WO2018223780A1 - 一种环氧树脂复合材料及其制备方法和应用 - Google Patents

一种环氧树脂复合材料及其制备方法和应用 Download PDF

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WO2018223780A1
WO2018223780A1 PCT/CN2018/083679 CN2018083679W WO2018223780A1 WO 2018223780 A1 WO2018223780 A1 WO 2018223780A1 CN 2018083679 W CN2018083679 W CN 2018083679W WO 2018223780 A1 WO2018223780 A1 WO 2018223780A1
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epoxy resin
bisphenol
fluorine
chloroether
etherate
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French (fr)
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刘若鹏
赵治亚
张璐
张运湘
徐志财
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洛阳尖端技术研究院
洛阳尖端装备技术有限公司
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Publication of WO2018223780A1 publication Critical patent/WO2018223780A1/zh

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    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • 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
    • C08G59/68—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 catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

Definitions

  • the invention relates to the field of composite materials, in particular to an epoxy resin composite material and preparation method and application thereof
  • Epoxy resin refers to a kind of organic polymer compound containing two or more epoxy groups in the molecule, which has good bonding property, small deformation shrinkage, high mechanical strength, abundant raw material source, low cost and easy Processing and other characteristics, widely used in printed circuit boards, coatings, microelectronics and other fields.
  • epoxy resin has the disadvantages of easy cracking, poor fatigue resistance and high dielectric constant after curing, which makes the dielectric properties of general epoxy resin unable to meet the requirements of today's low dielectric materials. Therefore, it is urgent to study the low dielectric. Constant epoxy resin composite.
  • low dielectric epoxy epoxy resin composites are generally prepared by adding a filler having a low dielectric constant to an epoxy resin, such as hollow glass microspheres, mesoporous silica, and POSS. It can effectively reduce the dielectric constant of the material, but it will significantly reduce the mechanical strength of the composite.
  • Chinese patent CN106189087 uses POSS as a modifier to prepare POSS epoxy resin composites, which can also reduce the dielectric constant of materials, but POSS is extremely expensive and increases the manufacturing cost of materials. Therefore, it is very important to prepare a dielectric material with good dielectric properties by a simple and cost-effective method.
  • the present invention provides a method for preparing an epoxy resin composite material which is low in manufacturing cost and simple in process, and provides an epoxy resin composite material having a low dielectric constant.
  • a method of preparing an epoxy resin composite comprising: dissolving bisphenol AF in epichlorohydrin, and then adding a phase shift catalyst to obtain a resin etherate; Ethyl ether and NaOH solution are reacted to obtain bisphenol AF chloroether alcohol; the NaOH solution is added dropwise to the bisphenol AF chloroether alcohol to obtain a fluorine-containing epoxy resin; and the fluorine-containing epoxy resin and curing agent are After mixing uniformly, the catalyst is added, mixed, and solidified to obtain an epoxy resin composite material.
  • the step of completely dissolving bisphenol AF in epichlorohydrin, and then adding a catalyst reaction to obtain a resin etherate comprises: completely dissolving bisphenol AF in epichlorohydrin at 60 to 80 ° C Then, a phase shift catalyst of tetrabutylammonium bromide having a mass fraction of 0.05% to 0.15% is added and reacted for 0.5 to 1.5 hours to obtain a resin etherate, wherein the bisphenol AF and the epichlorohydrin are obtained.
  • the molar ratio is 1:2 to 1:6.
  • the step of completely dissolving bisphenol AF in epichlorohydrin and then adding a phase shift catalyst to obtain a resin etherate further comprises: completely dissolving bisphenol AF in epoxy chlorinated at 70 ° C In a propane, a phase shift catalyst of tetrabutylammonium bromide having a mass fraction of 0.1% is added and reacted for 1 hour to obtain a resin etherate, wherein the molar ratio of the bisphenol AF to the epichlorohydrin is 1:4.
  • the step of reacting the resin etherate with a NaOH solution to obtain bisphenol AF chloroether alcohol comprises: subjecting the resin etherate to a NaOH solution having a mass fraction of 25% to 35% at 60 to 90 The reaction is incubated at ° C for 1 to 3 hours, after which excess unreacted epichlorohydrin is removed to obtain the bisphenol AF chloroether alcohol, wherein the molar ratio of the bisphenol AF to NaOH is 1:0.1 to 0.2. .
  • the step of reacting the resin etherate with a NaOH solution to obtain bisphenol AF chloroether alcohol further comprises: incubating the resin etherate with a mass fraction of 30% NaOH solution at 70 ° C After 2 hours, unreacted epichlorohydrin was removed to obtain the bisphenol AF chloroether alcohol, wherein the molar ratio of the bisphenol AF to NaOH was 1:0.2.
  • the step of adding the NaOH solution to the bisphenol AF chloroether alcohol to obtain a fluorine-containing epoxy resin comprises: adding a mass fraction of 35% to the bisphenol AF chloroether alcohol ⁇ 45% NaOH solution, the reaction is incubated for 1-3 hours, after the reaction is completed, filtered and washed to obtain a fluorine-containing epoxy resin, wherein the molar ratio of the bisphenol AF to NaOH is 1:1.5-2.
  • the step of adding the NaOH solution to the bisphenol AF chloroether alcohol to obtain a fluorine-containing epoxy resin further comprises: adding a mass fraction of 40 to the bisphenol AF chloroether alcohol The % NaOH solution was incubated for 2 hours. After the reaction was completed, it was filtered and washed to obtain a fluorine-containing epoxy resin, wherein the molar ratio of the bisphenol AF to NaOH was 1:2.
  • a catalyst is added, mixed, and solidified, and the epoxy resin composite material is obtained by the steps of: at 80 to 100 ° C, the After the fluorine-containing epoxy resin and the curing agent are uniformly mixed, a catalyst having a mass fraction of 0.05% to 0.15% is added, mixed and solidified to obtain an epoxy resin composite material; the fluorine-containing epoxy resin and the curing agent The mass ratio is in the range of 3:7 to 6:4.
  • the step of preparing the epoxy resin composite material further includes: at 90 ° C, the content is included
  • a catalyst having a mass fraction of 0.1% is added, mixed and solidified to obtain an epoxy resin composite material; and the ratio of the fluorine-containing epoxy resin to the mass of the curing agent For 3.5:6.5
  • the curing agent is an acid anhydride curing agent.
  • the curing agent is one of a cyanate ester, methyl hexahydrophthalic anhydride or a combination of two; and the catalyst is a manganese oxide having a mass fraction of 0.1% or a mass fraction of 0.1%.
  • an epoxy resin composite prepared by the above method.
  • an epoxy resin composite as an electronic material or a wave permeable material.
  • the preparation method of the epoxy resin composite material provided by the invention is prepared by dissolving bisphenol AF in epichlorohydrin, then adding a phase shift catalyst and a NaOH solution, and then reacting to obtain a fluorine-containing epoxy resin, and then adding the curing agent thereto. Agents and catalysts to prepare epoxy resin composites.
  • the present invention reduces the polarity of the resin structure by introducing F in the resin structure to form C-F instead of C-H, thereby lowering the dielectric constant and dielectric loss of the material, and at the same time improving the thermal stability of the material.
  • the low dielectric epoxy resin composite prepared by the invention can be used as a matrix resin in an integrated circuit to reduce power consumption and improve signal transmission speed; and can be used as a matrix resin of a wave-transparent composite material to improve electromagnetic wave transmittance.
  • FIG. 1 is a flow chart of a method of preparing an epoxy resin composite in accordance with a preferred embodiment of the present invention.
  • the preparation method of the epoxy resin composite material provided by the invention comprises the following steps:
  • step S101 in Fig. 1 bisphenol AF is completely dissolved in epichlorohydrin, and then a catalyst reaction is added to obtain a resin etherate.
  • bisphenol AF is completely dissolved in epichlorohydrin at 60-80 ° C, preferably 70 ° C, and then a phase shift catalyst tetrabutylammonium bromide is added in a mass fraction of 0.05% to 0.15%.
  • the reaction preferably a phase shift catalyst of 0.1% by mass, of tetrabutylammonium bromide, is incubated for 0.5 to 1.5 hours, preferably for 1 hour, to obtain a resin etherate, wherein the bisphenol AF and the epoxy
  • the molar ratio of chloropropane is from 1:2 to 1:6, preferably 1:4.
  • step S102 in Fig. 1 the resin etherate and the NaOH solution were reacted to obtain bisphenol AF chloroether alcohol.
  • the resin etherate is incubated with a NaOH solution having a mass fraction of 25% to 35% at 60 to 90 ° C for 1 to 3 hours, after which unreacted epichlorohydrin is removed to obtain the Bisphenol AF chloroether alcohol, wherein the molar ratio of bisphenol AF to NaOH is 1:0.1-0.2, and the mass fraction of NaOH is 25%-35%.
  • the resin etherate is reacted with a NaOH solution having a mass fraction of 30% at 70 ° C for 2 hours, wherein the molar ratio of the bisphenol AF to NaOH is 1:0.2.
  • step S103 in Fig. 1 the NaOH solution was added dropwise to the bisphenol AF chloroether alcohol to obtain a fluorine-containing epoxy resin.
  • a NaOH solution having a mass fraction of 35% to 45% is added dropwise to the bisphenol AF chloroether alcohol, and the reaction is kept for 1 to 3 hours. After the reaction is completed, it is filtered and washed to obtain a fluorine-containing epoxy resin.
  • the molar ratio of bisphenol AF to NaOH is 1:1.5-2.
  • a 40% by mass NaOH solution is added dropwise to the bisphenol AF chloroether alcohol, and the reaction is kept for 2 hours, and the molar ratio of bisphenol AF to NaOH is 1:1.5.
  • step S104 in FIG. 1 after the fluorine-containing epoxy resin and the curing agent are uniformly mixed, a catalyst is added, mixed, and solidified to obtain an epoxy resin composite material.
  • the step further comprises: after uniformly mixing the fluorine-containing epoxy resin and the curing agent at 80 to 100 ° C, adding a catalyst having a mass fraction of 0.05% to 0.15%, mixing and solidifying to obtain an epoxy resin.
  • Composite material Preferably, after the fluorine-containing epoxy resin and the curing agent are uniformly mixed at 90 ° C, a catalyst having a mass fraction of 0.1% is added.
  • the curing agent is an acid anhydride curing agent or one of a cyanate ester, methyl hexahydrophthalic anhydride or a combination of two.
  • the catalyst is one or a combination of two or more of manganese manganate having a mass fraction of 0.1% or DMP-30 having a mass fraction of 0.1%.
  • the ratio of the mass of the fluorine-containing epoxy resin to the curing agent is in the range of 3:7 to 6:4, preferably 3.5:6.5.
  • the unreacted epichlorohydrin is recovered, and then a 40 NaOH solution is added dropwise, and the molar ratio of bisphenol AF to NaOH is 1:2, and the reaction is completed for 2 hours.
  • the reaction is completed, filtered, and washed to obtain a fluorine-containing epoxy resin, wherein the fluorine-containing epoxy resin is obtained.
  • the purity of the resin was 97.5%.
  • Phenol AF chloroether alcohol wherein the molar ratio of bisphenol AF to NaOH is 1:0.1. After completion, unreacted epichlorohydrin is recovered by vacuum distillation, and then 35% NaOH solution, bisphenol AF and NaOH are added dropwise. The molar ratio is 1:1.5, the reaction is kept for 3 hours, the reaction is completed, and the mixture is filtered and washed to obtain a fluorine-containing epoxy resin, wherein the fluorine-containing epoxy resin has a purity of 96%.
  • Phenol AF chloroether alcohol wherein the molar ratio of bisphenol AF to NaOH is 1:0.1. After completion, unreacted epichlorohydrin is recovered by vacuum distillation, and then 35% NaOH solution, bisphenol AF and NaOH are added dropwise. The molar ratio is 1:1.5, the reaction is kept for 1 hour, the reaction is completed, and the mixture is filtered and washed to obtain a fluorine-containing epoxy resin, wherein the purity of the fluorine-containing epoxy resin is 97%.
  • Bisphenol AF chloroether alcohol wherein the molar ratio of bisphenol AF to NaOH is 1:0.1, after completion, unreacted epichlorohydrin is recovered by vacuum distillation, and then 40% NaOH solution is added dropwise, bisphenol AF and The molar ratio of NaOH is 1:1.5, the reaction is kept for 2.5 hours, the reaction is completed, and the mixture is filtered and washed to obtain a fluorine-containing epoxy resin, wherein the purity of the fluorine-containing epoxy resin is 95.5%.
  • the epoxy resin composites prepared in Examples 1 to 6 were tested for dielectric constant, dielectric loss and thermal stability, respectively.
  • the test results are as follows:
  • the epoxy resin obtained by the method has the advantages of low dielectric constant, dielectric loss, and good mechanical properties.
  • the preparation method of the epoxy resin composite material provided by the invention is obtained by reacting bisphenol AF, epichlorohydrin and NaOH solution to obtain a fluorine-containing epoxy resin, and then adding a curing agent and a catalyst to the fluorine-containing epoxy resin to prepare an epoxy resin. Resin composite.
  • the fluorine-containing epoxy resin prepared by the method has low impurity content and high purity, all of which are above 95%, and the highest purity is up to 98%, so that the epoxy resin composite material has low dielectric constant and dielectric loss, and has Good thermal stability.

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Abstract

本发明提供的环氧树脂复合材料的制备方法，包括：将双酚AF完全溶解在环氧氯丙烷中，然后加入催化剂反应以得到树脂醚化物；使树脂醚化物和NaOH溶液反应，得到双酚AF氯醚醇；在双酚AF氯醚醇中滴加NaOH溶液，得到含氟环氧树脂；将含氟环氧树脂和固化剂混合均匀后，加入催化剂，混合、固化，制得环氧树脂复合材料。本发明还提供了由上述方法制备的环氧树脂复合材料及其作为电子材料和透波材料的应用。本发明通过在树脂结构中引入F，形成C-F替代C-H，使树脂结构的极性降低，从而制备出具有低介电常数和介电损耗，并且同时具有良好的热稳定性的环氧树脂复合材料，其可广泛地应用于印刷电路板、涂料、微电子等领域。

Description

一种环氧树脂复合材料及其制备方法和应用 技术领域
本发明涉及复合材料领域，具体而言，一种环氧树脂复合材料及其制备方法和应用
背景技术
环氧树脂是指分子中含有两个或两个以上的环氧基团的一类有机高分子化合物，具有粘接性能好、变形收缩率小、机械强度高、原料来源丰富、成本低廉、易于加工成型等特点，广泛用于印刷电路板、涂料、微电子等领域。但是环氧树脂在固化后存在易开裂、耐疲劳性差以及介电常数高等缺点，使得一般环氧树脂的介电性能根本无法满足当今低介电材料的要求，因此，迫切需要研究具有低介电常数的环氧树脂复合材料。
目前，低介电环氧树脂复合材料的制备方法一般是通过在环氧树脂中添加具有低介电常数的填料，如中空玻璃微珠、介孔二氧化硅和POSS等，使用中空玻微珠可有效降低材料介电常数，但会明显降低复合材料的力学强度。中国专利CN106189087以POSS作为改性剂来制备POSS型环氧树脂复合材料，也可降低材料的介电常数，但POSS价格极其昂贵，增加了材料的制造成本。因此，通过简单易行、经济有效的方法制备介电性能良好的介电材料具有十分重要的意义。
发明内容
针对相关技术中的问题，本发明提供了一种制造成本低且工艺简单的环氧树脂复合材料的制备方法，以提供一种具有低介电常数的环氧树脂复合材料。
根据本发明的一个方面，提供了一种环氧树脂复合材料的制备方法，包括：将双酚AF溶解在环氧氯丙烷中，然后加入相移催化剂反应以得到树脂醚化物；使所述树脂醚化物和NaOH溶液反应，得到双酚AF氯醚醇； 在所述双酚AF氯醚醇中滴加所述NaOH溶液，得到含氟环氧树脂；将所述含氟环氧树脂和固化剂混合均匀后，加入催化剂，混合、固化，制得环氧树脂复合材料。
在上述制备方法中，将双酚AF完全溶解在环氧氯丙烷中，然后加入催化剂反应以得到树脂醚化物的步骤包括：在60～80℃下，将双酚AF完全溶解在环氧氯丙烷中，然后加入质量分数为0.05％～0.15％的相移催化剂四丁基溴化铵反应，保温0.5～1.5小时，以得到树脂醚化物，其中，所述双酚AF与所述环氧氯丙烷的摩尔比为1：2～1：6。
在上述制备方法中，将双酚AF完全溶解在环氧氯丙烷中，然后加入相移催化剂反应以得到树脂醚化物的步骤进一步包括：在70℃下，将双酚AF完全溶解在环氧氯丙烷中，然后加入质量分数为0.1％的相移催化剂四丁基溴化铵反应，保温1小时，以得到树脂醚化物，其中，所述双酚AF与所述环氧氯丙烷的摩尔比为1：4。
在上述制备方法中，使所述树脂醚化物和NaOH溶液反应，得到双酚AF氯醚醇的步骤包括：使所述树脂醚化物与质量分数为25％～35％的NaOH溶液在60～90℃下保温反应1～3小时，之后，去除过量的未反应的环氧氯丙烷，得到所述双酚AF氯醚醇，其中，所述双酚AF与NaOH的摩尔比为1：0.1～0.2。
在上述制备方法中，使所述树脂醚化物和NaOH溶液反应，得到双酚AF氯醚醇的步骤进一步包括：使所述树脂醚化物与质量分数为30％的NaOH溶液在70℃下保温反应2小时，之后，去除未反应的环氧氯丙烷，得到所述双酚AF氯醚醇，其中，所述双酚AF与NaOH的摩尔比为1：0.2。
在上述制备方法中，在所述双酚AF氯醚醇中滴加所述NaOH溶液，得到含氟环氧树脂的步骤包括：在所述双酚AF氯醚醇中滴加质量分数为35％～45％的NaOH溶液，保温反应1～3小时，反应结束后，过滤，洗涤，得到含氟环氧树脂，其中，所述双酚AF与NaOH的摩尔比为1：1.5～2。
在上述制备方法中，在所述双酚AF氯醚醇中滴加所述NaOH溶液，得到含氟环氧树脂的步骤进一步包括：在所述双酚AF氯醚醇中滴加质量分数为40％的NaOH溶液，保温反应2小时，反应结束后，过滤，洗涤， 得到含氟环氧树脂，其中，所述双酚AF与NaOH的摩尔比为1：2。
在上述制备方法中，将所述含氟环氧树脂和固化剂在混合均匀后，加入催化剂，混合、固化，制得环氧树脂复合材料的步骤包括：在80～100℃下，将所述含氟环氧树脂和所述固化剂混合均匀后，加入质量分数为0.05％～0.15％的催化剂，混合、固化，制得环氧树脂复合材料；所述含氟环氧树脂与所述固化剂的质量之比在3：7～6：4的范围内。
在上述制备方法中，将所述含氟环氧树脂和固化剂在混合均匀后，加入催化剂，混合、固化，制得环氧树脂复合材料的步骤进一步包括：在90℃下，将所述含氟环氧树脂和所述固化剂混合均匀后，加入质量分数为0.1％的催化剂，混合、固化，制得环氧树脂复合材料；所述含氟环氧树脂与所述固化剂的质量之比为3.5:6.5
在上述制备方法中，所述固化剂为酸酐固化剂。
在上述制备方法中，所述固化剂为氰酸酯、甲基六氢苯酐中的一种或者两种的组合；并且所述催化剂为质量分数为0.1％的锌酸锰或质量分数为0.1％的DMP～30中的一种或者两种的组合。
根据本发明的另一方面，还提供了一种由上述方法制备的环氧树脂复合材料。
根据本发明的又一方面，还提供了环氧树脂复合材料作为电子材料或透波材料的应用。
本发明提供的环氧树脂复合材料的制备方法，通过将双酚AF溶解在环氧氯丙烷中，然后加入相移催化剂和NaOH溶液，反应后，得到含氟环氧树脂，然后向其中加入固化剂和催化剂来制备环氧树脂复合材料。本发明通过在树脂结构中引入F，形成C-F替代C-H，使树脂结构的极性降低，从而使得材料介电常数和介电损耗下降，并且同时提高了材料的热稳定性。本发明所制备的低介电环氧树脂复合材料可作为集成电路中的基体树脂，降低功耗和提升信号传输速度；另外可以作为透波复合材料的基体树脂，提高电磁波的透过率。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是根据本发明优选实施例的制备环氧树脂复合材料的方法的流程图。
具体实施方式
下面将结合本发明实施例中的附图，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所获得的所有其他实施例，都属于本发明保护的范围。
本发明提供的环氧树脂复合材料的制备方法，包括以下步骤：
如图1中的步骤S101所示，将双酚AF完全溶解在环氧氯丙烷中，然后加入催化剂反应以得到树脂醚化物。在该步骤中，在60～80℃下，优选70℃下，将双酚AF完全溶解在环氧氯丙烷中，然后加入质量分数为0.05％～0.15％的相移催化剂四丁基溴化铵反应，优选质量分数为0.1％的相移催化剂四丁基溴化铵反应，保温0.5～1.5小时，优选地保温1小时，以得到树脂醚化物，其中，所述双酚AF与所述环氧氯丙烷的摩尔比为1：2～1：6，优选地1：4。
如图1中的步骤S102所示，使所述树脂醚化物和NaOH溶液，反应，得到双酚AF氯醚醇。在该步骤中，使所述树脂醚化物与质量分数为25％～35％的NaOH溶液在60～90℃下保温反应1～3小时，之后，去除未反应的环氧氯丙烷，得到所述双酚AF氯醚醇，其中，双酚AF与NaOH的摩尔比为1：0.1-0.2，NaOH质量分数为25％～35％。优选地，使所述树脂醚化物与质量分数为30％的NaOH溶液在70℃下保温反应2小时，其中，所述双酚AF与NaOH的摩尔比为1：0.2。
如图1中的步骤S103所示，在所述双酚AF氯醚醇中滴加所述NaOH 溶液，得到含氟环氧树脂。在该步骤中，在所述双酚AF氯醚醇中滴加质量分数为35％～45％的NaOH溶液，保温反应1～3小时，反应结束后，过滤，洗涤，得到含氟环氧树脂，其中，双酚AF与NaOH摩尔比为1：1.5-2。优选地，在双酚AF氯醚醇中滴加质量分数为40％的NaOH溶液，保温反应2小时，双酚AF与NaOH的摩尔比为1：1.5。
如图1中的步骤S104所示，将所述含氟环氧树脂和固化剂混合均匀后，加入催化剂，混合、固化，制得环氧树脂复合材料。该步骤进一步包括：在80～100℃下，将所述含氟环氧树脂和所述固化剂混合均匀后，加入质量分数为0.05％～0.15％的催化剂，混合、固化，制得环氧树脂复合材料。优选地，在90℃下，将所述含氟环氧树脂和所述固化剂混合均匀后，加入质量分数为0.1％的催化剂。所述固化剂为酸酐固化剂或者为氰酸酯、甲基六氢苯酐中的一种或者两种的组合。所述催化剂为质量分数为0.1％的锌酸锰或质量分数为0.1％的DMP～30中的一种或者两种的组合。所述含氟环氧树脂与所述固化剂的质量之比在3：7～6：4的范围内，优选为3.5:6.5。
实施例1
(1)含氟树脂的合成：将双酚AF与环氧氯丙烷按摩尔比1：4加入三颈圆底烧瓶，抽真空，通入氮气，升温至70℃，搅拌混合，待双酚AF完全溶解于环氧氯丙烷后，加入质量分数为0.1％的相转移催化剂四丁基溴化铵，保温反应1h，得到树脂醚化物，加入30％NaOH溶液，70℃保温反应2h，得到双酚AF氯醚醇，其中，双酚AF与NaOH的摩尔比为1：0.1，完毕后，减压蒸馏将未反应的环氧氯丙烷回收，然后在滴加40％NaOH溶液，双酚AF与NaOH的摩尔比为1：1.5，反应2h，反应结束，过滤，洗涤，得到含氟环氧树脂，其中，含氟环氧树脂的纯度为97％。
(2)低介电环氧树脂复合材料制备：将含氟环氧树脂与氰酸酯按质量比3：7在90℃混合均匀，加入质量分数为0.1％的催化剂锌酸锰，混合，抽真空，倒入模具，固化，得到低介电环氧树脂复合材料。
实施例2
(1)含氟树脂的合成：将双酚AF与环氧氯丙烷按摩尔比1：4加入三颈圆底烧瓶，抽真空，通入氮气，升温至70℃，搅拌混合，待双酚AF完全溶解于环氧氯丙烷后，加入质量分数为0.1％的相转移催化剂四丁基溴化铵，保温反应1h，得到树脂醚化物，加入30％NaOH溶液，70℃保温反应2h，得到双酚AF氯醚醇，其中，双酚AF与NaOH摩尔比为1：0.1。未反应的环氧氯丙烷回收，然后在滴加40NaOH溶液，双酚AF与NaOH的摩尔1：2，反应2h，反应结束，过滤，洗涤，得到含氟环氧树脂，其中，含氟环氧树脂的纯度为97.5％。
(2)低介电环氧树脂复合材料制备：将含氟环氧树脂与氰酸酯按质量比6：4在90℃混合均匀，加入质量分数为0.1％的催化剂锌酸锰，混合，抽真空，倒入模具，固化，得到低介电环氧树脂复合材料。
实施例3
(1)含氟树脂的合成：将双酚AF与环氧氯丙烷按摩尔比1：4加入三颈圆底烧瓶，抽真空，通入氮气，升温至70℃，搅拌混合，待双酚AF完全溶解于环氧氯丙烷后，加入质量分数为0.1％的相转移催化剂四丁基溴化铵，保温反应1h，得到树脂醚化物，加入30％NaOH溶液，70℃保温反应2h，得到双酚AF氯醚醇，其中，双酚AF与NaOH摩尔比为1：0.2，完毕后，减压蒸馏将未反应的环氧氯丙烷回收，然后在滴加40％NaOH溶液，双酚AF与NaOH的摩尔1：1.5，保温反应2h，反应结束，过滤，洗涤，得到含氟环氧树脂，其中，含氟环氧树脂的纯度为97％。
(2)低介电环氧树脂复合材料制备：将含氟环氧树脂与固化剂甲基六氢苯酐在90℃混合均匀，加入质量分数为0.1％的催化剂DMP-30，混合，抽真空，倒入模具，固化，得到低介电环氧树脂复合材料。
实施例4
(1)含氟树脂的合成：将双酚AF与环氧氯丙烷按摩尔比1：3加入三颈圆底烧瓶，抽真空，通入氮气，升温至60℃，搅拌混合，待双酚AF完全溶解于环氧氯丙烷后，加入质量分数为0.05％的相转移催化剂四丁基 溴化铵，保温反应1.5h，得到树脂醚化物，加入30％NaOH溶液，90℃保温反应3h，得到双酚AF氯醚醇，其中，双酚AF与NaOH摩尔比为1：0.1，完毕后，减压蒸馏将未反应的环氧氯丙烷回收，然后在滴加35％NaOH溶液，双酚AF与NaOH的摩尔1：1.5，保温反应3h，反应结束，过滤，洗涤，得到含氟环氧树脂，其中，含氟环氧树脂的纯度为96％。
(2)低介电环氧树脂复合材料制备：将含氟环氧树脂与氰酸酯按质量比3：7在100℃混合均匀，加入质量分数为0.15％的催化剂锌酸锰，混合，抽真空，倒入模具，固化，得到低介电环氧树脂复合材料。
实施例5
(1)含氟树脂的合成：将双酚AF与环氧氯丙烷按摩尔比1：6加入三颈圆底烧瓶，抽真空，通入氮气，升温至80℃，搅拌混合，待双酚AF完全溶解于环氧氯丙烷后，加入质量分数为0.15％的相转移催化剂四丁基溴化铵，保温反应0.5h，得到树脂醚化物，加入30％NaOH溶液，80℃保温反应1h，得到双酚AF氯醚醇，其中，双酚AF与NaOH摩尔比为1：0.1，完毕后，减压蒸馏将未反应的环氧氯丙烷回收，然后在滴加35％NaOH溶液，双酚AF与NaOH的摩尔1：1.5，保温反应1h，反应结束，过滤，洗涤，得到含氟环氧树脂，其中，含氟环氧树脂的纯度为97％。
(2)低介电环氧树脂复合材料制备：将含氟环氧树脂与氰酸酯按质量比6：4在80℃混合均匀，加入质量分数为0.05％的催化剂锌酸锰，混合，抽真空，倒入模具，固化，得到低介电环氧树脂复合材料。
实施例6
(1)含氟树脂的合成：将双酚AF与环氧氯丙烷按摩尔比1：5加入三颈圆底烧瓶，抽真空，通入氮气，升温至75℃，搅拌混合，待双酚AF完全溶解于环氧氯丙烷后，加入质量分数为0.1％的相转移催化剂四丁基溴化铵，保温反应1.5h，得到树脂醚化物，加入35％NaOH溶液，75℃保温反应2.5h，得到双酚AF氯醚醇，其中，双酚AF与NaOH摩尔比为1：0.1，完毕后，减压蒸馏将未反应的环氧氯丙烷回收，然后在滴加40％NaOH溶 液，双酚AF与NaOH的摩尔1：1.5，保温反应2.5h，反应结束，过滤，洗涤，得到含氟环氧树脂，其中，含氟环氧树脂的纯度为95.5％。
(2)低介电环氧树脂复合材料制备：将含氟环氧树脂与固化剂甲基六氢苯酐在100℃混合均匀，加入质量分数为0.15％的催化剂DMP-30，混合，抽真空，倒入模具，固化，得到低介电环氧树脂复合材料。
对实施例1至实施例6中制备得到的环氧树脂复合材料分别进行介电常数，介电损耗以及热稳定性测试，测试结果如下：
Figure PCTCN2018083679-appb-000001
结果显示：
利用此方法制得的环氧树脂，经固化后得到的复合材料具有较低的介电系数、介电损耗、以及良好的力学性能等优点。
本发明提供的环氧树脂复合材料的制备方法，通过双酚AF、环氧氯丙烷、NaOH溶液反应得到含氟环氧树脂，然后在含氟环氧树脂中加入固化剂和催化剂来制备环氧树脂复合材料。采用该方法制备的含氟环氧树脂杂质含量低，纯度高，均在95％以上，最高纯度可达98％，从而使得环氧树脂复合材料具有低的介电常数和介电损耗，且具有良好的热稳定性。
以上仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (13)

  1. 一种环氧树脂复合材料的制备方法，其特征在于，包括：
    将双酚AF溶解在环氧氯丙烷中，然后加入相移催化剂反应以得到树脂醚化物；
    使所述树脂醚化物和NaOH溶液反应，得到双酚AF氯醚醇；
    在所述双酚AF氯醚醇中滴加所述NaOH溶液，得到含氟环氧树脂；
    将所述含氟环氧树脂和固化剂混合均匀后，加入催化剂，混合、固化，制得环氧树脂复合材料。
  2. 根据权利要求1所述的制备方法，其特征在于，将双酚AF完全溶解在环氧氯丙烷中，然后加入催化剂反应以得到树脂醚化物的步骤包括：在60～80℃下，将双酚AF完全溶解在环氧氯丙烷中，然后加入质量分数为0.05％～0.15％的相移催化剂四丁基溴化铵反应，保温0.5～1.5小时，以得到树脂醚化物，其中，所述双酚AF与所述环氧氯丙烷的摩尔比为1：2～1：6。
  3. 根据权利要求2所述的制备方法，其特征在于，将双酚AF完全溶解在环氧氯丙烷中，然后加入相移催化剂反应以得到树脂醚化物的步骤进一步包括：在70℃下，将双酚AF完全溶解在环氧氯丙烷中，然后加入质量分数为0.1％的相移催化剂四丁基溴化铵反应，保温1小时，以得到树脂醚化物，其中，所述双酚AF与所述环氧氯丙烷的摩尔比为1：4。
  4. 根据权利要求1所述的制备方法，其特征在于，使所述树脂醚化物和NaOH溶液反应，得到双酚AF氯醚醇的步骤包括：使所述树脂醚化物与质量分数为25％～35％的NaOH溶液在60～90℃下保温反应1～3小时，之后，去除未反应的环氧氯丙烷，得到所述双酚AF氯醚醇，其中，所述双酚AF与NaOH的摩尔比为1：0.1～0.2。
  5. 根据权利要求4所述的制备方法，其特征在于，使所述树脂醚化物和NaOH溶液反应，得到双酚AF氯醚醇的步骤进一步包括：使所述树脂醚化物与质量分数为30％的NaOH溶液在70℃下保温反应2小时，之后，去除未反应的环氧氯丙烷，得到所述双酚AF氯醚醇，其中，所述双酚AF与NaOH的摩尔比为1：0.2。
  6. 根据权利要求1所述的制备方法，其特征在于，在所述双酚AF氯醚醇中滴加所述NaOH溶液，得到含氟环氧树脂的步骤包括：在所述双酚AF氯醚醇中滴加质量分数为35％～45％的NaOH溶液，保温反应1～3小时，反应结束后，过滤，洗涤，得到含氟环氧树脂，其中，所述双酚AF与NaOH的摩尔比为1：1.5～2。
  7. 根据权利要求6所述的制备方法，其特征在于，在所述双酚AF氯醚醇中滴加所述NaOH溶液，得到含氟环氧树脂的步骤进一步包括：在所述双酚AF氯醚醇中滴加质量分数为40％的NaOH溶液，保温反应2小时，反应结束后，过滤，洗涤，得到含氟环氧树脂，其中，所述双酚AF与NaOH的摩尔比为1：2。
  8. 根据权利要求1所述的制备方法，其特征在于，将所述含氟环氧树脂和固化剂在混合均匀后，加入催化剂，混合、固化，制得环氧树脂复合材料的步骤包括：在80～100℃下，将所述含氟环氧树脂和所述固化剂混合均匀后，加入质量分数为0.05％～0.15％的催化剂，混合、固化，制得环氧树脂复合材料；所述含氟环氧树脂与所述固化剂的质量之比在3：7～6：4的范围内。
  9. 根据权利要求8所述的制备方法，其特征在于，将所述含氟环氧树脂和固化剂在混合均匀后，加入催化剂，混合、固化，制得环氧树脂复合材料的步骤进一步包括：在90℃下，将所述含氟环氧树脂和所述固化剂混合均匀后，加入质量分数为0.1％的催化剂，混合、固化，制得环氧树脂复合材料；所述含氟环氧树脂与所述固化剂的质量之比为3.5:6.5。
  10. 根据权利要求1所述的制备方法，其特征在于，所述固化剂为酸酐固化剂。
  11. 根据权利要求1、8～9中任一项所述的制备方法，其特征在于，所述固化剂为氰酸酯、甲基六氢苯酐中的一种或者两种的组合；并且所述催化剂为质量分数为0.1％的锌酸锰或质量分数为0.1％的DMP～30中的一种或者两种的组合。
  12. 根据权利要求1～11中任一项所述的方法制备的环氧树脂复合材料。
  13. 一种根据权利要求1～12中任一项所述的环氧树脂复合材料作为电子材料或透波材料的应用。
PCT/CN2018/083679 2017-06-07 2018-04-19 一种环氧树脂复合材料及其制备方法和应用 WO2018223780A1 (zh)

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