CN104829837B - One kind of magnetic particles in the induction heating method for preparing a soluble polyimide - Google Patents

One kind of magnetic particles in the induction heating method for preparing a soluble polyimide Download PDF

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CN104829837B
CN104829837B CN201510267429.1A CN201510267429A CN104829837B CN 104829837 B CN104829837 B CN 104829837B CN 201510267429 A CN201510267429 A CN 201510267429A CN 104829837 B CN104829837 B CN 104829837B
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polyimide
soluble
reaction
solution
polyamic acid
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CN104829837A (en
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刘长威
曲春艳
王德志
宿凯
张杨
冯浩
李洪峰
杨海东
王海民
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黑龙江省科学院石油化学研究院
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Abstract

一种采用磁性粒子感应加热制备可溶性聚酰亚胺的方法,本发明涉及可溶性聚酰亚胺的制备方法。 One kind of method for preparing a soluble polyimide induction heating of the magnetic particles, the present invention relates to a method for preparing a soluble polyimide. 本发明要解决现有制备可溶性聚酰亚胺时,可溶性聚酰亚胺前驱体‑聚酰胺酸在酰亚胺环化过程中受外部热源加热不均带来的树脂性能不稳定,以及加热升温速率慢,亚胺化周期长的问题。 When the present invention is to solve the prior preparation of a soluble polyimide, a soluble polyimide precursor - inequality of polyamic acid resin brings an external heat source unstable in the process of an imide ring, and the heating temperature the slow rate of imidization cycle long. 制备方法:首先制备高磁响应聚酰亚胺/Fe3O4复合磁性纳米粒子,再将可溶性聚酰胺酸溶液、带水剂和高磁响应聚酰亚胺/Fe3O4复合磁性纳米粒子置于高频感应加热设备中加热反应,最后沉析,过滤,沉淀水洗,烘干。 Preparation: First of preparing high magnetically responsive polyimide / Fe3O4 composite magnetic nanoparticles, then a soluble polyamic acid solution with a liquid, and a high magnetic response polyimide / Fe3O4 magnetic nanoparticles disposed composite high frequency induction heating the reaction was heated apparatus, the final precipitation, filtration, precipitation, washing and drying. 本发明主要用于一种采用磁性粒子感应加热制备可溶性聚酰亚胺的方法。 The present invention a method for induction heating of magnetic particles prepared using a soluble polyimide.

Description

一种采用磁性粒子感应加热制备可溶性聚酰亚胺的方法 One kind of magnetic particles in the induction heating method for preparing a soluble polyimide

技术领域 FIELD

[0001 ]本发明涉及可溶性聚酰亚胺的制备方法。 [0001] The present invention relates to a method for preparing a soluble polyimide.

背景技术 Background technique

[0002] 聚酰亚胺是重复结构单元中含有酰亚胺环的芳杂环聚合物,它是迄今为止在工业领域应用的耐热等级最高的聚合物材料之一,加之其优异的综合性能,以薄膜、树脂、纤维、 分离膜等形式被广泛地应用于航空航天、电子电气等领域。 [0002] The polyimide is an aromatic heterocyclic polymers comprising repeating structural units of the imide ring, which is one of the highest levels of polymeric material heat-resistant applications to date in the industrial field, together with its excellent performance to films, resins, fibers, and other forms of separation membranes are widely used in aerospace, electrical and electronic fields. 传统的聚酰亚胺通常由芳香族四甲酸酐和芳香族二胺为原料通过先形成聚酰胺酸,再亚胺化脱水形成聚酰亚胺,常见的亚胺化方法有热亚胺化法和化学亚胺化法,具有良好的应用基础。 Typically by conventional polyimide to form a polyamic acid, a polyimide, a common method for imidization then dehydrating imidization thermal imidization method is formed from an aromatic dianhydride and an aromatic diamine as raw materials and a chemical imidization method, having good application basis. 但现有热亚胺化反应周期长,会极大增加能源消耗,如专利CN101985498B中聚酰亚胺的热亚胺化反应经历170-190 °C的10_12h回流反应,缓慢的升温反应和长时间的恒温加热过程也增加了设备损耗。 However, the conventional thermal imidization reaction period long, will greatly increase energy consumption, as described in Patent CN101985498B polyimide subjected to a thermal imidization reaction at reflux 10_12h 170-190 ° C, slow heating and prolonged reaction constant heating process also increases the device losses. 化学亚胺化除形成酰亚胺环以外,还可能形成异酰亚胺,亚胺化的不彻底会导致产物分子量分布变宽,难以直接得到高性能的聚酰亚胺,如专利CN1175031C中采用化学亚胺化后结合热酰亚胺化反应才能克服以上问题,但其后续热亚胺化反应时间也在2h-20h。 Chemical control to chemical imide ring form an imide, the isoimide is also possible to form, incomplete imidization leads to broadening the molecular weight distribution, it is difficult to directly obtain a high performance polyimide, as employed in Patent CN1175031C after the chemical imidization reaction is a combination of thermal imidization to overcome the above problems, but the subsequent thermal imidization reaction time also 2h-20h. 文献(Macromol .Rapid Comm.2011,32:254-288)和专利(CN101735457B)报道了采用微波辐照法制备软质聚酰亚胺泡沫的生产方法,明显提高聚酰亚胺泡沫的生产周期,但是所采用的方法只涉及聚酰亚胺泡沫,并不能推广到聚酰亚胺领域;同时采用热源对容器外部加热,会导致体系加热不均,因为聚酰亚胺的性能与亚胺化程度直接相关,局部加热效果的差异对聚酰亚胺产品稳定性带来问题。 Document (Macromol .Rapid Comm.2011,32: 254-288) and patents (CN101735457B) reported the use of microwave irradiation Preparation Method soft mass production methods of polyimide foam, polyimide foam significantly improve the production cycle, However, the method employed involves only a polyimide foam, the polyimide can not be extended to the art; while heating using a heat source external to the vessel, will cause uneven heating system, since the degree of imidization of the polyimide and the properties of directly related to the differences in local heating effects cause problems for the stability of the product polyimide.

[0003] 随着微电子和航空航天领域的飞速发展,由于聚酰亚胺易于制备并且性能稳定, 高性能聚酰亚胺需求急剧增加:文献(Thin Solid Film 2011,519:2339-2343)提到复合材料用聚酰亚胺预浸料,其固化过程出现的亚胺化周期过长,难以提升生产效率;文献(Adv .Funct .Mater. 2015,25:78-84)同样提到针对电子封装用聚酰亚胺,同样面临亚胺化速度慢、亚胺化程度不稳定的难题。 [0003] With the rapid development of the microelectronics and aerospace, due to the ease of preparation and polyimide stable, sharp increase in demand for high performance polyimide: document (Thin Solid Film 2011,519: 2339-2343) extract polyimide to the composite prepreg, the curing process cycle imidization occurs too long, it is difficult to improve production efficiency; literature (Adv .Funct .Mater 2015,25:. 78-84) Also mentioned for electronic polyimide encapsulation, also facing slow imidization degree of imidization instability problems. 通常所用的复合材料及胶粘剂用聚酰亚胺都需要经历5-15h不等的热亚胺化过程。 Composite materials are typically used for adhesives and polyimide undergo 5-15h require unequal thermal imidization process. 可以看出,聚酰亚胺常规制备过程的长时间热亚胺严重限制了材料的生产周期、应用时的能源效率和模具消耗。 As can be seen, a long thermal imidization of the polyimide prepared by conventional processes severely limit the material production cycle, energy efficiency and consumption of the mold during application.

[0004] 普通感应加热是一种易于实现磁性模具快速加热的方法。 [0004] The conventional induction heating method is an easy to mold magnetic achieve rapid heating. 是交变电流通过位于附近的导电线圈来产生磁场,外加磁场在工件中引起涡电流,涡电流由于电阻效应而产生热量。 Is alternating current magnetic field is generated by a conductive coil positioned near the magnetic field caused by eddy currents, eddy current effects due to the resistance heat is generated in the workpiece. 常规感应加热是在设备外采用加热源,但是对于较大体积(如玻璃容器)外部加热,同样会带来容器内受热不均以及加热速率慢等问题。 Induction heating is the use of a conventional heat source outside the device, but for larger volumes (e.g., a glass container) external heating, the vessel will also bring uneven heating and slow heating rate issues.

[0005] 利用纳米粒子特有的磁滞效应、弛豫效应等可将交变磁场能量转变为热能,并减少电能消耗。 [0005] The use of hysteresis effects, relaxation effects and other unique nanoparticles may be alternating magnetic field energy into thermal energy, and reduce power consumption. 但是高居里温度磁性纳米粒子(如Fe 3〇4、Fe203)在树脂和溶液体系中很容易团聚形成团簇,影响在体系中的分散性的同时,直接采用磁性纳米粒子在体系中加热到较高温度会导致明显的受热不均并且很难维持体系温度在一个稳定值。 However, high Curie temperature magnetic nanoparticles (such as Fe 3〇4, Fe203) in the resin solution and the system is easily agglomerated form clusters, in the system affect the dispersibility while, magnetic nanoparticles used directly in the system is heated to a higher high temperatures cause significant and uneven heating system is difficult to maintain the temperature at a stable value. 而采用包覆的磁性纳米粒子作为热源还未见报道,采用包覆能否提升制备效果是未知的。 The use of coated magnetic nanoparticles have not been reported as a heat source, using the coated preparation can enhance the effect is unknown.

发明内容 SUMMARY

[0006] 本发明要解决现有制备可溶性聚酰亚胺时,可溶性聚酰亚胺前驱体-聚酰胺酸在酰亚胺环化过程中受外部热源加热不均带来的树脂性能不稳定,以及加热升温速率慢,亚胺化周期长的问题,而提供一种采用磁性粒子感应加热制备可溶性聚酰亚胺的方法。 [0006] When the present invention is to solve the conventional preparation of soluble polyimide, a soluble polyimide precursor - by an external heat source polyamic acid resin brings uneven unstable in the process of imide ring, and heating the heating rate is slow, a long period of imidization problems, to provide a process for preparing a soluble polyimide is heated using inductive magnetic particles.

[0007] 本发明一种采用磁性粒子感应加热制备可溶性聚酰亚胺的方法是按以下步骤进行: [0007] The present invention is an induction heating method of preparing a soluble polyimide using magnetic particles is performed in the following steps:

[0008] 一、①、在氮气气氛、室温及搅拌条件下,向三颈瓶中加入高沸点极性溶剂和芳香二胺,反应〇.5h~lh,再向三颈瓶中加入芳香二酐,反应lh~5h,然后向三颈瓶中加入叔胺, 反应2h~3h,停止搅拌,得到反应液,在搅拌条件下,将反应液以2mL/s~10mL/s的速度滴入丙酮中,滴加完成后,继续搅拌lh~6h,然后静置3天~10天,得到含丝状物的静置液,将含丝状物的静置液中丝状物取出,在温度为20°C~30°C的真空烘箱中将丝状物烘干,得到聚酰胺酸胺盐; [0008] First, ①, under nitrogen atmosphere, and stirred at room temperature conditions, high-boiling polar solvent and an aromatic diamine were added to a three-necked flask, the reaction 〇.5h ~ lh, three-necked flask was added again aromatic dianhydride the reaction lh ~ 5h, three-necked flask was then added to the tertiary amine, the reaction 2h ~ 3h, the stirring was stopped to obtain a reaction solution, under stirring, the reaction solution was 2mL / s ~ 10mL / s speed was added dropwise acetone after completion of the dropwise addition, stirring was continued for lh ~ 6h, then allowed to stand for 3 days to 10 days, allowed to stand to give a solution containing the filament, the filament was allowed to stand in the solution containing the filament was taken out at a temperature of 20 ° C ~ 30 ° C vacuum oven drying the filaments, to give a polyamic acid salt;

[0009] 所述的芳香二胺与芳香二胺酐的摩尔比为1:(0.90~0.95);所述的芳香二胺与叔胺的摩尔比为1: (1.90~2.10);所述的芳香二酐和芳香二胺的总质量与高沸点极性溶剂的质量比为1:5; [0009] The molar ratio of aromatic diamine and an aromatic diamine anhydride is 1: (0.90 to 0.95); the molar ratio of aromatic diamine and a tertiary amine is 1: (1.90 to 2.10); the mass of the total mass of high-boiling polar solvent and an aromatic dianhydride and an aromatic diamine ratio of 1: 5;

[0010] 所述的芳香二胺为4,4'_二氨基二苯醚、3,4'_二氨基二苯醚、二(3-氨基苯氧基) 二苯甲酮或2-(3-氨基苯基)-5-氨基苯并噁唑; [0010] The aromatic diamine is oxydianiline 4,4'_, 3,4'_ diaminodiphenyl ether, bis (3-aminophenoxy) benzophenone, or 2- (3 - aminophenyl) -5-amino-benzoxazole;

[0011] 所述的芳香二酐为3,3,4',4'_联苯四羧酸二酐、3,3,4',4'-二苯醚四羧酸二酐或3,3,4',4'_二砜基四羧酸二酐; [0011] The aromatic dianhydride is 3,3,4 ', 4'_-biphenyl tetracarboxylic dianhydride, 3,3,4', 4'-diphenyl ether tetracarboxylic dianhydride or 3,3 , 4 ', disulfone group 4'_ tetracarboxylic dianhydride;

[0012] 所述的叔胺为三乙基胺、三烷基叔胺和十二烷基二甲基叔胺中的一种或其中几种的混合物; [0012] The tertiary amine is triethyl amine, or a mixture of several of trialkyl tertiary amine and dodecyl dimethyl amine in;

[0013] 所述的高沸点极性溶剂为N,N-二甲基乙酰胺、N,N-二甲基甲酰胺和N-甲基吡咯烷酮中的一种或其中几种的混合物; [0013] The high-boiling polar solvent is N, N- dimethylacetamide, N, N- dimethylformamide one kind and N- methylpyrrolidinone or a mixture of several of;

[0014] ②、在搅拌条件下,将聚酰胺酸胺盐置于水热反应釜中,并加入铁盐、聚乙二醇和乙二醇溶剂,反应5h~10h,然后将水热反应釜升温至温度为190°C~210°C,并在温度为190 °C~210°C下保温3h~7h,再将水热反应釜自然冷却至室温,得到粗产物,采用外强磁铁将粗产物分离水洗3次~5次,并在温度为80 °C~120 °C下烘干,得到高磁响应聚酰亚胺/Fe3〇4 复合磁性纳米粒子; [0014] ②, under stirring, an amine salt of polyamic acid was placed in a hydrothermal reaction vessel, and adding iron, polyethylene glycol and ethylene glycol solvents, reaction 5h ~ 10h, and then heating the hydrothermal reaction vessel to a temperature of 190 ° C ~ 210 ° C, and at a temperature of 190 ° C ~ 210 ° C heat at 3h ~ 7h, and then a hydrothermal reaction vessel cool to room temperature, a crude product was obtained, using a strong magnet exterior and the crude product separating water 3 to 5 times, and dried at a temperature of 80 ° C ~ 120 ° C under high magnetically responsive polyimide / Fe3〇4 composite magnetic nanoparticles;

[0015] 所述的聚酰胺酸胺盐与铁盐的质量比为10:(1~50);所述的聚酰胺酸胺盐与聚乙二醇的质量比为10: (〇. 1~3.0);所述的聚酰胺酸胺盐与乙二醇的质量比为10: (80~300); [0015] The mass of the iron salts and amine salts of polyamic acid ratio of 10: (1 to 50); mass ratio of said amine salt of polyamic acid with polyethylene glycol is 10: (~ 1 billion. 3.0); mass of the amine salt of polyamic acid with ethylene glycol is 10: (80 to 300);

[0016] 所述的铁盐为六水合三氯化铁、四水合氯化亚铁和四水合硫酸亚铁中的一种或其中几种的混合物; [0016] The ferric salt is ferric chloride hexahydrate, or a mixture of several of ferrous chloride tetrahydrate and ferrous sulfate tetrahydrate;

[0017] 所述的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子中聚酰亚胺的结构通式为: [0017] In response to the high magnetic structure of Formula polyimide polyimide / Fe3〇4 composite magnetic nanoparticles:

Figure CN104829837BD00071

所述的η为9~49; Η is the 9 to 49;

Figure CN104829837BD00081

[0019] 或所述的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子中聚酰亚胺的结构通式为: [0019] High or magnetically responsive polyimide polyimide / Fe3〇4 magnetic composite nanoparticles according to the structural formula:

Figure CN104829837BD00082

所述的η为9~49;所述的R2为 Η is the 9 to 49; said R2 is

Figure CN104829837BD00083

[0020] 二、将石棉布包裹的三颈瓶置于高频感应加热设备的加热环形线圈中,然后向三颈瓶内通氮气气氛,再向三颈瓶内加入可溶性聚酰胺酸溶液、带水剂和高磁响应聚酰亚胺/ Fe3〇4复合磁性纳米粒子,在搅拌速度为25rpm~lOOrpm,搅拌lh~5h,得到混合溶液; [0020] Second, the asbestos cloth wrapped three-necked flask placed in a heating loop coil high frequency induction heating device, a three-necked flask and nitrogen atmosphere, a three-necked flask was added again a soluble polyamic acid solution with agent and high magnetic response polyimide / Fe3〇4 composite magnetic nanoparticles, the stirring speed of 25rpm ~ lOOrpm, stirred for lh ~ 5h, to obtain a mixed solution;

[0021 ]所述的可溶性聚酰胺酸溶液和带水剂的质量比为10: (2~4.8);所述的高磁响应聚酰亚胺/Fe304复合磁性纳米粒子与可溶性聚酰胺酸溶液的质量比为(0.1~0.5): 1; [0021] The polyamic acid solution of the soluble agent and the mass ratio of 10 with: (2 to 4.8); high magnetic response of the polyimide / Fe304 magnetic composite nanoparticles soluble polyamic acid solution mass ratio of (0.1 to 0.5): 1;

[0022]三、在交变磁场的频率为80kHz~200kHz的条件下,调节高频感应加热设备的输出功率使得混合溶液升温至120 °C~145 °C,并在温度为120 °C~145 °C下回流反应0.5h~ 1.5h,排出带水剂和水,再调节高频感应加热设备的输出功率使得混合溶液升温至146 °C~ 164 °C,升温至146 °C~164 °C后停止反应,得到反应后的溶液; [0022] Third, the frequency of the alternating magnetic field under the condition of 80kHz ~ 200kHz adjusted high frequency induction heating device output power so that the mixed solution was heated to 120 ° C ~ 145 ° C, and at a temperature of 120 ° C ~ 145 under ° C reflow reaction 0.5h ~ 1.5h, with the discharge agent and water, and then adjusting the high frequency induction heating device output power so that the mixed solution was heated to 146 ° C ~ 164 ° C, warmed to 146 ° C ~ 164 ° C after stopping the reaction, the resulting solution after the reaction;

[0023]四、关闭高频感应加热设备,将反应后的溶液降至室温,利用永磁铁将三颈瓶中高磁响应聚酰亚胺/Fe304复合磁性纳米粒子移出,得到移除磁性纳米粒子后的溶液,再将移除磁性纳米粒子后的溶液滴加到蒸馏水中,沉析lh~4h,过滤,沉淀水洗,最后在温度为130°C ~140 °C下烘干,得到可溶性聚酰亚胺; [0023] Fourth, high frequency induction heating device off, the reaction solution was cooled to room temperature, using a permanent magnet three-necked flask high magnetically responsive polyimide / Fe304 magnetic composite nanoparticles was removed, to give after removal of the magnetic nanoparticles solution, and then removing the solution of magnetic nanoparticles dropwise to distilled water, precipitation lh ~ 4h, filtered and the precipitate washed with water, and finally at a temperature of 130 ° C ~ dried at 140 ° C, to obtain a soluble polyimide amine;

[0024]所述的可溶性聚酰亚胺结构通式为: [0024] The soluble polyimide of the structural formula:

Figure CN104829837BD00091

所述的η为3~49; The η 3 to 49;

Figure CN104829837BD00092

[0026] 所述的&为: [0026] & claim is:

[0027] 所述的R2为: [0027], wherein R2 is:

[0028]本发明的有益效果是:本发明采用高磁响应聚酰亚胺/Fe304复合磁性纳米粒子在交变外磁场下的磁热效应感应加热制备聚酰亚胺。 [0028] Advantageous effects of the present invention are: the present invention uses a high magneto-caloric effect sensor magnetically responsive polyimide / Fe304 composite magnetic nanoparticles under the alternating magnetic field producing a polyimide heating. 通过在聚酰胺酸溶液中内置聚酰亚胺包覆磁性纳米粒子,实现外部加热源不具备的内部快速热响应效果。 Coated magnetic nanoparticles through the polyamic acid solution built polyimide, it does not have an external heating source to achieve a rapid thermal response to an internal effect. 此外,整个过程涉及到升温加热-恒温带水-升温加热等多步过程,仅调节输出功率只能提高溶液现有温度,但是叠加依靠高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子,意外的快速得到响应一致、稳定保持并且较高的内外层温度。 Furthermore, the whole process involves heating the heating - temperature with water - heating heating multi-step process, only the adjusted solution can only improve the output power of the conventional temperature, but rely on high magnetically responsive superposed polyimide / Fe3〇4 composite magnetic nanoparticles , unexpectedly quick response to get a consistent, high stability and maintaining the temperature of the inner and outer layers.

[0029]本发明采用高磁响应聚酰亚胺/Fe304复合磁性纳米粒子作为相应热源,避免了磁性纳米粒子的高表面能和偶磁矩间作用力,导致的聚酰胺酸溶液中的磁性颗粒团聚现象, 难以在体系中形成单分散的纳米粒子,同时又会阻碍聚酰胺酸的脱水缩合反应的问题。 [0029] The present invention employ a high response polyimide / Fe304 nanoparticles as respective composite magnetic source, the magnetic particles is avoided polyamic acid solution having a high surface energy and magnetic nanoparticles coupling between magnetic moment force resulting in agglomeration is difficult to form monodisperse nanoparticles in the system, while dehydrating the polyamic acid will hinder condensation problems. 采用有机物包覆的磁性纳米粒子,依靠聚合物间的排斥力与粒子间的吸引力的平衡,实现超顺磁磁性纳米粒子的单分散,进一步利用粒子表面的聚酰亚胺和溶液中的聚酰胺酸之间相似的主链结构带来的分子间作用力,达到热源在聚酰胺酸溶液中的分散均一性,避免了不均匀分散在高温热亚胺化的温度不稳定,提高加热效果的稳定性,同时相比于其他有机物包覆磁性粒子,原位制备具有更为良好的磁响应效果,从而快速提高反应温度。 Using magnetic nanoparticles coated with organic material, relying attractive balance between repulsive forces between the particles and the polymer, to achieve monodisperse superparamagnetic magnetic nanoparticles, further polyimide particles with a surface and a solution of poly intermolecular brought similar backbone structure between the biasing force of the amic acid to achieve uniformity of dispersion of heat in the polyamic acid solution, to avoid the non-uniformly dispersed in the high-temperature thermal imidization temperature instability, improving heating effect stability, compared to other organics while the coated magnetic particles prepared in situ has a more favorable effect magnetic response, thereby rapidly increasing the reaction temperature.

[0030] 本发明适用于在热亚胺化过程,所形成的聚酰亚胺在极性溶剂中不析出的聚合结构类型,确保可以在聚合物制备后用永磁铁将溶液中磁性纳米粒子移取,从而不影响基体树脂性能。 [0030] The present invention is applicable to a thermal imidization process, the type of polymeric structure formed of polyimide in a polar solvent is not precipitated, may be used to ensure that the permanent magnet magnetic nanoparticles in the solution after the preparation of the polymer shift taken so as not to affect the properties of the matrix resin. 此方法可以极大提高亚胺化反应效率,缩短反应时间(从常规热亚胺化5-15小时缩短到0.5~1.5小时),同时获得性能稳定且良好的可溶性聚酰亚胺(从拉伸强度和弯曲强度、玻璃化转变温度、热分解温度数据),从而满足航空航天和微电子等领域对易于制备且性能稳定聚酰亚胺需求。 This method can greatly improve the efficiency of the imidization reaction, shortening the reaction time (shortened from the conventional 5-15 hours to thermal imidization 0.5 to 1.5 hours), while obtaining stable and well soluble polyimide (from the stretched strength and bending strength, glass transition temperature, thermal decomposition temperature data), to meet aerospace fields of microelectronics and ease of preparation and stable performance polyimide demand.

[0031] 本发明用于一种采用磁性粒子感应加热制备可溶性聚酰亚胺的方法。 [0031] The present invention is applied to a soluble polyimide prepared by a method of heating an induction magnetic particles.

附图说明 BRIEF DESCRIPTION

[0032]图1为实施例一制备的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子的扫描电子显微镜图; [0032] FIG. 1 is a diagram of a high magnetic response Preparation polyimide / Fe3〇4 a scanning electron microscope view of a composite magnetic nanoparticles;

[0033]图2为实施例一制备的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子的X射线衍射曲线图; [0033] FIG. 2 is a diagram of a high magnetic response Preparation polyimide / Fe3〇4 X-ray diffraction graph of the composite magnetic nanoparticles;

[0034]图3为实施例一制备的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子的红外曲线图; [0035]图4为实施例一制备的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子的振动样品磁强计曲线图; [0034] FIG. 3 is a diagram of a highly magnetically responsive prepared polyimide composite graph embodiment infrared magnetic nanoparticles / Fe3〇4; [0035] FIG. 4 is a diagram of a high magnetically responsive Preparation of Polyimide / vibrating sample magnetometer graph Fe3〇4 composite magnetic nanoparticles;

[0036] 图5为本发明采用磁性粒子感应加热制备可溶性聚酰亚胺的加热结构示意图;1为冷凝管,2为带水器,3为温度计,4为搅拌桨,5为氮气通口,6为环形线圈,7为高磁响应聚酰亚胺/Fe 3〇4复合磁性纳米粒子,8为聚酰胺酸溶液,9为高频感应加热设备; [0036] FIG. 5 is a schematic structure of the magnetic particles is heated induction heating prepared using the soluble polyimide of the present invention; 1 is a condenser, with a water heater 2, a thermometer 3, 4 is a stirring blade, a nitrogen port 5, an annular coil 6, 7 to a high magnetically responsive polyimide / Fe composite magnetic nanoparticles 3〇4, 8 polyamic acid solution, high frequency induction heating apparatus 9;

[0037] 图6为红外曲线图;1为实施例一制备的可溶性聚酰亚胺;2为实施例二制备的可溶性聚酰亚胺;3为实施例三制备的可溶性聚酰亚胺;4为实施例四制备的可溶性聚酰亚胺;5 为实施例五制备的可溶性聚酰亚胺;6为对比实验一制备的可溶性聚酰亚胺;7为对比实验二制备的可溶性聚酰亚胺。 [0037] FIG. 6 is a graph illustrating an infrared; 1 is a soluble polyimide prepared according to Example a; 2 a soluble polyimide prepared in Example II embodiment; 3 is a soluble polyimide was prepared according to a third embodiment; 4 is a soluble polyimide prepared in Example fourth embodiment; 5 is a soluble polyimide prepared in Example fifth embodiment; 6 is a soluble polyimide prepared by a comparative experiment; two for Comparative experiment 7 preparation of a soluble polyimide .

具体实施方式 Detailed ways

具体实施方式[0038] 一:结合图5具体说明本实施方式,本实施方式所述的一种采用磁性粒子感应加热制备可溶性聚酰亚胺的方法是按以下步骤进行: DETAILED DESCRIPTION [0038] a: 5 in conjunction with FIG specifically described embodiment according to the present embodiment, a soluble polyimide was prepared using the magnetic particle method of the present embodiment, the induction heating is carried out by the following steps:

[0039] 一、①、在氮气气氛、室温及搅拌条件下,向三颈瓶中加入高沸点极性溶剂和芳香二胺,反应〇.5h~lh,再向三颈瓶中加入芳香二酐,反应lh~5h,然后向三颈瓶中加入叔胺, 反应2h~3h,停止搅拌,得到反应液,在搅拌条件下,将反应液以2mL/s~10mL/s的速度滴入丙酮中,滴加完成后,继续搅拌lh~6h,然后静置3天~10天,得到含丝状物的静置液,将含丝状物的静置液中丝状物取出,在温度为20°C~30°C的真空烘箱中将丝状物烘干,得到聚酰胺酸胺盐; [0039] First, ①, under nitrogen atmosphere, and stirred at room temperature conditions, high-boiling polar solvent and an aromatic diamine were added to a three-necked flask, the reaction 〇.5h ~ lh, three-necked flask was added again aromatic dianhydride the reaction lh ~ 5h, three-necked flask was then added to the tertiary amine, the reaction 2h ~ 3h, the stirring was stopped to obtain a reaction solution, under stirring, the reaction solution was 2mL / s ~ 10mL / s speed was added dropwise acetone after completion of the dropwise addition, stirring was continued for lh ~ 6h, then allowed to stand for 3 days to 10 days, allowed to stand to give a solution containing the filament, the filament was allowed to stand in the solution containing the filament was taken out at a temperature of 20 ° C ~ 30 ° C vacuum oven drying the filaments, to give a polyamic acid salt;

[0040] 所述的芳香二胺与芳香二胺酐的摩尔比为1:(0.90~0.95);所述的芳香二胺与叔胺的摩尔比为1: (1.90~2.10);所述的芳香二酐和芳香二胺的总质量与高沸点极性溶剂的质量比为1:5; [0040] The molar ratio of aromatic diamine and an aromatic diamine anhydride is 1: (0.90 to 0.95); the molar ratio of aromatic diamine and a tertiary amine is 1: (1.90 to 2.10); the mass of the total mass of high-boiling polar solvent and an aromatic dianhydride and an aromatic diamine ratio of 1: 5;

[0041] 所述的芳香二胺为4,4'_二氨基二苯醚、3,4'_二氨基二苯醚、二(3-氨基苯氧基) 二苯甲酮或2-(3-氨基苯基)-5-氨基苯并噁唑; [0041] The aromatic diamine is oxydianiline 4,4'_, 3,4'_ diaminodiphenyl ether, bis (3-aminophenoxy) benzophenone, or 2- (3 - aminophenyl) -5-amino-benzoxazole;

[0042] 所述的芳香二酐为3,3,4',4'_联苯四羧酸二酐、3,3,4',4'_二苯醚四羧酸二酐或3,3,4',4'_二砜基四羧酸二酐; [0042] The aromatic dianhydride is 3,3,4 ', 4'_-biphenyl tetracarboxylic dianhydride, 3,3,4', 4'_ diphenyl ether tetracarboxylic dianhydride or 3,3 , 4 ', disulfone group 4'_ tetracarboxylic dianhydride;

[0043]所述的叔胺为三乙基胺、三烷基叔胺和十二烷基二甲基叔胺中的一种或其中几种的混合物; [0043] The tertiary amine is triethyl amine, or a mixture of several of trialkyl tertiary amine and dodecyl dimethyl amine in;

[0044] 所述的高沸点极性溶剂为N,N_二甲基乙酰胺、N,N_二甲基甲酰胺和N-甲基吡咯烷酮中的一种或其中几种的混合物; [0044] The high-boiling polar solvent is N, N_-dimethylacetamide, N, N_ one kind of dimethylformamide and N- methylpyrrolidinone or a mixture of several of;

[0045]②、在搅拌条件下,将聚酰胺酸胺盐置于水热反应釜中,并加入铁盐、聚乙二醇和乙二醇溶剂,反应5h~10h,然后将水热反应釜升温至温度为190°C~210°C,并在温度为190 °C~210°C下保温3h~7h,再将水热反应釜自然冷却至室温,得到粗产物,采用外强磁铁将粗产物分离水洗3次~5次,并在温度为80 °C~120 °C下烘干,得到高磁响应聚酰亚胺/Fe3〇4 复合磁性纳米粒子; [0045] ②, under stirring, an amine salt of polyamic acid was placed in a hydrothermal reaction vessel, and adding iron, polyethylene glycol and ethylene glycol solvents, reaction 5h ~ 10h, and then heating the hydrothermal reaction vessel to a temperature of 190 ° C ~ 210 ° C, and at a temperature of 190 ° C ~ 210 ° C heat at 3h ~ 7h, and then a hydrothermal reaction vessel cool to room temperature, a crude product was obtained, using a strong magnet exterior and the crude product separating water 3 to 5 times, and dried at a temperature of 80 ° C ~ 120 ° C under high magnetically responsive polyimide / Fe3〇4 composite magnetic nanoparticles;

[0046]所述的聚酰胺酸胺盐与铁盐的质量比为10:(1~50);所述的聚酰胺酸胺盐与聚乙二醇的质量比为10: (〇. 1~3.0);所述的聚酰胺酸胺盐与乙二醇的质量比为10: (80~300); [0047]所述的铁盐为六水合三氯化铁、四水合氯化亚铁和四水合硫酸亚铁中的一种或其中几种的混合物; [0046] The mass of the iron salts and amine salts of polyamic acid ratio of 10: (1 to 50); mass ratio of said amine salt of polyamic acid with polyethylene glycol is 10: (~ 1 billion. 3.0); mass ratio of said amine salt of polyamic acid with ethylene glycol is 10: (80 to 300); said iron salt [0047] the ferric chloride hexahydrate, ferrous chloride tetrahydrate, and one or more of a mixture of ferrous sulfate tetrahydrate;

[0048] 所述的高磁响应聚酰亚胺/Fe304复合磁性纳米粒子中聚酰亚胺的结构通式为: [0048] In response to the high magnetic structure of Formula polyimide polyimide / Fe304 magnetic composite nanoparticles:

Figure CN104829837BD00111

所述的η为9~49; Η is the 9 to 49;

[0049] 所述的R i为-0 -或 [0049], wherein R i -0 -, or

Figure CN104829837BD00112

、所述的R 2为 Said R 2 is

Figure CN104829837BD00113

Figure CN104829837BD00114

[0050] 或所述的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子中聚酰亚胺的结构通式为: [0050] High or magnetically responsive polyimide polyimide / Fe3〇4 magnetic composite nanoparticles according to the structural formula:

Figure CN104829837BD00115

所述的η为9~49;所述的R2为 Η is the 9 to 49; said R2 is

Figure CN104829837BD00116

[0051 ]二、将石棉布包裹的三颈瓶置于高频感应加热设备的加热环形线圈中,然后向三颈瓶内通氮气气氛,再向三颈瓶内加入可溶性聚酰胺酸溶液、带水剂和高磁响应聚酰亚胺/ Fe3〇4复合磁性纳米粒子,在搅拌速度为25rpm~lOOrpm,搅拌lh~5h,得到混合溶液; [0051] Second, the asbestos cloth wrapped three-necked flask placed in a heating loop coil high frequency induction heating device, a three-necked flask and nitrogen atmosphere, a three-necked flask was added again a soluble polyamic acid solution with agent and high magnetic response polyimide / Fe3〇4 composite magnetic nanoparticles, the stirring speed of 25rpm ~ lOOrpm, stirred for lh ~ 5h, to obtain a mixed solution;

[0052]所述的可溶性聚酰胺酸溶液和带水剂的质量比为10: (2~4.8);所述的高磁响应聚酰亚胺/Fe304复合磁性纳米粒子与可溶性聚酰胺酸溶液的质量比为(0.1~0.5): 1; [0052] The polyamic acid solution of the soluble agent and the mass ratio of 10 with: (2 to 4.8); high magnetic response of the polyimide / Fe304 magnetic composite nanoparticles soluble polyamic acid solution mass ratio of (0.1 to 0.5): 1;

[0053]三、在交变磁场的频率为80kHz~200kHz的条件下,调节高频感应加热设备的输出功率使得混合溶液升温至120 °C~145 °C,并在温度为120 °C~145 °C下回流反应0.5h~ 1.5h,排出带水剂和水,再调节高频感应加热设备的输出功率使得混合溶液升温至146 °C~ 164 °C,升温至146 °C~164 °C后停止反应,得到反应后的溶液; [0053] Third, the frequency of the alternating magnetic field under the condition of 80kHz ~ 200kHz adjusted high frequency induction heating device output power so that the mixed solution was heated to 120 ° C ~ 145 ° C, and at a temperature of 120 ° C ~ 145 under ° C reflow reaction 0.5h ~ 1.5h, with the discharge agent and water, and then adjusting the high frequency induction heating device output power so that the mixed solution was heated to 146 ° C ~ 164 ° C, warmed to 146 ° C ~ 164 ° C after stopping the reaction, the resulting solution after the reaction;

[0054]四、关闭高频感应加热设备,将反应后的溶液降至室温,利用永磁铁将三颈瓶中高磁响应聚酰亚胺/Fe304复合磁性纳米粒子移出,得到移除磁性纳米粒子后的溶液,再将移除磁性纳米粒子后的溶液滴加到蒸馏水中,沉析lh~4h,过滤,沉淀水洗,最后在温度为130°C ~140 °C下烘干,得到可溶性聚酰亚胺; [0054] Fourth, high frequency induction heating device off, the reaction solution was cooled to room temperature, using a permanent magnet three-necked flask high magnetically responsive polyimide / Fe304 magnetic composite nanoparticles was removed, to give after removal of the magnetic nanoparticles solution, and then removing the solution of magnetic nanoparticles dropwise to distilled water, precipitation lh ~ 4h, filtered and the precipitate washed with water, and finally at a temperature of 130 ° C ~ dried at 140 ° C, to obtain a soluble polyimide amine;

[0055]所述的可溶性聚酰亚胺结构通式为: [0055] The soluble polyimide of the structural formula:

[0056] [0056]

Figure CN104829837BD00121

所述的η为3~49; The η 3 to 49;

Figure CN104829837BD00122

[0057] 所述的办为: [0057] according to do is:

[0058] 所述的R2为 [0058], wherein R2 is

[0059] 图5为本发明采用磁性粒子感应加热制备可溶性聚酰亚胺的加热结构示意图;1为冷凝管,2为带水器,3为温度计,4为搅拌桨,5为氮气通口,6为环形线圈,7为高磁响应聚酰亚胺/Fe 304复合磁性纳米粒子,8为聚酰胺酸溶液,9为高频感应加热设备。 [0059] FIG. 5 is a schematic structure of the magnetic particles is heated induction heating prepared using the soluble polyimide of the present invention; 1 is a condenser, with a water heater 2, a thermometer 3, 4 is a stirring blade, a nitrogen port 5, an annular coil 6, 7 to a high magnetically responsive polyimide / Fe 304 composite magnetic nanoparticles, a polyamic acid solution is 8, 9 high frequency induction heating equipment.

[0060] 本实施方式的有益效果是:本发明采用高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子在交变外磁场下的磁热效应感应加热制备聚酰亚胺。 [0060] Advantageous effects of this embodiment are: the present invention uses a high magneto-caloric effect sensor magnetically responsive polyimide / Fe3〇4 composite magnetic nanoparticles under the alternating magnetic field producing a polyimide heating. 通过在聚酰胺酸溶液中内置聚酰亚胺包覆磁性纳米粒子,实现外部加热源不具备的内部快速热响应效果。 Coated magnetic nanoparticles through the polyamic acid solution built polyimide, it does not have an external heating source to achieve a rapid thermal response to an internal effect. 此外,整个过程涉及到升温加热-恒温带水-升温加热等多步过程,仅调节输出功率只能提高溶液现有温度,但是叠加依靠高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子,意外的快速得到响应一致、稳定保持并且较高的内外层温度。 Furthermore, the whole process involves heating the heating - temperature with water - heating heating multi-step process, only the adjusted solution can only improve the output power of the conventional temperature, but rely on high magnetically responsive superposed polyimide / Fe3〇4 composite magnetic nanoparticles , unexpectedly quick response to get a consistent, high stability and maintaining the temperature of the inner and outer layers.

[0061] 本发明采用高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子作为相应热源,避免了磁性纳米粒子的高表面能和偶磁矩间作用力,导致的聚酰胺酸溶液中的磁性颗粒团聚现象, 难以在体系中形成单分散的纳米粒子,同时又会阻碍聚酰胺酸的脱水缩合反应的问题。 [0061] The present invention employ a high response polyimide / Fe3〇4 composite magnetic nanoparticles as respective sources of heat and the high surface energy and magnetic nanoparticles coupling between magnetic moment force, resulting in a polyamic acid solution in Aggregation of magnetic particles, it is difficult to form monodisperse nanoparticles in the system, while dehydrating the polyamic acid will hinder condensation problems. 采用有机物包覆的磁性纳米粒子,依靠聚合物间的排斥力与粒子间的吸引力的平衡,实现超顺磁磁性纳米粒子的单分散,进一步利用粒子表面的聚酰亚胺和溶液中的聚酰胺酸之间相似的主链结构带来的分子间作用力,达到热源在聚酰胺酸溶液中的分散均一性,避免了不均匀分散在高温热亚胺化的温度不稳定,提高加热效果的稳定性,同时相比于其他有机物包覆磁性粒子,原位制备具有更为良好的磁响应效果,从而快速提高反应温度。 Using magnetic nanoparticles coated with organic material, relying attractive balance between repulsive forces between the particles and the polymer, to achieve monodisperse superparamagnetic magnetic nanoparticles, further polyimide particles with a surface and a solution of poly intermolecular brought similar backbone structure between the biasing force of the amic acid to achieve uniformity of dispersion of heat in the polyamic acid solution, to avoid the non-uniformly dispersed in the high-temperature thermal imidization temperature instability, improving heating effect stability, compared to other organics while the coated magnetic particles prepared in situ has a more favorable effect magnetic response, thereby rapidly increasing the reaction temperature.

[0062] 本发明适用于在热亚胺化过程,所形成的聚酰亚胺在极性溶剂中不析出的聚合结构类型,确保可以在聚合物制备后用永磁铁将溶液中磁性纳米粒子移取,从而不影响基体树脂性能。 [0062] The present invention is applicable to a thermal imidization process, the type of polymeric structure formed of polyimide in a polar solvent is not precipitated, may be used to ensure that the permanent magnet magnetic nanoparticles in the solution after the preparation of the polymer shift taken so as not to affect the properties of the matrix resin. 此方法可以极大提高亚胺化反应效率,缩短反应时间(从常规热亚胺化5-15小时缩短到0.5~1.5小时),同时获得性能稳定且良好的可溶性聚酰亚胺(从拉伸强度和弯曲强度、玻璃化转变温度、热分解温度数据),从而满足航空航天和微电子等领域对易于制备且性能稳定聚酰亚胺需求。 This method can greatly improve the efficiency of the imidization reaction, shortening the reaction time (shortened from the conventional 5-15 hours to thermal imidization 0.5 to 1.5 hours), while obtaining stable and well soluble polyimide (from the stretched strength and bending strength, glass transition temperature, thermal decomposition temperature data), to meet aerospace fields of microelectronics and ease of preparation and stable performance polyimide demand.

具体实施方式[0063] 二:本实施方式与一不同的是:步骤四中所述的永磁铁为磁感应强度为〇. 1特斯拉~1.5特斯拉。 DETAILED DESCRIPTION [0063] II: with an embodiment of the present embodiment is different: the procedure four permanent magnets magnetic induction square 1 Tesla to 1.5 Tesla. 其它与二相同。 With two otherwise identical.

[0064] [0064]

具体实施方式三:本实施方式与具体实施方式一或二之一不同的是:步骤二中所述的带水剂为甲苯和二甲苯中的一种或其中两种的混合物。 DETAILED DESCRIPTION III: or with one embodiment of the present embodiment DETAILED DESCRIPTION twelve different: two with the procedure in which the agent is a mixture of toluene and xylene, or in a two. 其它与具体实施方式一或二相同。 Other specific embodiments of the same one or two.

[0065] [0065]

具体实施方式四:本实施方式与具体实施方式一至三之一不同的是:步骤一中所述的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子的粒径为50nm~3um。 DETAILED DESCRIPTION four: one of one to three different embodiments according to the present embodiment is a specific embodiment: in step a magnetically responsive particle diameter of the high polyimide / Fe3〇4 composite magnetic nanoparticles of 50nm ~ 3um. 其它与具体实施方式一至三相同。 DETAILED other one to three of the same embodiment.

[0066] 具体实施方式五:本实施方式与具体实施方式一至四之一不同的是:步骤二中所述的可溶性聚酰胺酸溶液中可溶性聚酰胺酸的结构通式为: [0066] DETAILED DESCRIPTION five: one to four different embodiments of one embodiment with the description are: a soluble polyamic acid solution in two steps according to the general structure of a soluble polyamic acid:

Figure CN104829837BD00131

[0068] 所述的办为: -所述的η为3~49; Office according [0068] to: - the η 3 to 49;

Figure CN104829837BD00132

[0069] 所述的R2为: [0069], wherein R2 is:

Figure CN104829837BD00133

Figure CN104829837BD00134

其它与具体实施方式一至四相同。 The same as the other one to four specific embodiments.

具体实施方式[0070] 六:本实施方式与一至五之一不同的是:步骤二中所述的可溶性聚酰胺酸溶液具体是按以下步骤制备的: DETAILED DESCRIPTION [0070] VI: with one embodiment of the present embodiment is different from one to five: a soluble polyamic acid solution in the two specific steps are prepared by the following steps:

[0071] 在氮气气氛下,室温下将芳香二胺和强极性溶剂置于三颈瓶中,搅拌溶解lh~3h, 然后以lmg/s~10mg/s的滴加速度向三颈瓶中加入芳香族四酸二酐,得到反应体系,将反应体系继续搅拌并溶解lh~5h,得到可溶性聚酰胺酸溶液; [0071] Under a nitrogen atmosphere, at room temperature, strongly polar solvents and aromatic diamines placed in a three-necked flask, and dissolved with stirring lh ~ 3h, then dropping rate lmg / s ~ 10mg / s to a three-necked flask were added aromatic tetracarboxylic dianhydride, to obtain a reaction system, and the stirring was continued to dissolve lh ~ 5h, to give a soluble polyamic acid solution of the reaction system;

[0072] 所述的芳香二胺与芳香族四酸二酐的摩尔比为1:(0.75~0.98);所述的芳香二胺与芳香族四酸二酐的质量总和占反应体系质量的10%~15% ; [0072] The molar ratio of aromatic diamine and an aromatic tetracarboxylic acid anhydride is 1: (0.75 to 0.98); the total mass of the aromatic diamine and an aromatic dianhydride, the reaction system accounts for 10 mass % ~ 15%;

[0073] 所述强极性溶剂为N,N_二甲基甲酰胺和N,N_二甲基乙酰胺中的一种或两种的混合物; [0073] The strongly polar solvents are N, N_ mixture of dimethylformamide and N, N_ dimethylacetamide one or two;

[0074]所述的芳香二胺为2,2'_双(三氟甲基)-4,4_二氨基联苯、1,3_双(3-氨基苯氧基) 苯、1,3-双(4-氨基苯氧基)苯、3,3 二氨基二苯酿或3,3 二氨基二苯甲酮; [0074] The aromatic diamine is 2,2'_ bis (trifluoromethyl) diaminodiphenyl -4,4_, 1,3_-bis (3-aminophenoxy) benzene, 1,3 - bis (4-aminophenoxy) benzene, 3,3-diamino-3,3-diamino diphenyl stuffed or benzophenone;

[0075]所述的芳香族四酸二酐为3,3',4,4'_二苯酮四酸二酐、3,3,4',4'_二苯醚四羧酸二酐、双酸A型二醚二酐或4,4'_(六氟异丙烯)二酞酸酐。 Aromatic tetracarboxylic dianhydride [0075] the 3,3 ', 4,4'_ benzophenone tetracarboxylic dianhydride, 3,3,4', 4'_ diphenyl ether tetracarboxylic dianhydride, acid bis A diglycidyl ether dianhydride or 4,4 '_ (hexafluoroisopropylidene) diphthalic anhydride. 其它与具体实施方式一至五相同。 DETAILED other one to five same embodiment. [0076]采用以下实施例验证本发明的有益效果:结合图5具体说明实施例一至五。 [0076] The following example demonstrates the advantages of the present invention: DETAILED conjunction with FIG. 5 illustrates an embodiment of one to five.

[0077] 实施例一: [0077] Example a:

[0078]本实施例一种采用磁性粒子感应加热制备可溶性聚酰亚胺的方法,具体是按以下步骤进行的: [0078] A method of the present embodiment, the induction heating of the magnetic particles prepared using a soluble polyimide, in particular, perform the following steps:

[0079] 一、①、在氮气气氛、室温及搅拌条件下,向三颈瓶中加入101.8g N,N_二甲基乙酰胺和10.0(^(0.05111〇1)3,4'-二氨基二苯醚,反应111,再向三颈瓶中加入10.368(0.0475111〇1) 3,3,4',4'_联苯四羧酸二酐,反应3h,然后向三颈瓶中加入10.10g三乙基胺,反应3h,停止搅拌,得到反应液,在搅拌条件下,将反应液以5mL/s的速度滴入丙酮中,滴加完成后,继续搅拌2h,然后静置10天,得到含丝状物的静置,将含丝状物的静置中丝状物取出,在温度为25°C的真空烘箱中将丝状物烘干,得到聚酰胺酸胺盐; [0079] First, ①, under nitrogen atmosphere, at room temperature and with stirring, 101.8g N was added to the three-necked flask, of N_ dimethylacetamide and 10.0 (^ (0.05111〇1) 3,4'-diaminodiphenyl diphenyl ether, reaction 111, three-necked flask was added 10.368 again (0.0475111〇1) 3,3,4 ', 4'_-biphenyl tetracarboxylic dianhydride, the reaction 3h, then the three-necked flask was added 10.10g triethylamine, the reaction 3h, stirring was stopped to obtain a reaction solution, under stirring, the reaction mixture at a speed of 5mL / s of acetone was added dropwise. after completion of the dropwise addition, stirring was continued for 2h, then allowed to stand for 10 days to give the left-containing filaments, the filaments containing the left of filament removed, dried at a temperature of 25 ° C filament vacuum oven, to give a polyamic acid salt;

[0080]②、在搅拌条件下,将2g聚酰胺酸胺盐置于100mL水热反应釜中,并加入10g六水合三氯化铁、〇.5g聚乙二醇和40g乙二醇溶剂,反应10h,然后将水热反应釜升温至温度为205 °C,并在温度为205下保温6h,再将水热反应釜自然冷却至室温,得到粗产物,采用外强磁铁将粗产物分离水洗3次,并在温度为120°C下烘干,得到高磁响应聚酰亚胺/Fe 3〇4复合磁性纳米粒子; [0080] ②, under stirring, 2g polyamic acid amine salt of a 100mL hydrothermal reaction kettle and ferric chloride hexahydrate was added 10g, 40g ethylene glycol and polyethylene glycol 〇.5g solvent, reaction 10H, and then the hydrothermal reaction vessel warmed to a temperature of 205 ° C, and incubated at a temperature of 205 6h, and then a hydrothermal reaction vessel cool to room temperature, a crude product was obtained, using a strong outer magnets the crude product was isolated washed with water 3 times, and at a temperature of 120 ° C and dried at high magnetically responsive polyimide / Fe 3〇4 composite magnetic nanoparticles;

[0081 ]二、将石棉布包裹的三颈瓶置于高频感应加热设备的加热环形线圈中,然后向三颈瓶内通氮气气氛,再向三颈瓶内加入50g可溶性聚酰胺酸溶液、15g甲苯和5g高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子,在搅拌速度为lOOrprn,搅拌lh,得到混合溶液; [0081] Second, the asbestos cloth wrapped three-necked flask placed in a heating loop coil high frequency induction heating device, a three-necked flask and nitrogen atmosphere, a three-necked flask were added 50g again a soluble polyamic acid solution, 15g of toluene and 5g of high magnetic response polyimide / Fe3〇4 composite magnetic nanoparticles, the stirring speed lOOrprn, LH stirring, to give a mixed solution;

[0082]三、在交变磁场的频率为100kHz的条件下,调节高频感应加热设备的输出功率使得混合溶液升温至125°C,并在温度为125°C下回流反应0.5h,排出甲苯和水,再调节高频感应加热设备的输出功率使得混合溶液升温至149°C,升温至149°C后停止反应,得到反应后的溶液; [0082] Third, the frequency of the alternating magnetic field under the conditions of 100kHz, adjusting high frequency induction heating device output power so that the mixed solution was heated to 125 ° C, and the reaction was refluxed for 0.5h at a temperature of 125 ° C, the discharge toluene and water, and then adjusting the high frequency induction heating device output power so that the mixed solution was heated to 149 ° C, the reaction was stopped after the temperature was raised to 149 ° C, the solution obtained after the reaction;

[0083]四、关闭高频感应加热设备,将反应后的溶液降至室温,利用永磁铁将三颈瓶中高磁响应聚酰亚胺/Fe304复合磁性纳米粒子移出,得到移除磁性纳米粒子后的溶液,再将移除磁性纳米粒子后的溶液滴加到蒸馏水中,沉析lh,过滤,沉淀水洗,最后在温度为130°C下烘干,得到可溶性聚酰亚胺。 [0083] Fourth, high frequency induction heating device off, the reaction solution was cooled to room temperature, using a permanent magnet three-necked flask high magnetically responsive polyimide / Fe304 magnetic composite nanoparticles was removed, to give after removal of the magnetic nanoparticles solution, and then removing the solution of magnetic nanoparticles dropwise to distilled water, precipitation LH, filtered, the precipitate washed with water, and finally dried at a temperature of under 130 ° C, to obtain a soluble polyimide.

[0084]本实施例制备的可溶性聚酰亚胺的结构式为: [0084] The soluble polyimide of the formula is prepared in the present embodiment:

Figure CN104829837BD00141

[0085]步骤四中所述的永磁铁为磁感应强度在0.3特斯拉; In four of the [0085] Step permanent magnets magnetic flux density of 0.3 Tesla;

[0086] 步骤一中所述的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子的粒径为lum。 High magnetic response [0086] Step a polyimide in the diameter of the composite magnetic nanoparticles / Fe3〇4 of lum.

[0087]步骤一中所述的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子中聚酰亚胺的结构式为: [0087] Step a high magnetic response in the structural formula of the polyimide polyimide / Fe3〇4 composite magnetic nanoparticles:

Figure CN104829837BD00151

[0089]所述的步骤二中所述的可溶性聚酰胺酸溶液中可溶性聚酰胺酸的结构式为: [0089] a soluble polyamic acid solution according to step two in the structural formula of a soluble polyamic acid:

Figure CN104829837BD00152

[0091 ]所述的可溶性聚酰胺酸溶液具体是按以下步骤制备的: [0091] The soluble polyamic acid solution is prepared by the following specific steps:

[0092] 在氮气气氛下,室温下将2.45g(8.38mmol)l ,3-双(3-氨基苯氧基)苯和45g N,N-二甲基甲酰胺置于三颈瓶中,搅拌溶解3h,然后以1 Omg/s的滴加速度向三颈瓶中加入2.55g (8.22mmol)3,3,4 ',4' -二苯醚四羧酸二酐,得到反应体系,将反应体系继续搅拌并溶解lh ~5h,得到可溶性聚酰胺酸溶液。 [0092] Under a nitrogen atmosphere, at room temperature 2.45g (8.38mmol) l, 3- bis (3-aminophenoxy) benzene and 45g N, N- dimethylformamide was placed in a three-necked flask, stirred dissolved 3h, then dropping rate 1 Omg / s to a three-necked flask was added 2.55g (8.22mmol) 3,3,4 ', 4' - diphenyl tetracarboxylic dianhydride, to obtain a reaction system, the reaction system stirring was continued and dissolved lh ~ 5h, to give a soluble polyamic acid solution.

[0093] 实施例二: [0093] Example II:

[0094]本实施例一种采用磁性粒子感应加热制备可溶性聚酰亚胺的方法,具体是按以下步骤进行的: [0094] A method of the present embodiment, the induction heating of the magnetic particles prepared using a soluble polyimide, in particular, perform the following steps:

[0095] 一、①、在氮气气氛、室温及搅拌条件下,向三颈瓶中加入101.8g N,N_二甲基乙酰胺和10.0(^(0.05111〇1)3,4'-二氨基二苯醚,反应111,再向三颈瓶中加入10.368(0.0475111〇1) 3,3,4',4'_联苯四羧酸二酐,反应3h,然后向三颈瓶中加入10.10g三乙基胺,反应3h,停止搅拌,得到反应液,在搅拌条件下,将反应液以5mL/s的速度滴入丙酮中,滴加完成后,继续搅拌2h,然后静置10天,得到含丝状物的静置,将含丝状物的静置中丝状物取出,在温度为25°C的真空烘箱中将丝状物烘干,得到聚酰胺酸胺盐; [0095] First, ①, under nitrogen atmosphere, at room temperature and with stirring, 101.8g N was added to the three-necked flask, of N_ dimethylacetamide and 10.0 (^ (0.05111〇1) 3,4'-diaminodiphenyl diphenyl ether, reaction 111, three-necked flask was added 10.368 again (0.0475111〇1) 3,3,4 ', 4'_-biphenyl tetracarboxylic dianhydride, the reaction 3h, then the three-necked flask was added 10.10g triethylamine, the reaction 3h, stirring was stopped to obtain a reaction solution, under stirring, the reaction mixture at a speed of 5mL / s of acetone was added dropwise. after completion of the dropwise addition, stirring was continued for 2h, then allowed to stand for 10 days to give the left-containing filaments, the filaments containing the left of filament removed, dried at a temperature of 25 ° C filament vacuum oven, to give a polyamic acid salt;

[0096]②、在搅拌条件下,将2g聚酰胺酸胺盐置于100mL水热反应釜中,并加入10g六水合三氯化铁、〇.5g聚乙二醇和40g乙二醇溶剂,反应10h,然后将水热反应釜升温至温度为205 °C,并在温度为205°C下保温6h,再将水热反应釜自然冷却至室温,得到粗产物,采用外强磁铁将粗产物分离水洗3次,并在温度为120°C下烘干,得到高磁响应聚酰亚胺/Fe 304复合磁性纳米粒子; [0096] ②, under stirring, 2g polyamic acid amine salt of a 100mL hydrothermal reaction kettle and ferric chloride hexahydrate was added 10g, 40g ethylene glycol and polyethylene glycol 〇.5g solvent, reaction 10H, and then the hydrothermal reaction vessel warmed to a temperature of 205 ° C, and incubated 6h at a temperature of 205 ° C, and then a hydrothermal reaction vessel cool to room temperature, a crude product was obtained, using a strong magnet exterior and the crude product was isolated water 3 times, and dried at a temperature of 120 ° C under high magnetically responsive polyimide / Fe 304 composite magnetic nanoparticles;

[0097]二、将石棉布包裹的三颈瓶置于高频感应加热设备的加热环形线圈中,然后向三颈瓶内通氮气气氛,再向三颈瓶内加入50g可溶性聚酰胺酸溶液、15g甲苯和15g高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子,在搅拌速度为l〇〇rpm,搅拌lh,得到混合溶液; [0097] Second, the asbestos cloth wrapped three-necked flask placed in a heating loop coil high frequency induction heating device, a three-necked flask and nitrogen atmosphere, a three-necked flask were added 50g again a soluble polyamic acid solution, 15g toluene and 15g of high magnetic response polyimide / Fe3〇4 composite magnetic nanoparticles, the stirring speed l〇〇rpm, LH stirring, to give a mixed solution;

[0098]三、在交变磁场的频率为100kHz的条件下,调节高频感应加热设备的输出功率使得混合溶液升温至130 °C,并在温度为130°C下回流反应0.5h,排出甲苯和水,再调节高频感应加热设备的输出功率使得混合溶液升温至164 °C,升温至164°C后停止反应,得到反应后的溶液; [0098] Third, the frequency of the alternating magnetic field under the conditions of 100kHz, adjusting high frequency induction heating device output power so that the mixed solution was heated to 130 ° C, and the reaction was refluxed for 0.5h at a temperature of 130 ° C, the discharge toluene and water, and then adjusting the high frequency induction heating device output power so that the mixed solution was heated to 164 ° C, the reaction was stopped after the temperature was raised to 164 ° C, the solution obtained after the reaction;

[0099]四、关闭高频感应加热设备,将反应后的溶液降至室温,利用永磁铁将三颈瓶中高磁响应聚酰亚胺/Fe304复合磁性纳米粒子移出,得到移除磁性纳米粒子后的溶液,再将移除磁性纳米粒子后的溶液滴加到蒸馏水中,沉析lh,过滤,沉淀水洗,最后在温度为130°C下烘干,得到可溶性聚酰亚胺。 [0099] Fourth, high frequency induction heating device off, the reaction solution was cooled to room temperature, using a permanent magnet three-necked flask high magnetically responsive polyimide / Fe304 magnetic composite nanoparticles was removed, to give after removal of the magnetic nanoparticles solution, and then removing the solution of magnetic nanoparticles dropwise to distilled water, precipitation LH, filtered, the precipitate washed with water, and finally dried at a temperature of under 130 ° C, to obtain a soluble polyimide.

[0100]本实施例制备的可溶性聚酰亚胺的结构式为: [0100] soluble polyimide of the formula is prepared in the present embodiment:

Figure CN104829837BD00161

[0101 ]步骤四中所述的永磁铁为磁感应强度为0.3特斯拉; In four of the [0101] Step permanent magnets magnetic flux density of 0.3 Tesla;

[0102] 步骤一中所述的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子的粒径为lum。 High magnetic response [0102] Step a polyimide in the diameter of the composite magnetic nanoparticles / Fe3〇4 of lum.

[0103] 步骤一中所述的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子中聚酰亚胺的结构式为: [0103] Step a high magnetic response in the structural formula of the polyimide polyimide / Fe3〇4 composite magnetic nanoparticles:

Figure CN104829837BD00162

[0105]所述的步骤一中所述的可溶性聚酰胺酸溶液中可溶性聚酰胺酸的结构式为: [0105] The structural formula of the step in a soluble polyamic acid solution as a soluble polyamic acid:

Figure CN104829837BD00163

所述的可溶性聚酰胺酸溶液具体是按以下步骤制备的: The soluble polyamic acid solution is prepared by the following specific steps:

[0107] 在氮气气氛下,室温下将2.45g(8.38mmol)l,3-双(3-氨基苯氧基)苯和45g N,N-二甲基乙酰胺置于三颈瓶中,搅拌溶解3h,然后以1 Omg/s的滴加速度向三颈瓶中加入2.55g (8.22mmol)3,3,4',4'-二苯醚四羧酸二酐,得到反应体系,将反应体系继续搅拌并溶解2h, 得到可溶性聚酰胺酸溶液。 [0107] Under a nitrogen atmosphere, at room temperature 2.45g (8.38mmol) l, 3- bis (3-aminophenoxy) benzene and 45g N, N- dimethylacetamide placed in a three-necked flask, stirred dissolved 3h, then dropping rate 1 Omg / s was added 2.55g (8.22mmol) 3,3,4 three-neck flask ', 4'-diphenyl ether tetracarboxylic dianhydride, to obtain a reaction system, the reaction system stirring was continued and dissolved 2h, to give a soluble polyamic acid solution.

[0108] 实施例三: [0108] Example III:

[0109] 本实施例一种采用磁性粒子感应加热制备可溶性聚酰亚胺的方法,具体是按以下步骤进行的: [0109] A method of the present embodiment, the induction heating of the magnetic particles prepared using a soluble polyimide, in particular, perform the following steps:

[0110] 一、①、在氮气气氛、室温及搅拌条件下,向三颈瓶中加入101.8g N,N-二甲基乙酰胺和10.0(^(0.05111〇1)3,4'-二氨基二苯醚,反应111,再向三颈瓶中加入10.368(0.0475111〇1) 3,3,4',4'_联苯四羧酸二酐,反应3h,然后向三颈瓶中加入10.10g三乙基胺,反应3h,停止搅拌,得到反应液,在搅拌条件下,将反应液以5mL/s的速度滴入丙酮中,滴加完成后,继续搅拌2h,然后静置10天,得到含丝状物的静置,将含丝状物的静置中丝状物取出,在温度为25°C的真空烘箱中将丝状物烘干,得到聚酰胺酸胺盐; [0110] First, ①, under nitrogen atmosphere, at room temperature, with stirring, was added to the three-necked flask 101.8g N, N- dimethylacetamide and 10.0 (^ (0.05111〇1) 3,4'-diaminodiphenyl diphenyl ether, reaction 111, three-necked flask was added 10.368 again (0.0475111〇1) 3,3,4 ', 4'_-biphenyl tetracarboxylic dianhydride, the reaction 3h, then the three-necked flask was added 10.10g triethylamine, the reaction 3h, stirring was stopped to obtain a reaction solution, under stirring, the reaction mixture at a speed of 5mL / s of acetone was added dropwise. after completion of the dropwise addition, stirring was continued for 2h, then allowed to stand for 10 days to give the left-containing filaments, the filaments containing the left of filament removed, dried at a temperature of 25 ° C filament vacuum oven, to give a polyamic acid salt;

[0111]②、在搅拌条件下,将2g聚酰胺酸胺盐置于水热反应釜中,并加入10g六水合三氯化铁、〇.5g聚乙二醇和40g乙二醇溶剂,反应10h,然后将水热反应釜升温至温度为205°C,并在温度为205 °C下保温6h,再将水热反应釜自然冷却至室温,得到粗产物,采用外强磁铁将粗产物分离水洗3次,并在温度为120°C下烘干,得到高磁响应聚酰亚胺/Fe 304复合磁性纳米粒子; [0111] ②, under stirring, 2g polyamic acid amine salt was placed in a hydrothermal reaction vessel, and ferric chloride hexahydrate was added 10g, 40g 〇.5g glycol and polyethylene glycol, solvents, reaction 10h and then the hydrothermal reaction vessel warmed to a temperature of 205 ° C, and maintained at a temperature of 205 ° C at 6h, and then a hydrothermal reaction vessel cool to room temperature, a crude product was obtained, using a strong outer magnets the crude product was washed with water separation three times, and dried at a temperature of 120 ° C under high magnetically responsive polyimide / Fe 304 composite magnetic nanoparticles;

[0112]二、将石棉布包裹的三颈瓶置于高频感应加热设备的加热环形线圈中,然后向三颈瓶内通氮气气氛,再向三颈瓶内加入50g可溶性聚酰胺酸溶液、15g二甲苯和5g高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子,在搅拌速度为lOOrpm,搅拌lh,得到混合溶液; [0112] Second, the asbestos cloth wrapped three-necked flask placed in a heating loop coil high frequency induction heating device, a three-necked flask and nitrogen atmosphere, a three-necked flask were added 50g again a soluble polyamic acid solution, 5g 15g xylene and high magnetic response polyimide / Fe3〇4 composite magnetic nanoparticles at a stirring speed of lOOrpm, LH stirring, to give a mixed solution;

[0113]三、在交变磁场的频率为100kHz的条件下,调节高频感应加热设备的输出功率使得混合溶液升温至125°C,并在温度为125°C下回流反应0.5h,排出二甲苯和水,再调节高频感应加热设备的输出功率使得混合溶液升温至149°C,升温至149°C后停止反应,得到反应后的溶液; [0113] Third, the frequency of the alternating magnetic field under the conditions of 100kHz, adjusting high frequency induction heating device output power so that the mixed solution was heated to 125 ° C, and the reaction was refluxed for 0.5h at a temperature of 125 ° C, the two discharge toluene and water, and then adjusting the high frequency induction heating device output power so that the mixed solution was heated to 149 ° C, the reaction was stopped after the temperature was raised to 149 ° C, the solution obtained after the reaction;

[0114] 四、关闭高频感应加热设备,将反应后的溶液降至室温,利用永磁铁将三颈瓶中高磁响应聚酰亚胺/Fe30 4复合磁性纳米粒子移出,得到移除磁性纳米粒子后的溶液,再将移除磁性纳米粒子后的溶液滴加到蒸馏水中,沉析lh,过滤,沉淀水洗,最后在温度为130°C下烘干,得到可溶性聚酰亚胺。 [0114] Fourth, high frequency induction heating device off, the reaction solution was cooled to room temperature, using a permanent magnet three-necked flask high magnetically responsive polyimide / Fe30 4 out of the composite magnetic nanoparticles, magnetic nanoparticles removed to give after the solution, the solution is removed and then the magnetic nanoparticles dropwise to distilled water, precipitation LH, filtered, the precipitate washed with water, and finally dried at a temperature of under 130 ° C, to obtain a soluble polyimide.

[0115] 本实施例制备的可溶性聚酰亚胺的结构式为: [0115] This soluble polyimide prepared in Example structural formula is:

Figure CN104829837BD00171

[0117]步骤四中所述的永磁铁为磁感应强度为0.3特斯拉; In four of the [0117] Step permanent magnets magnetic flux density of 0.3 Tesla;

[0118]步骤一中所述的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子的粒径为lum。 High magnetic response [0118] Step a polyimide in the diameter of the composite magnetic nanoparticles / Fe3〇4 of lum.

[0119]步骤一中所述的高磁响应聚酰亚胺/Fe304复合磁性纳米粒子中聚酰亚胺的结构式为: [0119] Step a high magnetic response in the structural formula of the polyimide polyimide / Fe304 magnetic composite nanoparticles:

Figure CN104829837BD00172

[0121]所述的步骤一中所述的可溶性聚酰胺酸溶液中可溶性聚酰胺酸的结构式为: [0121] The structural formula of the step in a soluble polyamic acid solution as a soluble polyamic acid:

Figure CN104829837BD00173

[0123]所述的可溶性聚酰胺酸溶液具体是按以下步骤制备的: [0123] The soluble polyamic acid solution is prepared by the following specific steps:

[0124] 在氮气气氛下,室温下将1.60g(8.04mmol)l ,3-双(3-氨基苯氧基)苯和45g N,N-二甲基甲酰胺置于三颈瓶中,搅拌溶解3h,然后以lOmg/s的滴加速度向三颈瓶中加入3.39g (7.638111111〇1)4,4'-(六氟异丙烯)二酞酸酐,得到反应体系,将反应体系继续搅拌并溶解11 1 ~5h,得到可溶性聚酰胺酸溶液。 [0124] Under a nitrogen atmosphere, at room temperature 1.60g (8.04mmol) l, 3- bis (3-aminophenoxy) benzene and 45g N, N- dimethylformamide was placed in a three-necked flask, stirred dissolved 3h, then dropping rate lOmg / s to a three-necked flask was added 3.39g (7.638111111〇1) 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride, to obtain a reaction system, the reaction system was continued stirring and dissolved 11 1 ~ 5h, to give a soluble polyamic acid solution.

[0125] 实施例四: [0125] Example IV:

[0126] 本实施例一种采用磁性粒子感应加热制备可溶性聚酰亚胺的方法,具体是按以下步骤进行的: [0126] A method of the present embodiment, the induction heating of the magnetic particles prepared using a soluble polyimide, in particular, perform the following steps:

[0127] 一、①、在氮气气氛、室温及搅拌条件下,向三颈瓶中加入101.8g N,N_二甲基乙酰胺和10.0(^(0.05111〇1)3,4'-二氨基二苯醚,反应111,再向三颈瓶中加入10.368(0.0475111〇1) 3,3,4',4'_联苯四羧酸二酐,反应3h,然后向三颈瓶中加入10.10g三乙基胺,反应3h,停止搅拌,得到反应液,在搅拌条件下,将反应液以5mL/s的速度滴入丙酮中,滴加完成后,继续搅拌2h,然后静置10天,得到含丝状物的静置,将含丝状物的静置中丝状物取出,在温度为25°C的真空烘箱中将丝状物烘干,得到聚酰胺酸胺盐; [0127] First, ①, under nitrogen atmosphere, at room temperature and with stirring, 101.8g N was added to the three-necked flask, of N_ dimethylacetamide and 10.0 (^ (0.05111〇1) 3,4'-diaminodiphenyl diphenyl ether, reaction 111, three-necked flask was added 10.368 again (0.0475111〇1) 3,3,4 ', 4'_-biphenyl tetracarboxylic dianhydride, the reaction 3h, then the three-necked flask was added 10.10g triethylamine, the reaction 3h, stirring was stopped to obtain a reaction solution, under stirring, the reaction mixture at a speed of 5mL / s of acetone was added dropwise. after completion of the dropwise addition, stirring was continued for 2h, then allowed to stand for 10 days to give the left-containing filaments, the filaments containing the left of filament removed, dried at a temperature of 25 ° C filament vacuum oven, to give a polyamic acid salt;

[0128] ②、在搅拌条件下,将2g聚酰胺酸胺盐置于100mL水热反应釜中,并加入10g六水合三氯化铁、〇.5g聚乙二醇和40g乙二醇溶剂,反应10h,然后将水热反应釜升温至温度为205 °C,并在温度为205°C下保温6h,再将水热反应釜自然冷却至室温,得到粗产物,采用外强磁铁将粗产物分离水洗3次,并在温度为120°C下烘干,得到高磁响应聚酰亚胺/Fe 3〇4复合磁性纳米粒子; [0128] ②, under stirring, 2g polyamic acid amine salt of a 100mL hydrothermal reaction kettle and ferric chloride hexahydrate was added 10g, 40g ethylene glycol and polyethylene glycol 〇.5g solvent, reaction 10H, and then the hydrothermal reaction vessel warmed to a temperature of 205 ° C, and incubated 6h at a temperature of 205 ° C, and then a hydrothermal reaction vessel cool to room temperature, a crude product was obtained, using a strong magnet exterior and the crude product was isolated water 3 times, and dried at a temperature of 120 ° C under high magnetically responsive polyimide / Fe 3〇4 composite magnetic nanoparticles;

[0129] 二、将石棉布包裹的三颈瓶置于高频感应加热设备的加热环形线圈中,然后向三颈瓶内通氮气气氛,再向三颈瓶内加入50g可溶性聚酰胺酸溶液、15g二甲苯和5g高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子,在搅拌速度为lOOrprn,搅拌lh,得到混合溶液; [0129] Second, the asbestos cloth wrapped three-necked flask placed in a heating loop coil high frequency induction heating device, a three-necked flask and nitrogen atmosphere, a three-necked flask were added 50g again a soluble polyamic acid solution, 5g 15g xylene and high magnetic response polyimide / Fe3〇4 composite magnetic nanoparticles, the stirring speed lOOrprn, LH stirring, to give a mixed solution;

[0130]三、在交变磁场的频率为100kHz的条件下,调节高频感应加热设备的输出功率使得混合溶液升温至145°C,并在温度为145°C下回流反应lh,排出二甲苯和水,再调节高频感应加热设备的输出功率使得混合溶液升温至164 °C,升温至164°C后停止反应,得到反应后的溶液; [0130] Third, the frequency of the alternating magnetic field under the conditions of 100kHz, adjusting high frequency induction heating device output power so that the mixed solution was heated to 145 ° C, and the reaction was refluxed for lh at a temperature of 145 ° C, the xylene is discharged and water, and then adjusting the high frequency induction heating device output power so that the mixed solution was heated to 164 ° C, the reaction was stopped after the temperature was raised to 164 ° C, the solution obtained after the reaction;

[0131] 四、关闭高频感应加热设备,将反应后的溶液降至室温,利用永磁铁将三颈瓶中高磁响应聚酰亚胺/Fe30 4复合磁性纳米粒子移出,得到移除磁性纳米粒子后的溶液,再将移除磁性纳米粒子后的溶液滴加到蒸馏水中,沉析lh,过滤,沉淀水洗,最后在温度为130°C下烘干,得到可溶性聚酰亚胺。 [0131] Fourth, high frequency induction heating device off, the reaction solution was cooled to room temperature, using a permanent magnet three-necked flask high magnetically responsive polyimide / Fe30 4 out of the composite magnetic nanoparticles, magnetic nanoparticles removed to give after the solution, the solution is removed and then the magnetic nanoparticles dropwise to distilled water, precipitation LH, filtered, the precipitate washed with water, and finally dried at a temperature of under 130 ° C, to obtain a soluble polyimide.

[0132] 本实施例制备的可溶性聚酰亚胺的结构式为: [0132] This soluble polyimide prepared in Example structural formula is:

Figure CN104829837BD00181

[0134]步骤四中所述的永磁铁为磁感应强度为0.3特斯拉; In four of the [0134] Step permanent magnets magnetic flux density of 0.3 Tesla;

[0135] 步骤一中所述的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子的粒径为lum。 High magnetic response [0135] Step a polyimide in the diameter of the composite magnetic nanoparticles / Fe3〇4 of lum.

[0136]步骤一中所述的高磁响应聚酰亚胺/Fe304复合磁性纳米粒子中聚酰亚胺的结构式为: [0136] Step a high magnetic response in the structural formula of the polyimide polyimide / Fe304 magnetic composite nanoparticles:

Figure CN104829837BD00182

[0138]所述的步骤一中所述的可溶性聚酰胺酸溶液中可溶性聚酰胺酸的结构式为: [0138] The structural formula of the step in a soluble polyamic acid solution as a soluble polyamic acid:

Figure CN104829837BD00191

[0140] 所述的可溶性聚酰胺酸溶液具体是按以下步骤制备的: [0140] The soluble polyamic acid solution is prepared by the following specific steps:

[0141] 在氮气气氛下,室温下将1.998(9.93臟〇1)3,3'-二氨基二苯醚和458~少-二甲基乙酰胺置于三颈瓶中,搅拌溶解3h,然后以lOmg/s的滴加速度向三颈瓶中加入3.02g (9.74mmol)3,3,4',4'-二苯醚四羧酸二酐,得到反应体系,将反应体系继续搅拌并溶解2h, 得到可溶性聚酰胺酸溶液。 [0141] Under a nitrogen atmosphere, at room temperature 1.998 (9.93 dirty 〇1) of 3,3'-diaminodiphenyl ether and 458 ~ less - dimethylacetamide placed in a three-necked flask, and dissolved with stirring 3h, then a dropping rate of lOmg / s to a three-necked flask was added 3.02g (9.74mmol) 3,3,4 ', 4'- tetracarboxylic dianhydride diphenyl ether, to obtain a reaction system, the reaction system was continued stirring and dissolved 2h to give a soluble polyamic acid solution.

[0142] 实施例五: [0142] Example Five:

[0143] 本实施例一种采用磁性粒子感应加热制备可溶性聚酰亚胺的方法,具体是按以下步骤进行的: [0143] A method of the present embodiment, the induction heating of the magnetic particles prepared using a soluble polyimide, in particular, perform the following steps:

[0144] 一、①、在氮气气氛、室温及搅拌条件下,向三颈瓶中加入101.8g N,N_二甲基乙酰胺和10.0(^(0.05111〇1)3,4'-二氨基二苯醚,反应111,再向三颈瓶中加入10.368(0.0475111〇1) 3,3,4',4'_联苯四羧酸二酐,反应3h,然后向三颈瓶中加入10.10g三乙基胺,反应3h,停止搅拌,得到反应液,在搅拌条件下,将反应液以5mL/s的速度滴入丙酮中,滴加完成后,继续搅拌2h,然后静置10天,得到含丝状物的静置,将含丝状物的静置中丝状物取出,在温度为25°C的真空烘箱中将丝状物烘干,得到聚酰胺酸胺盐; [0144] First, ①, under nitrogen atmosphere, at room temperature and with stirring, 101.8g N was added to the three-necked flask, of N_ dimethylacetamide and 10.0 (^ (0.05111〇1) 3,4'-diaminodiphenyl diphenyl ether, reaction 111, three-necked flask was added 10.368 again (0.0475111〇1) 3,3,4 ', 4'_-biphenyl tetracarboxylic dianhydride, the reaction 3h, then the three-necked flask was added 10.10g triethylamine, the reaction 3h, stirring was stopped to obtain a reaction solution, under stirring, the reaction mixture at a speed of 5mL / s of acetone was added dropwise. after completion of the dropwise addition, stirring was continued for 2h, then allowed to stand for 10 days to give the left-containing filaments, the filaments containing the left of filament removed, dried at a temperature of 25 ° C filament vacuum oven, to give a polyamic acid salt;

[0145] ②、在搅拌条件下,将2g聚酰胺酸胺盐置于100mL水热反应釜中,并加入10g六水合三氯化铁铁盐、〇.5g聚乙二醇和40g乙二醇溶剂,反应10h,然后将水热反应釜升温至温度为205°C,并在温度为205°C下保温6h,再将水热反应釜自然冷却至室温,得到粗产物,采用外强磁铁将粗产物分离水洗3次,并在温度为120°C下烘干,得到高磁响应聚酰亚胺/Fe 304复合磁性纳米粒子; [0145] ②, under stirring, 2g polyamic acid amine salt of a 100mL hydrothermal reaction kettle and 10g of ferric chloride hexahydrate, ferric salt, 40g ethylene glycol and polyethylene glycol 〇.5g solvent , 10H reaction, and then a hydrothermal reaction vessel warmed to a temperature of 205 ° C, and incubated 6h at a temperature of 205 ° C, and then a hydrothermal reaction vessel cool to room temperature, a crude product was obtained, using a strong outer magnets crude the product was isolated washed with water three times, and dried at a temperature of 120 ° C under high magnetically responsive polyimide / Fe 304 composite magnetic nanoparticles;

[0146] 二、将石棉布包裹的三颈瓶置于高频感应加热设备的加热环形线圈中,然后向三颈瓶内通氮气气氛,再向三颈瓶内加入50g可溶性聚酰胺酸溶液、15g二甲苯和5g高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子,在搅拌速度为l〇〇rpm,搅拌lh,得到混合溶液; [0146] Second, the asbestos cloth wrapped three-necked flask placed in a heating loop coil high frequency induction heating device, a three-necked flask and nitrogen atmosphere, a three-necked flask were added 50g again a soluble polyamic acid solution, 5g 15g xylene and high magnetic response polyimide / Fe3〇4 composite magnetic nanoparticles, the stirring speed l〇〇rpm, LH stirring, to give a mixed solution;

[0147] 三、在交变磁场的频率为100kHz的条件下,调节高频感应加热设备的输出功率使得混合溶液升温至145°C,并在温度为145°C下回流反应lh,排出二甲苯和水,再调节高频感应加热设备的输出功率使得混合溶液升温至164 °C,升温至164°C后停止反应,得到反应后的溶液; [0147] Third, the frequency of the alternating magnetic field under the conditions of 100kHz, adjusting high frequency induction heating device output power so that the mixed solution was heated to 145 ° C, and the reaction was refluxed for lh at a temperature of 145 ° C, the xylene is discharged and water, and then adjusting the high frequency induction heating device output power so that the mixed solution was heated to 164 ° C, the reaction was stopped after the temperature was raised to 164 ° C, the solution obtained after the reaction;

[0148] 四、关闭高频感应加热设备,将反应后的溶液降至室温,利用永磁铁将三颈瓶中高磁响应聚酰亚胺/Fe30 4复合磁性纳米粒子移出,得到移除磁性纳米粒子后的溶液,再将移除磁性纳米粒子后的溶液滴加到蒸馏水中,沉析lh,过滤,沉淀水洗,最后在温度为130°C下烘干,得到可溶性聚酰亚胺。 [0148] Fourth, high frequency induction heating device off, the reaction solution was cooled to room temperature, using a permanent magnet three-necked flask high magnetically responsive polyimide / Fe30 4 out of the composite magnetic nanoparticles, magnetic nanoparticles removed to give after the solution, the solution is removed and then the magnetic nanoparticles dropwise to distilled water, precipitation LH, filtered, the precipitate washed with water, and finally dried at a temperature of under 130 ° C, to obtain a soluble polyimide.

[0149] 本实施例制备的可溶性聚酰亚胺的结构式为: [0149] soluble polyimide of the formula is prepared in the present embodiment:

Figure CN104829837BD00201

[0151 ]步骤四中所述的永磁铁为磁感应强度为0.3特斯拉; In four of the [0151] Step permanent magnets magnetic flux density of 0.3 Tesla;

[0152] 步骤一中所述的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子的粒径为lum。 High magnetic response [0152] Step a polyimide in the diameter of the composite magnetic nanoparticles / Fe3〇4 of lum.

[0153] 步骤一中所述的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子中聚酰亚胺的结构式为: [0153] Step a high magnetic response in the structural formula of the polyimide polyimide / Fe3〇4 composite magnetic nanoparticles:

Figure CN104829837BD00202

[0154] 所述的步骤一中所述的可溶性聚酰胺酸溶液中可溶性聚酰胺酸的结构式为: [0154] The structural formula of the step in a soluble polyamic acid solution as a soluble polyamic acid:

Figure CN104829837BD00203

[0156] 所述的可溶性聚酰胺酸溶液具体是按以下步骤制备的: [0156] The soluble polyamic acid solution is prepared by the following specific steps:

[0157] 在氮气气氛下,室温下将2.458(8.38臟〇1)1,3-双(3-氨基苯氧基)苯和458^ 二甲基乙酰胺置于三颈瓶中,搅拌溶解3h,然后以1 Omg/s的滴加速度向三颈瓶中加入2.55g (8.22mmol)3,3,4 ',4' -二苯醚四羧酸二酐,得到反应体系,将反应体系继续搅拌并溶解lh ~5h,得到可溶性聚酰胺酸溶液。 [0157] Under a nitrogen atmosphere, at room temperature 2.458 (8.38 dirty 〇1) of 1,3-bis (3-aminophenoxy) benzene and 458 ^ dimethylacetamide placed in a three-necked flask, and dissolved with stirring 3h and then dropping rate 1 Omg / s to a three-necked flask was added 2.55g (8.22mmol) 3,3,4 ', 4' - diphenyl tetracarboxylic dianhydride, to obtain a reaction system, the reaction system was continued stirring and dissolved lh ~ 5h, to give a soluble polyamic acid solution.

[0158] 对比实验一: [0158] Comparative Experiment 1:

[0159] 本对比实验制备可溶性聚酰亚胺的制备方法是按以下步骤进行: [0159] The method of preparing a soluble polyimide prepared in this comparative experiment was performed by the following steps:

[0160] 一、将石棉布包裹的三颈瓶置于高频感应加热设备的加热环形线圈中,然后向三颈瓶内通氮气气氛,再向三颈瓶内加入50g可溶性聚酰胺酸溶液和15g甲苯,在搅拌速度为lOOrpm,搅拌lh,得到混合溶液; [0160] First, the cotton wrapped stone 3-necked flask placed in a heating loop coil high frequency induction heating device, a three-necked flask and nitrogen atmosphere, was added again three-necked flask and 50g of soluble polyamic acid solution 15g of toluene, stirring speed of lOOrpm, LH stirring, to give a mixed solution;

[0161] 二、调节加热套功率使得混合溶液升温至125°C,并在温度为125°C下回流反应lh, 排出甲苯和水,再调节高频感应加热设备的输出功率使得混合溶液升温至149°C,升温至149 °C后停止反应,得到反应后的溶液; [0161] Second, adjusting the heating power so that the mixed solution jacket was heated to 125 ° C, and the reaction was refluxed for lh at the temperature of 125 ° C, toluene and water is discharged, and then adjust the output power of the high frequency induction heating apparatus so that the mixed solution was allowed to warm to 149 ° C, the temperature was raised to 149 ° C the reaction was stopped to obtain a solution after the reaction;

[0162] 三、将反应后的溶液降至室温,得到降温后的溶液,再将降温后的溶液滴加到蒸馏水中,沉析lh,过滤,沉淀水洗,最后在温度为130°C下烘干,得到可溶性聚酰亚胺。 [0162] Third, the reaction solution was cooled to room temperature, the resulting solution was cooled, then the cooled solution was added dropwise to distilled water, precipitation LH, filtered, the precipitate washed with water, and finally baked at a temperature of 130 ° C under dryness to obtain a soluble polyimide.

[0163] 本对比实验一制备的可溶性聚酰亚胺的结构式为: [0163] Structural Formula soluble polyimide prepared according to a comparative experiment:

Figure CN104829837BD00204

[0165]步骤一中所述的可溶性聚酰胺酸溶液中可溶性聚酰胺酸的结构式为: [0165] Step a structural formula soluble in said polyamic acid solution is a soluble polyamic acid:

Figure CN104829837BD00211

[0167]步骤一中所述的可溶性聚酰胺酸溶液具体是按以下步骤制备的: [0167] Step a soluble polyamic acid solution is prepared in particular according to the following steps:

[0168] 在氮气气氛下,室温下将2.45g(8.38mmol)l ,3-双(3-氨基苯氧基)苯和45g N,N-二甲基甲酰胺置于三颈瓶中,搅拌溶解3h,然后以1 Omg/s的滴加速度向三颈瓶中加入2.55g (8.22mmol)3,3,4',4'-二苯醚四羧酸二酐,得到反应体系,将反应体系继续搅拌并溶解2h, 得到可溶性聚酰胺酸溶液。 [0168] Under a nitrogen atmosphere, at room temperature 2.45g (8.38mmol) l, 3- bis (3-aminophenoxy) benzene and 45g N, N- dimethylformamide was placed in a three-necked flask, stirred dissolved 3h, then dropping rate 1 Omg / s was added 2.55g (8.22mmol) 3,3,4 three-neck flask ', 4'-diphenyl ether tetracarboxylic dianhydride, to obtain a reaction system, the reaction system stirring was continued and dissolved 2h, to give a soluble polyamic acid solution.

[0169] 对比实验二: [0169] Comparative Experiment II:

[0170] 本对比实验所述的可溶性聚酰亚胺的制备方法是按以下步骤进行: [0170] The method of preparing the soluble polyimide according to Comparative Experiment is carried out according to the following steps:

[0171] 一、将石棉布包裹的三颈瓶置于高频感应加热设备的加热环形线圈中,然后向三颈瓶内通氮气气氛,再向三颈瓶内加入50g可溶性聚酰胺酸溶液和15g二甲苯,在搅拌速度为1 OOrpm,搅拌lh,得到混合溶液; [0171] First, the cotton wrapped stone 3-necked flask placed in a heating loop coil high frequency induction heating device, a three-necked flask and nitrogen atmosphere, was added again three-necked flask and 50g of soluble polyamic acid solution 15g of xylene, stirring at a rate of 1 OOrpm, LH stirring, to give a mixed solution;

[0172] 二、调节加热套功率使得混合溶液升温至145°C,并在温度为145°C下回流反应10h,排出二甲苯和水,再调节高频感应加热设备的输出功率使得混合溶液升温至164°C,升温至164°C后停止反应,得到反应后的溶液; [0172] Second, adjusting the heating power so that the mixed solution jacket was heated to 145 ° C, and the reaction was refluxed for 10h at a temperature of 145 ° C, xylene and the discharge of water, then adjust the output power of the high frequency induction heating apparatus so that the mixed solution was warmed to 164 ° C, the temperature was raised to 164 ° C the reaction was stopped to obtain a solution after the reaction;

[0173] 三、将反应后的溶液降至室温,得到降温后的溶液,再将降温后的溶液滴加到蒸馏水中,沉析lh,过滤,沉淀水洗,最后在温度为130°C下烘干,得到可溶性聚酰亚胺。 [0173] Third, the reaction solution was cooled to room temperature, the resulting solution was cooled, then the cooled solution was added dropwise to distilled water, precipitation LH, filtered, the precipitate washed with water, and finally baked at a temperature of 130 ° C under dryness to obtain a soluble polyimide.

[0174] 本对比实验制备的可溶性聚酰亚胺的结构式为: [0174] The present comparative experiment was prepared soluble polyimide of the formula:

Figure CN104829837BD00212

[0176]步骤一中所述的可溶性聚酰胺酸溶液中可溶性聚酰胺酸的结构式为: [0176] Step a structural formula soluble in said polyamic acid solution is a soluble polyamic acid:

Figure CN104829837BD00213

[0178]步骤一中所述的可溶性聚酰胺酸溶液具体是按以下步骤制备的: [0178] Step a soluble polyamic acid solution is prepared in particular according to the following steps:

[0179] 在氮气气氛下,室温下将2.45g(8.38mmol)l ,3-双(3-氨基苯氧基)苯和45g N,N-二甲基乙酰胺置于三颈瓶中,搅拌溶解lh~3h,然后以1 Omg/s的滴加速度向三颈瓶中加入2.55g(8.22_〇1 )3,3,4',4'-二苯醚四羧酸二酐,得到反应体系,将反应体系继续搅拌并溶解2h,得到可溶性聚酰胺酸溶液。 [0179] Under a nitrogen atmosphere, at room temperature 2.45g (8.38mmol) l, 3- bis (3-aminophenoxy) benzene and 45g N, N- dimethylacetamide placed in a three-necked flask, stirred dissolved lh ~ 3h, then dropping rate 1 Omg / s to a three-necked flask was added 2.55g (8.22_〇1) 3,3,4 ', 4'-diphenyl ether tetracarboxylic dianhydride, to obtain a reaction system , the reaction system was continued stirring and dissolved 2h, to give a soluble polyamic acid solution.

[0180]图1为实施例一制备的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子的扫描电子显微镜图。 [0180] FIG. 1 is a response to the polyimide / Fe3〇4 scanning electron micrograph of the composite magnetic nanoparticles Example embodiments a high magnetic prepared. 由图可知,微球为高磁响应聚酰亚胺/Fe3〇4复合磁性微球,粗糙表面和较大的微球尺寸为聚酰亚胺包覆效果。 The figure shows that the microspheres polyimide / Fe3〇4 composite magnetic microspheres, the rough surface of the microsphere size and the larger the polyimide coating effect is high magnetically responsive.

[0181]图2为实施例一制备的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子的X射线衍射曲线图,由图可知,图中15deg~20deg弥漫峰为无定型聚酰亚胺,图中标示峰为Fe3〇4晶格的特征峰。 [0181] FIG. 2 is a diagram of a high magnetic response Preparation polyimide / Fe3〇4 X-ray diffraction graph of the composite magnetic nanoparticles is clear from FIG, FIG 15deg ~ 20deg diffuse peaks amorphous polyimide amine, denoted in FIG peaks characteristic peaks Fe3〇4 lattice.

[0182]图3为实施例一制备的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子的红外曲线图。 [0182] Figure 3 a graph of infrared polyimide / Fe3〇4 composite magnetic nanoparticles in response to a high magnetic embodiment of the prepared embodiment. 由图可知,1779cnf1和1720cnf1为羰基对称振动峰,570CHT1为Fe 3〇4晶体里Fe-Ο键的红外特征吸收峰。 It is seen from FIGS, 1779cnf1 1720cnf1 symmetric vibrational peak and a carbonyl group, 570CHT1 3〇4 crystals of Fe in Fe-Ο key characteristic infrared absorption peaks.

[0183]图4为实施例一制备的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子的振动样品磁强计曲线图。 [0183] FIG. 4 polyimide / Fe3〇4 vibrating sample magnetometer graph composite magnetic nanoparticles in response to a high magnetic prepared according to Example. 由图可知,高磁响应聚酰亚胺/Fe304复合磁性纳米粒子的饱和磁化强度依然达到70emu/g,具有良好的磁相应效果。 The figure shows a high magnetic response polyimide / Fe304 saturation magnetization of the magnetic composite nanoparticles still reached 70emu / g, a good effect of the respective magnetic.

[0184] 图6为红外曲线图;1为实施例一制备的可溶性聚酰亚胺;2为实施例二制备的可溶性聚酰亚胺;3为实施例三制备的可溶性聚酰亚胺;4为实施例四制备的可溶性聚酰亚胺;5 为实施例五制备的可溶性聚酰亚胺;6为对比实验一制备的可溶性聚酰亚胺;7为对比实验二制备的可溶性聚酰亚胺。 [0184] FIG. 6 is a graph illustrating an infrared; 1 is a soluble polyimide prepared according to Example a; 2 a soluble polyimide prepared in Example II embodiment; 3 is a soluble polyimide was prepared according to a third embodiment; 4 is a soluble polyimide prepared in Example fourth embodiment; 5 is a soluble polyimide prepared in Example fifth embodiment; 6 is a soluble polyimide prepared by a comparative experiment; two for Comparative experiment 7 preparation of a soluble polyimide . 利用傅里叶红外光谱仪对实施例一至五制备的可溶性聚酰亚胺及对比实验一至二制备的可溶性聚酰亚胺进行测试,FT-IR(KBr,cnf 1) : 1780cnf iand 1718cm-^0 = 0) ,1591cm-1亚胺对称振动峰;在1591cm-1为C = C伸缩振动峰;在1370cm-1是CN 对称(C = C) ,137001^((^)。由此可知,从结构来看,1780CHT1和1718CHT1为酰伸缩振动峰, 在1231CHT 1和1031CHT1分别是醚键的对称和不对称伸缩振动峰,因此,可证明实施例一至五制备的可溶型聚酰亚胺符合结构式。但是对比实验一的红外曲线,在1660CHT 1有酰亚不对称吸收振动峰,证明该条件下聚酰亚胺亚胺化程度不完全,在其他的实施例和对比例没有发现,说明亚胺化完全。 Preparation Example I to V using a Fourier transform infrared spectrometer Comparative Experiment soluble polyimide and the soluble polyimide prepared in one or two of the test, FT-IR (KBr, cnf 1): 1780cnf iand 1718cm- ^ 0 = 0), 1591cm-1 peak imine symmetric vibration; 1591cm-1 is in the C = C stretching vibration peak; CN at 1370cm-1 is symmetrical (C = C), 137001 ^ ((^) can be seen from the structure. view, 1780CHT1 and 1718CHT1 acyl stretching vibration peak, and in 1231CHT 1 1031CHT1 are symmetric and asymmetric stretching vibration peak ether bond, therefore, prove soluble polyimide prepared according to Example I to V according to formula. However, infrared curve of a comparative experiment, in other embodiments and comparative embodiments is not found, there is described imidization 1660CHT 1 imido asymmetric vibrational peak absorption prove this condition the degree of imidization of the polyimide incomplete, in complete.

[0185] 表1玻璃化转变温度测试数据 [0185] Table 1 Glass Transition Temperature Test Data

Figure CN104829837BD00221

[0187] 表1为玻璃化转变温度测试数据。 [0187] Table 1 is the glass transition temperature of the test data. 对实施例一至实施例五制备的可溶型聚酰亚胺及对比实验一至二制备的聚酰亚胺进行DSC测试数据,利用差示扫描量热仪,升温速率10 °C/min,N 2气氛,测试同一批次树脂多次取样的玻璃化转变温度差异;实施例相比于对比例,具有更为良好的数值稳定性,玻璃化转变温度均在± 2°C以内,并且除了实施例三的玻璃化转变温度在212°C以外,其余均在213°C~214°C,显示了亚胺化反应完全,聚酰亚胺主链结构稳定。 Example polyimide soluble polyimide prepared in Example and Comparative Experiment fifty-one to two embodiments to be prepared in a DSC test data, differential scanning calorimetry, heating rate 10 ° C / min, N 2 atmosphere, the same test batch resin has a glass transition temperature of the multiple sampling difference; compared to the Comparative Example, has a more favorable numerical stability, glass transition temperature within ± 2 ° C, and in addition to Example the glass transition temperature of the three other than 212 ° C, the rest were 213 ° C ~ 214 ° C, shows the imidization reaction was complete, the polyimide main chain in a stable structure. 然而对比试验一显示相同时间下的聚合反应玻璃化转变温度只有195°C~203 °C,亚胺化反应不完全,同时树脂的稳定性较差。 However, comparative test under the same polymerization reaction time of only a glass transition temperature of 195 ° C ~ 203 ° C, incomplete imidization a display, while the poor stability of the resin.

[0188] 表2热失重测试数据 [0188] TGA test data in Table 2

Figure CN104829837BD00231

[0190]表2为热失重测试数据,对实施例一至实施例五制备的可溶型聚酰亚胺及对比实验一至二制备的可溶型聚酰亚胺进行热失重测试;热失重:测试采用热失重分析仪(TGA), 升温速率:1(TC/min,N 2气氛,测试其氮气中热失重性能;由表可知,实施例一至五远高于对比实验一,其氮气下的600°C残炭率提高到70%以上,5%热失重温度在500°C以上,等同或高于标准制备方法,即对比实验二,能够达到聚酰亚胺的热性能,满足对耐温等级和热稳定性的需求。 [0190] Table 2 shows the TGA test data, examples of soluble polyimides soluble polyimide prepared in Example and Comparative Experiment prepared fifty-one to two to one embodiment Thermogravimetric testing; TGA: Test thermal gravimetric analyzer (TGA), heating rate: 1 (TC / min, N 2 atmosphere, the weight loss test in which hot nitrogen properties; seen from the table, much higher than the first to fifth embodiments of a comparative experiment, in which nitrogen 600 ° C char yield increased to above 70%, 5% heat loss temperature above 500 ° C, equal to or higher than the standard method of preparation, i.e., two comparative experiments, to achieve thermal properties of the polyimide, meet the temperature rating demand and thermal stability.

[0191]表3聚酰亚胺材料板的性能 [0191] Table 3 properties of polyimide material plate

Figure CN104829837BD00232

[0193] 将实施例一至实施例五制备的可溶型聚酰亚胺及对比实验一至二制备的聚酰亚胺至于模具中,于室温下放入热压机,将磨具逐渐升温。 Polyimide [0193] Examples of soluble polyimide prepared in Example and Comparative Experiment fifty-one to two to one embodiment of As prepared mold, placed in a hot press at room temperature, gradually warming abrasive. 当模具升温至300Γ时,加压2MPa, 然后将温度从300°C升温至370°C,并施压15MPa,在温度为370°C和压力为15MPa的条件下固化lh,再降至室温后解除压力取出模具,得到聚酰亚胺材料板。 When the mold temperature was raised to 300Γ, 2MPa pressure, and then the temperature was raised from 300 ° C to 370 ° C, and pressure 15MPa, lh cured at a temperature of 370 ° C and a pressure of 15MPa conditions, then cooled to room temperature remove the mold pressure was released, a polyimide material sheet. 按GB/T 2567-2008树脂浇铸体性能试验方法测试,结果见表3。 According to GB / T 2567-2008 Test method of a resin molded body performance results shown in Table 3.

[0194] 表3为聚酰亚胺材料板的性能,由实施例一至五制备的可溶型聚酰亚胺制成的板材,其力学性能(拉伸强度和弯曲强度)均远远高于相同制备时间采用单纯热亚胺化法合成的聚酰亚胺板材,并且等同或高于采用常规制备时间得到的聚酰亚胺板材。 [0194] Table 3 Polyimide sheet of material, made of a sheet-soluble polyimides prepared from the first to fifth embodiments, the mechanical properties (tensile strength and flexural strength) were much higher than the prepared in the same time a simple synthetic method of thermal imidization of the polyimide sheet, and is equivalent to or higher than a conventional polyimide sheet obtained preparation time.

Claims (6)

1. 一种采用磁性粒子感应加热制备可溶性聚酰亚胺的方法,其特征在于一种采用磁性粒子感应加热制备可溶性聚酰亚胺的方法是按以下步骤进行: 一、①、在氮气气氛、室温及搅拌条件下,向三颈瓶中加入高沸点极性溶剂和芳香二胺, 反应0.5h~lh,再向三颈瓶中加入芳香二酐,反应lh~5h,然后向三颈瓶中加入叔胺,反应2h~3h,停止搅拌,得到反应液,在搅拌条件下,将反应液以2mL/s~10mL/ S的速度滴入丙酮中,滴加完成后,继续搅拌lh~6h,然后静置3天~10天,得到含丝状物的静置液,将含丝状物的静置液中丝状物取出,在温度为20°C~30°C的真空烘箱中将丝状物烘干,得到聚酰胺酸胺盐; 所述的芳香二胺与芳香二酐的摩尔比为1:(0.90~0.95);所述的芳香二胺与叔胺的摩尔比为1: (1.90~2.10);所述的芳香二酐和芳香二胺的总质量与高沸点极性溶剂的质量比为1:5; 所述的 An induction heating method of preparing a soluble polyimide magnetic particles, wherein one kind of magnetic particles in the induction heating method for preparing a soluble polyimide is carried out by the following steps: First, ①, in a nitrogen atmosphere, at room temperature with stirring, high-boiling polar solvent and an aromatic diamine were added to a three-necked flask, the reaction 0.5h ~ lh, three-necked flask was added again an aromatic dianhydride, the reaction lh ~ 5h, then three-neck flask a tertiary amine, the reaction 2h ~ 3h, the stirring was stopped to obtain a reaction solution, under stirring, the reaction solution was added dropwise to acetone, and after completion of the dropwise addition, stirring was continued 2mL / s ~ 10mL / S speed lh ~ 6h, and then allowed to stand for 3 days to 10 days, allowed to stand to give a solution containing the filament, the filament was allowed to stand in the solution containing the filament was taken out at a temperature of 20 ° C ~ 30 ° C in a vacuum oven in the wire It was dried to give a polyamic acid salt; the molar ratio of aromatic diamine and aromatic dicarboxylic anhydride is 1: (0.90 to 0.95); the molar ratio of aromatic diamine and a tertiary amine is 1: ( from 1.90 to 2.10); the total mass of the aromatic dianhydride and an aromatic diamine with a mass ratio of high-boiling polar solvent is 1: 5; the 香二胺为4,4'-二氨基二苯醚、3,4'_二氨基二苯醚、二(3-氨基苯氧基)二苯甲酮或2-( 3-氨基苯基)-5-氨基苯并噁唑; 所述的芳香二酐为3,3',4,4'_联苯四羧酸二酐、3,3',4,4'_二苯醚四羧酸二酐或3, 3 ',4,4 ' -二砜基四羧酸二酐; 所述的叔胺为三烷基叔胺; 所述的高沸点极性溶剂为N,N-二甲基乙酰胺、N,N-二甲基甲酰胺和N-甲基吡咯烷酮中的一种或其中几种的混合物; ②、在搅拌条件下,将聚酰胺酸胺盐置于水热反应釜中,并加入铁盐、聚乙二醇和乙二醇溶剂,反应5h~10h,然后将水热反应釜升温至温度为190°C~210°C,并在温度为190°C~ 210°C下保温3h~7h,再将水热反应釜自然冷却至室温,得到粗产物,采用外强磁铁将粗产物分离水洗3次~5次,并在温度为80°C~120°C下烘干,得到高磁响应聚酰亚胺/Fe 3〇4复合磁性纳米粒子; 所述的聚酰胺酸胺盐与铁盐的质量 Hong diamine is 4,4'-oxydianiline, 3,4'_ diaminodiphenyl ether, bis (3-aminophenoxy) benzophenone, or 2- (3-aminophenyl) - 5-amino-benzoxazole; said aromatic dianhydride is 3,3 ', 4,4'_-biphenyl tetracarboxylic dianhydride, 3,3', diphenyl ether tetracarboxylic acid 4,4'_ anhydrides or 3, 3 ', 4,4' - sulfone tetracarboxylic dianhydride; said tertiary amine is a trialkyl tertiary; the high-boiling polar solvent is N, N- dimethylacetamide or a mixture of several of the amides, N, N- dimethylformamide and N- methylpyrrolidone; ②, with stirring, an amine salt of polyamic acid was placed in a hydrothermal reaction vessel, and was added iron salts, polyethylene glycols and glycol solvents, reaction 5h ~ 10h, and then the hydrothermal reaction vessel warmed to a temperature of 190 ° C ~ 210 ° C, and at a temperature of 190 ° C ~ 210 ° C for 3h under ~ 7H, hydrothermal reaction vessel and then naturally cooled to room temperature to obtain a crude product, using the strong outer magnets the crude product was isolated washed with water 3 to 5 times, and dried at a temperature of 80 ° C ~ 120 ° C, to obtain a high magnetically responsive polyimide / Fe composite magnetic nanoparticles 3〇4; mass of the polyamic acid and the amine salts of iron salts 为10:(1~50);所述的聚酰胺酸胺盐与聚乙二醇的质量比为10: (〇. 1~3.0);所述的聚酰胺酸胺盐与乙二醇的质量比为10: (80~300); 所述的铁盐为六水合三氯化铁、四水合氯化亚铁和四水合硫酸亚铁中的一种或其中几种的混合物; 所述的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子中聚酰亚胺的结构通式为: 10: (1 to 50); said amine salt of polyamic acid with a polyethylene glycol of mass ratio of 10: (3.0 ~ 1 billion.); Mass of the amine salt of polyamic acid with ethylene glycol ratio of 10: (80 to 300); said iron salt is ferric chloride hexahydrate, or a mixture of several of ferrous chloride tetrahydrate and ferrous sulfate tetrahydrate; said high magnetically responsive structural formula polyimide polyimide / Fe3〇4 composite magnetic nanoparticles:
Figure CN104829837BC00021
所述的η为9~49; L - .? 所述的R i为-0 -或 Η is the 9 ~ 49; L - R i according -0 -, or.?
Figure CN104829837BC00022
所述的R 2为、 Said R 2 is,
Figure CN104829837BC00023
Figure CN104829837BC00024
或所述的高磁响应聚酰亚胺/Fe304复合磁性纳米粒子中聚酰亚胺的结构通式为: High structural formula or magnetically responsive polyimide polyimide / Fe304 magnetic composite nanoparticles according to:
Figure CN104829837BC00031
所述的η为9~4 9 ;所述的R 2为 Η is the 9 to 49; the R 2 is
Figure CN104829837BC00032
二、 将石棉布包裹的三颈瓶置于高频感应加热设备的加热环形线圈中,然后向三颈瓶内通氮气气氛,再向三颈瓶内加入可溶性聚酰胺酸溶液、带水剂和高磁响应聚酰亚胺/Fe 304 复合磁性纳米粒子,在搅拌速度为25rpm~lOOrpm,搅拌lh~5h,得到混合溶液; 所述的可溶性聚酰胺酸溶液和带水剂的质量比为10: (2~4.8);所述的高磁响应聚酰亚胺/Fe304复合磁性纳米粒子与可溶性聚酰胺酸溶液的质量比为(0.1~0.5): 1; 三、 在交变磁场的频率为80kHz~200kHz的条件下,调节高频感应加热设备的输出功率使得混合溶液升温至120 °C~145 °C,并在温度为120 °C~145 °C下回流反应0.5h~1.5h,排出带水剂和水,再调节高频感应加热设备的输出功率使得混合溶液升温至146°C~164°C, 升温至146 °C~164 °C后停止反应,得到反应后的溶液; 四、 关闭高频感应加热设备,将反应后的溶液降至室温,利用 Second, the cotton wrapped stone 3-necked flask placed in a heating loop coil high frequency induction heating device, a three-necked flask and nitrogen atmosphere, a three-necked flask was added again a soluble polyamic acid solution with a liquid, and high magnetically responsive polyimide / Fe 304 composite magnetic nanoparticles, the stirring speed of 25rpm ~ lOOrpm, stirred for lh ~ 5h, to obtain a mixed solution; the quality of a soluble polyamic acid solution and the water carrier ratio of 10: (2 to 4.8); high-quality composite magnetic response of the magnetic nanoparticles with a solution of a soluble polyamic acid, polyimide / Fe304 ratio of (0.1 to 0.5): 1; Third, the frequency of the alternating magnetic field is 80kHz ~ 200kHz under the adjusted high frequency induction heating device output power so that the mixed solution was heated to 120 ° C ~ 145 ° C, and the reaction was refluxed for 0.5h ~ 1.5h at a temperature of 145 ° C to 120 ° C ~, with discharge agent and water, and then adjusting the high frequency induction heating device output power so that the mixed solution was heated to 146 ° C ~ 164 ° C, warmed to 146 ° C ~ 164 ° C after the reaction was stopped to obtain a reaction solution;, Close high-frequency induction heating apparatus, the reaction solution was cooled to room temperature, using 永磁铁将三颈瓶中高磁响应聚酰亚胺/Fe30 4复合磁性纳米粒子移出,得到移除磁性纳米粒子后的溶液,再将移除磁性纳米粒子后的溶液滴加到蒸馏水中,沉析lh~4h,过滤,沉淀水洗,最后在温度为130°C~ 140 °C下烘干,得到可溶性聚酰亚胺; 所述的可溶性聚酰亚胺结构通式为: 所述的η为3~49; w Three-necked flask permanent magnet with high magnetic response polyimide / Fe30 4 out of the composite magnetic nanoparticles, the solution obtained after removal of the magnetic nanoparticles, and then removing the magnetic nanoparticles solution was added dropwise to distilled water, precipitation lh ~ 4h, filtered and the precipitate washed with water, and finally at a temperature of 130 ° C ~ dried at 140 ° C, to obtain a soluble polyimide; soluble polyimide according to the structural formula: said η 3 ~ 49; w
Figure CN104829837BC00033
w > 所述的办为: w> is said to do:
Figure CN104829837BC00034
Figure CN104829837BC00041
2. 根据权利要求1所述的一种采用磁性粒子感应加热制备可溶性聚酰亚胺的方法,其特征在于步骤四中所述的永磁铁的磁感应强度为0.1特斯拉~1.5特斯拉。 1 2. The one of the soluble polyimide prepared by a method of heating an induction magnetic particles, wherein magnetic flux density of the permanent magnet in the four steps of 0.1 Tesla to 1.5 Tesla claims.
3. 根据权利要求1所述的一种采用磁性粒子感应加热制备可溶性聚酰亚胺的方法,其特征在于步骤二中所述的带水剂为甲苯和二甲苯中的一种或其中两种的混合物。 3. A method according to one of claim 1 prepared by heating a soluble polyimide using inductive magnetic particles, wherein A tape agent in step two of the xylene and toluene, or two of the claims mixture.
4. 根据权利要求1所述的一种采用磁性粒子感应加热制备可溶性聚酰亚胺的方法,其特征在于步骤一中所述的高磁响应聚酰亚胺/Fe3〇4复合磁性纳米粒子的粒径为50nm~3μηι。 According to one of the claim 1 for preparing a soluble polyimide using magnetic particles induction heating method, characterized by high magnetically responsive polyimide / Fe3〇4 composite magnetic nanoparticles in said step a a particle size of 50nm ~ 3μηι.
5. 根据权利要求1所述的一种采用磁性粒子感应加热制备可溶性聚酰亚胺的方法,其特征在于步骤二中所述的可溶性聚酰胺酸溶液中可溶性聚酰胺酸的结构通式为: 或 1, according to one of the magnetic particles in the induction heating method for preparing a soluble polyimide of the general formula wherein a solution of a soluble polyamic acid in step two of the polyamic acid is soluble claim: or
Figure CN104829837BC00042
Figure CN104829837BC00051
6.根据权利要求1所述的一种采用磁性粒子感应加热制备可溶性聚酰亚胺的方法,其特征在于步骤二中所述的可溶性聚酰胺酸溶液具体是按以下步骤制备的: 在氮气气氛下,室温下将芳香二胺和强极性溶剂置于三颈瓶中,搅拌溶解lh~3h,然后以lmg/s~10mg/s的滴加速度向三颈瓶中加入芳香族四酸二酐,得到反应体系,将反应体系继续搅拌并溶解lh~5h,得到可溶性聚酰胺酸溶液; 所述的芳香二胺与芳香族四酸二酐的摩尔比为1:(0.75~0.98);所述的芳香二胺与芳香族四酸二酐的质量总和占反应体系质量的10%~15% ; 所述强极性溶剂为N,N-二甲基甲酰胺和N,N-二甲基乙酰胺中的一种或两种的混合物; 所述的芳香二胺为2,2 双(二氟甲基)-4,4-二氨基联苯、1,3-双(3-氨基苯氧基)苯、 1,3-双(4-氨基苯氧基)苯、3,3 二氨基二苯酿或3,3 二氨基二苯甲酮; 所述的芳香族四酸二酐 6. A method according to one of claim 1 prepared by heating a soluble polyimide using inductive magnetic particles, characterized in that a soluble polyamic acid solution according to step II is prepared by the following specific steps claim: in a nitrogen atmosphere , the aromatic diamine at room temperature and strongly polar solvents placed in a three-necked flask, and dissolved with stirring lh ~ 3h, then dropping rate lmg / s ~ 10mg / s aromatic tetracarboxylic dianhydride was added to the three-necked flask to obtain a reaction system, the stirring was continued for lh ~ 5h and dissolved the reaction system, to give a soluble polyamic acid solution; the molar ratio of aromatic diamine and an aromatic tetracarboxylic acid anhydride is 1: (0.75 to 0.98); the the sum of the mass of an aromatic diamine and an aromatic tetracarboxylic dianhydride is 10% to 15% by weight of the reaction system; the highly polar solvent is N, N- dimethylformamide and N, N- dimethylacetamide mixture of one amide or two; the aromatic diamine is 2,2-bis (difluoromethyl) -4,4-diamino-biphenyl, 1,3-bis (3-aminophenoxy ) benzene, 1,3-bis (4-aminophenoxy) benzene, 3,3-diamino-3,3-diamino diphenyl stuffed or benzophenone; the aromatic tetracarboxylic dianhydride 3,3',4,4'_二苯酮四酸二酐、3,3',4,4'_二苯醚四羧酸二酐、双酸A型二醚二酐或4,4 (六氟异丙烯)二酞酸酐。 3,3 ', 4,4'_ benzophenone tetracarboxylic dianhydride, 3,3', 4,4'_ diphenyl ether tetracarboxylic dianhydride, bis A diglycidyl ether, an acid dianhydride or 4,4 ( hexafluoroisopropylidene) diphthalic anhydride.
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