CN102617857A - Polyimide and preparation process thereof - Google Patents

Polyimide and preparation process thereof Download PDF

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CN102617857A
CN102617857A CN 201210109580 CN201210109580A CN102617857A CN 102617857 A CN102617857 A CN 102617857A CN 201210109580 CN201210109580 CN 201210109580 CN 201210109580 A CN201210109580 A CN 201210109580A CN 102617857 A CN102617857 A CN 102617857A
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polyimide
reaction
mixture
added
isocyanate
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CN102617857B (en )
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印杰
史子兴
白静
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上海交通大学
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Abstract

The invention relates to a polyimide containing a structure represented by the following formula and a preparation process thereof. The preparation process includes using a rapid two-step polymerization process, subjecting di-anhydride and a mixture of two kinds of diisocyanate to co-condensation and polymerization to obtain the polyimide. A solvent containing low toxicity is used as a reaction medium in the process of reaction so that fewer by-products are produced, separation purification is absent, and the reaction process is simple. The post-treatment of the final products is very easy, and the purity of the products is high. The polyimide has wide application fields and can be used in the fields of filter screens for high-temperature filtering, protective clothing, heat insulation materials and aerospace, and also in various high-temperature extreme environments. The formula is shown in the desctiption.

Description

一种聚酰亚胺及其制备方法 A polyimide and preparation method

技术领域 FIELD

[0001] 本发明涉及化学高分子材料制备技术领域,特别是一种高性能的聚酰亚胺及其制备方法。 [0001] Technical Field The present invention relates to the preparation of polymer materials chemistry, in particular a high-performance polyimide and its preparation method.

背景技术 Background technique

[0002] 一种由芳香族酸酐和芳香族的异氰酸酯反应制得的聚酰亚胺,具有优异的热稳定性和不易熔化性,玻璃化表面温度为315°C。 [0002] A polyimide obtained by reacting an aromatic isocyanate and an aromatic acid anhydride having excellent thermal stability and easy meltability, the glass surface temperature of 315 ° C. 而且这种材料的纤维炭化温度在370°C。 And the fibers of such materials in the carbonization temperature 370 ° C. 同时,由于芳环结构的存在,这种聚酰亚胺材料就具有高的防火性能,不易燃烧。 Meanwhile, due to the presence of the aromatic ring structure, such a polyimide material to have a high fire resistance, easy to burn. 氧指数为38。 Oxygen index of 38. 一般情况下,可以在260°C下使用。 Under normal circumstances, it can be used at 260 ° C. 这种聚酰亚胺耐多种有机试剂,如醇类,醚类,卤代烃类。 The polyimide resistant to a variety of organic reagents, such as alcohols, ethers, halogenated hydrocarbons. 但是强的极性,质子性溶剂是可以将其溶解的。 However, strong polar, protic solvent can be solubilized. 如N,N'-二甲基甲酰胺(DMF),N,N'_ 二甲基乙酰胺(DMAc),N-甲基吡咯烷酮(NMP),浓硫酸等。 Such as N, N'- dimethylformamide (DMF), N, N'_ dimethylacetamide (DMAc), N- methylpyrrolidone (NMP), concentrated sulfuric acid and the like. 由于其优异的化学性能,其的应用领域很广泛,可以用在高温过滤的滤网,防护服,隔热材料以及航空航天的领域,以及各种高温的极端环境。 Due to its excellent chemical properties, its application field is very wide, can be used in the field of filters, protective clothing, insulation materials and aerospace high-temperature filtration, and a variety of high temperature extreme environment.

[0003] 传统的合成方法(US5066760)是将二苯甲酮四酸二酐(BTDI)加入到溶剂中,机械搅拌,通入氮气保护,加热80°C溶解,溶解之后,滴加两种二异氰酸酯一4,4'_二苯基甲烷二异氰酸酯(MDI)和甲苯二异氰酸(TDI)的混合物。 [0003] The conventional synthesis method (US5066760) is benzophenone tetracarboxylic dianhydride (BTDI,) was added to a solvent, mechanical stirring, into nitrogen and heated 80 ° C and the dissolution after dropping two dihydroxy polyisocyanate mixtures methane diisocyanate (MDI) and toluene diisocyanate (TDI) is a diphenyl 4,4'_. 其中TDI与MDI的摩尔比为4:1。 Wherein the molar ratio of MDI to TDI of 4: 1. 滴加过程为控制在6小时以上,滴加完成之后反应I小时以上。 Process control is added dropwise over 6 hours, the reaction After completion of dropwise over I h. 之后停止反应,将混合物倒入到水,丙酮,甲醇等中洗去溶剂即可,缺点是反应时间为7小时以上,费时耗能。 After stopping the reaction, the mixture was poured into water, acetone, methanol and the like to a solvent wash, the disadvantage is the reaction time of 7 hours or more, consuming energy.

发明内容 SUMMARY

[0004] 本发明的目的在于,供合成这种高性能聚酰亚胺的技术路线,这种合成路线大大节省了反应时间,有着节能和提高生产效率的功效。 [0004] The object of the present invention, for the synthesis of such a high-performance polyimide technical route, this reaction Scheme saves time, energy, and improve the effectiveness with productivity.

[0005] 为实现这一目的,本发明提供一种聚酰亚胺及其制备方法,采用缩合聚合方法,由二酸酐与两种二异氰酸酯的混合物共缩聚合成聚酰亚胺,反应过程中使用毒性小的溶剂作反应介质,副产物生成较少,不需分离纯化,反应过程简单,速度快,最终产物的后处理也十分容易,产物纯度很高。 [0005] To achieve this object, the present invention provides a method for preparing polyimide and polyethylene, using condensation polymerization method, from a mixture of isocyanates with two dihydroxy dianhydride copolycondensation synthesis of the polyimide, the reaction process used less toxic solvents as a reaction medium, less by-product, without separation and purification, the reaction process is simple, fast, after the final product is also very easy handling, high product purity.

[0006] 本发明的技术解决方案如下: [0006] The technical solutions of the present invention are as follows:

一种聚酰亚胺,具有如下重复结构式: A polyimide having the following repeating structural formula:

Figure CN102617857AD00041

其中R的结构为: R is the structure wherein:

Figure CN102617857AD00051

[0007] —种制备所述的聚酰亚胺的方法,包括化学式(I)所示的二苯甲酮四酸二酐和两种异氰酸的混合物按摩尔比1:0. 97-1. 101为原料,碱和水作为催化剂,进行缩聚反应; [0007] - preparing polyimides species, comprising a mixture of Formula (I) benzophenone tetracarboxylic dianhydride and represented by two kinds of isocyanate molar ratio of 1: 097-1 . 101 as raw materials, base and water as a catalyst, a polycondensation reaction;

Figure CN102617857AD00052

所述的两种异氰酸的混合物是化学式(2)所示的甲苯二异氰酸酯和化学式(3)所示的4,4' - 二苯基甲烷二异氰酸酯按摩尔比4:1混合。 The mixture of the two isocyanates (3) 4,4 'represented by the formula (2) toluene diisocyanate and Chemical Formula - diphenylmethane diisocyanate molar ratio of 4: 1 and mixed.

[0008] [0008]

Figure CN102617857AD00053

[0009] 本发明制备聚酰亚胺的整个反应方程式可表示为: [0009] The overall reaction for preparing polyimides of the present invention may be expressed as the equation:

Figure CN102617857AD00061

其中R的结构为: R is the structure wherein:

Figure CN102617857AD00062

[0010] 聚酰亚胺的制备方法的具体步骤如下: [0010] The polyimide of the specific step of the method is as follows:

将二苯甲酮四酸二酐加入到的有机溶剂中,加碱和水作为催化剂;机械搅拌,通入氮气保护,加热60— 120°C溶解,溶解之后,首先将70%-80%的两种异氰酸的混合物一次性加入反应体系,搅拌反应I小时;然后在I小时内滴加完剩余的20%-30%的两种异氰酸的混合物,再反应1-2小时,反应结束后,除去溶剂即可。 The benzophenone tetracarboxylic dianhydride was added to the organic solvent, alkali and water as a catalyst; mechanical agitation, into nitrogen, heated 60- 120 ° C and the dissolution after first 70% -80% a mixture of two isocyanate added in one reaction system, the reaction was stirred for I h; then finished mixture the remaining 20% ​​-30% of the two isocyanate was added dropwise over I h, then the reaction for 1-2 hours, the reaction after completion, the solvent can be removed.

[0011] 所述的有机溶剂为,N,N' -二甲基甲酰胺,N,N' -二甲基乙酰胺,N-甲基吡咯烷酮,四氢呋喃,二甲基亚砜,苯,甲苯或二甲苯。 [0011] The organic solvent is, N, N '- dimethylformamide, N, N' - dimethylacetamide, N- methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, benzene, toluene or xylene.

[0012] 所述的碱为碱金属的烷氧基化合物或者碱金属的氢氧化物,碱的加入量相对于每Imol异氰酸酯的混合物加入O. 0001一O. 2mol的碱。 [0012] The hydroxide base is an alkali metal alkoxide or an alkali metal, a mixture amount of the base added per Imol isocyanate was added to a 0001 O. O. a 2 mol of a base.

[0013] 每g的碱对应于O. 5-2g的水。 [0013] corresponding to base per g of water O. 5-2g.

[0014] 本发明的有益效果如下: [0014] Advantageous effects of the present invention are as follows:

与传统的合成技术相比不同在于:第一、反应分为两步即第一步一次性加入80%异氰酸酯混合液进行预聚合反应;第二、将余下的20%异氰酸酯滴加入体系中。 Compared with conventional synthetic techniques except that: a first, i.e., the first step in the reaction in two steps of 80% was added in one isocyanate pre-polymerization mixture; second, the remaining 20% ​​of the isocyanate dropwise added to the system. 通过两步法,制备了高分子量的聚酰亚胺纺丝浆液。 By a two-step process, a high molecular weight polyimide spin dope was prepared. 而传统的反应体系是一步法将异氰酸酯滴加入反应体系中,滴加时间通常在6—8小时。 The traditional one-step reaction system was dropwise added to the isocyanate reaction system, dropping time is usually 6-8 hours. 与传统反应工艺相比,本专利设计由于将反应分为两步,大大缩短了滴加时间,提高了生产效率,节约了能源。 Compared with the conventional reaction process, since the design of this patent two steps reaction, greatly reducing the time of the dropwise addition, increased production efficiency, saving energy. 本发明所制得的聚酰亚胺,性能,强度都能满足目前各种领域的应用要求,在实际应用上有着广阔的前景,深远的意义和影响以及可观的经济价值。 The present invention is made of polyimide, performance, strength can meet the current requirements of various application areas, there are broad prospects in the practical application of far-reaching significance and impact as well as considerable economic value. 具体实施方式 detailed description

[0015] 以下结合实施例对本发明的技术方案作进一步描述,但不以此限制本发明的保护范围。 [0015] Examples of embodiments in conjunction with the following technical solution of the present invention will be further described in, but not limit the scope of the present invention.

[0016] 实施例I [0016] Example I

将80. 5 二苯甲酮四酸二酐(BTDI)加入到250ml的N,N' - 二甲基甲酰胺(DMF)中,力口入O. 075gNa0H,溶解在O. 2ml水中。 The 80.5 benzophenone tetracarboxylic dianhydride (BTDI,) was added to 250ml of N, N '- dimethylformamide (DMF), the force mouth O. 075gNa0H, O. 2ml dissolved in water. 机械搅拌,通入氮气保护,加热80°C溶解,溶解之后,一次性加入两种二异氰酸酯一4,4' - 二苯基甲烷二异氰酸酯(MDI)和甲苯二异氰酸(TDI)的混合物(其中TDI与MDI的摩尔比为4:1)37. 88g,反应I小时,温度控制在80°C。 Mechanical stirring, into nitrogen and heated 80 ° C and the dissolution after addition of the two one-time a diisocyanate 4,4 '- a mixture of diphenylmethane diisocyanate (MDI) and toluene diisocyanate (TDI) of (wherein the molar ratio of MDI to TDI of 4: 1). 37 88g, I h the reaction temperature was controlled at 80 ° C. 接着,将9. 47g 二异氰酸酯混合物通过滴加入反应体系中,滴加时间I小时,温度控制在80°C。 Subsequently, 9. 47g diisocyanate mixture by dropwise addition of the reaction system dropwise over I hour, temperature was controlled at 80 ° C. 滴加完成之后反应I小时。 After completion of dropwise I hr reaction. 将混合物倒入到丙酮中洗去溶剂。 The mixture was poured into acetone wash solvent. 比浓粘度测试结果约为0.8(NMP为溶剂,C=O. 005g/ml)。 The reduced viscosity of the test results of about 0.8 (NMP as the solvent, C = O. 005g / ml).

[0017] 实施例2 [0017] Example 2

将161g 二苯甲酮四酸二酐(BTDI)加入到500ml的N,N'- 二甲基乙酰胺(DMAc)中,加入O. 15gNa0H,溶解在O. 4ml水中。 The 161g benzophenone tetracarboxylic dianhydride (BTDI,) was added to 500ml of N, N'- dimethylacetamide in (DMAc), was added O. 15gNa0H, O. 4ml dissolved in water. 机械搅拌,通入氮气保护,加热120°C溶解,溶解之后,一次加入两种二异氰酸酯一4,4' - 二苯基甲烷二异氰酸酯(MDI)和甲苯二异氰酸(TDI)的混合物(其中TDI与MDI的摩尔比为4:1) 66. 29g,反应45分钟,温度控制在120°C。 Mechanical stirring, into nitrogen, was heated 120 ° C was dissolved, then dissolved, was added in two kinds of a diisocyanate, 4,4 '- a mixture of diphenylmethane diisocyanate (MDI) and toluene diisocyanate (TDI) of ( wherein the molar ratio of MDI to TDI of 4: 1) 66. 29g, 45 minutes, temperature was controlled at 120 ° C. 将28. 41g 二异氰酸酯混合物通过滴加入反应体系中,滴加时间I小时,温度控制在120°C。 28. 41g of the diisocyanate mixture was added dropwise to the reaction system by the dropwise over I hour, temperature was controlled at 120 ° C. 滴加完成之后反应2小时。 After completion of the dropwise addition the reaction for 2 hours. 之后停止反应,将混合物倒入到丙酮中洗去溶剂。 After stopping the reaction, the mixture was poured into acetone wash solvent. 比浓粘度测试结果约为O. 8 (NMP为溶剂,C=O. 005g/ml)。 The reduced viscosity results about O. 8 (NMP as the solvent, C = O. 005g / ml).

[0018] 实施例3 [0018] Example 3

将322g 二苯甲酮四酸二酐(BTDI)加入到500ml的N,N' - 二甲基乙酰胺(DMAc)中,加入O. 3gNa0H,溶解在O. 8ml水中。 The 322g benzophenone tetracarboxylic dianhydride (BTDI,) was added to 500ml of N, N '- dimethylacetamide (DMAc) was added O. 3gNa0H, O. 8ml dissolved in water. 机械搅拌,通入氮气保护,加热60°C溶解,溶解之后,一次加入两种二异氰酸酯一4,4' - 二苯基甲烷二异氰酸酯(MDI)和甲苯二异氰酸(TDI)的混合物(其中TDI与MDI的摩尔比为4:1)151. 52g,反应I小时,温度控制在60°C。 Mechanical stirring, into nitrogen, heated 60 ° C was dissolved, then dissolved, was added in two kinds of a diisocyanate, 4,4 '- a mixture of diphenylmethane diisocyanate (MDI) and toluene diisocyanate (TDI) of ( wherein the molar ratio of MDI to TDI of 4:. 1) 151 52g, I h the reaction temperature was controlled at 60 ° C. 将37. 88g二异氰酸酯混合物通过滴加入反应体系中,滴加时间I小时,温度控制在60°C。 37. 88g of the diisocyanate mixture was added dropwise to the reaction system by the dropwise over I hour, temperature was controlled at 60 ° C. 滴加完成之后反应I. 5小时。 After completion of the dropwise addition the reaction I. 5 hours. 之后停止反应,将混合物倒入到丙酮中洗去溶剂。 After stopping the reaction, the mixture was poured into acetone wash solvent. 比浓粘度测试结果约为O. 8 (NMP 为溶剂,C=O. 005g/ml)。 The reduced viscosity results about O. 8 (NMP as the solvent, C = O. 005g / ml).

[0019] 对比实施例: [0019] Comparative Example:

将161g 二苯甲酮四酸二酐(BTDI)加入到500ml的N,N'- 二甲基乙酰胺(DMAc)中,加入O. 15gNa0H,溶解在O. 4ml水中。 The 161g benzophenone tetracarboxylic dianhydride (BTDI,) was added to 500ml of N, N'- dimethylacetamide in (DMAc), was added O. 15gNa0H, O. 4ml dissolved in water. 机械搅拌,通入氮气保护,加热60— 120°C溶解,溶解之后,滴加两种二异氰酸酯一4,4' - 二苯基甲烷二异氰酸酯(MDI)和甲苯二异氰酸(TDI)的混合物94. 7g。 Mechanical stirring, into nitrogen, heated to dissolve 60- 120 ° C, after dissolving, a solution of two kinds of a diisocyanate 4,4 '- diphenylmethane diisocyanate (MDI) and toluene diisocyanate (TDI) of a mixture of 94. 7g. 其中其中TDI与MDI的摩尔比为4:1。 Wherein the molar ratio of TDI and MDI is 4: 1. 滴加过程为7小时。 During the addition of 7 hours. 滴加完成之后反应I小时。 After completion of dropwise I hr reaction. 之后停止反应,将混合物倒入到丙酮中洗去溶剂。 After stopping the reaction, the mixture was poured into acetone wash solvent. 比浓粘度测试结果约为 The reduced viscosity of about test results

O. 8 (NMP 为溶剂,C=O. 005g/ml)。 O. 8 (NMP as the solvent, C = O. 005g / ml).

[0020] 由此看出,本发明在缩短了反应时间后, 仍能达到较好的结果。 [0020] This shows that the present invention is to shorten the reaction time, can still achieve better results. 聚合物分子量仍能达到要求,大大节约了能源和成本提高了效率。 The polymer molecular weight can still meet the requirements, significant savings in energy costs and improves efficiency.

[0021] 由此看出,本发明在缩短了反应时间后,仍能达到较好的结果。 [0021] This shows that the present invention is to shorten the reaction time, can still achieve better results. 聚合物分子量仍能达到要求,大大节约了能源和成本提高了效率。 The polymer molecular weight can still meet the requirements, significant savings in energy costs and improves efficiency.

Claims (6)

  1. 1. 一种聚酰亚胺,具有如下结构式: A polyimide having the following structural formula:
    Figure CN102617857AC00021
    其中R的结构为: R is the structure wherein:
    Figure CN102617857AC00022
  2. 2. 一种制备如权利要求I所述的聚酰亚胺的方法,包括化学式(I)所示的二苯甲酮四酸二酐和两种异氰酸的混合物按摩尔比1:0. 97-1. 101为原料,碱和水作为催化剂,进行缩聚反应; 2. A method of the polyimide prepared as claimed in claim I, comprising a mixture of 1 molar ratio of formula (I) benzophenone tetracarboxylic dianhydride and represented by two kinds of isocyanate: 0. . 97-1101 as raw materials, base and water as a catalyst, a polycondensation reaction;
    Figure CN102617857AC00023
    所述的两种异氰酸的混合物是化学式(2)所示的甲苯二异氰酸酯和化学式(3)所示的4,4'-二苯基甲烷二异氰酸酯按摩尔比4:1混合 The mixture of the two isocyanates are toluene diisocyanate chemical formula (2) and 4,4'-diphenylmethane diisocyanate chemical formula (3) a molar ratio of 4: 1 mixture
    Figure CN102617857AC00024
  3. 3.根据权利要求2所述的聚酰亚胺的制备方法,具体步骤如下: 将二苯甲酮四酸二酐加入到的有机溶剂中,加碱和水作为催化剂;机械搅拌,通入氮气保护,加热60— 120°C溶解,溶解之后,首先将70%-80%的两种异氰酸的混合物一次性加入反应体系,搅拌反应45分钟-I小时;然后在I小时内滴加完剩余的20%-30%的两种异氰酸的混合物,再反应1-2小时,反应结束后,除去溶剂即可。 The method for preparing the polyimides as claimed in claim 2, the specific steps are as follows: benzophenone tetracarboxylic acid dianhydride was added to the organic solvent, alkali and water as a catalyst; mechanical stirring, introducing nitrogen protection, heating to dissolve 60- 120 ° C, after dissolving, the first mixture of 70% -80% of the two isocyanate added in one reaction system, the reaction stirred for 45 min hours -I; I h then completed dropwise over 20% -30% mixture of two remaining isocyanate, the reaction and then 1-2 hours. after completion of the reaction, the solvent can be removed.
  4. 4.根据权利要求2或3所述的聚酰亚胺的制备方法,其特征在于所述的有机溶剂为,N, N'-二甲基甲酰胺,N,N'-二甲基乙酰胺,N-甲基吡咯烷酮,四氢呋喃,二甲基亚砜,苯,甲苯或二甲苯。 The production method of claim 2 or claim 3 polyimide, wherein said organic solvent is, N, N'- dimethylformamide, N, N'- dimethylacetamide , N- methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, benzene, toluene or xylene.
  5. 5. 根据权利要求2或3所述的聚酰亚胺的制备方法,其特征在于所述的碱为碱金属的烷氧基化合物或者碱金属的氢氧化物,碱的加入量相对于每Imol异氰酸酯的混合物加入O. 0001—O. 2mol 白勺喊。 The production method of claim 2 or claim 3 polyimide, wherein said base is a hydroxide of an alkali metal alkoxide or an alkali metal, the amount of base added per Imol the mixture was added the isocyanate O. 0001-O. 2mol white spoon call.
  6. 6.根据权利要求5所述的聚酰亚胺的制备方法,其特征在于每g的碱对应于O. 5-2g的水。 6. A method for preparing a polyimide as claimed in claim 5, wherein each of the base corresponding to O. 5-2g g water.
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* Cited by examiner, † Cited by third party
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CN103628172A (en) * 2013-11-04 2014-03-12 东华大学 Preparation method of ternary copolyimide fiber
CN105073813A (en) * 2012-12-17 2015-11-18 巴斯夫欧洲公司 Porous branched/highly branched polyimides
CN105175739A (en) * 2015-09-25 2015-12-23 哈尔滨工程大学 Preparation method of organic silicon and polyimide material

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CN105073813A (en) * 2012-12-17 2015-11-18 巴斯夫欧洲公司 Porous branched/highly branched polyimides
CN103628172A (en) * 2013-11-04 2014-03-12 东华大学 Preparation method of ternary copolyimide fiber
CN105175739A (en) * 2015-09-25 2015-12-23 哈尔滨工程大学 Preparation method of organic silicon and polyimide material

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