CN105331104A - A kind of modified thermosetting resin and preparation method thereof - Google Patents

The invention discloses modified thermosetting resin and a preparation method thereof. 100 parts of molten state thermosetting resin and 1-20 parts of fluorine-containing-polyimide-b-polysiloxane rigid-flexible segmented copolymer with amino end groups are evenly mixed and undergo a curing and postprocessing process to obtain fluorine-containing-polyimide-b-polysiloxane rigid-flexible segmented copolymer modified thermosetting resin. The modified thermosetting resin has high heat resistance, high toughness, low dielectric constant and good curing manufacturability. The method for preparing the modified thermosetting resin is simple and practical, no solvent is used, and the modified thermosetting resin undergoes large-scale and cleaning production easily.

一种改性热固性树脂及其制备方法A kind of modified thermosetting resin and preparation method thereof

技术领域 technical field

本发明涉及改性热固性树脂及其制备方法，特别涉及一种含氟聚酰亚胺-聚硅氧烷嵌段共聚物改性热固性树脂及其制备方法。 The invention relates to a modified thermosetting resin and a preparation method thereof, in particular to a fluorine-containing polyimide-polysiloxane block copolymer modified thermosetting resin and a preparation method thereof.

背景技术 Background technique

电子信息、绝缘电气、新能源、航空航天等尖端工业领域的飞速发展，对它们的共同关键基础材料----热固性树脂提出了更多更高的性能要求，其中主要包括高耐热性、优良韧性、低介电常数和优良的固化工艺性等。 The rapid development of electronic information, electrical insulation, new energy, aerospace and other cutting-edge industries has put forward more and higher performance requirements for their common key basic materials - thermosetting resins, which mainly include high heat resistance, Excellent toughness, low dielectric constant and excellent curing process, etc.

为了满足高性能热固性树脂的要求，一般以耐热热固性树脂为基础进行改性研究。“脆性”是热固性树脂所固有的突出问题。如何在不牺牲原有热固性树脂优良性能的基础上实现增韧，一直是热固性树脂研发的重要内容，也是一个极富挑战性的工作。 In order to meet the requirements of high-performance thermosetting resins, the modification research is generally carried out on the basis of heat-resistant thermosetting resins. "Brittleness" is a prominent problem inherent in thermosetting resins. How to achieve toughness without sacrificing the excellent performance of the original thermosetting resin has always been an important content of thermosetting resin research and development, and it is also a very challenging task.

近年来，利用嵌段共聚物增韧环氧热固性树脂的研究引起了人们的关注。与传统工程性热塑性聚合物相比，嵌段共聚物中不同极性链段的存在能使嵌段共聚物与树脂相容，解决了工程热塑性聚合物增韧时出现的相容性差，难以在热固性树脂中分散的问题。同时，嵌段共聚物的链段间化学结构和极性差异使其在树脂内形成纳米结构，所形成的纳米微球通过软核的空穴化作用，将空穴周围的三轴向应力转变为二维从而引发大量剪切带而增韧，纳米微球与界面脱粘也吸收掉部分应力。因此，嵌段共聚物的增韧机理包括了界面解离、空穴化，裂纹偏转等多重机制。然而，该方向的相关研究多集中在环氧树脂的增韧方面。值得指出，所采用的嵌段共聚物多为两亲性嵌段共聚物，基本含有聚己内酯、聚氧化乙烯等亲水链段，它们不仅耐热性较低，而且易吸湿，不适用于耐热性热固性树脂的改性。 In recent years, the use of block copolymers to toughen epoxy thermosetting resins has attracted people's attention. Compared with traditional engineering thermoplastic polymers, the presence of different polar segments in block copolymers can make block copolymers compatible with resins, which solves the problem of poor compatibility when engineering thermoplastic polymers are toughened. Dispersion problems in thermosetting resins. At the same time, the chemical structure and polarity differences between the chain segments of the block copolymer make it form a nanostructure in the resin, and the formed nanospheres transform the triaxial stress around the hole through the cavitation of the soft core. Toughening is two-dimensional, which induces a large number of shear bands, and the debonding of nanospheres and interfaces also absorbs part of the stress. Therefore, the toughening mechanism of block copolymers includes multiple mechanisms such as interfacial dissociation, cavitation, and crack deflection. However, the relevant research in this direction mostly focuses on the toughening of epoxy resins. It is worth pointing out that most of the block copolymers used are amphiphilic block copolymers, which basically contain hydrophilic segments such as polycaprolactone and polyethylene oxide. They not only have low heat resistance, but also are easy to absorb moisture, so they are not suitable for For the modification of heat-resistant thermosetting resins.

另一方面，现有的两亲性嵌段共聚物的嵌段共聚物都是以柔性链为主，耐热性和刚性相对不足。截至目前，刚柔嵌段共聚物（由刚性和柔性链段组成）与耐热热固性树脂共混的工作可参见Deng等人的研究报道（参见文献：WDeng,YZhong,JQin,XHuangandJPeng.Morphologycontrolofporousepoxyresinbyrod-coilblockoligomer:aself-assembly-inducedphaseseparationbydiphenylfluorene-modifiedsiliconeepoxy[J].RSCAdvances,2014,4(57):30028-30034）。通过刚柔嵌段共聚物低聚物自组装诱导相分离来控制多孔环氧树脂的形貌，说明刚柔嵌段共聚物在树脂中可以自组装，然而，所作的研究，并未涉及该嵌段共聚物对环氧树脂的物理化学性能的影响。并且，由于与刚柔嵌段共聚物共混制得的环氧树脂变成多孔树脂，大大限制了树脂的应用范围。从文献的报道中还可得知，该嵌段共聚物的自组装结构为球形胶束。而在现有的两亲性嵌段共聚物改性树脂的研究中发现，蠕虫状胶束的增韧效果优于球形胶束。如Liu等人的研究报道（参见文献：JLiu,ZJThompson,HJSue,FSBates,MAHillmyer,MDettloff,GJacob,NVergheseandHPham.Tougheningofepoxieswithblockcopolymermicellesofwormlikemorphology[J].Macromolecules,2010,43(17):7238-7243），当自组装结构为球形胶束时，增韧幅度在84%，而蠕虫状结构的增韧幅度在106%。因此，研发具有蠕虫状结构的刚柔嵌段共聚物可获得更高的韧性，也有利于保持甚至提高耐热热固性树脂的耐热性。 On the other hand, the block copolymers of the existing amphiphilic block copolymers are mainly flexible chains, and the heat resistance and rigidity are relatively insufficient. Up to now, the work of blending rigid-flexible block copolymers (composed of rigid and flexible segments) with heat-resistant thermosetting resins can be found in the research report of Deng et al. (see literature: WDeng, YZhong, JQin, XHuang and JPeng. : aself-assembly-induced phase separation by diphenylfluorene-modified silicone epoxy [J]. RSCAdvances, 2014, 4(57): 30028-30034). The morphology of porous epoxy resins is controlled by self-assembly of rigid-flexible block copolymer oligomers to induce phase separation, indicating that rigid-flexible block copolymers can self-assemble in resins. Effect of segment copolymers on the physicochemical properties of epoxy resins. Moreover, since the epoxy resin blended with the rigid-flexible block copolymer becomes a porous resin, the application range of the resin is greatly limited. It can also be known from literature reports that the self-assembled structure of the block copolymer is a spherical micelle. In the existing research on amphiphilic block copolymer modified resins, it is found that the toughening effect of worm-like micelles is better than that of spherical micelles. As reported by Liu et al. (see literature: JLiu, ZJThompson, HJSue, FSBates, MA Hillmyer, MDettloff, GJacob, NVerghese and HPham. Toughening of epoxies with blockcopolymermicelles of wormlike morphology [J]. Macromolecules, 2010, 43(17): 7238-7243), when the self-assembled structure When it is a spherical micelle, the toughening range is 84%, while that of the worm-like structure is 106%. Therefore, the development of rigid-flexible block copolymers with worm-like structures can obtain higher toughness, and is also conducive to maintaining or even improving the heat resistance of heat-resistant thermosetting resins.

如前所述，低介电常数是电子信息、绝缘电气等领域用高性能树脂的重要性能指标，但是，对嵌段共聚物改性热固性树脂的研究中，现有技术尚未涉及其介电性能。 As mentioned above, low dielectric constant is an important performance index of high-performance resins used in the fields of electronic information, electrical insulation, etc. However, in the research on block copolymer modified thermosetting resins, the prior art has not yet involved its dielectric properties .

发明内容 Contents of the invention

本发明针对现有技术存在的不足，提供一种具有高韧性、低介电常数和良好固化工艺性的新型耐热热固性树脂及其制备方法。 Aiming at the shortcomings of the prior art, the invention provides a novel heat-resistant thermosetting resin with high toughness, low dielectric constant and good curing manufacturability and a preparation method thereof.

实现本发明目的所采用的技术方案是提供一种改性热固性树脂的制备方法，按质量计，将100份熔融态的可热固化树脂与1～20份由含氟聚酰亚胺和聚硅氧烷链段组成的嵌段共聚物混合，经固化、后处理工艺后，即得到一种改性热固性树脂。 The technical solution adopted to realize the purpose of the present invention is to provide a preparation method of modified thermosetting resin, by mass, 100 parts of molten thermosetting resin and 1 to 20 parts of fluorine-containing polyimide and polysilicon Block copolymers composed of oxane chain segments are mixed, and after curing and post-treatment processes, a modified thermosetting resin is obtained.

本发明所述的可热固化树脂至少含有双马来酰亚胺、氰酸酯树脂中的一种或者它们的组合。所述的含氟聚酰亚胺和聚硅氧烷链段组成的嵌段共聚物的数均分子量为5000～20000。按质量比，含氟聚酰亚胺与聚硅氧烷链段为9∶1～7∶3。 The heat-curable resin of the present invention contains at least one of bismaleimide and cyanate resin or a combination thereof. The number average molecular weight of the block copolymer composed of fluorine-containing polyimide and polysiloxane segment is 5000-20000. According to the mass ratio, the fluorine-containing polyimide and the polysiloxane segment are 9:1-7:3.

本发明所述的含氟聚酰亚胺和聚硅氧烷链段组成的嵌段共聚物的制备方法包括如下步骤：按质量计， The preparation method of the block copolymer composed of fluorine-containing polyimide and polysiloxane segment of the present invention comprises the following steps: by mass,

1、在温度为20～30℃、惰性气体保护条件下，将10份二胺溶于168～337份N，N’-二甲基乙酰胺中，得到溶液A； 1. Dissolve 10 parts of diamine in 168 to 337 parts of N,N'-dimethylacetamide at a temperature of 20-30°C and inert gas protection to obtain solution A;

2、在搅拌条件下，将24份六氟二酐加入到溶液A中，加完后，温度升至150～155℃，保温反应1～3h，得到溶液B； 2. Under the condition of stirring, add 24 parts of hexafluorodianhydride into the solution A, after the addition, the temperature rises to 150-155°C, keep the reaction for 1-3 hours, and obtain the solution B;

3、在温度为20～30℃的条件下，将4.3～12.8份端氨基聚二甲基硅氧烷溶于30～89份N，N’-二甲基乙酰胺中，得到溶液C； 3. Dissolve 4.3-12.8 parts of amino-terminated polydimethylsiloxane in 30-89 parts of N,N'-dimethylacetamide at a temperature of 20-30°C to obtain solution C;

4、在温度为150～155℃的条件下，将溶液C逐滴加入到溶液B中；滴加完毕后，加入30～60份甲苯；升温至180～185℃，保温反应4～8h；反应结束后，得到反应体系D； 4. At a temperature of 150-155°C, add solution C to solution B dropwise; after the dropwise addition, add 30-60 parts of toluene; heat up to 180-185°C, and keep warm for 4-8 hours; After finishing, obtain reaction system D;

5、将反应体系D的温度降至20～30℃，缓慢加入到840～1685份的甲醇中，搅拌得到粉末状沉淀物，再经过干燥，得到粗产物E； 5. Lower the temperature of the reaction system D to 20-30°C, slowly add it to 840-1685 parts of methanol, stir to obtain a powdery precipitate, and then dry it to obtain the crude product E;

6、粗产物E经提纯、干燥处理后，即得到一种含氟聚酰亚胺和聚硅氧烷链段组成的嵌段共聚物。 6. After the crude product E is purified and dried, a block copolymer composed of fluorine-containing polyimide and polysiloxane segments is obtained.

所述的二胺为4,4’-二氨基二苯醚、4,4’-二氨基二苯砜中的一种，或它们的任意组合。所述的惰性气体为氮气、氩气有中的一种。上述步骤2中，六氟二酐分成三批次加入，每次相隔5～10min。 The diamine is one of 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, or any combination thereof. The inert gas is one of nitrogen and argon. In the above step 2, the hexafluorodianhydride is added in three batches, with an interval of 5-10 minutes each time.

本发明技术方案还包括按上述制备方法得到的一种改性热固性树脂。 The technical solution of the present invention also includes a modified thermosetting resin obtained by the above preparation method.

与现有技术相比，本发明所取得的有益效果是： Compared with prior art, the beneficial effect that the present invention obtains is:

1、本发明设计合成了一种由聚酰亚胺（刚性）和聚硅氧烷（柔性）链段组成的刚柔嵌段共聚物（本发明中记作含氟聚酰亚胺-b-聚硅氧烷），其在热固性树脂中自发地形成一种纳米尺寸的具有疏溶剂性核与溶剂化壳的蠕虫状胶束结构，具有高增韧效果。同时，该嵌段共聚物（含氟聚酰亚胺-b-聚硅氧烷）与双马来酰亚胺和氰酸酯树脂具有良好的相容性，能够使前者均匀分散于树脂中，充分发挥增韧效果。 1. The present invention designs and synthesizes a rigid-flexible block copolymer composed of polyimide (rigid) and polysiloxane (flexible) segments (referred to as fluorine-containing polyimide -b- Polysiloxane), which spontaneously forms a nanometer-sized worm-like micellar structure with a solvate core and a solvate shell in a thermosetting resin, which has a high toughening effect. At the same time, the block copolymer (fluorine-containing polyimide -b -polysiloxane) has good compatibility with bismaleimide and cyanate resin, and can make the former uniformly dispersed in the resin, Give full play to the toughening effect.

2、本发明制得的改性热固性树脂在获得良好韧性的同时，还具有突出的耐热性、刚性和介电性能。这是源于聚酰亚胺刚性链段上具有芳杂环结构，确保了树脂的热稳定性和刚性，而含氟刚性链段及具有低介电常数的聚硅氧烷链段确保了树脂具有更低的介电常数。 2. The modified thermosetting resin prepared by the present invention has outstanding heat resistance, rigidity and dielectric properties while obtaining good toughness. This is due to the aromatic heterocyclic structure on the polyimide rigid segment, which ensures the thermal stability and rigidity of the resin, while the fluorine-containing rigid segment and the polysiloxane segment with a low dielectric constant ensure that the resin Has a lower dielectric constant.

3、本发明采用的嵌段共聚物（含氟聚酰亚胺-b-聚硅氧烷）与耐热热固性树脂具有良好的相容性，可通过熔融法制备，而不使用溶剂，因此，制备改性热固性树脂的工艺简单易行，成型条件不苛刻。 3. The block copolymer (fluorine-containing polyimide -b -polysiloxane) used in the present invention has good compatibility with heat-resistant thermosetting resins, and can be prepared by melting without using solvents. Therefore, The process for preparing the modified thermosetting resin is simple and easy, and the molding conditions are not harsh.

4、本发明所公开的刚柔嵌段共聚物（记为含氟聚酰亚胺-b-聚硅氧烷）的结构可以通过调节软、硬段的比例以制得具有不同结构的嵌段共聚物，以制备结构与性能可调的改性热固性树脂，满足不同应用领域的要求，具有适用性广的特点。 4. The structure of the rigid-flexible block copolymer (referred to as fluorine-containing polyimide -b -polysiloxane) disclosed in the present invention can be obtained by adjusting the ratio of soft and hard segments to obtain blocks with different structures The copolymer is used to prepare a modified thermosetting resin with adjustable structure and performance, which meets the requirements of different application fields and has the characteristics of wide applicability.

附图说明 Description of drawings

图1是本发明实施例1提供的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的合成反应流程示意图； Fig. 1 is the synthesizing reaction flow schematic diagram of the fluorine-containing polyimide -b -polysiloxane block copolymer provided by Example 1 of the present invention;

图2是本发明实施例1提供的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的核磁共振氢谱（¹H-NMR）图； Figure 2 is a hydrogen nuclear magnetic resonance spectrum ( ¹ H-NMR) diagram of the fluorine-containing polyimide -b -polysiloxane block copolymer provided in Example 1 of the present invention;

图3是本发明实施例1提供的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的红外（FTIR）谱图； Figure 3 is an infrared (FTIR) spectrum of the fluorine-containing polyimide -b -polysiloxane block copolymer provided in Example 1 of the present invention;

图4是本发明实施例1～3提供的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的热失重（TG）曲线和微商热失重分析（DTG）曲线对比图； Fig. 4 is a comparison chart of the thermogravimetric (TG) curve and the derivative thermogravimetric analysis (DTG) curve of the fluorine-containing polyimide -b -polysiloxane block copolymer provided in Examples 1 to 3 of the present invention;

图5是本发明实施例1、2和3及比较例1所提供的热固性树脂的预聚体的扫描差示量热（DSC）曲线对比图； Fig. 5 is a comparison chart of scanning differential calorimetry (DSC) curves of prepolymers of thermosetting resins provided by Examples 1, 2 and 3 of the present invention and Comparative Example 1;

图6是本发明实施例1～6提供的改性氰酸酯树脂和比较例1提供的氰酸酯树脂的热失重曲线图。 FIG. 6 is a thermogravimetric graph of the modified cyanate resin provided in Examples 1-6 of the present invention and the cyanate resin provided in Comparative Example 1. FIG.

图7是本发明实施例1～6提供的改性氰酸酯树脂和比较例1提供的氰酸酯树脂的冲击强度对比图。 FIG. 7 is a comparison chart of the impact strength of the modified cyanate resin provided in Examples 1-6 of the present invention and the cyanate resin provided in Comparative Example 1. FIG.

图8是本发明实施例1～6提供的改性氰酸酯树脂和比较例1提供的氰酸酯树脂的断裂韧性对比图。 FIG. 8 is a comparison chart of the fracture toughness of the modified cyanate resin provided in Examples 1-6 of the present invention and the cyanate resin provided in Comparative Example 1. FIG.

图9是本发明实施例1～6提供的改性氰酸酯树脂和比较例1提供的氰酸酯树脂的弯曲强度对比图。 FIG. 9 is a comparison chart of the flexural strength of the modified cyanate resin provided in Examples 1-6 of the present invention and the cyanate resin provided in Comparative Example 1. FIG.

图10是本发明实施例1～6提供的改性氰酸酯树脂和比较例1提供的氰酸酯树脂的介电常数-频率曲线对比图。 FIG. 10 is a graph comparing the dielectric constant-frequency curves of the modified cyanate resins provided in Examples 1 to 6 of the present invention and the cyanate resins provided in Comparative Example 1. FIG.

图11是本发明实施例2提供的改性氰酸酯树脂的原子力显微镜图。 Fig. 11 is an atomic force microscope image of the modified cyanate ester resin provided in Example 2 of the present invention.

图12是本发明实施例3提供的改性氰酸酯树脂的原子力显微镜图。 Fig. 12 is an atomic force microscope image of the modified cyanate ester resin provided in Example 3 of the present invention.

具体实施方式 detailed description

下面结合附图、实施例和比较例，对本发明技术方案作进一步的描述。 The technical solutions of the present invention will be further described below in conjunction with the accompanying drawings, examples and comparative examples.

实施例1 Example 1

（1）含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物共聚物的制备 (1) Preparation of fluorine-containing polyimide -b -polysiloxane block copolymer copolymer

N₂保护下，在25℃下，将0.6726g4,4’-二氨基二苯醚溶于15mLN，N’-二甲基乙酰胺，得到溶液A；将1.5927g六氟二酐加入溶液A，而后温度升至150℃，并保温反应2h，得到溶液B；在25℃下，将0.2870g端氨基聚二甲基硅氧烷（分子量为1280g/mol，粘度为40mm²/g）溶于2mLN，N’-二甲基乙酰胺，得到溶液C；在150℃下，往溶液B内逐滴加入溶液C，而后加入3mL甲苯；升温至180℃，反应4h，得到反应体系D；将反应体系D的温度降至25℃，缓慢将其倒入100mL甲醇内并搅拌，沉淀出粉末状产物，经过干燥，得到粗产物E。将粗产物E溶于10mL二氯甲烷，再用80mL甲醇沉淀。在120℃下干燥5h，80℃下干燥10h后，得到含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物。该含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的数均分子量为10105g/mol，含氟聚酰亚胺与聚硅氧烷链段的比例为9:1。含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的合成反应式、核磁共振氢谱、红外谱图和热失重曲线分别见附图1、2、3和4。 Under the protection of _N2 , at 25°C, 0.6726g of 4,4'-diaminodiphenyl ether was dissolved in 15mL of N,N'-dimethylacetamide to obtain solution A; 1.5927g of hexafluorodianhydride was added to solution A, Then the temperature was raised to 150°C, and kept for 2 hours to obtain solution B; at 25°C, 0.2870g of amino-terminated polydimethylsiloxane (molecular weight: 1280g/mol, viscosity: 40mm ² /g) was dissolved in 2mLN , N'-dimethylacetamide, to obtain solution C; at 150°C, add solution C dropwise to solution B, and then add 3mL toluene; raise the temperature to 180°C, react for 4 hours, and obtain reaction system D; The temperature of D was lowered to 25°C, it was slowly poured into 100mL of methanol and stirred, the powdery product was precipitated, and the crude product E was obtained after drying. The crude product E was dissolved in 10 mL of dichloromethane and precipitated with 80 mL of methanol. After drying at 120° C. for 5 hours and at 80° C. for 10 hours, a fluorine-containing polyimide -b -polysiloxane block copolymer was obtained. The number average molecular weight of the fluorine-containing polyimide-b-polysiloxane block copolymer is 10105 g/mol, and the ratio of the fluorine-containing polyimide to the polysiloxane segment is 9:1. The synthetic reaction formula, hydrogen nuclear magnetic resonance spectrum, infrared spectrum and thermal weight loss curve of the fluorine-containing polyimide -b -polysiloxane block copolymer are shown in accompanying drawings 1, 2, 3 and 4, respectively.

（2）改性氰酸酯树脂固化物的制备 (2) Preparation of modified cyanate resin cured product

3.5g步骤（1）制备的聚酰亚胺-b-聚硅氧烷嵌段共聚物与70g2,2'-双（4-氰氧苯基）丙烷（又称双酚A型氰酸酯）加入烧杯中，在160℃下机械搅拌至聚酰亚胺-b-聚硅氧烷嵌段共聚物完全溶解，得深棕色澄清透明液体；在160℃下预聚2h，得到预聚体，其DSC曲线参见附图5。 3.5g of polyimide -b -polysiloxane block copolymer prepared in step (1) and 70g of 2,2'-bis(4-cyanophenyl)propane (also known as bisphenol A cyanate) Add it into a beaker and stir mechanically at 160°C until the polyimide -b -polysiloxane block copolymer is completely dissolved to obtain a dark brown clear transparent liquid; prepolymerize at 160°C for 2 hours to obtain a prepolymer, which See accompanying drawing 5 for the DSC curve.

将制得的预聚体倒入预热好的模具中，在160℃下抽真空1h；而后按照150℃/2h+180℃/2h+200℃/2h+220℃/2h和240℃/4h工艺进行固化和后处理，得到一种含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物改性氰酸酯树脂，记为PI-b-PDMS/氰酸酯。其热失重曲线、冲击强度、断裂韧性、弯曲强度、介电常数-频率曲线分别见附图6、7、8、9和10。 Pour the prepared prepolymer into a preheated mold and vacuumize at 160°C for 1h; then follow the steps of 150°C/2h+180°C/2h+200°C/2h+220°C/2h and 240°C/4h The process is cured and post-treated to obtain a fluorine-containing polyimide -b -polysiloxane block copolymer modified cyanate resin, which is denoted as PI -b- PDMS/cyanate. Its thermal weight loss curve, impact strength, fracture toughness, bending strength, dielectric constant-frequency curve are shown in Figures 6, 7, 8, 9 and 10, respectively.

参见附图1，它是本实施例提供的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的合成流程示意图（反应式），该反应涉及缩合聚合反应，所得到的嵌段共聚物是两端为氨基的嵌段共聚物。 Referring to accompanying drawing 1, it is the synthesizing flow diagram (reaction formula) of the fluorine-containing polyimide -b -polysiloxane block copolymer provided by this embodiment, this reaction involves condensation polymerization reaction, the obtained block The copolymer is a block copolymer with amino groups at both ends.

参见附图2，它是本实施例提供的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的核磁共振氢谱。位移在δ=8.05~7.19处的5组峰为聚酰亚胺苯环上氢原子的信号，各组峰的位移及信号强度比例基本相同；δ=3.76~3.60处的峰对应于-CH₂-N-上亚甲基的质子，δ=1.74~1.62处的振动峰对应于-CH₂-上亚甲基的质子，δ=0.5~0.6处的振动峰对应于-CH₂-Si-上亚甲基的质子，δ=0~0.2处的峰对应于-Si-CH₃上甲基的质子。通过核磁峰的积分面积和理论计算值一致，从而可以确定该产物确实为聚酰亚胺-b-聚硅氧烷嵌段共聚物共聚物。 Referring to accompanying drawing 2, it is the hydrogen nuclear magnetic resonance spectrum of the fluorine-containing polyimide -b -polysiloxane block copolymer provided in this embodiment. The five groups of peaks shifted at δ=8.05~7.19 are the signals of hydrogen atoms on the polyimide benzene ring, and the ratios of shifts and signal intensities of each group of peaks are basically the same; the peaks at δ=3.76~3.60 correspond to -CH ₂ The proton of the methylene group on -N-, the vibration peak at δ=1.74~1.62 corresponds to the proton of the methylene group on -CH ₂ -, and the vibration peak at δ=0.5~0.6 corresponds to the proton on the -CH ₂ -Si- The proton of the methylene group, the peak at δ=0~0.2 corresponds to the proton of the methyl group on -Si-CH ₃ . The integral area of the nuclear magnetic peak is consistent with the theoretically calculated value, so it can be determined that the product is indeed a polyimide-b-polysiloxane block copolymer copolymer.

参见附图3，它是本实施例提供的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的红外谱图。该谱图上相继出现了代表聚硅氧烷中甲基的特征吸收峰（2960cm^-1）、聚酰亚胺结构中C-O的反对称和对称伸缩振动吸收峰（1783cm^-1、1728cm^-1）、苯环上C=C的伸缩振动吸收（1623cm^-1）、C-F的特征吸收峰（1502cm^-1）、C-N的伸缩振动吸收峰（1376cm^-1）、Si-O-Si的伸缩振动吸收峰（1148cm^-1、1094cm^-1）和Si-C键吸收峰（801cm^-1），说明已成功合成了目标产物。 Referring to accompanying drawing 3, it is the infrared spectrogram of the fluorine-containing polyimide -b -polysiloxane block copolymer provided in this embodiment. The characteristic absorption peak (2960cm ^-1 ) representing the methyl group in polysiloxane, and the antisymmetric and symmetric stretching vibration absorption peaks (1783cm ^-1 , 1728cm ^-1 ) of CO in the polyimide structure appeared successively in the spectrum. , the stretching vibration absorption of C=C on the benzene ring (1623cm ^-1 ), the characteristic absorption peak of CF (1502cm ^-1 ), the stretching vibration absorption peak of CN (1376cm ^-1 ), the stretching vibration absorption peak of Si-O-Si (1148cm ^-1 , 1094cm ^-1 ) and Si-C bond absorption peaks (801cm ^-1 ), indicating that the target product has been successfully synthesized.

实施例2 Example 2

（1）含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的制备 (1) Preparation of fluorine-containing polyimide -b -polysiloxane block copolymer

N₂保护下，在25℃下，将0.5381g4,4’-二氨基二苯醚溶于13mLN，N’-二甲基乙酰胺，得到溶液A；将1.3439g六氟二酐加入溶液A；而后温度升至150℃，并保温反应2h，得到溶液B；在25℃下，将0.4305g端氨基聚二甲基硅氧烷（分子量为1280g/mol，粘度为40mm²/g）溶于3mLN，N’-二甲基乙酰胺，得到溶液C。在150℃下，往溶液B内逐滴加入溶液C，而后加入2.5mL甲苯，升温至180℃，反应4h，得到反应体系D；将反应体系D温度降至25℃，缓慢将其倒入80mL甲醇内并搅拌，沉淀出粉末状产物，经过干燥，得到粗产物E，将其溶于8mL二氯甲烷，再次用65mL甲醇沉淀。在120℃下干燥5h，80℃下干燥10h后得到含氟聚酰亚胺-聚硅氧烷嵌段共聚物共聚物。该含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的数均分子量为7805g/mol，含氟聚酰亚胺与聚硅氧烷链段的比例为8:2。含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的热失重和微商热失重（DTG）曲线见附图4。 Under the protection of N ₂ , at 25°C, 0.5381g of 4,4'-diaminodiphenyl ether was dissolved in 13mL of N,N'-dimethylacetamide to obtain solution A; 1.3439g of hexafluorodianhydride was added to solution A; Then the temperature was raised to 150°C, and kept for 2 hours to obtain solution B; at 25°C, 0.4305g of amino-terminated polydimethylsiloxane (molecular weight: 1280g/mol, viscosity: 40mm ² /g) was dissolved in 3mLN , N'-dimethylacetamide to obtain solution C. At 150°C, add solution C dropwise to solution B, then add 2.5mL toluene, raise the temperature to 180°C, and react for 4 hours to obtain reaction system D; lower the temperature of reaction system D to 25°C, and slowly pour it into 80mL In methanol and stirring, the powdery product precipitated out, and after drying, the crude product E was obtained, which was dissolved in 8 mL of dichloromethane, and precipitated with 65 mL of methanol again. After drying at 120° C. for 5 hours and at 80° C. for 10 hours, a fluorine-containing polyimide-polysiloxane block copolymer copolymer was obtained. The number average molecular weight of the fluorine-containing polyimide-b-polysiloxane block copolymer is 7805 g/mol, and the ratio of fluorine-containing polyimide to polysiloxane segment is 8:2. See Figure 4 for the thermogravimetric and derivative thermogravimetric (DTG) curves of the fluorine-containing polyimide -b -polysiloxane block copolymer.

（2）改性氰酸酯树脂固化物的制备 (2) Preparation of modified cyanate resin cured product

称取3.5g步骤（1）提供的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物与70g2,2'-双（4-氰氧苯基）丙烷于烧杯中，在160℃下机械搅拌至嵌段共聚物完全溶解，得深棕色澄清透明液体，在160℃下预聚2h，得到预聚体，其DSC曲线见附图5。 Weigh 3.5g of the fluorine-containing polyimide -b -polysiloxane block copolymer provided in step (1) and 70g of 2,2'-bis(4-cyanophenyl)propane in a beaker, at 160°C Stir mechanically at low temperature until the block copolymer is completely dissolved to obtain a dark brown clear transparent liquid. Prepolymerize at 160°C for 2 hours to obtain a prepolymer. The DSC curve is shown in Figure 5.

将得到的预聚体倒入预热好的模具中，在160℃下抽真空1h，在按照150℃/2h+180℃/2h+200℃/2h+220℃/2h和240℃/4h工艺进行固化和后处理，得到一种含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物改性氰酸酯树脂，记为PI-b-PDMS/氰酸酯。其热失重曲线、冲击强度、断裂韧性、弯曲强度、介电常数-频率曲线和原子力显微镜图分别见附图6、7、8、9、10和11。 Pour the obtained prepolymer into the preheated mold, vacuumize at 160°C for 1h, and follow the process of 150°C/2h+180°C/2h+200°C/2h+220°C/2h and 240°C/4h After curing and post-treatment, a fluorine-containing polyimide -b -polysiloxane block copolymer modified cyanate resin is obtained, which is denoted as PI -b- PDMS/cyanate. Its thermal weight loss curve, impact strength, fracture toughness, bending strength, dielectric constant-frequency curve and atomic force microscope diagram are shown in Figures 6, 7, 8, 9, 10 and 11, respectively.

实施例3 Example 3

（1）含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的制备 (1) Preparation of fluorine-containing polyimide -b -polysiloxane block copolymer

N₂保护下，在25℃下，将0.4484g4,4’-二氨基二苯醚溶于10mLN，N’-二甲基乙酰胺，得到溶液A；将1.1945g六氟二酐加入溶液A；加完后，温度升至150℃，保温反应2h，得到溶液B；在25℃下，将0.5740g端氨基聚二甲基硅氧烷（分子量为1280g/mol，粘度为40mm²/g）溶于4mLN，N’-二甲基乙酰胺，得到溶液C。在150℃下，往溶液B内逐滴加入溶液C，而后加入2mL甲苯，升温至180℃，反应4h，得到反应体系D；将反应体系D温度降至25℃，缓慢将其倒入70mL甲醇内并搅拌，沉淀出粉末状产物，经过干燥，得到粗产物E，将其溶于7mL二氯甲烷，再次用50mL甲醇沉淀。在120℃下干燥5h，80℃下干燥10h后得到含氟聚酰亚胺-聚硅氧烷嵌段共聚物共聚物。该含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的数均分子量为5486g/mol，含氟聚酰亚胺与聚硅氧烷链段的比例为7:3。含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的热失重曲线见附图4。 Under the protection of N ₂ , at 25°C, 0.4484g of 4,4'-diaminodiphenyl ether was dissolved in 10mL of N,N'-dimethylacetamide to obtain solution A; 1.1945g of hexafluorodianhydride was added to solution A; After the addition, the temperature was raised to 150°C, and the reaction was kept for 2 hours to obtain solution B; at 25°C, 0.5740g of amino-terminated polydimethylsiloxane (molecular weight: 1280g/mol, viscosity: 40mm ² /g) was dissolved In 4 mL of N, N'-dimethylacetamide, solution C was obtained. At 150°C, add solution C dropwise to solution B, then add 2mL of toluene, raise the temperature to 180°C, react for 4 hours, and obtain reaction system D; lower the temperature of reaction system D to 25°C, and slowly pour it into 70mL of methanol With stirring, the powdery product precipitated out, and after drying, the crude product E was obtained, which was dissolved in 7 mL of dichloromethane and precipitated again with 50 mL of methanol. After drying at 120° C. for 5 hours and at 80° C. for 10 hours, a fluorine-containing polyimide-polysiloxane block copolymer copolymer was obtained. The number average molecular weight of the fluorine-containing polyimide-b-polysiloxane block copolymer is 5486 g/mol, and the ratio of the fluorine-containing polyimide to the polysiloxane segment is 7:3. The thermal weight loss curve of fluorine-containing polyimide -b -polysiloxane block copolymer is shown in Figure 4.

（2）改性氰酸酯树脂固化物的制备 (2) Preparation of modified cyanate resin cured product

称取3.5g步骤（1）提供的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物与70g2,2'-双（4-氰氧苯基）丙烷于烧杯中，在160℃下机械搅拌至嵌段共聚物完全溶解，得深棕色澄清透明液体，在160℃下预聚2h，得到预聚体，其DSC曲线见附图5。 Weigh 3.5g of the fluorine-containing polyimide -b -polysiloxane block copolymer provided in step (1) and 70g of 2,2'-bis(4-cyanophenyl)propane in a beaker, at 160°C Stir mechanically at low temperature until the block copolymer is completely dissolved to obtain a dark brown clear transparent liquid. Prepolymerize at 160°C for 2 hours to obtain a prepolymer. The DSC curve is shown in Figure 5.

将得到的预聚体倒入预热好的模具中，在160℃下抽真空1h，在按照150℃/2h+180℃/2h+200℃/2h+220℃/2h和240℃/4h工艺进行固化和后处理，得到一种含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物改性氰酸酯树脂，记为PI-b-PDMS/氰酸酯。其热失重曲线、冲击强度、断裂韧性、弯曲强度、介电常数-频率曲线和原子力显微镜图分别见附图6、7、8、9、10和12。 Pour the obtained prepolymer into the preheated mold, vacuumize at 160°C for 1h, and follow the process of 150°C/2h+180°C/2h+200°C/2h+220°C/2h and 240°C/4h After curing and post-treatment, a fluorine-containing polyimide -b -polysiloxane block copolymer modified cyanate resin is obtained, which is denoted as PI -b- PDMS/cyanate. Its thermal weight loss curve, impact strength, fracture toughness, bending strength, dielectric constant-frequency curve and atomic force microscope diagram are shown in Figures 6, 7, 8, 9, 10 and 12, respectively.

参见附图4，它是本发明实施例1～3合成的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的热失重（TG）曲线和微商热失重（DTG）分析曲线，由图可知，实施例1、2和3合成的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的起始分解温度（初始失重5wt%时的温度，T_di）分别是482℃，469℃和461℃。结合DTG曲线可知，嵌段共聚物的分解分两步进行，从400℃左右开始分解，至520℃时为达到最大热分解速率对应温度（T_max）；接下来在540℃时开始第二阶段的分解，至560℃时分解速率达到最大。说明合成的嵌段共聚物具有优异的耐热性。 Referring to accompanying drawing 4, it is the thermogravimetric (TG) curve and derivative thermogravimetric (DTG) analysis curve of the fluorine-containing polyimide -b -polysiloxane block copolymer synthesized in Examples 1 to 3 of the present invention , it can be seen from the figure that the initial decomposition temperature (the temperature at initial weight loss of 5wt%, T _di ) of the fluorine-containing polyimide -b -polysiloxane block copolymers synthesized in Examples 1, 2 and 3 are respectively 482°C, 469°C and 461°C. Combined with the DTG curve, it can be seen that the decomposition of the block copolymer is carried out in two steps, starting from about 400°C, and reaching the temperature corresponding to the maximum thermal decomposition rate (T _max ) at 520°C; and then starting the second stage at 540°C The decomposition rate reaches the maximum at 560°C. It shows that the synthesized block copolymer has excellent heat resistance.

比较例1的制备：称取70g2,2'-双（4-氰氧苯基）丙烷于烧杯中，在160℃下机械搅拌至融化，得浅黄色澄清透明液体。在160℃下预聚2h后，得到预聚体，其DSC曲线见附图5。将预聚体倒入预热好的模具中，与160℃下抽真空1h，再按照150℃/2h+180℃/2h+200℃/2h+220℃/2h和240℃/4h工艺进行固化和后处理，得到氰酸酯热固性树脂，记为氰酸酯。其热失重曲线、冲击强度、断裂韧性、弯曲强度和介电常数分别见附图6、7、8、9和10。 Preparation of Comparative Example 1: Weigh 70g of 2,2'-bis(4-cyanophenyl)propane into a beaker, and stir it mechanically at 160°C until it melts to obtain a light yellow clear liquid. After prepolymerization at 160° C. for 2 hours, a prepolymer was obtained, and its DSC curve is shown in Fig. 5 . Pour the prepolymer into the preheated mold, vacuumize at 160°C for 1h, and then cure according to the process of 150°C/2h+180°C/2h+200°C/2h+220°C/2h and 240°C/4h And post-processing, get cyanate ester thermosetting resin, recorded as cyanate ester. Its thermal weight loss curve, impact strength, fracture toughness, bending strength and dielectric constant are shown in Figures 6, 7, 8, 9 and 10, respectively.

参见附图5，它是本发明实施例1～3及比较例1所提供的热固性树脂的预聚体的DSC曲线。从中可以看出，添加含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物后，改性树脂的整个固化反应峰出现在低温方向，这是因为嵌段共聚物两端有活性端氨基，可以催化氰酸酯单体聚合并与氰酸酯单体共聚。这个优势克服了耐热树脂常常存在的高反应温度的缺点。 Referring to accompanying drawing 5, it is the DSC curve of the prepolymer of the thermosetting resin provided by Examples 1-3 and Comparative Example 1 of the present invention. It can be seen that after adding fluorine-containing polyimide -b -polysiloxane block copolymer, the entire curing reaction peak of the modified resin appears in the low temperature direction, which is because there are active ends at both ends of the block copolymer Amino groups can catalyze the polymerization of cyanate monomers and copolymerize with cyanate monomers. This advantage overcomes the disadvantage of high reaction temperature that heat-resistant resins often have.

实施例4 Example 4

（1）含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物共聚物的制备 (1) Preparation of fluorine-containing polyimide -b -polysiloxane block copolymer copolymer

N₂保护下，在25℃下，将0.6726g4,4’-二氨基二苯醚溶于15mLN，N’-二甲基乙酰胺，得到溶液A；将1.5927g六氟二酐加入溶液A，而后温度升至150℃，并保温反应2h，得到溶液B；在25℃下，将0.2870g端氨基聚二甲基硅氧烷（分子量为1280g/mol，粘度为40mm²/g）溶于2mLN，N’-二甲基乙酰胺，得到溶液C；在150℃下，往溶液B内逐滴加入溶液C，而后加入3mL甲苯；升温至180℃，反应4h，得到反应体系D；将反应体系D的温度降至25℃，缓慢将其倒入100mL甲醇内并搅拌，沉淀出粉末状产物，经过干燥，得到粗产物E。将粗产物E溶于10mL二氯甲烷，再用80mL甲醇沉淀。在120℃下干燥5h，80℃下干燥10h后，得到含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物。该含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的数均分子量为10105g/mol，含氟聚酰亚胺与聚硅氧烷链段的比例为9:1。 Under the protection of _N2 , at 25°C, 0.6726g of 4,4'-diaminodiphenyl ether was dissolved in 15mL of N,N'-dimethylacetamide to obtain solution A; 1.5927g of hexafluorodianhydride was added to solution A, Then the temperature was raised to 150°C, and kept for 2 hours to obtain solution B; at 25°C, 0.2870g of amino-terminated polydimethylsiloxane (molecular weight: 1280g/mol, viscosity: 40mm ² /g) was dissolved in 2mLN , N'-dimethylacetamide, to obtain solution C; at 150°C, add solution C dropwise to solution B, and then add 3mL toluene; raise the temperature to 180°C, react for 4 hours, and obtain reaction system D; The temperature of D was lowered to 25°C, it was slowly poured into 100mL of methanol and stirred, the powdery product was precipitated, and the crude product E was obtained after drying. The crude product E was dissolved in 10 mL of dichloromethane and precipitated with 80 mL of methanol. After drying at 120° C. for 5 hours and at 80° C. for 10 hours, a fluorine-containing polyimide -b -polysiloxane block copolymer was obtained. The number average molecular weight of the fluorine-containing polyimide-b-polysiloxane block copolymer is 10105 g/mol, and the ratio of the fluorine-containing polyimide to the polysiloxane segment is 9:1.

（2）改性氰酸酯树脂固化物的制备 (2) Preparation of modified cyanate resin cured product

称取7g步骤（1）提供的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物与70g2,2'-双（4-氰氧苯基）丙烷于烧杯中，在160℃下机械搅拌至嵌段共聚物完全溶解，得深棕色澄清透明液体，在160℃下预聚2h后，得到预聚体。 Weigh 7g of the fluorine-containing polyimide -b -polysiloxane block copolymer provided in step (1) and 70g of 2,2'-bis(4-cyanophenyl)propane in a beaker, at 160°C Stir mechanically until the block copolymer is completely dissolved, and a dark brown clear transparent liquid is obtained. After prepolymerization at 160°C for 2 hours, a prepolymer is obtained.

将得到的预聚体倒入预热好的模具中，在160℃下抽真空1h，在按照150℃/2h+180℃/2h+200℃/2h+220℃/2h和240℃/4h工艺进行固化和后处理，得到一种含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物改性氰酸酯树脂，记为PI-b-PDMS/氰酸酯。其热失重曲线、冲击强度、断裂韧性、弯曲强度和介电常数-频率曲线分别见附图6、7、8、9和10。 Pour the obtained prepolymer into the preheated mold, vacuumize at 160°C for 1h, and follow the process of 150°C/2h+180°C/2h+200°C/2h+220°C/2h and 240°C/4h After curing and post-treatment, a fluorine-containing polyimide -b -polysiloxane block copolymer modified cyanate resin is obtained, which is denoted as PI -b- PDMS/cyanate. Its thermal weight loss curve, impact strength, fracture toughness, bending strength and dielectric constant-frequency curve are shown in Figures 6, 7, 8, 9 and 10, respectively.

实施例5 Example 5

（1）含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的制备 (1) Preparation of fluorine-containing polyimide -b -polysiloxane block copolymer

N₂保护下，在25℃下，将0.5381g4,4’-二氨基二苯醚溶于13mLN，N’-二甲基乙酰胺，得到溶液A；将1.3439g六氟二酐加入溶液A；而后温度升至150℃，并保温反应2h，得到溶液B；在25℃下，将0.4305g端氨基聚二甲基硅氧烷（分子量为1280g/mol，粘度为40mm²/g）溶于3mLN，N’-二甲基乙酰胺，得到溶液C。在150℃下，往溶液B内逐滴加入溶液C，而后加入2.5mL甲苯，升温至180℃，反应4h，得到反应体系D；将反应体系D温度降至25℃，缓慢将其倒入80mL甲醇内并搅拌，沉淀出粉末状产物，经过干燥，得到粗产物E，将其溶于8mL二氯甲烷，再次用65mL甲醇沉淀。在120℃下干燥5h，80℃下干燥10h后得到含氟聚酰亚胺-聚硅氧烷嵌段共聚物共聚物。该含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的数均分子量为7805g/mol，含氟聚酰亚胺与聚硅氧烷链段的比例为8:2。 Under the protection of N ₂ , at 25°C, 0.5381g of 4,4'-diaminodiphenyl ether was dissolved in 13mL of N,N'-dimethylacetamide to obtain solution A; 1.3439g of hexafluorodianhydride was added to solution A; Then the temperature was raised to 150°C, and kept for 2 hours to obtain solution B; at 25°C, 0.4305g of amino-terminated polydimethylsiloxane (molecular weight: 1280g/mol, viscosity: 40mm ² /g) was dissolved in 3mLN , N'-dimethylacetamide to obtain solution C. At 150°C, add solution C dropwise to solution B, then add 2.5mL toluene, raise the temperature to 180°C, and react for 4 hours to obtain reaction system D; lower the temperature of reaction system D to 25°C, and slowly pour it into 80mL In methanol and stirring, the powdery product precipitated out, and after drying, the crude product E was obtained, which was dissolved in 8 mL of dichloromethane, and precipitated with 65 mL of methanol again. After drying at 120° C. for 5 hours and at 80° C. for 10 hours, a fluorine-containing polyimide-polysiloxane block copolymer copolymer was obtained. The number average molecular weight of the fluorine-containing polyimide-b-polysiloxane block copolymer is 7805 g/mol, and the ratio of fluorine-containing polyimide to polysiloxane segment is 8:2.

（2）改性氰酸酯树脂固化物的制备 (2) Preparation of modified cyanate resin cured product

称取7g步骤（1）提供的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物与70g2,2'-双（4-氰氧苯基）丙烷于烧杯中，在160℃下机械搅拌至嵌段共聚物完全溶解，得深棕色澄清透明液体，在160℃下预聚2h后，得到预聚体。 Weigh 7g of the fluorine-containing polyimide -b -polysiloxane block copolymer provided in step (1) and 70g of 2,2'-bis(4-cyanophenyl)propane in a beaker, at 160°C Stir mechanically until the block copolymer is completely dissolved, and a dark brown clear transparent liquid is obtained. After prepolymerization at 160°C for 2 hours, a prepolymer is obtained.

将得到的预聚体倒入预热好的模具中，在160℃下抽真空1h，在按照150℃/2h+180℃/2h+200℃/2h+220℃/2h和240℃/4h工艺进行固化和后处理，得到一种聚酰亚胺-b-聚硅氧烷嵌段共聚物改性氰酸酯树脂，记为PI-b-PDMS/氰酸酯。其热失重曲线、冲击强度、断裂韧性、弯曲强度和介电常数分别见附图6、7、8、9和10。 Pour the obtained prepolymer into the preheated mold, vacuumize at 160°C for 1h, and follow the process of 150°C/2h+180°C/2h+200°C/2h+220°C/2h and 240°C/4h After curing and post-treatment, a polyimide -b -polysiloxane block copolymer modified cyanate resin is obtained, which is denoted as PI -b- PDMS/cyanate. Its thermal weight loss curve, impact strength, fracture toughness, bending strength and dielectric constant are shown in Figures 6, 7, 8, 9 and 10, respectively.

实施例6 Example 6

（1）含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的制备 (1) Preparation of fluorine-containing polyimide -b -polysiloxane block copolymer

N₂保护下，在25℃下，将0.4484g4,4’-二氨基二苯醚溶于10mLN，N’-二甲基乙酰胺，得到溶液A；将1.1945g六氟二酐加入溶液A；加完后，温度升至150℃，保温反应2h，得到溶液B；在25℃下，将0.5740g端氨基聚二甲基硅氧烷（分子量为1280g/mol，粘度为40mm²/g）溶于4mLN，N’-二甲基乙酰胺，得到溶液C。在150℃下，往溶液B内逐滴加入溶液C，而后加入2mL甲苯，升温至180℃，反应4h，得到反应体系D；将反应体系D温度降至25℃，缓慢将其倒入70mL甲醇内并搅拌，沉淀出粉末状产物，经过干燥，得到粗产物E，将其溶于7mL二氯甲烷，再次用50mL甲醇沉淀。在120℃下干燥5h，80℃下干燥10h后得到含氟聚酰亚胺-聚硅氧烷嵌段共聚物共聚物。该含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的数均分子量为5486g/mol，含氟聚酰亚胺与聚硅氧烷链段的比例为7:3。 Under the protection of N ₂ , at 25°C, 0.4484g of 4,4'-diaminodiphenyl ether was dissolved in 10mL of N,N'-dimethylacetamide to obtain solution A; 1.1945g of hexafluorodianhydride was added to solution A; After the addition, the temperature was raised to 150°C, and the reaction was kept for 2 hours to obtain solution B; at 25°C, 0.5740g of amino-terminated polydimethylsiloxane (molecular weight: 1280g/mol, viscosity: 40mm ² /g) was dissolved In 4 mL of N, N'-dimethylacetamide, solution C was obtained. At 150°C, add solution C dropwise to solution B, then add 2mL of toluene, raise the temperature to 180°C, react for 4 hours, and obtain reaction system D; lower the temperature of reaction system D to 25°C, and slowly pour it into 70mL of methanol With stirring, the powdery product precipitated out, and after drying, the crude product E was obtained, which was dissolved in 7 mL of dichloromethane and precipitated again with 50 mL of methanol. After drying at 120° C. for 5 hours and at 80° C. for 10 hours, a fluorine-containing polyimide-polysiloxane block copolymer copolymer was obtained. The number average molecular weight of the fluorine-containing polyimide-b-polysiloxane block copolymer is 5486 g/mol, and the ratio of the fluorine-containing polyimide to the polysiloxane segment is 7:3.

（2）改性氰酸酯树脂固化物的制备 (2) Preparation of modified cyanate resin cured product

称取7g步骤（1）提供的聚酰亚胺-b-聚硅氧烷嵌段共聚物与70g2,2'-双（4-氰氧苯基）丙烷于烧杯中，在160℃下机械搅拌至嵌段共聚物完全溶解，得深棕色澄清透明液体，在160℃预聚2h后，得到预聚体。 Weigh 7g of the polyimide -b -polysiloxane block copolymer provided in step (1) and 70g of 2,2'-bis(4-cyanophenyl)propane in a beaker, and mechanically stir at 160°C Until the block copolymer is completely dissolved, a dark brown clear transparent liquid is obtained. After prepolymerization at 160°C for 2 hours, a prepolymer is obtained.

将得到的预聚体倒入预热好的模具中，在160℃下抽真空1h，在按照150℃/2h+180℃/2h+200℃/2h+220℃/2h和240℃/4h工艺进行固化和后处理，得到一种聚酰亚胺-b-聚硅氧烷嵌段共聚物改性氰酸酯树脂，记为PI-b-PDMS/氰酸酯。其热失重曲线、冲击强度、断裂韧性、弯曲强度和介电常数分别见附图6、7、8、9和10。 Pour the obtained prepolymer into the preheated mold, vacuumize at 160°C for 1h, and follow the process of 150°C/2h+180°C/2h+200°C/2h+220°C/2h and 240°C/4h After curing and post-treatment, a polyimide -b -polysiloxane block copolymer modified cyanate resin is obtained, which is denoted as PI -b- PDMS/cyanate. Its thermal weight loss curve, impact strength, fracture toughness, bending strength and dielectric constant are shown in Figures 6, 7, 8, 9 and 10, respectively.

参见附图6，它是本发明实施例1～6制备的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物改性氰酸酯树脂和比较例1制备的氰酸酯树脂的热重曲线。可以看出，这些树脂具有基本相同的曲线，而且T_di几乎一样，说明采用聚酰亚胺-b-聚硅氧烷嵌段共聚物改性没有劣化氰酸酯树脂原有的优异热稳定性。 Referring to accompanying drawing 6, it is the fluorine-containing polyimide -b -polysiloxane block copolymer modified cyanate resin that the embodiment of the present invention 1～6 prepares and the cyanate resin that comparative example 1 prepares TGA curve. It can be seen that these resins have basically the same curve, and T _di is almost the same, indicating that the modification with polyimide -b -polysiloxane block copolymer does not deteriorate the original excellent thermal stability of cyanate resin .

参见附图7，它是本发明实施例1～6制备的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物改性氰酸酯树脂和比较例1制备的氰酸酯树脂的冲击强度图。可以看出，实施例1～6提供的改性氰酸酯树脂的冲击强度均远高于比较例1提供的氰酸酯树脂的冲击强度，提高幅度在140%～253%之间，这个提高幅度显著高于文献中所报道的提高幅度。如，Hu等人将5wt%的PEO-PPO-PEO嵌段共聚物单独添加入氰酸酯-环氧树脂，其切口冲击强度上升了20%，将添加量提高至10wt%时，切口冲击强度上升了30%（见：CHu,JYu,JHuo,YChen,HFMa.EffectofclayandPEO-PPO-PEOblockcopolymeronthemicrostructureandpropertiesofcyanateester/epoxycomposite[J].CompositesPartA:AppliedScienceandManufacturing,2015,78:113-123.），说明本发明制备的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物具有显著的增韧能力。 Referring to accompanying drawing 7, it is the fluorine-containing polyimide -b -polysiloxane block copolymer modified cyanate resin that the embodiment of the present invention 1～6 prepares and the cyanate resin that comparative example 1 prepares Impact strength diagram. It can be seen that the impact strength of the modified cyanate resins provided in Examples 1 to 6 is much higher than that of the cyanate resins provided in Comparative Example 1, and the increase range is between 140% and 253%. The magnitude is significantly higher than that reported in the literature. For example, Hu et al. added 5wt% of PEO-PPO-PEO block copolymer to cyanate-epoxy resin alone, and its notched impact strength increased by 20%. When the addition amount was increased to 10wt%, the notched impact strength increased by 30% (see: CHu, JYu, JHuo, YChen, HFMa.EffectofclayandPEO-PPO-PEOblockcopolymeronthemicrostructureandpropertiesofcyanateester/epoxycomposite[J].CompositesPartA:AppliedScienceandManufacturing,2015,78:113-123.), indicating that the polyfluorine-containing Imide -b -polysiloxane block copolymers have remarkable toughening ability.

上述结论，可以通过比较断裂韧性得到进一步的证实。参见附图8，它是本发明实施例1～6制备的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物改性氰酸酯树脂和比较例1制备的氰酸酯树脂的断裂韧性图。改性树脂的断裂韧性值均高于比较例1制备的氰酸酯树脂的值。从实施例1～3，嵌段共聚物的添加量均为5wt%，软段含量逐渐上升；从实施例4～6，嵌段共聚物的添加量均为10wt%，而软段含量逐渐上升。可见，随着含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物中的软段含量上升，体系的断裂韧性随之上升。而实施例3制备的改性树脂中，嵌段共聚物在基体内以蠕虫状胶束分布，改性树脂的断裂韧性达到最大值，是比较例1制备的氰酸酯树脂值的3.9倍。实施例6制备的改性树脂中，嵌段共聚物的柔性链含量最高，改性树脂的断裂韧性达到了氰酸酯树脂值的3.7倍。Wu等人将磺化聚苯乙烯-b-聚（乙烯-co-丁烯）-b-苯乙烯加入环氧树脂，当嵌段共聚物的添加量分别为5wt%和10wt%时，改性树脂的断裂韧性依次为环氧树脂值的1.7和1.8倍（见：SWu,QGuo,MKraska,BStuhn,YWMai.Tougheningepoxythermosetswithblockionomers:theroleofphasedomainsize[J].Macromolecules,2013,46(20):8190-8202.）。通过对比文献，可以看出，本发明提供的嵌段共聚物具有优异的增韧效果。 The above conclusions can be further confirmed by comparing the fracture toughness. Referring to accompanying drawing 8, it is the fluorine-containing polyimide -b -polysiloxane block copolymer modified cyanate resin that the embodiment of the present invention 1～6 prepares and the cyanate resin that comparative example 1 prepares Fracture Toughness Diagram. The fracture toughness values of the modified resins are all higher than those of the cyanate resin prepared in Comparative Example 1. From Examples 1 to 3, the addition amount of the block copolymer is 5wt%, and the soft segment content gradually increases; from Examples 4 to 6, the addition amount of the block copolymer is 10wt%, and the soft segment content gradually increases . It can be seen that as the soft segment content in the fluorine-containing polyimide -b -polysiloxane block copolymer increases, the fracture toughness of the system increases accordingly. In the modified resin prepared in Example 3, the block copolymer is distributed as worm-like micelles in the matrix, and the fracture toughness of the modified resin reaches the maximum value, which is 3.9 times that of the cyanate resin prepared in Comparative Example 1. In the modified resin prepared in Example 6, the flexible chain content of the block copolymer is the highest, and the fracture toughness of the modified resin reaches 3.7 times of the value of the cyanate resin. Wu et al added sulfonated polystyrene -b- poly(ethylene- co -butylene) -b- styrene to epoxy resin, when the addition of block copolymer was 5wt% and 10wt%, the modified The fracture toughness of the resin is 1.7 and 1.8 times that of the epoxy resin in turn (see: SWu, QGuo, MKraska, BStuhn, YWMai. Toughening epoxythermosets with blockionomers: therole of phase domain size [J]. Macromolecules, 2013, 46(20): 8190-8202.). By comparing the literature, it can be seen that the block copolymer provided by the present invention has an excellent toughening effect.

参见附图9，它是本发明实施例1～6制备的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物改性氰酸酯树脂和比较例1制备的氰酸酯树脂的弯曲强度图。一般弯曲强度常用来表征材料的综合力学性能，是刚性与韧性综合作用的结果。附图9显示，实施例1～6提供的改性树脂的弯曲强度均远高于比较例1提供的氰酸酯树脂的弯曲强度（126MPa），提高幅度在45%～73%之间，并且对比相关文献，添加嵌段会造成树脂的弯曲性能的下降。如Hu等人将5%的PEO-PPO-PEO嵌段共聚物单独添加入氰酸酯-环氧树脂，复合材料的弯曲强度下降了2.6%（见：CHu,JYu,JHuo,YChen,HFMa.EffectofclayandPEO-PPO-PEOblockcopolymeronthemicrostructureandpropertiesofcyanateester/epoxycomposite[J].CompositesPartA:AppliedScienceandManufacturing,2015,78:113-123.），证明了本发明制备的嵌段共聚物可以显著改善氰酸酯树脂的综合力学性能，这是一般增韧改性剂所不具有的优势。 Referring to accompanying drawing 9, it is the fluorine-containing polyimide -b -polysiloxane block copolymer modified cyanate resin prepared by the embodiment of the present invention 1～6 and the cyanate resin prepared by comparative example 1 Bending Strength Diagram. Generally, flexural strength is often used to characterize the comprehensive mechanical properties of materials, which is the result of the combined effects of rigidity and toughness. Figure 9 shows that the flexural strengths of the modified resins provided in Examples 1 to 6 are much higher than that of the cyanate resin provided in Comparative Example 1 (126 MPa), and the increase range is between 45% and 73%, and Comparing with the relevant literature, the addition of blocks will cause the decrease of the flexural properties of the resin. For example, Hu et al. added 5% of PEO-PPO-PEO block copolymer to cyanate-epoxy resin alone, and the flexural strength of the composite material decreased by 2.6% (see: CHu, JYu, JHuo, YChen, HFMa. EffectofclayandPEO-PPO-PEOblockcopolymeronthemicrostructureandpropertiesofcyanateester/epoxycomposite[J].CompositesPartA:AppliedScienceandManufacturing,2015,78:113-123.), proved that the block copolymer prepared by the present invention can significantly improve the comprehensive mechanical properties of cyanate ester resin, which is general Advantages that toughening modifiers do not have.

参见附图10，它是本发明实施例1～6制备的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物改性氰酸酯树脂和比较例1制备的氰酸酯树脂的介电常数-频率曲线。可以看到，在氰酸酯树脂中加入含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物能有效降低树脂的介电常数。,这是源于嵌段共聚物中含有的氟原子具备较低的摩尔极化率，使聚酰亚胺的介电常数降低，同时聚硅氧烷也是低介电常数物质。 Referring to accompanying drawing 10, it is the fluorine-containing polyimide -b -polysiloxane block copolymer modified cyanate resin that the embodiment of the present invention 1～6 prepares and the cyanate resin that comparative example 1 prepares Permittivity-frequency curve. It can be seen that adding fluorine-containing polyimide -b -polysiloxane block copolymer to cyanate resin can effectively reduce the dielectric constant of the resin. , This is due to the low molar polarizability of the fluorine atoms contained in the block copolymer, which reduces the dielectric constant of polyimide, and polysiloxane is also a low dielectric constant material.

参见附图11，它是本发明实施例2制备的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物改性氰酸酯树脂的原子力显微镜图。可以看到聚酰亚胺-b-聚硅氧烷嵌段共聚物在树脂基体内形成了蠕虫状胶束。 Referring to accompanying drawing 11, it is the atomic force microscope image of the fluorine-containing polyimide -b -polysiloxane block copolymer modified cyanate resin prepared in Example 2 of the present invention. It can be seen that the polyimide -b -polysiloxane block copolymer forms worm-like micelles within the resin matrix.

参见附图12，它是本发明实施例3制备的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物改性氰酸酯树脂的原子力显微镜图。可以看到，含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物在树脂基体内形成了蠕虫状胶束。 Referring to accompanying drawing 12, it is the atomic force microscope image of the fluorine-containing polyimide -b -polysiloxane block copolymer modified cyanate ester resin prepared in Example 3 of the present invention. It can be seen that the fluorine-containing polyimide -b -polysiloxane block copolymer forms worm-like micelles in the resin matrix.

上述数据表明，相比原始氰酸酯树脂（比较例1），本发明公开的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物改性热固性树脂在保持优异的热稳定性的基础上，不仅具有较低的固化温度和介电常数，显著提高的韧性和综合力学性能，证明本发明公开的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物是一种多功能改性剂。 The above data show that compared with the original cyanate resin (Comparative Example 1), the fluorine-containing polyimide -b -polysiloxane block copolymer modified thermosetting resin disclosed by the present invention maintains excellent thermal stability. On the basis, it not only has lower curing temperature and dielectric constant, but also significantly improved toughness and comprehensive mechanical properties, proving that the fluorine-containing polyimide -b -polysiloxane block copolymer disclosed in the present invention is a multi- Function modifier.

实施例7 Example 7

（1）含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物共聚物的制备 (1) Preparation of fluorine-containing polyimide -b -polysiloxane block copolymer copolymer

在氩气保护下，在20℃下，将0.6726g4,4’-二氨基二苯醚溶于11.3mLN，N’-二甲基乙酰胺，得到溶液A；将1.5927g六氟二酐加入溶液A，而后温度升至155℃，并保温反应1h，得到溶液B；在20℃下，将0.2870g端氨基聚二甲基硅氧烷（分子量为1280g/mol，粘度为40mm²/g）溶于2mLN，N’-二甲基乙酰胺，得到溶液C；在155℃下，往溶液B内逐滴加入溶液C，而后加入2mL甲苯；升温至183^oC，反应8h，得到反应体系D；将反应体系D的温度降至20℃，缓慢将其倒入56.5mL甲醇内并搅拌，沉淀出粉末状产物，经过干燥，得到粗产物E。将粗产物E溶于6.7mL二氯甲烷，再用33.6mL甲醇沉淀。在120℃下干燥5h，80℃下干燥10h后，得到含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物。该含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的数均分子量为11033g/mol，含氟聚酰亚胺与聚硅氧烷链段的比例为9:1。 Under argon protection, at 20°C, 0.6726g of 4,4'-diaminodiphenyl ether was dissolved in 11.3mL of N,N'-dimethylacetamide to obtain solution A; 1.5927g of hexafluorodianhydride was added to the solution A, then the temperature was raised to 155°C, and the reaction was kept for 1 hour to obtain solution B; at 20°C, 0.2870g of amino-terminated polydimethylsiloxane (molecular weight: 1280g/mol, viscosity: 40mm ² /g) was dissolved Add solution C to 2mL N,N'-dimethylacetamide; add solution C dropwise to solution B at 155°C, then add 2mL toluene; heat up to 183 ^o C, react for 8 hours, and obtain reaction system D; The temperature of the reaction system D was lowered to 20° C., slowly poured into 56.5 mL of methanol and stirred, a powdery product was precipitated, and the crude product E was obtained after drying. The crude product E was dissolved in 6.7 mL of dichloromethane and precipitated with 33.6 mL of methanol. After drying at 120° C. for 5 hours and at 80° C. for 10 hours, a fluorine-containing polyimide -b -polysiloxane block copolymer was obtained. The number average molecular weight of the fluorine-containing polyimide-b-polysiloxane block copolymer is 11033 g/mol, and the ratio of the fluorine-containing polyimide to the polysiloxane segment is 9:1.

（2）改性氰酸酯树脂固化物的制备 (2) Preparation of modified cyanate resin cured product

0.7g步骤（1）制备的聚酰亚胺-b-聚硅氧烷嵌段共聚物与70g2,2'-双（4-氰氧苯基）丙烷（又称双酚A型氰酸酯）加入烧杯中，在160℃下机械搅拌至聚酰亚胺-b-聚硅氧烷嵌段共聚物完全溶解，得深棕色澄清透明液体。在160℃下预聚2h，得到预聚体，将制得的预聚体倒入预热好的模具中，在160℃下抽真空1h；而后按照150℃/2h+180℃/2h+200℃/2h+220℃/2h和240℃/4h工艺进行固化和后处理，得到一种含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物改性氰酸酯树脂，记为PI-b-PDMS/氰酸酯。 0.7g of polyimide -b -polysiloxane block copolymer prepared in step (1) and 70g of 2,2'-bis(4-cyanophenyl)propane (also known as bisphenol A cyanate) Add it into a beaker, and stir mechanically at 160°C until the polyimide -b -polysiloxane block copolymer is completely dissolved to obtain a dark brown clear transparent liquid. Prepolymerize at 160°C for 2 hours to obtain a prepolymer, pour the prepared prepolymer into a preheated mold, and vacuumize at 160°C for 1 hour; then follow 150°C/2h+180°C/2h+200 ℃/2h+220℃/2h and 240℃/4h for curing and post-treatment to obtain a fluorine-containing polyimide -b -polysiloxane block copolymer modified cyanate resin, denoted as PI -b- PDMS/cyanate.

实施例8 Example 8

（1）含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的制备 (1) Preparation of fluorine-containing polyimide -b -polysiloxane block copolymer

在氩气保护下，在30℃下，将0.5381g4,4’-二氨基二苯醚溶于18mLN，N’-二甲基乙酰胺，得到溶液A；将1.3439g六氟二酐加入溶液A；加完后，温度升至152^oC，保温反应3h，得到溶液B；在30℃下，将0.4305g端氨基聚二甲基硅氧烷（分子量为1280g/mol，粘度为40mm²/g）溶于3mLN，N’-二甲基乙酰胺，得到溶液C。在152^oC下，往溶液B内逐滴加入溶液C，而后加入3.2mL甲苯，升温至185℃，反应6h，得到反应体系D；将反应体系D温度降至30℃，缓慢将其倒入90.7mL甲醇内并搅拌，沉淀出粉末状产物，经过干燥，得到粗产物E，将其溶于10.8mL二氯甲烷，再次用80.7mL甲醇沉淀。在120℃下干燥5h，80℃下干燥10h后得到含氟聚酰亚胺-聚硅氧烷嵌段共聚物共聚物。该含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的数均分子量为6716g/mol，含氟聚酰亚胺与聚硅氧烷链段的比例为8:2。 Under argon protection, at 30°C, 0.5381g of 4,4'-diaminodiphenyl ether was dissolved in 18mL of N,N'-dimethylacetamide to obtain solution A; 1.3439g of hexafluorodianhydride was added to solution A ; After the addition, the temperature rose to 152 ^o C, and the reaction was kept for 3 hours to obtain solution B; at 30 ° C, 0.4305 g of amino-terminated polydimethylsiloxane (molecular weight 1280 g/mol, viscosity 40 mm ² /g ) was dissolved in 3 mL of N,N'-dimethylacetamide to obtain solution C. At 152 ^o C, add solution C dropwise to solution B, then add 3.2mL toluene, raise the temperature to 185°C, and react for 6h to obtain reaction system D; lower the temperature of reaction system D to 30°C, and slowly pour it into In 90.7 mL of methanol with stirring, a powdery product was precipitated, and after drying, the crude product E was obtained, which was dissolved in 10.8 mL of dichloromethane, and precipitated again with 80.7 mL of methanol. After drying at 120° C. for 5 hours and at 80° C. for 10 hours, a fluorine-containing polyimide-polysiloxane block copolymer copolymer was obtained. The number average molecular weight of the fluorine-containing polyimide-b-polysiloxane block copolymer is 6716 g/mol, and the ratio of fluorine-containing polyimide to polysiloxane segment is 8:2.

（2）改性氰酸酯树脂固化物的制备 (2) Preparation of modified cyanate resin cured product

称取14g步骤（1）提供的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物与70g2,2'-双（4-氰氧苯基）丙烷于烧杯中，在160℃下机械搅拌至嵌段共聚物完全溶解，得深棕色澄清透明液体，在160℃下预聚2h，得到预聚体，将得到的预聚体倒入预热好的模具中，在160℃下抽真空1h，在按照150℃/2h+180℃/2h+200℃/2h+220℃/2h和240℃/4h工艺进行固化和后处理，得到一种含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物改性氰酸酯树脂，记为PI-b-PDMS/氰酸酯。 Weigh 14g of the fluorine-containing polyimide -b -polysiloxane block copolymer provided in step (1) and 70g of 2,2'-bis(4-cyanophenyl)propane in a beaker, at 160°C Stir mechanically until the block copolymer is completely dissolved to obtain a dark brown clear transparent liquid. Prepolymerize at 160°C for 2 hours to obtain a prepolymer. Pour the obtained prepolymer into a preheated mold and pump it at 160°C. Vacuum for 1h, curing and post-treatment according to 150°C/2h+180°C/2h+200°C/2h+220°C/2h and 240°C/4h processes to obtain a fluorine-containing polyimide -b -polysilicon Oxylkane block copolymer modified cyanate resin, denoted as PI -b- PDMS/cyanate.

实施例9 Example 9

（1）含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物的制备 (1) Preparation of fluorine-containing polyimide -b -polysiloxane block copolymer

N₂保护下，在25℃下，将0.5567g4,4’-二氨基二苯砜溶于11mLN，N’-二甲基乙酰胺，得到溶液A；将1.1945g六氟二酐加入溶液A；加完后，温度升至155℃，保温反应3h，得到溶液B；在25℃下，将0.5740g端氨基聚二甲基硅氧烷（分子量为1280g/mol，粘度为40mm²/g）溶于4mLN，N’-二甲基乙酰胺，得到溶液C。在155℃下，往溶液B内逐滴加入溶液C，而后加入2.5mL甲苯，升温至180℃，反应4h，得到反应体系D；将反应体系D温度降至25℃，缓慢将其倒入60mL甲醇内并搅拌，沉淀出粉末状产物，经过干燥，得到粗产物E，将其溶于9mL二氯甲烷，再次用60mL甲醇沉淀。在120℃下干燥5h，80℃下干燥10h后得到含氟聚酰亚胺-聚硅氧烷嵌段共聚物共聚物。 Under the protection of N ₂ , at 25°C, 0.5567g of 4,4'-diaminodiphenylsulfone was dissolved in 11mL of N,N'-dimethylacetamide to obtain solution A; 1.1945g of hexafluorodianhydride was added to solution A; After the addition, the temperature rose to 155°C, and the reaction was kept for 3 hours to obtain solution B; at 25°C, 0.5740g of amino-terminated polydimethylsiloxane (molecular weight: 1280g/mol, viscosity: 40mm ² /g) was dissolved In 4 mL of N, N'-dimethylacetamide, solution C was obtained. At 155°C, add solution C dropwise to solution B, then add 2.5mL toluene, raise the temperature to 180°C, and react for 4 hours to obtain reaction system D; lower the temperature of reaction system D to 25°C, and slowly pour it into 60mL In methanol and stirred, the powdery product precipitated out, and after drying, the crude product E was obtained, which was dissolved in 9 mL of dichloromethane, and precipitated with 60 mL of methanol again. After drying at 120° C. for 5 hours and at 80° C. for 10 hours, a fluorine-containing polyimide-polysiloxane block copolymer copolymer was obtained.

（2）改性氰酸酯树脂固化物的制备 (2) Preparation of modified cyanate resin cured product

称取3.5g步骤（1）提供的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物与70g2,2'-双（4-氰氧苯基）丙烷于烧杯中，在160℃下机械搅拌至嵌段共聚物完全溶解，得深棕色澄清透明液体，在160℃下预聚2h，得到预聚体。将得到的预聚体倒入预热好的模具中，在160℃下抽真空1h，在按照150℃/2h+180℃/2h+200℃/2h+220℃/2h和240℃/4h工艺进行固化和后处理，得到一种含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物改性氰酸酯树脂，记为PI-b-PDMS/氰酸酯。 Weigh 3.5g of the fluorine-containing polyimide -b -polysiloxane block copolymer provided in step (1) and 70g of 2,2'-bis(4-cyanophenyl)propane in a beaker, at 160°C Stir mechanically at low temperature until the block copolymer is completely dissolved to obtain a dark brown clear transparent liquid. Prepolymerize at 160°C for 2 hours to obtain a prepolymer. Pour the obtained prepolymer into the preheated mold, vacuumize at 160°C for 1h, and follow the process of 150°C/2h+180°C/2h+200°C/2h+220°C/2h and 240°C/4h After curing and post-treatment, a fluorine-containing polyimide -b -polysiloxane block copolymer modified cyanate resin is obtained, which is denoted as PI -b- PDMS/cyanate.

实施例10 Example 10

本实施例提供一种改性氰酸酯-环氧树脂的制备方法：将2.88g实施例1步骤（1）提供的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物、50.01g双酚A型氰酸酯和7.61g环氧树脂（牌号E-51）混合加入到烧杯中，在100℃下搅拌25min，得到预聚体；将预聚体浇入到模具中，真空脱泡30min，按照150℃/2h+180℃/2h+200℃/2h+220℃/2h和240℃/4h工艺进行固化和热处理，即得到改性氰酸酯-环氧树脂。 This example provides a method for preparing a modified cyanate-epoxy resin: 2.88 g of the fluorine-containing polyimide -b -polysiloxane block copolymer provided in step (1) of Example 1, 50.01 1g of bisphenol A cyanate and 7.61g of epoxy resin (grade E-51) were mixed into a beaker and stirred at 100°C for 25min to obtain a prepolymer; the prepolymer was poured into a mold and vacuum removed Soak for 30 minutes, then cure and heat treatment according to the process of 150°C/2h+180°C/2h+200°C/2h+220°C/2h and 240°C/4h to obtain the modified cyanate-epoxy resin.

实施例11 Example 11

本实施例提供一种改性双马来酰亚胺-氰酸酯固化树脂的制备方法：在搅拌条件下，在135℃将8.91g4,4’-双马来酰亚胺基二苯甲烷（BDM）与6.59g的2,2’-二烯丙基双酚A（DBA）混合并预聚35min，得到BDM/DBA预聚物。在BDM/DBA预聚物中加入2.88g实施例1步骤（1）提供的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物及42.01g2,2'-双（4-氰氧苯基）丙烷，在150℃下搅拌30min，得到预聚体；将预聚体浇入到模具中，真空脱泡30min，按照150℃/2h+180℃/2h+200℃/2h+220℃/2h和240℃/3h工艺进行固化和热处理，即得到改性双马来酰亚胺-氰酸酯树脂。 This example provides a method for preparing a modified bismaleimide-cyanate ester curing resin: 8.91 g of 4,4'-bismaleimide diphenylmethane ( BDM) was mixed with 6.59 g of 2,2'-diallyl bisphenol A (DBA) and prepolymerized for 35 min to obtain a BDM/DBA prepolymer. Add 2.88g of the fluorine-containing polyimide -b -polysiloxane block copolymer provided in step (1) of Example 1 and 42.01g of 2,2'-bis(4-oxycyanide) to the BDM/DBA prepolymer Phenyl)propane, stirred at 150°C for 30min to obtain a prepolymer; pour the prepolymer into a mold, vacuum degassing for 30min, according to 150°C/2h+180°C/2h+200°C/2h+220°C /2h and 240°C/3h processes for curing and heat treatment to obtain modified bismaleimide-cyanate resin.

实施例12 Example 12

本实施例提供一种改性双马来酰亚胺树脂的制备方法：称取20g4,4’-双马来酰亚胺基二苯甲烷（BDM）和14.8g2,2’-二烯丙基双酚A（DBA）于烧杯中，在135℃下机械搅拌预聚10min，得到棕黄色透明澄清液体。在液体中加入1.74g实施例1步骤（1）提供的含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物，机械搅拌预聚15min，得到澄清透明的预聚物。将预聚物倒入预热好的模具中，于135℃抽真空1h，再分别按照150℃/2h+180℃/2h+200℃/2h+220℃/2h和240℃/4h工艺进行固化和后处理，即得一种含氟聚酰亚胺-b-聚硅氧烷嵌段共聚物改性双马来酰亚胺树脂。 This example provides a preparation method of modified bismaleimide resin: weigh 20g of 4,4'-bismaleimide diphenylmethane (BDM) and 14.8g of 2,2'-diallyl Bisphenol A (DBA) was pre-polymerized in a beaker with mechanical stirring at 135°C for 10 minutes to obtain a brown-yellow transparent clear liquid. Add 1.74 g of the fluorine-containing polyimide -b -polysiloxane block copolymer provided in step (1) of Example 1 to the liquid, and mechanically stir for prepolymerization for 15 minutes to obtain a clear and transparent prepolymer. Pour the prepolymer into the preheated mold, vacuumize at 135°C for 1h, and then cure according to the processes of 150°C/2h+180°C/2h+200°C/2h+220°C/2h and 240°C/4h And after treatment, a kind of fluorine-containing polyimide -b -polysiloxane block copolymer modified bismaleimide resin is obtained.