Low-dielectric toughened bismaleimide containing siloxane-fluorinated polyether chain segment and preparation method of low-dielectric toughened bismaleimide

Abstract

The invention discloses low-dielectric toughened bismaleimide containing a siloxane-fluorinated polyether chain segment and a preparation method of the low-dielectric toughened bismaleimide, and belongs to the field of high polymer materials, the low-dielectric toughened bismaleimide comprises an amino-terminated siloxane-fluorinated polyether copolymer and maleic anhydride, and by introducing the siloxane-fluorinated polyether copolymer, the low-dielectric toughened bismaleimide can be used for preparing the low-dielectric toughened bismaleimide. The flexibility and low polarizability characteristics of siloxane are combined with the ultralow dielectric and high hydrophobicity advantages of fluorinated polyether, so that the dielectric constant is reduced, the flexibility and hydrophobicity of the resin are remarkably improved, and the limitation of single performance optimization of a traditional modifier is overcome.

Description

Technical Field

[0001] The invention belongs to the field of polymer materials and relates to a low-dielectric toughening bismaleimide containing a siloxane-fluorinated polyether segment and a preparation method thereof. Background Art

[0002] Electronic resin is a basic material used to manufacture printed circuit boards (PCBs). It needs to have excellent electrical insulation, good insulation and corrosion resistance, and can protect the wires and components on the circuit board. Electronic resin is mainly used in electronic information, communications, electronic devices, aerospace, automotive electronics, industrial automation and other fields. With the rapid development of electronic products, the demand for electronic resin is also increasing.

[0003] Bismaleimide is a bifunctional compound with maleimide as the active end group. It is widely used in electronic packaging materials, printed circuit boards (PCBs), high-frequency communication equipment and other fields due to its excellent heat resistance, mechanical properties and electrical insulation properties. However, traditional BMI resins have the following disadvantages:

[0004] High dielectric constant: The dielectric constant of traditional BMI resin is usually between 3.0 and 3.5, which is difficult to meet the demand for ultra-low dielectric materials in 5G communications and high-frequency electronic devices.

[0005] Brittleness: BMI resin has a high cross-linking density after curing, resulting in insufficient toughness and prone to cracking during processing or use.

[0006] Insufficient hydrophobicity: Traditional BMI resins have high surface energy and are easily hygroscopic, which affects the stability of their electrical properties in high humidity environments.

[0007] In order to solve the above problems, the existing technology optimizes the performance of BMI resin by introducing flexible segments (such as polyetheramines), low polarizability components (such as fluorinated compounds) or siloxane modifiers. However, the existing technology usually only introduces a single modifier, which makes it difficult to take into account dielectric properties, toughness and hydrophobicity at the same time. Summary of the invention

[0008] The purpose of the present invention is to provide a low dielectric toughening bismaleimide containing a siloxane-fluorinated polyether segment and a preparation method thereof, which solves the problem in the prior art that it is difficult to take into account dielectric properties, toughness and hydrophobicity at the same time when optimizing the performance of BMI resin.

[0009] The technical solution adopted by the present invention is as follows:

[0010] A low dielectric toughening bismaleimide containing a siloxane-fluorinated polyether segment, the structural formula of which is as follows:

[0011]

[0012] The present invention combines the flexibility and low polarizability of siloxane with the ultra-low dielectric and high hydrophobicity of fluorinated polyether by introducing siloxane-fluorinated polyether copolymer, and achieves comprehensive optimization of performance at the molecular design level, thereby obtaining a high-performance bismaleimide resin suitable for high-frequency electronic devices. This solves the problem that the existing BMI resin is difficult to simultaneously take into account dielectric properties, toughness and hydrophobicity.

[0013] Furthermore, the low dielectric toughening bismaleimide containing siloxane-fluorinated polyether segments comprises the following components: amine-terminated siloxane-fluorinated polyether copolymer and maleic anhydride, wherein the molar ratio of the amine-terminated siloxane-fluorinated polyether copolymer to the maleic anhydride is 1:2.1-3;

[0014] Wherein, the molecular formula of the amino-terminated siloxane-fluorinated polyether copolymer is:

[0015] NH 2 -[CH 2 -CF 2 -O] n -[Si-O] m -[CH 2 -CH(R)-O] p -NH 2 ;

[0016] The amino-terminated siloxane-fluorinated polyether copolymer reacts with maleic anhydride through an azeotropic dehydration ring-closing method to obtain the low-dielectric toughening bismaleimide containing siloxane-fluorinated polyether chain segments.

[0017] The low dielectric toughening bismaleimide containing siloxane-fluorinated polyether chain segments prepared by the present invention has the following characteristics:

[0018] Ultra-low dielectric constant: At 1 GHz frequency, the dielectric constant is as low as 2.5 to 2.7, meeting the requirements of 5G communications and high-frequency electronic devices;

[0019] High flexibility and toughness: By introducing siloxane segments, the brittleness of the resin is significantly reduced and the impact resistance is improved;

[0020] Excellent hydrophobicity: The contact angle reaches over 110°, which significantly improves the moisture resistance and anti-fouling performance of the material;

[0021] Good thermal stability: Maintaining the excellent heat resistance of BMI resin, the glass transition temperature (Tg) is higher than 250℃.

[0022] The thermosetting electronic resin obtained after curing the low dielectric toughening bismaleimide containing siloxane-fluorinated polyether segments of the present invention has excellent dielectric properties, toughening effect and high hydrophobicity, and is particularly suitable for use as a material for high-frequency and high-speed copper-clad laminates.

[0023] Furthermore, the terminal amino siloxane-fluorinated polyether copolymer is prepared with fluorinated polyether alcohol, hydrogen-containing siloxane and amino-containing silane as main components; wherein the molar ratio of fluorinated polyether alcohol, hydrogen-containing siloxane and amino-containing silane is 1:1:2.

[0024] Furthermore, in the structural formula, the number of repeating units n=5-25, and the number of repeating units m=4-40.

[0025] Furthermore, the amino-containing silane is at least one of 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane.

[0026] A method for preparing a low dielectric toughening bismaleimide containing a siloxane-fluorinated polyether segment, comprising the following steps:

[0027] S1. Synthesis of terminal amino-siloxane-fluorinated polyether copolymer: using fluorinated polyether alcohol, hydrogen-containing siloxane and amino-containing silane as main components to react and synthesize terminal amino-siloxane-fluorinated polyether copolymer;

[0028] S2. Preparation of low dielectric toughening bismaleimide containing siloxane-fluorinated polyether chain segments: reacting the amino-terminated siloxane-fluorinated polyether copolymer prepared in step S1 with maleic anhydride through an azeotropic dehydration ring-closing method to obtain low dielectric toughening bismaleimide containing siloxane-fluorinated polyether chain segments.

[0029] Furthermore, the method for preparing the low dielectric toughening bismaleimide containing siloxane-fluorinated polyether segments comprises the following specific steps:

[0030] S1. Under nitrogen protection, dissolving fluorinated polyether alcohol, hydrogen-containing siloxane and amino-containing silane in solvent A in proportion, adding catalyst A, and stirring and reacting at 60-80°C for 4-10 hours; after the reaction is completed, removing the solvent by reduced pressure distillation to obtain an amino-terminated siloxane-fluorinated polyether copolymer; wherein the molar ratio of fluorinated polyether alcohol, hydrogen-containing siloxane and amino-containing silane is 1:1:2, and the total mass ratio of organic solvent A, catalyst A and fluorinated polyether alcohol, hydrogen-containing siloxane and amino-containing silane is 2-10:0.0005-0.005:1;

[0031] S2. Maleic anhydride, organic solvent B, and catalyst B are added to an autoclave equipped with a thermometer, a cooling tube, an azeotropic distillation separator, and a stirrer, and heated to 110-140°C. The amino-terminated siloxane-fluorinated polyether copolymer dissolved in organic solvent C is added dropwise over 1-5 hours. After the addition is completed, the reaction is continued for 1-5 hours. The reflux state is maintained during the whole process. The azeotropic water and solvent B are cooled and separated, and then the solvent B is refluxed into the autoclave for dehydration. After the reaction is completed, the mixture is repeatedly washed with water. The catalyst, organic solvent C and excess maleic anhydride are removed multiple times, and the organic solvent B is removed by heating and reduced pressure distillation to obtain a low dielectric toughening bismaleimide containing a siloxane-fluorinated polyether segment; wherein the molar ratio of the terminal amino siloxane-fluorinated polyether copolymer to the maleic anhydride is 1:2.1-3, and the total mass ratio of the organic solvent B, the catalyst B, the organic solvent C to the terminal amino siloxane-fluorinated polyether copolymer and the maleic anhydride is 2-10:0.01-0.05:0.2-1:1.

[0032] Furthermore, the organic solvent A is at least one of toluene, xylene, and tetrahydrofuran; the catalyst A is a platinum catalyst, specifically including at least one of divinyltetramethyldisiloxane platinum complex, chloroplatinic acid, and platinum-carbon catalyst.

[0033] Furthermore, the organic solvent B is at least one of toluene, xylene, and butyl acetate; and the catalyst B is at least one of p-toluenesulfonic acid, hydroxyp-toluenesulfonic acid, and methanesulfonic acid.

[0034] Furthermore, the organic solvent C is at least one of N,N-dimethylformamide, N-methylpyrrolidone and N,N-dimethylacetamide.

[0035] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0036] 1. A low-dielectric toughening bismaleimide containing siloxane-fluorinated polyether segments combines the flexibility and low polarizability characteristics of siloxane with the ultra-low dielectric and high hydrophobicity advantages of fluorinated polyether by introducing siloxane-fluorinated polyether copolymers. While reducing the dielectric constant, it significantly improves the flexibility and hydrophobicity of the resin, overcoming the limitations of single performance optimization of traditional modifiers;

[0037] 2. The preparation method of the present invention synthesizes an amino-terminated siloxane-fluorinated polyether copolymer by reacting a fluorinated polyether alcohol, a hydrogen-containing siloxane and an aminosilane, and then reacts the copolymer with maleic anhydride by an azeotropic dehydration closed-loop method to obtain a low dielectric toughening bismaleimide containing a siloxane-fluorinated polyether segment. The thermosetting electronic resin obtained after curing the low dielectric toughening bismaleimide containing a siloxane-fluorinated polyether segment has excellent dielectric properties, toughening effect and high hydrophobicity, and is particularly suitable for use as a material for high-frequency and high-speed copper-clad laminates. DETAILED DESCRIPTION

[0038] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention, that is, the embodiments described are only part of the embodiments of the present invention, rather than all the embodiments. The components of the embodiments of the present invention described and shown herein can be arranged and designed in various different configurations.

[0039] Therefore, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making creative work are within the scope of protection of the present invention.

[0040] It should be noted that relational terms such as "first" and "second" are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprise a ..." do not exclude the existence of other identical elements in the process, method, article or device including the elements.

[0041] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0042] The present invention discloses a low dielectric toughening bismaleimide containing a siloxane-fluorinated polyether segment, and the structural formula is as follows:

[0043] The invention comprises the following components: an amino-terminated siloxane-fluorinated polyether copolymer and maleic anhydride, wherein the molar ratio of the amino-terminated siloxane-fluorinated polyether copolymer to the maleic anhydride is 1:2.1-3;

[0044] Wherein, the molecular formula of the amino-terminated siloxane-fluorinated polyether copolymer is:

[0045] NH 2 -[CH 2 -CF 2 -O] n -[Si-O] m -[CH 2 -CH(R)-O]p -NH 2 ;

[0046] The amino-terminated siloxane-fluorinated polyether copolymer reacts with maleic anhydride through an azeotropic dehydration ring-closing method to obtain the low-dielectric toughening bismaleimide containing siloxane-fluorinated polyether chain segments.

[0047] The terminal amino siloxane-fluorinated polyether copolymer is prepared with fluorinated polyether alcohol, hydrogen-containing siloxane and amino-containing silane as main components; wherein the molar ratio of fluorinated polyether alcohol, hydrogen-containing siloxane and amino-containing silane is 1:1:2.

[0048] The number of repeating units in the structural formula is n=5-25, and the number of repeating units is m=4-40.

[0049] The amino-containing silane is at least one of 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane.

[0050] The method for preparing a low dielectric toughening bismaleimide containing a siloxane-fluorinated polyether segment comprises the following specific steps:

[0051] S1. Under nitrogen protection, dissolving fluorinated polyether alcohol, hydrogen-containing siloxane and amino-containing silane in solvent A in proportion, adding catalyst A, and stirring and reacting at 60-80°C for 4-10 hours; after the reaction is completed, removing the solvent by reduced pressure distillation to obtain an amino-terminated siloxane-fluorinated polyether copolymer; wherein the molar ratio of fluorinated polyether alcohol, hydrogen-containing siloxane and amino-containing silane is 1:1:2, and the total mass ratio of organic solvent A, catalyst A and fluorinated polyether alcohol, hydrogen-containing siloxane and amino-containing silane is 2-10:0.0005-0.005:1;

[0052] S2. Maleic anhydride, organic solvent B, and catalyst B are added to an autoclave equipped with a thermometer, a cooling tube, an azeotropic distillation separator, and a stirrer, and heated to 110-140°C. The amino-terminated siloxane-fluorinated polyether copolymer dissolved in organic solvent C is added dropwise over 1-5 hours. After the addition is completed, the reaction is continued for 1-5 hours. The reflux state is maintained during the whole process. The azeotropic water and solvent B are cooled and separated, and then the solvent B is refluxed into the autoclave for dehydration. After the reaction is completed, the mixture is repeatedly washed with water. The catalyst, organic solvent C and excess maleic anhydride are removed multiple times, and the organic solvent B is removed by heating and reduced pressure distillation to obtain a low dielectric toughening bismaleimide containing a siloxane-fluorinated polyether segment; wherein the molar ratio of the terminal amino siloxane-fluorinated polyether copolymer to the maleic anhydride is 1:2.1-3, and the total mass ratio of the organic solvent B, the catalyst B, the organic solvent C to the terminal amino siloxane-fluorinated polyether copolymer and the maleic anhydride is 2-10:0.01-0.05:0.2-1:1.

[0053] The organic solvent A is at least one of toluene, xylene and tetrahydrofuran; the catalyst A is a platinum catalyst, specifically including at least one of divinyltetramethyldisiloxane platinum complex, chloroplatinic acid and platinum-carbon catalyst.

[0054] The organic solvent B is at least one of toluene, xylene and butyl acetate; the catalyst B is at least one of p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid and methanesulfonic acid.

[0055] The organic solvent C is at least one of N,N-dimethylformamide, N-methylpyrrolidone and N,N-dimethylacetamide.

[0056] The present invention combines the flexibility and low polarizability of siloxane with the ultra-low dielectric and high hydrophobicity of fluorinated polyether by introducing siloxane-fluorinated polyether copolymer, and achieves comprehensive optimization of performance at the molecular design level, thereby obtaining a high-performance bismaleimide resin suitable for high-frequency electronic devices. This solves the problem that the existing BMI resin is difficult to simultaneously take into account dielectric properties, toughness and hydrophobicity.

[0057] Example 1

[0058] A low dielectric toughening bismaleimide containing a siloxane-fluorinated polyether segment provided in a preferred embodiment of the present invention is prepared by the following method:

[0059] S1. Under nitrogen protection, 8.18 kg HO-[CH 2 -CF 2 -O] 10 -H, 8.82Kg H-[Si-O] 20 -H and 4.43 kg 3-aminopropyltriethoxysilane were dissolved in 100 kg toluene in proportion, 0.05 kg chloroplatinic acid was added, and the mixture was stirred at 70 ° C for 8 hours; after the reaction was completed, the solvent was removed by reduced pressure distillation to obtain an amino-terminated siloxane-fluorinated polyether copolymer;

[0060] S2. 1.2 kg of maleic anhydride, 50 kg of toluene and 0.25 kg of p-toluenesulfonic acid are added to an autoclave equipped with a thermometer, a cooling tube, an azeotropic distillation separator and a stirrer, and heated to 120°C. 10 kg of amino-terminated siloxane-fluorinated polyether copolymer dissolved in 5 kg of N, N-dimethylformamide is added dropwise over 3 hours. After the addition is completed, the reaction is continued for 3 hours. The whole process is kept in a reflux state. The azeotropic water and toluene are cooled and separated, and then only the solvent toluene is refluxed into the autoclave for dehydration. After the reaction is completed, the autoclave is repeatedly washed with water to remove p-toluenesulfonic acid, N, N-dimethylformamide and excess maleic anhydride, and the toluene is removed by heating and reduced pressure distillation to obtain a low dielectric toughening bismaleimide containing siloxane-fluorinated polyether segments.

[0061] Example 2

[0062] The present invention provides a method for preparing a low dielectric toughening bismaleimide containing a siloxane-fluorinated polyether segment, comprising the following steps:

[0063] S1. Under nitrogen protection, 4.18 kg HO-[CH 2 -CF 2 -O] 5 -H, 1.78Kg H-[Si-O] 4 -H and 4.43 kg 3-aminopropyltriethoxysilane were dissolved in 21 kg xylene in proportion, 0.006 kg divinyltetramethyldisiloxane platinum complex was added, and the mixture was stirred at 80 ° C for 10 hours; after the reaction was completed, the solvent was removed by reduced pressure distillation to obtain an amino-terminated siloxane-fluorinated polyether copolymer;

[0064] S2. 2Kg of maleic anhydride, 120Kg of xylene and 0.12Kg of hydroxy-p-toluenesulfonic acid were added to an autoclave equipped with a thermometer, a cooling tube, an azeotropic distillation separator and a stirrer, and heated to 110°C. 10Kg of amino-terminated siloxane-fluorinated polyether copolymer dissolved in 2.4Kg of N-methylpyrrolidone was added dropwise for 1 hour. After the addition was completed, the reaction was continued for 5 hours. The whole process was kept in a reflux state. The azeotropic water and xylene were cooled and separated, and then only the solvent xylene was refluxed into the autoclave for dehydration. After the reaction was completed, the autoclave was repeatedly washed with water to remove hydroxy-p-toluenesulfonic acid, N-methylpyrrolidone and excess maleic anhydride, and the xylene was removed by heating and reduced pressure distillation to obtain a low dielectric toughening bismaleimide containing siloxane-fluorinated polyether segments.

[0065] Example 3

[0066] The present invention provides a method for preparing a low dielectric toughening bismaleimide containing a siloxane-fluorinated polyether segment, comprising the following steps:

[0067] S1. Under nitrogen protection, 20.18 kg HO-[CH 2 -CF 2 -O] 25 -H, 17.62Kg H-[Si-O] 40 -H and 3.58Kg 3-aminopropyltrimethoxysilane were dissolved in 400Kg tetrahydrofuran in proportion, 0.2Kg platinum-carbon catalyst was added, and the reaction was stirred at 80°C for 4h; after the reaction was completed, the solvent was removed by reduced pressure distillation to obtain an amino-terminated siloxane-fluorinated polyether copolymer.

[0068] S2. 0.75 kg of maleic anhydride, 100 kg of ethyl acetate and 0.5 kg of methanesulfonic acid are added to an autoclave equipped with a thermometer, a cooling tube, an azeotropic distillation separator and a stirrer, and heated to 110 ° C. 10 kg of amino-terminated siloxane-fluorinated polyether copolymer dissolved in 5 kg of N, N-dimethylacetamide is added dropwise over 5 hours. After the addition is completed, the reaction is continued for 1 hour. The whole process is kept in a reflux state. The azeotropic water and ethyl acetate are cooled and separated, and then only the solvent toluene is refluxed into the autoclave for dehydration; after the reaction is completed, the methanesulfonic acid, N, N-dimethylacetamide and excess maleic anhydride are repeatedly washed with water for multiple times, and the ethyl acetate is removed by heating and reduced pressure distillation to obtain a low dielectric toughening bismaleimide containing siloxane-fluorinated polyether segments.

[0069] Example 4

[0070] The present invention provides a method for preparing a low dielectric toughening bismaleimide containing a siloxane-fluorinated polyether segment, comprising the following steps:

[0071] S1. Under nitrogen protection, 12.18 kg HO-[CH 2 -CF 2 -O] 15 -H, 13.22Kg H-[Si-O] 30 -H and 4.43 kg 3-aminopropyltriethoxysilane were dissolved in 15 kg toluene in proportion, 0.003 kg divinyltetramethyldisiloxane platinum complex was added, and the mixture was stirred at 60 ° C for 10 hours; after the reaction was completed, the solvent was removed by reduced pressure distillation to obtain an amino-terminated siloxane-fluorinated polyether copolymer;

[0072] S2. 0.8 kg of maleic anhydride, 60 kg of xylene and 0.12 kg of p-toluenesulfonic acid were added to an autoclave equipped with a thermometer, a cooling tube, an azeotropic distillation separator and a stirrer, and heated to 140°C. 10 kg of amino-terminated siloxane-fluorinated polyether copolymer dissolved in 5 kg of N, N-dimethylformamide was added dropwise over 2 hours. After the addition was completed, the reaction was continued for 3 hours. The whole process was kept in a reflux state. The azeotropic water and xylene were cooled and separated, and then only the solvent xylene was refluxed into the autoclave for dehydration. After the reaction was completed, the autoclave was repeatedly washed with water to remove p-toluenesulfonic acid, N, N-dimethylformamide and excess maleic anhydride, and the xylene was removed by heating and reduced pressure distillation to obtain a low dielectric toughening bismaleimide containing siloxane-fluorinated polyether segments.

[0073] Comparative Example 1

[0074] This comparison uses a single hydrogen-containing siloxane to prepare bismaleimide, and the specific preparation method is as follows:

[0075] S1. Under nitrogen protection, 8.82Kg H-[Si-O]20-H and 4.43Kg 3-aminopropyltriethoxysilane were dissolved in 100Kg toluene in proportion, 0.05Kg chloroplatinic acid was added, and the reaction was stirred at 70°C for 8h; after the reaction was completed, the solvent was removed by reduced pressure distillation to obtain terminal amino siloxane;

[0076] S2. 1.2 kg of maleic anhydride, 50 kg of toluene and 0.25 kg of p-toluenesulfonic acid were added to an autoclave equipped with a thermometer, a cooling tube, an azeotropic distillation separator and a stirrer, and heated to 120°C. 6.18 kg of amino-terminated siloxane dissolved in 5 kg of N, N-dimethylformamide was added dropwise over 3 hours. After the addition was completed, the reaction was continued for 3 hours. The whole process was kept in a reflux state. The azeotropic water and toluene were cooled and separated, and then only the solvent toluene was refluxed into the autoclave for dehydration. After the reaction was completed, the p-toluenesulfonic acid, N, N-dimethylformamide and excess maleic anhydride were repeatedly washed with water for several times, and toluene was removed by heating and reduced pressure distillation to obtain bismaleimide.

[0077] Comparative Example 2

[0078] This comparative example uses a single fluorinated polyether alcohol to prepare bismaleimide, and the specific preparation method is as follows:

[0079] S1. Under nitrogen protection, 8.18 kg HO-[CH 2 -CF 2 -O] 10 -H and 4.43 kg of 3-aminopropyltriethoxysilane were dissolved in 100 kg of toluene in proportion, 0.05 kg of chloroplatinic acid was added, and the mixture was stirred at 70 ° C for 8 hours; after the reaction was completed, the solvent was removed by reduced pressure distillation to obtain an amino-terminated fluorinated polyether;

[0080] S2. 1.2 kg of maleic anhydride, 50 kg of toluene, and 0.25 kg of p-toluenesulfonic acid were added to an autoclave equipped with a thermometer, a cooling tube, an azeotropic distillation separator, and a stirrer, and heated to 120°C. 5.88 kg of amine-terminated fluorinated polyether dissolved in 5 kg of N, N-dimethylformamide was added dropwise over 3 hours. After the addition was completed, the reaction was continued for 3 hours. The entire process was kept in a reflux state. The azeotropic water and toluene were cooled and separated, and then only the solvent toluene was refluxed into the autoclave for dehydration. After the reaction was completed, the p-toluenesulfonic acid, N, N-dimethylformamide, and excess maleic anhydride were repeatedly washed with water for several times, and the toluene was removed by heating and reduced pressure distillation to obtain a low dielectric toughening bismaleimide containing a siloxane-fluorinated polyether segment. .

[0081] Test example

[0082] The low dielectric toughening bismaleimide containing siloxane-fluorinated polyether segments prepared by the present invention (Examples 1-4) and the products of Comparative Examples 1-3 were heated to 280° C. and cured for 2 hours to obtain bismaleimide thermosetting resins. The dielectric properties, mechanical properties and hydrophobicity of the bismaleimide thermosetting resins were tested. The results are shown in Table 1. The detection method is as follows:

[0083] Dielectric property test: the material is prepared into a uniform film with a thickness of about 0.1 to 0.5 mm; a metal electrode (such as aluminum or gold) is coated on the surface of the film to ensure good contact between the electrode and the sample; the dielectric properties of the material are measured using an LCR tester (such as Agilent E4980A) at a frequency of 1 GHz and room temperature (25°C), and the parameters include dielectric constant (ε′) and loss factor (tanδ);

[0084] Mechanical properties test: dumbbell-shaped specimens with a thickness of 2 to 4 mm were prepared according to ASTM D638 standard; a universal material testing machine (such as Instron 5967) was used to measure the mechanical properties of the material at room temperature (25°C) at a tensile speed of 10 mm / min. The parameters included tensile strength and elongation at break, and the unit of tensile strength was MPa.

[0085] Hydrophobic performance test: The material is prepared into a flat film (thickness is about 0.1-0.5 mm); a contact angle meter (such as Dataphysics OCA series) is used to measure the contact angle of deionized water on the sample surface at room temperature (25°C).

[0086] Table 1 Detection method of bismaleimide thermosetting resin

[0087] Dielectric constant Loss Factor Tensile Strength Elongation at break Water contact angle Example 1 2.6 0.0028 87 16％ 115° Example 2 2.5 0.0027 86 15％ 119° Example 3 2.6 0.0028 85 15％ 117° Example 4 2.7 0.0029 86 14％ 113° Comparative Example 1 3.4 0.0053 86 15％ 95° Comparative Example 2 2.6 0.0030 84 7％ 111°

[0088] Combined with the above data, it can be seen that the thermosetting electronic resin obtained after curing the low dielectric toughening bismaleimide containing siloxane-fluorinated polyether chain segments of the present invention has excellent dielectric properties, toughening effect and high hydrophobicity, and is particularly suitable for use as a material for high-frequency and high-speed copper clad laminates; among them, Example 1 has better comprehensive indicators.

[0089] The above description is only a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions and improvements made by any technician familiar with the field within the spirit and principle of the present invention should be included in the scope of protection of the present invention.

Claims

1. A low dielectric toughening bismaleimide containing siloxane-fluorinated polyether segments, characterized in that: The structural formula of the low dielectric toughening bismaleimide containing siloxane-fluorinated polyether chain segment is as follows:

2. The low dielectric toughening bismaleimide containing siloxane-fluorinated polyether segments according to claim 1, characterized in that: The invention comprises the following components: an amino-terminated siloxane-fluorinated polyether copolymer and maleic anhydride, wherein the molar ratio of the amino-terminated siloxane-fluorinated polyether copolymer to the maleic anhydride is 1:2.1-3; Wherein, the molecular formula of the amino-terminated siloxane-fluorinated polyether copolymer is: NH2-(CH2)3-[Si-O] m -[CH2-CF2-O] n -[And-Oh] m -(CH2)3-NH2; The amino-terminated siloxane-fluorinated polyether copolymer reacts with maleic anhydride through an azeotropic dehydration ring-closing method to obtain the low-dielectric toughening bismaleimide containing siloxane-fluorinated polyether chain segments.

3. The low dielectric toughening bismaleimide containing siloxane-fluorinated polyether segments according to claim 2, characterized in that: The terminal amino siloxane-fluorinated polyether copolymer is prepared with fluorinated polyether alcohol, hydrogen-containing siloxane and amino-containing silane as main components; wherein the molar ratio of fluorinated polyether alcohol, hydrogen-containing siloxane and amino-containing silane is 1:1:

2.

4. The low dielectric toughening bismaleimide containing siloxane-fluorinated polyether segments according to claim 1, characterized in that: The number of repeating units in the structural formula is n=5-25, and the number of repeating units is m=4-40.

5. The low dielectric toughening bismaleimide containing siloxane-fluorinated polyether segments according to claim 3, characterized in that: The amino-containing silane is at least one of 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane.

6. A method for preparing a low dielectric toughening bismaleimide containing siloxane-fluorinated polyether segments according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1. Synthesis of terminal amino-siloxane-fluorinated polyether copolymer: using fluorinated polyether alcohol, hydrogen-containing siloxane and amino-containing silane as main components to react and synthesize terminal amino-siloxane-fluorinated polyether copolymer; S2. Preparation of low dielectric toughening bismaleimide containing siloxane-fluorinated polyether chain segments: reacting the amino-terminated siloxane-fluorinated polyether copolymer prepared in step S1 with maleic anhydride through an azeotropic dehydration ring-closing method to obtain low dielectric toughening bismaleimide containing siloxane-fluorinated polyether chain segments.

7. The method for preparing a low dielectric toughening bismaleimide containing siloxane-fluorinated polyether segments according to claim 6, characterized in that: The specific steps include: S1. Under nitrogen protection, dissolving fluorinated polyether alcohol, hydrogen-containing siloxane and amino-containing silane in solvent A in proportion, adding catalyst A, and stirring and reacting at 60-80°C for 4-10 hours; after the reaction is completed, removing the solvent by reduced pressure distillation to obtain an amino-terminated siloxane-fluorinated polyether copolymer; wherein the molar ratio of fluorinated polyether alcohol, hydrogen-containing siloxane and amino-containing silane is 1:1:2, and the total mass ratio of organic solvent A, catalyst A and fluorinated polyether alcohol, hydrogen-containing siloxane and amino-containing silane is 2-10:0.0005-0.005:1; S2. Maleic anhydride, organic solvent B, and catalyst B are added to an autoclave equipped with a thermometer, a cooling tube, an azeotropic distillation separator, and a stirrer, and heated to 110-140°C. The amino-terminated siloxane-fluorinated polyether copolymer dissolved in organic solvent C is added dropwise over 1-5 hours. After the addition is completed, the reaction is continued for 1-5 hours. The reflux state is maintained during the whole process. The azeotropic water and solvent B are cooled and separated, and then the solvent B is refluxed into the autoclave for dehydration. After the reaction is completed, the mixture is repeatedly washed with water. The catalyst, organic solvent C and excess maleic anhydride are removed multiple times, and the organic solvent B is removed by heating and reduced pressure distillation to obtain a low dielectric toughening bismaleimide containing a siloxane-fluorinated polyether segment; wherein the molar ratio of the terminal amino siloxane-fluorinated polyether copolymer to the maleic anhydride is 1:2.1-3, and the total mass ratio of the organic solvent B, the catalyst B, the organic solvent C to the terminal amino siloxane-fluorinated polyether copolymer and the maleic anhydride is 2-10:0.01-0.05:0.2-1:

1.

8. The method for preparing a low dielectric toughening bismaleimide containing siloxane-fluorinated polyether segments according to claim 7, characterized in that: The organic solvent A is at least one of toluene, xylene and tetrahydrofuran; the catalyst A is a platinum catalyst, specifically including at least one of divinyltetramethyldisiloxane platinum complex, chloroplatinic acid and platinum-carbon catalyst.

9. The method for preparing a low dielectric toughening bismaleimide containing siloxane-fluorinated polyether segments according to claim 7, characterized in that: The organic solvent B is at least one of toluene, xylene and butyl acetate; the catalyst B is at least one of p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid and methanesulfonic acid.

10. The method for preparing a low dielectric toughening bismaleimide containing siloxane-fluorinated polyether segments according to claim 7, characterized in that: The organic solvent C is at least one of N,N-dimethylformamide, N-methylpyrrolidone and N,N-dimethylacetamide.

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