WO2024060583A1 - 一种聚酯酰亚胺共聚物及其制备方法和应用 - Google Patents

一种聚酯酰亚胺共聚物及其制备方法和应用 Download PDF

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WO2024060583A1
WO2024060583A1 PCT/CN2023/086559 CN2023086559W WO2024060583A1 WO 2024060583 A1 WO2024060583 A1 WO 2024060583A1 CN 2023086559 W CN2023086559 W CN 2023086559W WO 2024060583 A1 WO2024060583 A1 WO 2024060583A1
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polyester imide
anhydride
polyesterimide
preparation
imide copolymer
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French (fr)
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方省众
温雅青
陈国飞
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中国科学院宁波材料技术与工程研究所
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Publication of WO2024060583A1 publication Critical patent/WO2024060583A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/16—Polyester-imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the invention belongs to the field of polymer technology, and specifically relates to a polyester imide copolymer and its preparation method and application.
  • polyimide Due to its excellent thermal stability, chemical stability and dielectric properties, polyimide has been widely used in aerospace, electronic appliances, automobiles, chemical machinery and other fields.
  • Traditional polyimide films will produce electron transfer complexes during the polymerization of dianhydride monomers and diamine monomers, which will affect the optical properties of the product film, further limiting the application of polyimide in the optical field.
  • Polyesterimide refers to a type of polymer in which ester bonds are introduced into the main chain of polyimide, and the repeating units have ester groups and imide groups as structural characteristic groups.
  • the unique molecular structure makes it conducive to coordination and coordination.
  • the advantages of both traditional polyester and polyimide include excellent thermal stability, insulation, electromagnetic shielding, solvent resistance, and excellent mechanical properties.
  • the transmittance of the polyesterimide film prepared from tert-butylhydroquinone bis(trimellitic anhydride) as raw material reported in the prior art is only 58.7% at 400nm, the glass transition temperature is 234°C, and the thermal properties and optical properties need to be further improved (Hasegawa M, Ishigami T, Ishii J. Optically transparent aromatic poly(ester imide)s with low coefficients of thermal expansion(1). Self-orientation behavior during solution casting process and substituent effect[J]. Polymer,2015,74:1-15.).
  • the Chinese patent document with publication number CN114656636A discloses a polyester imide.
  • acid monomers, alcohol monomers, acid anhydride monomers and amine monomers are mixed under a protective atmosphere, and Adjust the molar ratio of alcohol monomers and acid monomers to 2.5-4.0:1, react under the action of a catalyst, and prepare polyester imide without adding a solvent.
  • the glass transition of the polyester imide The temperature is between 117-178°C, and the thermal properties need to be improved;
  • the Chinese patent document with publication number CN106810695A discloses an aromatic polyester imide. In this method, asymmetric acyl-containing polyester imide is prepared in advance during melt processing.
  • the aromatic diphenol monomer with imine bond and the meta-positioned fully aromatic diacid monomer are condensed to form a polyester imide molecular chain that is not easy to crystallize, while the polyester molecular chain formed from the AB-type fully aromatic monomer is easy to crystallize.
  • the two are connected through the meta-position fully aromatic dicarbonyl group
  • an aromatic polyester imide with self-reinforced tensile strength and Tg is obtained.
  • this method is relatively complex and has high requirements on parameters.
  • the present invention provides a polyesterimide copolymer.
  • the film made from the polyesterimide copolymer has a high glass transition temperature, a low thermal expansion coefficient and good optical properties.
  • x, y, z are integers from 1 to 100;
  • R 1 is selected from any one of the groups represented by formula (II):
  • R 2 is selected from any one of the groups represented by formula (III):
  • R 1 is R 2 is
  • the present invention introduces an amide structure into the main chain of polyesterimide, forms hydrogen bonds between molecular chains, enhances the rigidity and linearity of the chain, and enhances the interaction between molecular chains, thereby increasing the glass transition temperature of the polyesterimide and reducing its thermal expansion coefficient; in addition, the introduction of a strong electron-withdrawing group - trifluoromethyl and a bulky side group - tert-butyl can improve its optical properties.
  • the ratio of x and z is 0.1-7:1; when the ratio of amide segment and polyester segment is within the above range, the product polyester imide exhibits more excellent thermal properties and optical properties.
  • the invention also provides a preparation method of the polyester imide copolymer, which includes the following steps:
  • step (1) The polyamic acid solution in step (1) is imidized under the action of a dehydrating agent and a catalyst, and a polyester imide copolymer is obtained through post-treatment.
  • the ratio of the molar amount of the aromatic diamine monomer to the total molar amount of the aromatic acid chloride monomer, tert-butylhydroquinone bis(trimellitic anhydride) and 4,4'-(hexafluoroisopropylene) diphthalic anhydride is 1 :1-1.05.
  • the molar ratio of aromatic acid chloride monomer to tert-butylhydroquinone bis(trimellitic anhydride) is 0.1-7:1; within the above preferred range, as the aromatic acid chloride content increases, polyester imide copolymerization The thermal expansion coefficient of the material decreases and the glass transition temperature increases.
  • the organic solvent includes N,N-dimethylformamide, N,N-dimethylacetamide, sulfolane, dimethyl sulfoxide, N-methylpyrrolidone or m-cresol.
  • the dehydrating agent is at least one of acetic anhydride, propionic anhydride, n-butyric anhydride, valeric anhydride and benzoic anhydride;
  • the catalyst is at least one of pyridine, isoquinoline and triethylamine;
  • the molar ratio of the dehydrating agent to the catalyst The ratio is 1:0.5-1; the molar ratio of dehydrating agent and diamine monomer is 1-3:1.
  • step (2) the temperature of the imidization reaction is 25-100°C, and the time is 2-24 hours.
  • the temperature of the imidization reaction is 70-90°C and the time is 2-3 hours. This reaction condition is conducive to achieving complete imidization in a short time.
  • the invention also provides a polyesterimide film, which is prepared from the polyesterimide copolymer.
  • the polyesterimide copolymer is dissolved to obtain a polyesterimide solution, and then cast Or coating to form a film and then curing to obtain the polyester imide film.
  • programmed temperature rise is used during curing.
  • the programmed temperature rise steps are 60-100°C for 1-2 hours, 100-160°C for 1-2 hours, 180-250°C for 1-2 hours, and 300-350°C for 1-2 hours. 2 hours.
  • the programmed temperature rise step is 80°C for 1-2 hours, 100°C for 1-2 hours, 150°C for 1-2 hours, 200°C for 1-2 hours, and 250°C for 1-2 hours.
  • the glass transition temperature of the polyester imide film is ⁇ 300°C and the thermal expansion coefficient is ⁇ 30 ppm/K, optical transmittance at 400nm ⁇ 70%.
  • the polyesterimide film has a glass transition temperature of 300-350° C., a thermal expansion coefficient of 10-26 ppm/K, and an optical transmittance of ⁇ 74% at 400 nm.
  • the present invention introduces the amide structure into the polyester imide system to form hydrogen bonds between molecular chains and enhance the rigidity and linearity of the chains, thereby making the thermal expansion coefficient of the polyester imide film ⁇ 30 ppm/K. Glass transition temperature ⁇ 300°C;
  • the presence of amide groups will relatively reduce the proportion of imide groups.
  • the polyester imide in the present invention introduces a strong electron-withdrawing group—trifluoromethyl group and a bulky side group—tert-butyl group, so that The product polyesterimide film has a transmittance of ⁇ 70% at 400nm and has potential applications in the optical field.
  • Figure 1 is the infrared spectrum of the polyester imide copolymer in Examples 1 to 4 and Comparative Example 1.
  • polyesterimide copolymer powder added to N,N-dimethylacetamide and dissolve it completely to obtain a polyesterimide solution with a solid content of 10%, and apply the solution to the glass substrate on the top, place it in an oven for temperature curing, specifically 80°C/2 hours, 100°C/1 hour, 150°C/1 hour, 200°C/1 hour, 250°C/1 hour, and remove from the oven after cooling to room temperature. Glass plate, soak the glass plate in water, the polyesterimide film will automatically peel off, and put it in the oven to dry for later use.
  • the FT-IR spectrum of the polyester imide copolymer of this embodiment is shown in Figure 1.
  • the appearance of the characteristic peaks at 1788, 1722, and 1367 cm -1 can prove the successful synthesis of the polyester imide copolymer.
  • polyesterimide copolymer powder added to N,N-dimethylacetamide and dissolve it completely to obtain a polyesterimide solution with a solid content of 10%, and apply the solution to the glass substrate on the top, place it in an oven for temperature curing, specifically 80°C/2 hours, 100°C/1 hour, 150°C/1 hour, 200°C/1 hour, 250°C/1 hour, and remove from the oven after cooling to room temperature. Glass plate, soak the glass plate in water, the polyesterimide film will automatically peel off, and put it in the oven to dry for later use.
  • the FT-IR spectrum of the polyester imide copolymer of this embodiment is shown in Figure 1.
  • the appearance of the characteristic peaks at 1784, 1722, and 1369 cm -1 can prove the successful synthesis of the polyester imide copolymer.
  • the FT-IR spectrum of the polyester imide copolymer of this example is shown in FIG1 .
  • the appearance of characteristic peaks at 1786, 1726, and 1369 cm ⁇ 1 can prove the successful synthesis of the polyester imide copolymer.
  • polyesterimide copolymer powder added to N,N-dimethylacetamide and dissolve it completely to obtain a polyesterimide solution with a solid content of 10%, and apply the solution to the glass substrate on the top, place it in the oven for heating and curing, specifically 80°C/2 hours, 100°C/1 hour, 150°C/1 hour, 200°C/1 hour, 250°C/2 hours, and take it out from the oven after cooling to room temperature. Glass plate, soak the glass plate in water, the polyesterimide film will automatically peel off, and put it in the oven to dry for later use.
  • the FT-IR spectrum of the polyester imide copolymer of this embodiment is shown in Figure 1.
  • the appearance of the characteristic peaks at 1788, 1724, and 1369 cm -1 can prove the successful synthesis of the polyester imide copolymer.
  • polyesterimide copolymer powder added to N,N-dimethylacetamide and dissolve it completely to obtain a polyesterimide solution with a solid content of 10%, and apply the solution to the glass substrate on the top, place it in an oven for heating and curing, specifically 80°C/2 hours, 100°C/1 hour, 150°C/1 hour, 200°C/1 hour, 250°C/2 hours, and take it out from the oven after cooling to room temperature. Glass plate, soak the glass plate in water, the polyesterimide film will automatically peel off, and put it in the oven to dry for later use.
  • polyester imide copolymer powder is added to N,N-dimethylacetamide and dissolved completely to obtain a polyester imide solution with a solid content of 10%.
  • the solution is coated on a glass substrate and placed in an oven for temperature curing, specifically 80°C/2 hours, 100°C/1 hour, 150°C/1 hour, 200°C/1 hour, and 250°C/1 hour. After cooling to room temperature, the glass plate is taken out of the oven and immersed in water.
  • the polyester imide film is automatically peeled off and placed in an oven to dry for use.
  • R 1 is R 2 is
  • the structural formula of the polyesterimide copolymer prepared in Comparative Example 1 is as follows:
  • R1 is
  • the main properties of the polyesterimide films prepared in Examples 1-4 are shown in Table 1. Compared with the comparative examples, the glass transition temperature and T 400nm of the examples have been improved, and the thermal expansion coefficient has been significantly improved. decline.

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Abstract

本发明公开了一种聚酯酰亚胺共聚物及其制备方法和应用，属于高分子技术领域，该聚酯酰亚胺共聚物的结构式如式(Ⅰ)所示，其中，x，y，z均为1-100的整数；R1为芳香二胺单体残基，R2为芳香酰氯单体残基；其制备方法包括以下步骤：惰性气体保护下，以叔丁基对苯二酚双(偏苯三酸酐)、4,4'-(六氟异丙烯)二酞酸酐、芳香二胺单体和芳香酰氯单体为聚合单体在有机溶剂中进行聚合反应，得到聚酰胺酸溶液；将聚酰胺酸溶液进行酰亚胺化，后处理得到聚酯酰亚胺共聚物。利用该聚酯酰亚胺共聚物制得的薄膜玻璃化转变温度≥300℃，热膨胀系数≤30ppm/K，在400nm的透过率≥70％，在光学领域有着潜在的应用。

Description

一种聚酯酰亚胺共聚物及其制备方法和应用 技术领域
本发明属于高分子技术领域，具体涉及一种聚酯酰亚胺共聚物及其制备方法和应用。
背景技术
聚酰亚胺由于其优异的热稳定性、化学稳定性和介电性能，在航空航天、电子电器、汽车和化工机械等领域都得到了广泛的应用。传统的聚酰亚胺薄膜由于二酐单体和二胺单体在聚合过程中，会产生电子转移络合物，影响产品薄膜的光学性能，从而进一步限制了聚酰亚胺在光学领域的应用。
聚酯酰亚胺是指在聚酰亚胺主链中引入酯键，重复单元以酯基和酰亚胺基为结构特征基团的一类聚合物，独特的分子结构使其有利于协调统筹传统聚酯和聚酰亚胺两者的优势，具有优异的热稳定性、绝缘性、电磁屏蔽性、耐溶剂性以及出色的机械性能。现有技术中报道的以叔丁基对苯二酚双(偏苯三酸酐)为原料制备的聚酯酰亚胺薄膜在400nm处的透过率仅为58.7％，玻璃化转变温度为234℃，热性能和光学性能有待进一步改善(Hasegawa M,Ishigami T,Ishii J.Optically transparent aromatic poly(ester imide)s with low coefficients of thermal expansion(1).Self-orientation behavior during solution casting process and substituent effect[J].Polymer,2015,74:1-15.)。
另外，公开号为CN114656636A的中国专利文献公开了一种聚酯酰亚胺，该发明在保护气氛下，将酸类单体、醇类单体、酸酐类单体和胺类单体混合，并调整醇类单体和酸类单体的摩尔比为2.5-4.0：1，在催化剂作用下进行反应，不添加溶剂，制备得到聚酯酰亚胺，但该聚酯酰亚胺的玻璃化转变温度在117-178℃之间，热学性能有待提高；公开号为CN106810695A的中国专利文献公开了一种芳香族聚酯酰亚胺，该方法在熔融加工过程中，预先制备的非对称的含酰亚胺键的芳香族二酚单体与间位全芳香族二酸单体缩聚形成不易结晶的聚酯酰亚胺分子链，而AB型全芳香族单体形成的聚酯分子链易结晶，两者通过间位全芳香族二羰基连 接，分子链间存在动态的酯交换反应，有利于建立较强的分子链间化学键作用力；在后续冷却过程中，聚酯分子链迅速结晶，并且均匀分散在不易结晶的含聚酯酰亚胺分子链中，从而得到一种拉伸强度和Tg自增强的芳香族聚酯酰亚胺。但该方法较为复杂，对参数的要求高。
发明内容
为了提高现有技术中聚酯酰亚胺薄膜的热性能和光学性能，本发明提供了一种聚酯酰亚胺共聚物，利用该聚酯酰亚胺共聚物制得的薄膜玻璃化转变温度高，热膨胀系数低，光学性能好。
具体采用的技术方案如下：
一种聚酯酰亚胺共聚物，结构式如式(Ⅰ)所示：
其中，x，y，z均为1-100的整数；
R1选自式(Ⅱ)所示基团中的任一种：
R2选自式(Ⅲ)所示基团中的任一种：
优选的，R1为R2为
本发明将酰胺结构引入到聚酯酰亚胺主链中，在分子链间形成氢键，增强链的刚性和线性度，并增强分子链间的作用力，从而提高了聚酯酰亚胺的玻璃化转变温度，降低了其热膨胀系数；另外引入强吸电子基团—三氟甲基和大体积侧基—叔丁基，可以提升其光学性能。
优选的，x和z的比例为0.1-7：1；当酰胺链段和聚酯链段的比例在上述范围内时，产物聚酯酰亚胺表现出更加优异的热性能和光学性能。
本发明还提供了所述的聚酯酰亚胺共聚物的制备方法，包括以下步骤：
(1)在惰性气体保护下，以叔丁基对苯二酚双(偏苯三酸酐)、4,4'-(六氟异丙烯)二酞酸酐、芳香二胺单体和芳香酰氯单体为聚合单体，在有机溶剂中进行聚合反应，得到聚酰胺酸溶液；
(2)步骤(1)中的聚酰胺酸溶液在脱水剂和催化剂作用下进行酰亚胺化，经后处理得到聚酯酰亚胺共聚物。
所述的芳香二胺单体的摩尔量与芳香酰氯单体、叔丁基对苯二酚双(偏苯三酸酐)和4,4'-(六氟异丙烯)二酞酸酐总摩尔量的比例为1：1-1.05。
优选的，芳香酰氯单体与叔丁基对苯二酚双(偏苯三酸酐)的摩尔比为0.1-7：1；在上述优选的范围内，随着芳香酰氯含量的增加，聚酯酰亚胺共聚物的热膨胀系数降低，玻璃化转变温度提高。
所述的有机溶剂包括N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、环丁砜、二甲基亚砜、N-甲基吡咯烷酮或间甲酚。
所述的脱水剂为乙酸酐、丙酸酐、正丁酸酐、戊酸酐和苯甲酸酐中的至少一种；催化剂为吡啶、异喹啉和三乙胺中至少一种；脱水剂与催化剂的摩尔比为1：0.5-1；脱水剂与二胺单体的摩尔比为1-3：1。
步骤(2)中，酰亚胺化反应的温度为25-100℃，时间为2-24h。
优选的，酰亚胺化反应的温度为70-90℃，时间为2～3h。该反应条件有利于在短时间内实现酰亚胺化完全。
本发明还提供了一种聚酯酰亚胺薄膜，由所述的聚酯酰亚胺共聚物制备得到，优选的，将聚酯酰亚胺共聚物溶解得到聚酯酰亚胺溶液，流延或涂布成膜后固化，得到所述的聚酯酰亚胺薄膜。
优选的，固化时采用程序升温，程序升温步骤为60-100℃固化1-2小时，100-160℃固化1-2小时，180-250℃固化1-2小时，300-350℃固化1-2小时。
进一步优选的，程序升温步骤为80℃固化1-2小时，100℃固化1-2小时，150℃固化1-2小时，200℃固化1-2小时，250℃固化1-2小时。
所述的聚酯酰亚胺薄膜的玻璃化转变温度≥300℃，热膨胀系数≤30 ppm/K，在400nm的光学透过率≥70％。
优选的，所述的聚酯酰亚胺薄膜的玻璃化转变温度为300-350℃，热膨胀系数为10-26ppm/K；在400nm的光学透过率≥74％。
与现有技术相比，本发明的有益效果在于：
(1)本发明将酰胺结构引入到聚酯酰亚胺体系中，在分子链间形成氢键，增强链的刚性和线性度，从而使得聚酯酰亚胺薄膜的热膨胀系数≤30ppm/K，玻璃化转变温度≥300℃；
(2)酰胺基团的存在会相对减少酰亚胺基团的比例，本发明中的聚酯酰亚胺引入强吸电子基团—三氟甲基和大体积侧基—叔丁基，使得产品聚酯酰亚胺薄膜在400nm处的透过率≥70％，在光学领域有着潜在的应用。
附图说明
图1为实施例1～4和对比例1中聚酯酰亚胺共聚物的红外光谱图。
具体实施方式
下面结合实施例，进一步阐明本发明。应理解，这些实施例仅用于说明本发明，而不用于限制本发明的范围。
实施例1
(1)氮气保护下，将1.6015g(5.001mmol)2,2'-双(三氟甲基)-4,4'-二氨基联苯，1.3247g(2.575mmol)叔丁基对苯二酚双(偏苯三酸酐)、0.3137g(1.545mmol)对苯二甲酰氯和0.4576g(1.030mmol)4,4'-(六氟异丙烯)二酞酸酐，20.6233g N,N-二甲基乙酰胺加入100mL反应瓶中，室温搅拌10小时，得到透明聚酰胺酸溶液；
(2)将透明聚酰胺酸溶液稀释至固含量为10％，加入1.2759g(12.498mmol)乙酸酐以及0.9884g(12.496mmol)吡啶，80℃酰亚胺化反应2.5h，反应结束后冷却至室温，在乙醇/水中沉淀得到纤维状的聚酯酰亚胺共聚物，煮洗烘干，得到聚酯酰亚胺共聚物；
(3)将上述聚酯酰亚胺共聚物粉末加入到N,N-二甲基乙酰胺中溶解完全，得到固含量为10％的聚酯酰亚胺溶液，将该溶液涂布到玻璃基板上，置于烘箱中进行升温固化，具体为80℃/2小时、100℃/1小时、150℃/1小时、200℃/1小时、250℃/1小时，降至室温后从烘箱中取出玻璃板，将玻璃板浸泡于水中，聚酯酰亚胺薄膜自动剥离，并将其放入烘箱中干燥备用。
本实施例的聚酯酰亚胺共聚物的FT-IR图谱如图1所示，1788，1722，1367cm-1特征峰的出现能够证明该聚酯酰亚胺共聚物的成功合成。
实施例2
(1)氮气保护下，将1.6013g(5.000mmol)2,2'-双(三氟甲基)-4,4'-二氨基联苯，1.0597g(2.060mmol)叔丁基对苯二酚双(偏苯三酸酐)、0.4182g(2.060mmol)对苯二甲酰氯和0.4578g(1.030mmol)4,4'-(六氟异丙烯)二酞酸酐，19.7209g N,N-二甲基乙酰胺加入100mL反应瓶中，室温搅拌10小时，得到透明聚酰胺酸溶液；
(2)将透明聚酰胺酸溶液稀释至固含量为10％，加入1.2764g(12.503mmol)乙酸酐以及0.9890g(12.503mmol)吡啶，90℃亚胺化2h，反应结束后冷却至室温，在乙醇/水中沉淀得到纤维状的聚酯酰亚胺共聚物，煮洗烘干，得到聚酯酰亚胺共聚物；
(3)将上述聚酯酰亚胺共聚物粉末加入到N,N-二甲基乙酰胺中溶解完全，得到固含量为10％的聚酯酰亚胺溶液，将该溶液涂布到玻璃基板上，置于烘箱中进行升温固化，具体为80℃/2小时、100℃/1小时、150℃/1小时、200℃/1小时、250℃/1小时，降至室温后从烘箱中取出玻璃板，将玻璃板浸泡于水中，聚酯酰亚胺薄膜自动剥离，并将其放入烘箱中干燥备用。
本实施例的聚酯酰亚胺共聚物的FT-IR图谱如图1所示，1784，1722，1369cm-1特征峰的出现能够证明该聚酯酰亚胺共聚物的成功合成。
实施例3
(1)氮气保护下，将1.6012g(4.999mmol)2,2'-双(三氟甲基)-4,4'-二氨基联苯，0.7794g(1.515mmol)叔丁基对苯二酚双(偏苯三酸酐)、0.5127g(2.525mmol)对苯二甲酰氯和0.4487g(1.010mmol)4,4'-(六氟异丙烯)二酞酸酐，29.9219g N,N-二甲基乙酰胺加入100mL反应瓶中，室温搅拌10小时，得到透明聚酰胺酸溶液；
(2)将透明聚酰胺酸溶液稀释至固含量为10％，加入1.2762g(12.500mmol)乙酸酐以及0.9885g(12.497mmol)吡啶，80℃酰亚胺化反应2.5h，反应结束后冷却至室温，在乙醇/水中沉淀得到纤维状的聚酯酰亚胺共聚物，煮洗烘干，得到聚酯酰亚胺共聚物；
(3)将上述聚酯酰亚胺共聚物粉末加入到N,N-二甲基乙酰胺中溶解 完全，得到固含量为10％的聚酯酰亚胺溶液，将该溶液涂布到玻璃基板上，置于烘箱中进行升温固化，具体为80℃/2小时、100℃/1小时、150℃/1小时、200℃/1小时、250℃/1小时，降至室温后从烘箱中取出玻璃板，将玻璃板浸泡于水中，聚酯酰亚胺薄膜自动剥离，并将其放入烘箱中干燥备用。
本实施例的聚酯酰亚胺共聚物的FT-IR图谱如图1所示，1786，1726，1369cm-1特征峰的出现能够证明该聚酯酰亚胺共聚物的成功合成。
实施例4
(1)氮气保护下，将1.6015g(5.001mmol)2,2'-双(三氟甲基)-4,4'-二氨基联苯，0.5299g(1.030mmol)叔丁基对苯二酚双(偏苯三酸酐)、0.6273g(3.090mmol)对苯二甲酰氯和0.4576g(1.030mmol)4,4'-(六氟异丙烯)二酞酸酐，28.5461g N,N-二甲基乙酰胺加入100mL反应瓶中，室温搅拌10小时，得到透明聚酰胺酸溶液；
(2)将透明聚酰胺酸溶液稀释至固含量为10％，加入1.2766g(12.505mmol)乙酸酐以及0.9890g(12.503mmol)吡啶，70℃酰亚胺化反应3h，反应结束后冷却至室温，在乙醇/水中沉淀得到纤维状的聚酯酰亚胺共聚物，煮洗烘干，得到聚酯酰亚胺共聚物；
(3)将上述聚酯酰亚胺共聚物粉末加入到N,N-二甲基乙酰胺中溶解完全，得到固含量为10％的聚酯酰亚胺溶液，将该溶液涂布到玻璃基板上，置于烘箱中进行升温固化，具体为80℃/2小时、100℃/1小时、150℃/1小时、200℃/1小时、250℃/2小时，降至室温后从烘箱中取出玻璃板，将玻璃板浸泡于水中，聚酯酰亚胺薄膜自动剥离，并将其放入烘箱中干燥备用。
本实施例的聚酯酰亚胺共聚物的FT-IR图谱如图1所示，1788，1724，1369cm-1特征峰的出现能够证明该聚酯酰亚胺共聚物的成功合成。
实施例5
(1)氮气保护下，将1.6812g(5.000mmol)2,2'-双(三氟甲基)-4,4'-二氨基二苯醚，2.0583g(4.001mmol)叔丁基对苯二酚双(偏苯三酸酐)、0.1015g(0.500mmol)间苯二甲酰氯和0.2230g(0.502mmol)4,4'-(六氟异丙烯)二酞酸酐，16.2564g N,N-二甲基乙酰胺加入100mL反应瓶中，室温搅拌10小时，得到透明聚酰胺酸溶液；
(2)将透明聚酰胺酸溶液稀释至固含量为10％，加入1.2762g(12.500mmol)乙酸酐以及0.9888g(12.500mmol)吡啶，80℃酰亚胺化反应2.5h，反应结束后冷却至室温，在乙醇/水中沉淀得到纤维状的聚酯酰亚胺共聚物，煮洗烘干，得到聚酯酰亚胺共聚物；
(3)将上述聚酯酰亚胺共聚物粉末加入到N,N-二甲基乙酰胺中溶解完全，得到固含量为10％的聚酯酰亚胺溶液，将该溶液涂布到玻璃基板上，置于烘箱中进行升温固化，具体为80℃/2小时、100℃/1小时、150℃/1小时、200℃/1小时、250℃/2小时，降至室温后从烘箱中取出玻璃板，将玻璃板浸泡于水中，聚酯酰亚胺薄膜自动剥离，并将其放入烘箱中干燥备用
对比例1
(1)氮气保护下，将1.6011g(5.000mmol)2,2'-双(三氟甲基)-4,4'-二氨基联苯，2.0583g(4.001mmol)叔丁基对苯二酚双(偏苯三酸酐)、0.4442g(1.000mmol)4,4'-(六氟异丙烯)二酞酸酐，10.1482g N,N-二甲基乙酰胺加入50mL反应瓶中，室温搅拌10小时，得到透明聚酰胺酸溶液；
(2)将透明聚酰胺酸溶液稀释至固含量为10％，加入1.2769g(12.508mmol)乙酸酐以及0.9894g(12.508mmol)吡啶，80℃亚胺化2.5h，反应结束后冷却至室温，在乙醇/水中沉淀得到纤维状的聚酯酰亚胺共聚物，煮洗烘干，得到聚酯酰亚胺共聚物；
(3)将上述聚酯酰亚胺共聚物粉末加入到N,N-二甲基乙酰胺中溶解完全，得到固含量为10％的聚酯酰亚胺溶液，将该溶液涂布到玻璃基板上，置于烘箱中进行升温固化，具体为80℃/2小时、100℃/1小时、150℃/1小时、200℃/1小时、250℃/1小时，降至室温后从烘箱中取出玻璃板，将玻璃板浸泡于水中，聚酯酰亚胺薄膜自动剥离，并将其放入烘箱中干燥备用。
本对比例的聚酯酰亚胺共聚物的FT-IR图谱如图1所示，1788，1724，1367cm-1特征峰的出现能够证明该聚酯酰亚胺共聚物的成功合成。
样品分析
实施例1-4制得的聚酯酰亚胺共聚物的结构式如下式所示，
其中，R1为R2为
对比例1制得的聚酯酰亚胺共聚物的结构式如下式所示，
其中，R1为
实施例1-4制得的聚酯酰亚胺薄膜的主要性能如表1所示，相比于对比例，实施例的玻璃化转变温度以及T400nm均有所提升，且热膨胀系数有明显的下降。
表1实施例1-4所制备的聚酯酰亚胺薄膜的主要性能
以上所述的实施例对本发明的技术方案进行了详细说明，应理解的是以上所述的仅为本发明的具体实施例，并不用于限制本发明，凡在本发明的原则范围内所做的任何修改、补充或类似方式替代等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种聚酯酰亚胺共聚物，其特征在于，结构式如式(Ⅰ)所示：
    其中，x，y，z均为1-100的整数；
    R1选自式(Ⅱ)所示基团中的任一种：
    R2选自式(Ⅲ)所示基团中的任一种：
  2. 根据权利要求1所述的聚酯酰亚胺共聚物的制备方法，其特征在于，包括以下步骤：
    (1)在惰性气体保护下，以叔丁基对苯二酚双(偏苯三酸酐)、4,4'-(六氟异丙烯)二酞酸酐、芳香二胺单体和芳香酰氯单体为聚合单体，在有机溶剂中进行聚合反应，得到聚酰胺酸溶液；
    (2)步骤(1)中的聚酰胺酸溶液在脱水剂和催化剂作用下进行酰亚胺化，经后处理得到聚酯酰亚胺共聚物。
  3. 根据权利要求2所述的聚酯酰亚胺共聚物的制备方法，其特征在于，所述的芳香二胺单体的摩尔量与芳香酰氯单体、叔丁基对苯二酚双(偏苯三酸酐)和4,4'-(六氟异丙烯)二酞酸酐总摩尔量的比例为1：1-1.05。
  4. 根据权利要求2所述的聚酯酰亚胺共聚物的制备方法，其特征在于，芳香酰氯单体与叔丁基对苯二酚双(偏苯三酸酐)的摩尔比为0.1-7：1。
  5. 根据权利要求2所述的聚酯酰亚胺共聚物的制备方法，其特征在于，步骤(1)中，所述的有机溶剂包括N,N-二甲基甲酰胺、N,N-二甲基 乙酰胺、环丁砜、二甲基亚砜、N-甲基吡咯烷酮或间甲酚。
  6. 根据权利要求2所述的聚酯酰亚胺共聚物的制备方法，其特征在于，所述的脱水剂为乙酸酐、丙酸酐、正丁酸酐、戊酸酐和苯甲酸酐中的至少一种；催化剂为吡啶、异喹啉和三乙胺中至少一种；脱水剂与催化剂的摩尔比为1：0.5-1；脱水剂与二胺单体的摩尔比为1-3：1。
  7. 根据权利要求2所述的聚酯酰亚胺共聚物的制备方法，其特征在于，步骤(2)中，酰亚胺化反应的温度为25-100℃，时间为2-24h。
  8. 一种聚酯酰亚胺薄膜，其特征在于，由权利要求1所述的聚酯酰亚胺共聚物制备得到。
  9. 根据权利要求8所述的聚酯酰亚胺薄膜，其特征在于，所述的聚酯酰亚胺薄膜的玻璃化转变温度≥300℃，热膨胀系数≤30ppm/K，在400nm的光学透过率≥70％。
  10. 根据权利要求8或9所述的聚酯酰亚胺薄膜在光学领域中的应用。
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