备方法通过使用改性环氧树脂为主要材料，经过改性的环氧树脂具有更高的耐热性能，从而避免电子元件释放热量对电子封装材料的性能有不利影响，通过加入改性氮化硼能够有效提高环氧树脂的导热性能，从而便于将电子元件释放的热量快速导出，能够使得该电子封装材料在高温条件下仍然具有高的绝缘性能，能够满足电子封装发展的需要。

Description

高绝缘性的低温电子封装材料的制备方法 技术领域
本发明涉及电子封装材料领域，具体涉及高绝缘性的低温电子封装材料的制备方法。
背景技术
电子封装的功能是对微电子器材(IC)进行保护，作为封装材料最重要的性能指标是导热系数和热膨胀系数，高集成度的IC在工作中产生的热量必须及时释放，以防在过热的状态下工作，影响其寿命和性能；
与此同时，封装材料的热膨胀系数(CTE)尽量与芯片及载体保持一致，随着工作温度升高，将不可避免地在相邻部件间及焊接点处产生热应力，从而导致结合处蠕变、疲劳以致断裂，电子封装技术的飞速发展促进了封装材料的发展，即从过去的以金属和陶瓷封装为主转向塑料封装，塑料封装由于具有价格相对便宜、成型工艺简单、适合大规模生产、可靠性与陶瓷封装相当等诸多优点，已占到整个封装材料的95％以上，而塑料封装中应用最广泛的是环氧树脂塑封料。环氧树脂具有优良的耐热性、电绝缘性、密着性、介电性、力学性能及较小的收缩率、耐化学药品性，加入固化剂后又有较好的加工性和可操作性。
但是，现有的塑料电子封装材料的耐高温性能以及导热性能仍然不佳，限制了塑料电子封装材料的发展。
发明内容
为了克服上述的技术问题，本发明的目的在于提供高绝缘性的低温电子封装材料的制备方法：通过将改性环氧树脂、改性氮化硼加入至高速混合机中混合，得到混合料，将4，4’-二氨基二苯砜加入至混合料中，搅拌至溶解，之后 固化，得到该高绝缘性的低温电子封装材料，解决了现有的塑料电子封装材料的耐高温性能以及导热性能仍然不佳，限制了塑料电子封装材料的发展的问题。
本发明的目的可以通过以下技术方案实现：
高绝缘性的低温电子封装材料的制备方法，包括以下步骤：
步骤一：按照重量份称取改性环氧树脂100-150份、改性氮化硼5-25份以及4，4’-二氨基二苯砜10-15份，备用；
步骤二：将改性环氧树脂、改性氮化硼加入至高速混合机中，在搅拌速率为1200-2500r/min的条件下混合4-6h，得到混合料；
步骤三：将4，4’-二氨基二苯砜加入至混合料中，之后升温至130-140℃搅拌至4，4’-二氨基二苯砜完全溶解，之后抽真空3-4h后，在130-140℃固化1-2h，在200-210℃固化1-2h，得到该高绝缘性的低温电子封装材料。
作为本发明进一步的方案：所述改性环氧树脂的制备方法如下：
S11：将饱和碳酸钠溶液加入至安装有搅拌器以及恒压滴液漏斗的三口烧瓶中，在温度为20-30℃，搅拌速率为300-500r/min的条件下边搅拌边逐滴加入二苯基二氯硅烷，控制滴加速率为1滴/s，滴加完毕后继续搅拌反应10-30min，之后将反应产物用蒸馏水洗涤至pH为7，之后真空抽滤，将滤饼冷冻干燥，得到中间体1；
反应原理如下：
Figure PCTCN2022089223-appb-000001
S12：将环氧树脂、无水乙醇加入至安装有搅拌器、冷凝回流管以及氮气导管的三口烧瓶中，通入氮气保护，在温度为20-30℃，搅拌速率为500-800r/min的条件下搅拌至环氧树脂完全溶解，之后加入中间体1以及二丁基二月桂酸锡， 之后继续搅拌反应3-4h，反应结束后将反应产物用饱和碳酸钠溶液调节pH为7，之后将反应产物旋转蒸发，之后得到中间体2；
反应原理如下：
Figure PCTCN2022089223-appb-000002
S13：将中间体2加入至安装有搅拌器、冷凝回流管以及氮气导管的三口烧瓶中，通入氮气保护，在温度为100-110℃，搅拌速率为500-800r/min的条件下搅拌至中间体2完全熔融，之后加入DOPO，加入完毕继续搅拌至DOPO完全溶解，之后加入三苯基膦，之后边搅拌边升温至120-130℃，控制升温速率为1℃/min，之后恒温搅拌反应6-8h，得到改性环氧树脂。
反应原理如下：
Figure PCTCN2022089223-appb-000003
作为本发明进一步的方案：步骤S11中的所述饱和碳酸钠溶液、二苯基二氯硅烷的用量比为10-20mL∶5-8mL。
作为本发明进一步的方案：步骤S12中的所述环氧树脂为环氧树脂E-44，所述环氧树脂、无水乙醇、中间体1以及二丁基二月桂酸锡的用量比为10g∶50-100mL∶0.5-1.0g∶0.01-0.15g。
作为本发明进一步的方案：步骤S13中的所述中间体2、DOPO以及三苯基膦的质量比为100-200∶1-5∶0.01-0.05。
作为本发明进一步的方案：所述改性氮化硼的制备方法如下：
S21：将浓硫酸和浓硝酸加入至安装有搅拌器的三口烧瓶中，在搅拌速率为300-500r/min的条件下搅拌10-20min，之后加入立方氮化硼粉末，升温至60-70℃的条件下搅拌3-4h，反应结束将反应产物离心处理，将离心产物用蒸馏水洗涤至中性，之后放置于真空干燥箱中，在温度为60-70℃的条件下烘干至恒 重，得到预处理氮化硼；
S22：将硅烷偶联剂、乙醇溶液加入至安装有搅拌器的三口烧瓶中，在搅拌速率为300-500r/min的条件下搅拌10-20min，之后静置3-5h，之后加入预处理氮化硼，在搅拌速率为800-1000r/min的条件下搅拌1-3h，反应结束后将反应产物离心，将离心产物用无水乙醇洗涤2-3次，之后放置于真空干燥箱中，在温度为60-70℃的条件下烘干至恒重，得到改性氮化硼。
作为本发明进一步的方案：步骤S21中的所述浓硫酸的质量分数为95-98％，所述浓硝酸的质量分数为65-68％，所述浓硫酸、浓硝酸以及立方氮化硼粉末的用量比为30mL∶10mL∶1-5g。
作为本发明进一步的方案：步骤S22中的所述硅烷偶联剂为硅烷偶联剂KH-560，所述硅烷偶联剂、乙醇溶液以及预处理氮化硼的用量比为2-5g∶50-70mL∶1-3g，所述乙醇溶液的质量分数为90％。
本发明的有益效果：
本发明的高绝缘性的低温电子封装材料的制备方法，通过将改性环氧树脂、改性氮化硼加入至高速混合机中混合，得到混合料，将4，4’-二氨基二苯砜加入至混合料中，搅拌至溶解，之后固化，得到该高绝缘性的低温电子封装材料；该制备方法通过使用改性环氧树脂为主要材料，环氧树脂具有优良的耐热性、电绝缘性、密着性、介电性、力学性能及较小的收缩率、耐化学药品性，加入固化剂后又有较好的加工性和可操作性，适用于作为电子封装材料，经过改性的环氧树脂具有更高的耐热性能，从而避免电子元件释放热量对电子封装材料的性能有不利影响，通过加入改性氮化硼能够有效提高环氧树脂的导热性能，从而便于将电子元件释放的热量快速导出，能够使得该电子封装材料在高温条件下仍然具有高的绝缘性能，能够满足电子封装发展的需要。
制备低温电子封装材料的过程中也制备了一种改性环氧树脂，通过二苯基二氯硅烷水解形成中间体1，之后中间体1上的羟基与环氧树脂上的羟基反应，引入硅元素以及苯环，得到中间体2，之后中间体2上的部分环氧基团与DOPO反应，从而引入有机磷与苯环，得到该改性环氧树脂，引入的苯环具有良好的稳定性，引入的硅元素、磷元素具有更高的键能，从而能够提升环氧树脂的热稳定性，进而维持环氧树脂的高稳定性能。
制备低温电子封装材料的过程中也制备了一种改性氮化硼，六方氮化硼导热系数高、机械性能较好，并且抗氧化能力强，同时还具有很强的中子吸收能力和良好的电绝缘性能，具有高导热性能的同时具有高绝缘性，因此适用于对环氧树脂进行改性，但是六方氮化硼表面具有不饱和键和悬挂键，从而使得会发生团聚现象，导致其在环氧树脂中不易分散，影响环氧树脂性能，首先通过浓硫酸和浓硝酸酸化立方氮化硼粉末，从而将羟基或者羧基引入至立方氮化硼粉末表面，之后利用硅烷偶联剂水解形成硅醇后，紧接着脱水缩合成低聚硅氧烷，从而改善氮化硼粉末在环氧树脂中的分散性，避免其团聚，从而实现了提升环氧树脂导热性能的同时不降低其绝缘性能的目的。
具体实施方式
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
实施例1：
本实施例为一种改性环氧树脂的制备方法，包括如下步骤：
S11：将10mL饱和碳酸钠溶液加入至安装有搅拌器以及恒压滴液漏斗的三 口烧瓶中，在温度为20℃，搅拌速率为300r/min的条件下边搅拌边逐滴加入5mL二苯基二氯硅烷，控制滴加速率为1滴/s，滴加完毕后继续搅拌反应10min，之后将反应产物用蒸馏水洗涤至pH为7，之后真空抽滤，将滤饼冷冻干燥，得到中间体1；
S12：将10g环氧树脂E-44、50mL无水乙醇加入至安装有搅拌器、冷凝回流管以及氮气导管的三口烧瓶中，通入氮气保护，在温度为20℃，搅拌速率为500r/min的条件下搅拌至环氧树脂完全溶解，之后加入0.5g中间体1以及0.01g二丁基二月桂酸锡，之后继续搅拌反应3h，反应结束后将反应产物用饱和碳酸钠溶液调节pH为7，之后将反应产物旋转蒸发，之后得到中间体2；
S13：将100g中间体2加入至安装有搅拌器、冷凝回流管以及氮气导管的三口烧瓶中，通入氮气保护，在温度为100℃，搅拌速率为500r/min的条件下搅拌至中间体2完全熔融，之后加入1gDOPO，加入完毕继续搅拌至DOPO完全溶解，之后加入0.01g三苯基膦，之后边搅拌边升温至120℃，控制升温速率为1℃/min，之后恒温搅拌反应6h，得到改性环氧树脂。
实施例2：
本实施例为一种改性环氧树脂的制备方法，包括如下步骤：
S11：将20mL饱和碳酸钠溶液加入至安装有搅拌器以及恒压滴液漏斗的三口烧瓶中，在温度为30℃，搅拌速率为500r/min的条件下边搅拌边逐滴加入8mL二苯基二氯硅烷，控制滴加速率为1滴/s，滴加完毕后继续搅拌反应30min，之后将反应产物用蒸馏水洗涤至pH为7，之后真空抽滤，将滤饼冷冻干燥，得到中间体1；
S12：将10g环氧树脂E-44、100mL无水乙醇加入至安装有搅拌器、冷凝回流管以及氮气导管的三口烧瓶中，通入氮气保护，在温度为30℃，搅拌速率为 800r/min的条件下搅拌至环氧树脂完全溶解，之后加入1.0g中间体1以及0.15g二丁基二月桂酸锡，之后继续搅拌反应4h，反应结束后将反应产物用饱和碳酸钠溶液调节pH为7，之后将反应产物旋转蒸发，之后得到中间体2；
S13：将200g中间体2加入至安装有搅拌器、冷凝回流管以及氮气导管的三口烧瓶中，通入氮气保护，在温度为110℃，搅拌速率为800r/min的条件下搅拌至中间体2完全熔融，之后加入5gDOPO，加入完毕继续搅拌至DOPO完全溶解，之后加入0.05g三苯基膦，之后边搅拌边升温至130℃，控制升温速率为1℃/min，之后恒温搅拌反应8h，得到改性环氧树脂。
实施例3：
本实施例为一种改性氮化硼的制备方法，包括如下步骤：
S21：将30mL质量分数为98％的浓硫酸和10mL质量分数为68％的浓硝酸加入至安装有搅拌器的三口烧瓶中，在搅拌速率为500r/min的条件下搅拌20min，之后加入5g立方氮化硼粉末，升温至70℃的条件下搅拌4h，反应结束将反应产物离心处理，将离心产物用蒸馏水洗涤至中性，之后放置于真空干燥箱中，在温度为70℃的条件下烘干至恒重，得到预处理氮化硼；
S22：将5g硅烷偶联剂KH-560、70mL质量分数为90％的乙醇溶液加入至安装有搅拌器的三口烧瓶中，在搅拌速率为500r/min的条件下搅拌20min，之后静置5h，之后加入3g预处理氮化硼，在搅拌速率为1000r/min的条件下搅拌3h，反应结束后将反应产物离心，将离心产物用无水乙醇洗涤3次，之后放置于真空干燥箱中，在温度为70℃的条件下烘干至恒重，得到改性氮化硼。
实施例4：
本实施例为一种高绝缘性的低温电子封装材料的制备方法，包括以下步骤：
步骤一：按照重量份称取来自于实施例1中的改性环氧树脂100份、来自 于实施例3中的改性氮化硼5份以及4，4’-二氨基二苯砜10份，备用；
步骤二：将改性环氧树脂、改性氮化硼加入至高速混合机中，在搅拌速率为1200r/min的条件下混合4h，得到混合料；
步骤三：将4，4’-二氨基二苯砜加入至混合料中，之后升温至130℃搅拌至4，4’-二氨基二苯砜完全溶解，之后抽真空3h后，在130℃固化1h，在200℃固化1h，得到该高绝缘性的低温电子封装材料。
实施例5：
本实施例为一种高绝缘性的低温电子封装材料的制备方法，包括以下步骤：
步骤一：按照重量份称取来自于实施例2中的改性环氧树脂150份、来自于实施例3中的改性氮化硼25份以及4，4’-二氨基二苯砜15份，备用；
步骤二：将改性环氧树脂、改性氮化硼加入至高速混合机中，在搅拌速率为2500r/min的条件下混合6h，得到混合料；
步骤三：将4，4’-二氨基二苯砜加入至混合料中，之后升温至140℃搅拌至4，4’-二氨基二苯砜完全溶解，之后抽真空4h后，在140℃固化2h，在210℃固化2h，得到该高绝缘性的低温电子封装材料。
对比例1：
对比例1与实施例5的不同之处在于，使用环氧树脂E-44代替改性环氧树脂，不添加改性氮化硼。
对比例2：
对比例2与实施例5的不同之处在于，使用环氧树脂E-44代替改性环氧树脂。
对实施例4-5以及对比例1-2的高绝缘性的低温电子封装材料的性能进行检测，检测结果如下：
样品 实施例4 实施例5 对比例1 对比例2
25℃电阻率/Ω.m 1.56×10 15 2.13×10 15 6.48×10 14 7.22×10 14
400℃电阻率/Ω.m 8.23×10 12 1.04×10 13 7.21×10 10 2.14×10 11
导热系数/(W/m.K) 0.768 0.847 0.175 0.626
参阅上表数据，根据实施例与对比例1比较，可以得知在改性环氧树脂以及改性氮化硼的作用下该高绝缘性的低温电子封装材料表现出高绝缘性以及高导热性，根据实施例与对比例2比较，可以得知经过改性的环氧树脂E-44具有更高的耐高温性能，在高温环境下仍然能够保持高的电阻率，从而实现高的绝缘性能，根据对比例1与实施例2比较，可以得知添加改性氮化硼能够明显提高环氧树脂E-44的导热性能，同时提升了一定的耐热性能。
在本说明书的描述中，参考术语“一个实施例”、“示例”、“具体示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
以上内容仅仅是对本发明所作的举例和说明，所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代，只要不偏离发明或者超越本权利要求书所定义的范围，均应属于本发明的保护范围。

Claims (8)

  1. 高绝缘性的低温电子封装材料的制备方法，其特征在于，包括以下步骤：
    步骤一：按照重量份称取改性环氧树脂100-150份、改性氮化硼5-25份以及4，4’-二氨基二苯砜10-15份，备用；
    步骤二：将改性环氧树脂、改性氮化硼加入至高速混合机中，在搅拌速率为1200-2500r/min的条件下混合4-6h，得到混合料；
    步骤三：将4，4’-二氨基二苯砜加入至混合料中，之后升温至130-140℃搅拌至4，4’-二氨基二苯砜完全溶解，之后抽真空3-4h后，在130-140℃固化1-2h，在200-210℃固化1-2h，得到该高绝缘性的低温电子封装材料。
  2. 根据权利要求1所述的高绝缘性的低温电子封装材料的制备方法，其特征在于，所述改性环氧树脂的制备方法如下：
    S11：将饱和碳酸钠溶液加入至三口烧瓶中，边搅拌边逐滴加入二苯基二氯硅烷，滴加完毕后继续搅拌反应，之后将反应产物用蒸馏水洗涤至pH为7，之后真空抽滤，将滤饼冷冻干燥，得到中间体1；
    S12：将环氧树脂、无水乙醇加入至三口烧瓶中，搅拌至环氧树脂完全溶解，之后加入中间体1以及二丁基二月桂酸锡继续搅拌反应，反应结束后将反应产物调节pH为7，之后将反应产物旋转蒸发，之后得到中间体2；
    S13：将中间体2加入至三口烧瓶中，搅拌至中间体2完全熔融，之后加入DOPO并将DOPO搅拌至完全溶解，之后加入三苯基膦，升温后恒温搅拌反应，得到改性环氧树脂。
  3. 根据权利要求2所述的高绝缘性的低温电子封装材料的制备方法，其特征在于，步骤S11中的所述饱和碳酸钠溶液、二苯基二氯硅烷的用量比为10-20mL∶5-8mL。
  4. 根据权利要求2所述的高绝缘性的低温电子封装材料的制备方法，其特征在于，步骤S12中的所述环氧树脂为环氧树脂E-44，所述环氧树脂、无水乙醇、中间体1以及二丁基二月桂酸锡的用量比为10g∶50-100mL∶0.5-1.0g∶0.01-0.15g。
  5. 根据权利要求2所述的高绝缘性的低温电子封装材料的制备方法，其特征在于，步骤S13中的所述中间体2、DOPO以及三苯基膦的质量比为100-200∶1-5∶0.01-0.05。
  6. 根据权利要求1所述的高绝缘性的低温电子封装材料的制备方法，其特征在于，所述改性氮化硼的制备方法如下：
    S21：将浓硫酸和浓硝酸加入至三口烧瓶中，搅拌后加入立方氮化硼粉末，升温并搅拌，反应结束将反应产物离心处理，将离心产物洗涤至中性，之后烘干至恒重，得到预处理氮化硼；
    S22：将硅烷偶联剂、乙醇溶液加入至三口烧瓶中，搅拌后静置，之后加入预处理氮化硼搅拌，反应结束后将反应产物离心，将离心产物洗涤，之后烘干至恒重，得到改性氮化硼。
  7. 根据权利要求6所述的高绝缘性的低温电子封装材料的制备方法，其特征在于，步骤S21中的所述浓硫酸的质量分数为95-98％，所述浓硝酸的质量分数为65-68％，所述浓硫酸、浓硝酸以及立方氮化硼粉末的用量比为30mL∶10mL∶1-5g。
  8. 根据权利要求6所述的高绝缘性的低温电子封装材料的制备方法，其特征在于，步骤S22中的所述硅烷偶联剂为硅烷偶联剂KH-560，所述硅烷偶联剂、乙醇溶液以及预处理氮化硼的用量比为2-5g∶50-70mL∶1-3g，所述乙醇溶液的质量分数为90％。
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