技术领域Technical field
本发明属于有机高分子材料领域，尤其涉及一种聚酰亚胺及其制备方法。The invention belongs to the field of organic polymer materials, and in particular relates to a polyimide and a preparation method thereof.
背景技术Background technique
随着5G通信技术的飞速发展，微电子产品的信号处理和传输频率迅速提升，这种高频高速的应用条件对电子电路材料提出了更高的要求：第一，高频下传输介质材料具有低介电常数和低损耗的特性；第二，具有高热尺寸稳定性，受热后尺寸形变小，便于柔性覆铜板的加工；第三，吸水率低，避免柔性覆铜板在图形制作的高温过程产生气泡或剥离现象。目前，可以应用于5G通讯的传输介质基料主要包括液晶聚合物(LCP)及聚酰亚胺薄膜。LCP材料的制造工艺复杂、良率低和价格高昂等缺点限制了其规模化应用。传统的聚酰亚胺薄膜是目前微电子工业的关键绝缘材料之一，其制造工艺相对简单、成熟，但由于高频下介电常数、介损偏大，热膨胀系数和吸水率较高，无法满足高频高速工况的应用要求。With the rapid development of 5G communication technology, the signal processing and transmission frequencies of microelectronic products have rapidly increased. This high-frequency and high-speed application conditions have put forward higher requirements for electronic circuit materials: First, transmission medium materials at high frequencies have It has the characteristics of low dielectric constant and low loss; secondly, it has high thermal dimensional stability and small dimensional deformation after heating, which facilitates the processing of flexible copper-clad laminates; thirdly, it has low water absorption to avoid the occurrence of flexible copper-clad laminates during the high-temperature process of pattern production. Bubbles or peeling phenomena. At present, the transmission medium base materials that can be used in 5G communications mainly include liquid crystal polymer (LCP) and polyimide film. LCP materials have shortcomings such as complex manufacturing processes, low yields, and high prices, which limit their large-scale application. Traditional polyimide film is one of the key insulating materials in the current microelectronics industry. Its manufacturing process is relatively simple and mature. However, due to its large dielectric constant and dielectric loss at high frequencies, as well as its high thermal expansion coefficient and water absorption, it cannot Meet the application requirements of high-frequency and high-speed working conditions.
改善介电性能的方法主要包括四种，第一是引入含氟结构单元来降低PI分子的电子和离子极化率，但同时会引起热膨胀系数增大、耐热性下降等其他问题，而且也会降低薄膜与基材的附着性，影响材料加工应用；第二是在树脂中添加聚四氟乙烯粉末等氟塑料填料，但是氟填料极性低，与高极性聚酰亚胺树脂体系的相容性差，而且高粘度杂化树脂需要经过脱泡等工艺处理才能流延成膜，过长的存储时间引起填料沉降或者二次团聚，造成薄膜性能不均一，给规模化应用带来极大风险；第三是在聚酰亚胺分子结构中引入微孔结构来降低介电性，而微孔必然会降低薄膜的电气绝缘性能等关键指标，难以满足应用要求；第四是使用含有芴或者苯并噁唑的单体合成树脂并进一步制备薄膜，通过这类大体积基团，阻碍聚合物链段的堆积从而增大自由体积，形成介电限制效应，这种方法制备的薄膜综合性能较好，但含有上述特殊结构单元的单体材料价格昂贵，反应活性低，难以实现规模化生产。There are four main methods to improve dielectric properties. The first is to introduce fluorine-containing structural units to reduce the electron and ion polarizability of PI molecules, but this will also cause other problems such as an increase in the thermal expansion coefficient and a decrease in heat resistance. It will reduce the adhesion between the film and the substrate and affect the material processing and application; the second is to add fluoroplastic fillers such as polytetrafluoroethylene powder to the resin, but the fluorine filler has low polarity and is incompatible with the highly polar polyimide resin system. The compatibility is poor, and the high-viscosity hybrid resin needs to undergo degassing and other processes before it can be cast into a film. Excessive storage time causes filler settlement or secondary agglomeration, resulting in uneven film performance, which brings great challenges to large-scale applications. Risk; the third is to introduce microporous structure into the polyimide molecular structure to reduce the dielectric property, and the micropores will inevitably reduce key indicators such as the electrical insulation performance of the film, making it difficult to meet application requirements; the fourth is to use materials containing fluorene or Monomers of benzoxazole are used to synthesize resins and further prepare films. Through such large-volume groups, they hinder the accumulation of polymer chain segments, thereby increasing the free volume and forming a dielectric confinement effect. The comprehensive properties of films prepared by this method are better. Good, but monomer materials containing the above-mentioned special structural units are expensive and have low reactivity, making it difficult to achieve large-scale production.
同时，热膨胀系数与吸水率是相矛盾问题，难以同时使其二者满足要求。比如，现有技术中一般通过加入对苯二胺等刚性棒状单体来降低热膨胀系数，但是该方法会导致吸水率增加。At the same time, the thermal expansion coefficient and water absorption are contradictory issues, and it is difficult to make them meet the requirements at the same time. For example, in the prior art, the thermal expansion coefficient is generally reduced by adding rigid rod-shaped monomers such as p-phenylenediamine, but this method will lead to an increase in water absorption.
由上可知，针对聚酰亚胺薄膜在高频高速工况所需要的介电性能、尺寸稳定性和吸水率的性能需求，现有技术中难以找出一种易于工业化实际应用、成本低、对聚酰亚胺本身影响小，且同时能使聚酰亚胺具备高尺寸稳定性、低吸水率和介电性能优异的方法。It can be seen from the above that for the performance requirements of dielectric properties, dimensional stability and water absorption required by polyimide films under high-frequency and high-speed operating conditions, it is difficult to find a method in the existing technology that is easy for industrial application, low cost, and It has little impact on the polyimide itself, and at the same time, it can make the polyimide have high dimensional stability, low water absorption and excellent dielectric properties.
发明内容Contents of the invention
本发明所要解决的技术问题是克服以上背景技术中提到的不足和缺陷，提供一种具备高尺寸稳定性、低吸水率、高力学性能和介电性能优异的高频低介损聚酰亚胺薄膜及其制备方法。为解决上述技术问题，本发明提出的技术方案为：The technical problem to be solved by the present invention is to overcome the shortcomings and defects mentioned in the above background technology and provide a high-frequency low dielectric loss polyimide with high dimensional stability, low water absorption, high mechanical properties and excellent dielectric properties. Amine films and methods for their preparation. In order to solve the above technical problems, the technical solutions proposed by the present invention are:
一种高频低介损聚酰亚胺薄膜的制备方法，包括以下步骤：A method for preparing a high-frequency, low-dielectric-loss polyimide film, including the following steps:
(1)合成聚酰胺酸树脂，其中，合成单体至少包括3,3'-二羟基联苯胺；(1) Synthetic polyamic acid resin, wherein the synthetic monomers at least include 3,3'-dihydroxybenzidine;
(2)将疏水型纳米二氧化硅与分散于化学亚胺法试剂中，再与步骤(1)中的聚酰胺酸树脂混合得到前驱体树脂，经亚胺化得到所述高频低介损聚酰亚胺薄膜。(2) Disperse hydrophobic nanosilica in a chemical imine reagent, then mix it with the polyamic acid resin in step (1) to obtain a precursor resin, and obtain the high-frequency low dielectric loss through imidization Polyimide film.
上述制备方法中，优选的，合成聚酰胺酸树脂包括以下步骤：将柔性芳香族二胺、刚性芳香族二胺与芳香族酸酐混合反应，且柔性芳香族二胺、刚性芳香族二胺与芳香族酸酐的摩尔比为(10-40)：(60-90)：(99-101)。本发明中，采用刚性芳香族二胺单体可以降低线膨胀系数，同时分子紧密堆砌可以降低吸水率，但是过多的刚性芳香族二胺会导致薄膜很脆，无法应用，因此本发明还同步引入柔性芳香族二胺单体，提高伸长率，提高应用性能。但柔性芳香族二胺单体不宜过多，否则又造成线膨胀系数过高，介电性能劣化。In the above preparation method, preferably, the synthesis of polyamic acid resin includes the following steps: mixing and reacting flexible aromatic diamine, rigid aromatic diamine and aromatic anhydride, and reacting the flexible aromatic diamine, rigid aromatic diamine and aromatic acid anhydride. The molar ratio of anhydrides is (10-40): (60-90): (99-101). In the present invention, the use of rigid aromatic diamine monomers can reduce the linear expansion coefficient, and at the same time, the close packing of molecules can reduce water absorption. However, too much rigid aromatic diamine will cause the film to be brittle and cannot be used. Therefore, the present invention also synchronizes Introduce flexible aromatic diamine monomer to increase elongation and improve application performance. However, the flexible aromatic diamine monomer should not be too much, otherwise the linear expansion coefficient will be too high and the dielectric properties will be deteriorated.
上述制备方法中，优选的，所述柔性芳香族二胺包括4,4'-二氨基二苯醚、3,4'-二氨基二苯醚、1,3-双(3-氨基苯氧基)苯、1,3-双(4'-氨基苯氧基)苯和2,2-双[4-(4-氨基苯氧基)苯基]丙烷中的一种或几种；In the above preparation method, preferably, the flexible aromatic diamine includes 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy) ) benzene, one or more of 1,3-bis(4'-aminophenoxy)benzene and 2,2-bis[4-(4-aminophenoxy)phenyl]propane;
所述刚性芳香族二胺包括4,4'-二氨基联苯、3,3'-二羟基联苯胺、4,4'-二氨基-3,3'-二甲基联苯、4,4'-二氨基-2,2'-二甲基联苯、4,4'-二氨基二苯甲烷、3,3'-二氨基二苯甲烷、3,4'-二氨基二苯甲烷、对苯二胺、间苯二胺、对苯二甲胺、1,5-二氨基萘和4,4'-双(二甲胺基)二苯甲酮中的多种，且至少包括3,3'-二羟基联苯胺；The rigid aromatic diamines include 4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4 '-Diamino-2,2'-dimethylbiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, p- Multiple types of phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,5-diaminonaphthalene and 4,4'-bis(dimethylamino)benzophenone, and including at least 3,3 '-Dihydroxybenzidine;
所述芳香族酸酐包括均苯四甲酸二酐、3,3',4,4'-联苯四甲酸二酐、2,3,3',4'-联苯四甲酸二酐、3,3',4,4'-二苯甲酮四甲酸二酐、3,3',4,4'-二苯醚四甲酸二酐和2,3,3',4'二苯醚四甲酸二酐中的一种或几种。The aromatic acid anhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3 ',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and 2,3,3',4' diphenyl ether tetracarboxylic dianhydride one or more of them.
上述制备方法中，优选的，3,3'-二羟基联苯胺与所述刚性芳香族二胺的摩尔比为(10-40)：(60-90)。更优选的，为(15-25)：(60-90)。刚性芳香族二胺中必须包含3,3'-二羟基联苯胺和其他至少另外一种刚性芳香族二胺，且3,3'-二羟基联苯胺在刚性芳香族二胺中的占比，会决定3,3'-二羟基联苯胺改善介电性能的效果。我们研究表明，控制刚性芳香族二胺的组成及配比，有利于3,3'-二羟基联苯胺在高温下可环化形成具有一定比例苯并噁唑结构的聚酰亚胺薄膜，可以改善最终产品聚酰亚胺的介电性能。同时，3,3'-二羟基联苯胺的占比还会影响到其对后续疏水型纳米二氧化硅的影响，通过控制其占比，有利于疏水型纳米二氧化硅与3,3'-二羟基联苯胺的协同作用发挥。In the above preparation method, preferably, the molar ratio of 3,3'-dihydroxybenzidine and the rigid aromatic diamine is (10-40): (60-90). More preferably, it is (15-25): (60-90). The rigid aromatic diamine must contain 3,3'-dihydroxybenzidine and at least one other rigid aromatic diamine, and the proportion of 3,3'-dihydroxybenzidine in the rigid aromatic diamine, Will determine the effect of 3,3'-dihydroxybenzidine on improving dielectric properties. Our research shows that controlling the composition and ratio of rigid aromatic diamines is conducive to the cyclization of 3,3'-dihydroxybenzidine at high temperatures to form a polyimide film with a certain proportion of benzoxazole structure, which can Improve the dielectric properties of the final polyimide product. At the same time, the proportion of 3,3'-dihydroxybenzidine will also affect its impact on subsequent hydrophobic nanosilica. By controlling its proportion, it is beneficial to the interaction between hydrophobic nanosilica and 3,3'- The synergistic effect of dihydroxybenzidine is exerted.
上述制备方法中，优选的，混合反应时调整反应体系粘度至1500-3500P，固含量为13-25％。更优选的固含量为15-20％。粘度太低，分子量小，薄膜性能差；粘度太高，流平性差，薄膜厚度难均一。In the above preparation method, preferably, during the mixing reaction, the viscosity of the reaction system is adjusted to 1500-3500P and the solid content is 13-25%. A more preferred solid content is 15-20%. If the viscosity is too low, the molecular weight is small, and the film performance is poor; if the viscosity is too high, the leveling property is poor, and the film thickness is difficult to be uniform.
上述制备方法中，优选的，首先将疏水型纳米二氧化硅分散于化学亚胺法试剂中，并通过高速混合机与聚酰胺酸树脂快速混合，控制高速混合机的转速为1000-5000rpm。本发明使用高速混合机将疏水型纳米二氧化硅、化学亚胺法试剂与高分子量聚酰胺酸快速搅拌混合，其中液态的化学亚胺法试剂可以显著降低树脂粘度，有助于实现三者均匀混合；同时利用化学亚胺法试剂促进树脂在短时间内流延成膜并实现亚胺化，锁定氧化硅在薄膜的分布，避免过长的存储或反应时间造成纳米材料的沉降和二次团聚，实现纳米材料在薄膜内均一分布，从而进一步降低高频介电常数。In the above preparation method, preferably, hydrophobic nanosilica is first dispersed in a chemical imine reagent, and quickly mixed with the polyamic acid resin through a high-speed mixer, and the rotation speed of the high-speed mixer is controlled to 1000-5000 rpm. The present invention uses a high-speed mixer to quickly stir and mix hydrophobic nanosilica, chemical imine reagents and high molecular weight polyamic acid. The liquid chemical imine reagent can significantly reduce the resin viscosity and help achieve uniformity among the three. Mixing; at the same time, the chemical imine method reagent is used to promote the resin to be cast into a film in a short time and achieve imidization, locking the distribution of silicon oxide in the film, and avoiding the sedimentation and secondary agglomeration of nanomaterials caused by excessive storage or reaction time. , achieving uniform distribution of nanomaterials within the film, thereby further reducing the high-frequency dielectric constant.
上述制备方法中，优选的，所述疏水型二氧化硅占所述高频低介损聚酰亚胺薄膜质量的0.5-5％，更优选的为1-3％，所述疏水型二氧化硅的粒径为0.2-2μm。疏水型二氧化硅占比过少，对降低介电常数和介电损耗无明显效果，占比过多，会降低力学性能。疏水型二氧化硅粒径太小，填料容易团聚，比表面积大，会提高吸水率，粒径太大，则填料易沉降，难以分散均匀，同时会造成力学性能劣化。In the above preparation method, preferably, the hydrophobic silica accounts for 0.5-5% of the mass of the high-frequency low dielectric loss polyimide film, more preferably 1-3%, and the hydrophobic silica The particle size of silicon is 0.2-2μm. If the proportion of hydrophobic silica is too small, it will have no obvious effect on reducing the dielectric constant and dielectric loss. If the proportion is too large, the mechanical properties will be reduced. If the particle size of hydrophobic silica is too small, the filler will easily agglomerate, and the specific surface area will be large, which will increase the water absorption rate. If the particle size is too large, the filler will easily settle and will be difficult to disperse evenly, and it will also cause deterioration of mechanical properties.
上述制备方法中，优选的，亚胺化时首先将前驱体树脂流延成膜，再控制温度为500-600℃加热。控制在上述温度范围内，3,3'-二羟基联苯胺的环化反应效果好，有利于改善介电性能。In the above preparation method, preferably, during imidization, the precursor resin is first cast to form a film, and then the temperature is controlled to 500-600°C for heating. Controlled within the above temperature range, the cyclization reaction of 3,3'-dihydroxybenzidine has a good effect and is beneficial to improving the dielectric properties.
上述制备方法中，优选的，所述化学亚胺法试剂包括有机溶剂、催化剂和脱水剂，所述有机溶剂包括二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮和乙酸丁酯中的一种或几种；所述催化剂包括吡啶及衍生物、喹啉、异喹啉和三乙胺的一种或几种，所述催化剂的用量为聚酰胺酸树脂质量的0.5-4％；所述脱水剂包括乙酸酐、丙酸酐和苯甲酸酐中的一种或几种，所述脱水剂的用量为聚酰胺酸树脂质量的10-30％。In the above preparation method, preferably, the chemical imine method reagents include organic solvents, catalysts and dehydrating agents, and the organic solvents include dimethylformamide, dimethylacetamide, N-methylpyrrolidone and butyl acetate. One or more of them; the catalyst includes one or more of pyridine and its derivatives, quinoline, isoquinoline and triethylamine, and the amount of the catalyst is 0.5-4% of the mass of the polyamic acid resin ; The dehydrating agent includes one or more of acetic anhydride, propionic anhydride and benzoic anhydride, and the amount of the dehydrating agent is 10-30% of the mass of the polyamic acid resin.
作为一个总的技术构思，本发明还提供一种上述制备方法制备得到的高频低介损聚酰亚胺薄膜。As a general technical concept, the present invention also provides a high-frequency low dielectric loss polyimide film prepared by the above preparation method.
本发明的高频低介损聚酰亚胺薄膜的制备方法，该薄膜利用廉价且高活性的3,3'-二羟基联苯胺单体合成高分子量聚酰胺酸，再将疏水型纳米二氧化硅分散于化学亚胺法试剂中，并通过高速混合机与聚酰胺酸树脂快速混合得到前驱体树脂，再由模头挤出成型，在钢带上加热除溶剂得到凝胶膜，剥离后进一步加热到500-600℃以上亚胺化得到具有苯并噁唑结构的纳米氧化硅杂化聚酰亚胺薄膜(高频低介损聚酰亚胺薄膜)，增大分子链摩尔体积，改善薄膜的介电性能，抑制了分子链运动，降低热膨胀系数，同时3,3'-二羟基联苯胺的联苯结构降低了亚胺环密度和极性，也控制了吸水率，使本发明的聚酰亚胺薄膜不仅具备高尺寸稳定性、低吸水率和优异力学性能，在高频下还拥有低介电常数和低介电损耗的特点，满足新一代信息技术的需求。The preparation method of the high-frequency low-dielectric loss polyimide film of the present invention uses cheap and highly active 3,3'-dihydroxybenzidine monomer to synthesize high-molecular-weight polyamic acid, and then hydrophobic nano-dioxide Silicon is dispersed in the chemical imine method reagent, and is quickly mixed with polyamic acid resin through a high-speed mixer to obtain a precursor resin, which is then extruded through a die. The solvent is removed by heating on a steel belt to obtain a gel film, which is further peeled off. Heating to above 500-600℃ for imidization to obtain a nano-silicon oxide hybrid polyimide film (high frequency low dielectric loss polyimide film) with benzoxazole structure, increasing the molar volume of the molecular chain and improving the film The dielectric properties of 3,3'-dihydroxybenzidine inhibit the movement of molecular chains and reduce the thermal expansion coefficient. At the same time, the biphenyl structure of 3,3'-dihydroxybenzidine reduces the density and polarity of the imine ring, and also controls the water absorption rate, making the polyethylene of the present invention Imide films not only have high dimensional stability, low water absorption and excellent mechanical properties, but also have low dielectric constant and low dielectric loss at high frequencies, meeting the needs of the new generation of information technology.
具体而言，本发明通过廉价且高活性的3,3'-二羟基联苯胺单体合成高分子量聚酰胺酸，并配合疏水型纳米二氧化硅，其二者协同作用可以使聚酰亚胺薄膜不仅具备高尺寸稳定性、低吸水率和优异力学性能，在高频下还拥有低介电常数和低介电损耗的特点。其中，3,3'-二羟基联苯胺是聚酰亚胺具备低介电损耗性能的关键所在，使用一定数量廉价且高活性的3,3'-二羟基联苯胺单体合成高分子量聚酰胺酸，在高温下可环化形成具有一定比例苯并噁唑结构的聚酰亚胺薄膜，可以改善最终产品聚酰亚胺的介电性能。但需要对3,3'-二羟基联苯胺单体的使用环境进行限定，需要限定3,3'-二羟基联苯胺单体在刚性芳香族二胺中的占比，以使3,3'-二羟基联苯胺单体在高温下环化形成苯并噁唑结构，以改善聚酰亚胺产品的介电性能。单独采用3,3'-二羟基联苯胺单体作为二胺单体与二酐单体配合形成聚酰胺酸，高温环化后分子链柔韧性太差，无法实际应用。此外，疏水型纳米二氧化硅可配合3,3'-二羟基联苯胺单体改善聚酰亚胺产品的介电性能，但需要保证疏水型纳米二氧化硅分布均匀。本发明的采用的3,3'-二羟基联苯胺单体在聚酰胺酸中引入大量的羟基基团，与疏水型纳米二氧化硅表面的氢键等基团紧密结合，显著改善疏水型纳米二氧化硅与有机树脂的相容性，提高了纳米材料在成膜过程中的稳定性和分散性，有利于改善聚酰亚胺产品的综合性能。Specifically, the present invention synthesizes high molecular weight polyamic acid through cheap and highly active 3,3'-dihydroxybenzidine monomer, and cooperates with hydrophobic nanosilica. The synergistic effect of the two can make polyimide The film not only has high dimensional stability, low water absorption and excellent mechanical properties, but also has low dielectric constant and low dielectric loss at high frequencies. Among them, 3,3'-dihydroxybenzidine is the key to the low dielectric loss performance of polyimide. A certain amount of cheap and highly active 3,3'-dihydroxybenzidine monomer is used to synthesize high molecular weight polyamide. Acid can be cyclized at high temperature to form a polyimide film with a certain proportion of benzoxazole structure, which can improve the dielectric properties of the final polyimide product. However, the use environment of 3,3'-dihydroxybenzidine monomer needs to be limited, and the proportion of 3,3'-dihydroxybenzidine monomer in rigid aromatic diamines needs to be limited so that 3,3' -Dihydroxybenzidine monomer is cyclized at high temperature to form a benzoxazole structure to improve the dielectric properties of polyimide products. Using 3,3'-dihydroxybenzidine monomer alone as the diamine monomer and dianhydride monomer to form polyamic acid, the molecular chain flexibility after high-temperature cyclization is too poor for practical application. In addition, hydrophobic nano-silica can be combined with 3,3'-dihydroxybenzidine monomer to improve the dielectric properties of polyimide products, but it is necessary to ensure that the hydrophobic nano-silica is evenly distributed. The 3,3'-dihydroxybenzidine monomer used in the present invention introduces a large number of hydroxyl groups into the polyamic acid, which is closely combined with the hydrogen bonding and other groups on the surface of the hydrophobic nanometer silica, and significantly improves the hydrophobic nanometer silica. The compatibility between silica and organic resin improves the stability and dispersion of nanomaterials during the film formation process, which is beneficial to improving the overall performance of polyimide products.
与现有技术相比，本发明的优点在于：Compared with the prior art, the advantages of the present invention are:
本发明的高频低介损聚酰亚胺薄膜的制备方法使用廉价且高活性的3,3'-二羟基联苯胺单体合成高分子量聚酰胺酸，具备可量产性。并且，采用聚酰胺酸中二羟基联苯结构的羟基可以与体系内的纳米二氧化硅紧密结合，在成膜过程中进一步提高纳米材料的分散稳定性。此外，采用二羟基联苯结构的经高温处理形成具有苯并噁唑结构的聚酰亚胺薄膜，具有高尺寸稳定性、低吸水率、高力学性能和高频低介电等优异性能。The preparation method of the high-frequency low-dielectric loss polyimide film of the present invention uses cheap and highly active 3,3'-dihydroxybenzidine monomer to synthesize high-molecular-weight polyamic acid, and is mass-produced. In addition, the hydroxyl group of the dihydroxybiphenyl structure in the polyamic acid can be tightly combined with the nano-silica in the system, further improving the dispersion stability of the nano-materials during the film formation process. In addition, a polyimide film with a benzoxazole structure formed by high-temperature treatment using a dihydroxybiphenyl structure has excellent properties such as high dimensional stability, low water absorption, high mechanical properties, and high frequency and low dielectric properties.
具体实施方式Detailed ways
为了便于理解本发明，下文将结合较佳的实施例对本发明作更全面、细致地描述，但本发明的保护范围并不限于以下具体的实施例。In order to facilitate understanding of the present invention, the present invention will be described more comprehensively and in detail below with reference to preferred embodiments, but the protection scope of the present invention is not limited to the following specific embodiments.
除非另有定义，下文中所使用的所有专业术语与本领域技术人员通常理解的含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的，并不是旨在限制本发明的保护范围。Unless otherwise defined, all technical terms used below have the same meanings as commonly understood by those skilled in the art. The technical terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of the present invention.
除非另有特别说明，本发明中用到的各种原材料、试剂、仪器和设备等均可通过市场购买得到或者可通过现有方法制备得到。Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased in the market or prepared by existing methods.
实施例1：Example 1:
一种高频低介损聚酰亚胺薄膜的制备方法，包括以下步骤：A method for preparing a high-frequency, low-dielectric-loss polyimide film, including the following steps:
1、聚合1. Aggregation
将24.9kg的4,4'-二氨基二苯醚、3.6kg的3,3'-二羟基联苯胺和38.8kg的4,4'-二氨基二苯甲烷溶于845.7kg的二甲基甲酰胺中，分批次加入47.8kg的均苯四甲酸二酐和34.7的3,3',4,4'-联苯四甲酸二酐反应5hr，得到粘度1850P的聚酰胺酸树脂。Dissolve 24.9kg of 4,4'-diaminodiphenyl ether, 3.6kg of 3,3'-dihydroxybenzidine and 38.8kg of 4,4'-diaminodiphenylmethane in 845.7kg of dimethylmethane In the amide, add 47.8kg of pyromellitic dianhydride and 34.7kg of 3,3',4,4'-biphenyltetracarboxylic dianhydride in batches and react for 5 hours to obtain a polyamic acid resin with a viscosity of 1850P.
2、制膜2. Film making
在高速混合机内中加入5.9kg粒径为0.5μm的疏水性二氧化硅、18.3kg的吡啶、180.4kg的乙酸酐，与树脂在1850rpm转速下混合均匀，经管道输送至模头，挤出成型，再经流延、纵横向拉伸、550℃高温加热等工艺得到25μm厚度的聚酰亚胺薄膜。Add 5.9kg of hydrophobic silica with a particle size of 0.5μm, 18.3kg of pyridine, and 180.4kg of acetic anhydride into the high-speed mixer, mix evenly with the resin at 1850rpm, transport it to the die through a pipeline, and extrude Molding, and then through processes such as casting, longitudinal and transverse stretching, and high-temperature heating at 550°C, a polyimide film with a thickness of 25 μm is obtained.
本实施例制备得到的聚酰亚胺薄膜，可满足高频高速工况的应用要求。The polyimide film prepared in this embodiment can meet the application requirements of high-frequency and high-speed working conditions.
实施例2：Example 2:
一种高频低介损聚酰亚胺薄膜的制备方法，包括以下步骤：A method for preparing a high-frequency, low-dielectric-loss polyimide film, including the following steps:
1、聚合1. Aggregation
将19.4kg的1,3-双(4'-氨基苯氧基)苯、25.5kg的3,3'-二羟基联苯胺、31.2kg的对苯二胺溶于815.7kg的二甲基甲酰胺中，分批次加入103.7kg的均苯四甲酸二酐反应5hr，得到粘度2950P的聚酰胺酸树脂。Dissolve 19.4kg of 1,3-bis(4'-aminophenoxy)benzene, 25.5kg of 3,3'-dihydroxybenzidine, and 31.2kg of p-phenylenediamine in 815.7kg of dimethylformamide , add 103.7kg of pyromellitic dianhydride in batches and react for 5 hours to obtain a polyamic acid resin with a viscosity of 2950P.
2、制膜2. Film making
在高速混合机内中加入3.6kg粒径为0.8μm的疏水性氧化硅、33kg的吡啶、230.8kg的乙酸酐，与树脂在2650rpm转速下混合均匀，经管道输送至模头，挤出成型，再经流延、纵横向拉伸、585℃高温加热等工艺得到25μm厚度的聚酰亚胺薄膜。Add 3.6kg of hydrophobic silica with a particle size of 0.8μm, 33kg of pyridine, and 230.8kg of acetic anhydride into the high-speed mixer. Mix evenly with the resin at 2650rpm, then transport it to the die through a pipeline for extrusion molding. Then, a polyimide film with a thickness of 25 μm is obtained through processes such as casting, longitudinal and transverse stretching, and high-temperature heating at 585°C.
本实施例制备得到的聚酰亚胺薄膜，可满足高频高速工况的应用要求。The polyimide film prepared in this embodiment can meet the application requirements of high-frequency and high-speed working conditions.
实施例3：Example 3:
一种高频低介损聚酰亚胺薄膜的制备方法，包括以下步骤：A method for preparing a high-frequency, low-dielectric-loss polyimide film, including the following steps:
1、聚合1. Aggregation
将54.8kg的2,2-双[4-(4-氨基苯氧基)苯基]丙烷、31.5kg的3,3'-二羟基联苯胺、23.2kg的4,4'-二氨基联苯于785.1kg的二甲基乙酰胺中，分批次加入39.1kg的二苯甲酮四甲酸二酐和71.4kg的3,3',4,4'-联苯四甲酸二酐反应7hr，得到粘度3170P的聚酰胺酸树脂。Mix 54.8kg of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 31.5kg of 3,3'-dihydroxybenzidine, and 23.2kg of 4,4'-diaminobiphenyl In 785.1kg of dimethylacetamide, add 39.1kg of benzophenone tetracarboxylic dianhydride and 71.4kg of 3,3',4,4'-biphenyltetracarboxylic dianhydride in batches and react for 7 hours to obtain Polyamic acid resin with viscosity 3170P.
2、制膜2. Film making
在高速混合机内中加入2.2kg粒径为1.2μm的疏水性氧化硅、14kg的异喹啉、270.4kg的苯甲酸酐，与树脂在2650rpm转速下混合均匀，经管道输送至模头，挤出成型，再经流延、纵横向拉伸、515℃高温加热等工艺得到25μm厚度的聚酰亚胺薄膜。Add 2.2kg of hydrophobic silica with a particle size of 1.2μm, 14kg of isoquinoline, and 270.4kg of benzoic anhydride into the high-speed mixer, mix evenly with the resin at 2650rpm, transport it to the die through a pipeline, and extrude After molding, a polyimide film with a thickness of 25 μm is obtained through processes such as casting, longitudinal and transverse stretching, and high-temperature heating at 515°C.
本实施例制备得到的聚酰亚胺薄膜，可满足高频高速工况的应用要求。The polyimide film prepared in this embodiment can meet the application requirements of high-frequency and high-speed working conditions.
实施例4：Example 4:
一种高频低介损聚酰亚胺薄膜的制备方法，包括以下步骤：A method for preparing a high-frequency, low-dielectric-loss polyimide film, including the following steps:
1、聚合1. Aggregation
将18.5kg的3,4'-二氨基二苯醚、17kg的3,3'-二羟基联苯胺、33.8kg的4,4'-二氨基二苯甲烷于839kg的二甲基乙酰胺中，分批次加入49.6kg的二苯甲酮四甲酸二酐和41kg的均苯四甲酸二酐反应7hr，得到粘度2030P的聚酰胺酸树脂。Add 18.5kg of 3,4'-diaminodiphenyl ether, 17kg of 3,3'-dihydroxybenzidine, and 33.8kg of 4,4'-diaminodiphenylmethane into 839kg of dimethylacetamide, Add 49.6 kg of benzophenone tetracarboxylic dianhydride and 41 kg of pyromellitic acid dianhydride in batches and react for 7 hours to obtain a polyamic acid resin with a viscosity of 2030P.
2、制膜2. Film making
在高速混合机内中加入5.6kg粒径为1.5μm的疏水性氧化硅、10kg的吡啶、250.2kg的乙酸酐，与树脂在4150rpm转速下混合均匀，经管道输送至模头，挤出成型，再经流延、纵横向拉伸、538℃高温加热等工艺得到25μm厚度的聚酰亚胺薄膜。Add 5.6kg of hydrophobic silica with a particle size of 1.5μm, 10kg of pyridine, and 250.2kg of acetic anhydride into the high-speed mixer. Mix evenly with the resin at 4150rpm, then transport it to the die through a pipeline for extrusion molding. Then, a polyimide film with a thickness of 25 μm is obtained through processes such as casting, longitudinal and transverse stretching, and high-temperature heating at 538°C.
本实施例制备得到的聚酰亚胺薄膜，可满足高频高速工况的应用要求。The polyimide film prepared in this embodiment can meet the application requirements of high-frequency and high-speed working conditions.
实施例5：Example 5:
一种高频低介损聚酰亚胺薄膜的制备方法，包括以下步骤：A method for preparing a high-frequency, low-dielectric-loss polyimide film, including the following steps:
1、聚合1. Aggregation
将22.1kg的1,3-双(3-氨基苯氧基)苯、14.7kg的3,3'-二羟基联苯胺、49.8kg的4,4'-二氨基-2,2'-二甲基联苯于800kg的N-甲基吡咯烷酮中，分批次加入35.2kg的3,3',4,4'-二苯醚四甲酸二酐和78kg的2,3,3',4'-联苯四甲酸二酐反应8.5hr，得到粘度1790P的聚酰胺酸树脂。Add 22.1kg of 1,3-bis(3-aminophenoxy)benzene, 14.7kg of 3,3'-dihydroxybenzidine, and 49.8kg of 4,4'-diamino-2,2'-dimethyl To 800kg of N-methylpyrrolidone, add 35.2kg of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and 78kg of 2,3,3',4'- The biphenyltetracarboxylic dianhydride was reacted for 8.5 hours to obtain a polyamic acid resin with a viscosity of 1790P.
2、制膜2. Film making
在高速混合机内中加入3.9kg粒径为1.8μm的疏水性氧化硅、20kg的吡啶、190.5kg的丙酸酐，与树脂在4650rpm转速下混合均匀，经管道输送至模头，挤出成型，再经流延、纵横向拉伸、573℃高温加热等工艺得到25μm厚度的聚酰亚胺薄膜。Add 3.9kg of hydrophobic silica with a particle size of 1.8μm, 20kg of pyridine, and 190.5kg of propionic anhydride into the high-speed mixer. Mix evenly with the resin at 4650rpm, then transport it to the die through a pipeline for extrusion molding. Then, a polyimide film with a thickness of 25 μm is obtained through processes such as casting, longitudinal and transverse stretching, and high-temperature heating at 573°C.
本实施例制备得到的聚酰亚胺薄膜，可满足高频高速工况的应用要求。The polyimide film prepared in this embodiment can meet the application requirements of high-frequency and high-speed working conditions.
实施例6：Example 6:
一种高频低介损聚酰亚胺薄膜的制备方法，包括以下步骤：A method for preparing a high-frequency, low-dielectric-loss polyimide film, including the following steps:
1、聚合1. Aggregation
将64.8kg的2,2-双[4-(4-氨基苯氧基)苯基]丙烷、8.9kg的3,3'-二羟基联苯胺、34.2kg的1,5-二氨基萘于769kg的乙酸丁酯中，分批次加入122kg的3,3,4',4'-联苯四甲酸二酐反应6.5hr，得到粘度2160P的聚酰胺酸树脂。Add 64.8kg of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 8.9kg of 3,3'-dihydroxybenzidine, and 34.2kg of 1,5-diaminonaphthalene to 769kg In butyl acetate, 122kg of 3,3,4',4'-biphenyltetracarboxylic dianhydride was added in batches and reacted for 6.5 hours to obtain a polyamic acid resin with a viscosity of 2160P.
2、制膜2. Film making
在高速混合机内中加入5.7kg粒径为1.4μm的疏水性氧化硅、36kg的喹啉235.5kg的丙酸酐，与树脂在3050rpm转速下混合均匀，经管道输送至模头，挤出成型，再经流延、纵横向拉伸、538℃高温加热等工艺得到25μm厚度的聚酰亚胺薄膜。Add 5.7kg of hydrophobic silica with a particle size of 1.4μm, 36kg of quinoline and 235.5kg of propionic anhydride into the high-speed mixer, mix it evenly with the resin at 3050rpm, transport it to the die through a pipeline, and extrusion molding. Then, a polyimide film with a thickness of 25 μm is obtained through processes such as casting, longitudinal and transverse stretching, and high-temperature heating at 538°C.
本实施例制备得到的聚酰亚胺薄膜，可满足高频高速工况的应用要求。The polyimide film prepared in this embodiment can meet the application requirements of high-frequency and high-speed working conditions.
对比例1：Comparative example 1:
一种聚酰亚胺薄膜的制备方法，包括以下步骤：A method for preparing a polyimide film, including the following steps:
将19.4kg的1,3-双(4'-氨基苯氧基)苯、62.3kg的对苯二胺溶于841.2kg的二甲基甲酰胺中，分批次加入103.7kg的均苯四甲酸二酐反应5hr，得到粘度2950P的聚酰胺酸树脂。其余与实施例2相同。Dissolve 19.4kg of 1,3-bis(4'-aminophenoxy)benzene and 62.3kg of p-phenylenediamine in 841.2kg of dimethylformamide, and add 103.7kg of pyromellitic acid in batches The dianhydride was reacted for 5 hours to obtain a polyamic acid resin with a viscosity of 2950P. The rest is the same as Example 2.
对比例2：Comparative example 2:
一种聚酰亚胺薄膜的制备方法，包括以下步骤：A method for preparing a polyimide film, including the following steps:
将19.4kg的1,3-双(4'-氨基苯氧基)苯和88kg的3,3'-二羟基联苯胺溶于957.6kg的二甲基甲酰胺中，分批次加入103.7kg的均苯四甲酸二酐反应5hr，得到粘度2950P的聚酰胺酸树脂。其余与实施例2相同。Dissolve 19.4kg of 1,3-bis(4'-aminophenoxy)benzene and 88kg of 3,3'-dihydroxybenzidine in 957.6kg of dimethylformamide, and add 103.7kg of dimethylformamide in batches The pyromellitic dianhydride was reacted for 5 hours to obtain a polyamic acid resin with a viscosity of 2950P. The rest is the same as Example 2.
对比例3：Comparative example 3:
一种聚酰亚胺薄膜的制备方法，包括以下步骤：A method for preparing a polyimide film, including the following steps:
不加入疏水型氧化硅，其余与实施例3相同。No hydrophobic silica was added, and the rest was the same as in Example 3.
对比例4：Comparative example 4:
一种聚酰亚胺薄膜的制备方法，包括以下步骤：A method for preparing a polyimide film, including the following steps:
疏水型氧化硅平均粒径1.5μm，质量17.8kg，高速混合机转速为3500rpm，其余与实施例3相同。The average particle size of hydrophobic silicon oxide is 1.5 μm, the mass is 17.8 kg, the rotation speed of the high-speed mixer is 3500 rpm, and the rest is the same as in Example 3.
对比例5：Comparative example 5:
一种聚酰亚胺薄膜的制备方法，包括以下步骤：A method for preparing a polyimide film, including the following steps:
疏水型氧化硅平均粒径5μm，质量8.6kg，高速混合机转速为3300rpm，其余与对实施例3相同。The average particle size of hydrophobic silicon oxide is 5 μm, the mass is 8.6 kg, the rotation speed of the high-speed mixer is 3300 rpm, and the rest is the same as in Example 3.
对比例6：Comparative example 6:
一种聚酰亚胺薄膜的制备方法，包括以下步骤：A method for preparing a polyimide film, including the following steps:
疏水型氧化硅使用原位聚合方式制备杂化树脂，其余与实施例3相同。The hydrophobic silica was prepared by in-situ polymerization, and the rest was the same as in Example 3.
对比例1-6和实施例1-6中得到的聚酰亚胺薄膜根据GB/T13542.6-2021的方法测试拉伸强度、断裂伸长率和吸水率，根据TMA方法测试线膨胀系数，根据IEC61189-2-721的方法测试15GHz下的介电常数及介电损耗，其结果如下表所示。The polyimide films obtained in Comparative Examples 1-6 and Examples 1-6 were tested for tensile strength, elongation at break and water absorption according to the method of GB/T13542.6-2021, and the linear expansion coefficient was tested according to the TMA method. The dielectric constant and dielectric loss at 15GHz were tested according to the method of IEC61189-2-721. The results are shown in the table below.
表1：对比例1-6和实施例1-6中得到的聚酰亚胺薄膜的综合性能对比Table 1: Comparison of comprehensive properties of polyimide films obtained in Comparative Examples 1-6 and Examples 1-6
通过表1的数据表明，通过引入3,3'-二羟基联苯胺单体并在高温下环化得到含有苯并噁唑结构的聚酰亚胺薄膜，具有优异的力学性能、高频介电性能、尺寸稳定性和低吸水率(参见实施例2与对比例1)。同时，3,3'-二羟基联苯胺单体的用量需要优化，否则难以达到提高介电性能的效果(参见实施例2与对比例2)。参见实施例3与对比例3-6，使用高速混合工艺在树脂中加入特定的疏水型二氧化硅之后，增加有机/无机体系的均匀性，改善力学性能、尺寸稳定性和介电性能，这种具备优异综合性能的聚酰亚胺薄膜，可以满足高频高速下的电子电路对绝缘材料的要求。The data in Table 1 shows that by introducing 3,3'-dihydroxybenzidine monomer and cyclizing it at high temperature, a polyimide film containing a benzoxazole structure is obtained, which has excellent mechanical properties and high-frequency dielectric properties. performance, dimensional stability and low water absorption (see Example 2 and Comparative Example 1). At the same time, the amount of 3,3'-dihydroxybenzidine monomer needs to be optimized, otherwise it will be difficult to achieve the effect of improving dielectric properties (see Example 2 and Comparative Example 2). Referring to Example 3 and Comparative Examples 3-6, after using a high-speed mixing process to add specific hydrophobic silica to the resin, the uniformity of the organic/inorganic system is increased, and the mechanical properties, dimensional stability and dielectric properties are improved. This A polyimide film with excellent comprehensive properties that can meet the requirements for insulating materials in electronic circuits under high frequency and high speed.
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