CN108530308A - 一种多氟取代的二胺化合物及其制备方法 - Google Patents
一种多氟取代的二胺化合物及其制备方法 Download PDFInfo
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- CN108530308A CN108530308A CN201810576391.XA CN201810576391A CN108530308A CN 108530308 A CN108530308 A CN 108530308A CN 201810576391 A CN201810576391 A CN 201810576391A CN 108530308 A CN108530308 A CN 108530308A
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- -1 diamine compound Chemical class 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 14
- 239000011737 fluorine Substances 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 34
- 150000001721 carbon Chemical group 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- AZSZCFSOHXEJQE-UHFFFAOYSA-N dibromodifluoromethane Chemical group FC(F)(Br)Br AZSZCFSOHXEJQE-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical class OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003282 alkyl amino group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 125000004438 haloalkoxy group Chemical group 0.000 claims 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
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- 125000002252 acyl group Chemical group 0.000 claims 1
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- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims 1
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- 150000002989 phenols Chemical class 0.000 claims 1
- 125000000547 substituted alkyl group Chemical group 0.000 claims 1
- 229920001721 polyimide Polymers 0.000 abstract description 15
- 239000004642 Polyimide Substances 0.000 abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- AQHJZQNRAWNMKF-UHFFFAOYSA-N 1,2,3,4,5,6-hexafluoronaphthalene Chemical group FC1=C(F)C(F)=C(F)C2=C(F)C(F)=CC=C21 AQHJZQNRAWNMKF-UHFFFAOYSA-N 0.000 abstract description 3
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- 239000002904 solvent Substances 0.000 description 9
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- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
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- 239000003054 catalyst Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
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- 125000005591 trimellitate group Chemical group 0.000 description 5
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 150000001350 alkyl halides Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
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- 150000002170 ethers Chemical class 0.000 description 3
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- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
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Abstract
公开了一种用于合成聚酰亚胺单体的新型多氟取代的二胺化合物，所述化合物由式(I)表示。此外还公开了上述二胺化合物的制备方法。由于引入六氟萘结构，结合含氟桥键，在远紫外和近红外区光的透过性较佳。与此同时，上述结构进一步增加聚酰亚胺分子主链之间的相互作用，从而在保持较高透明性的同时，兼具优良的力学性能；同时与其它基体的亲和性较好。此外，该制备方法简单方便，合成收率和纯度较高。
Description
技术领域
本发明属于光学材料领域。具体地，涉及一种多氟取代的二胺化合物及其制备方法。
背景技术
聚酰亚胺(PI)是分子结构含有酰亚胺五元环的一类高分子材料，主要通过芳香族二酐化合物与二胺化合物通过缩聚方法制得。这类化合物由于其具有优良的热稳定性、机械强度、介电性能、绝缘特性，并且具有突出的韧性和柔软性等特点，逐渐应用于很多领域，特别是近年来发展较快的柔性显示行业。
随着航空航天、太阳能、微电子等工业的发展，不断对聚酰亚胺材料的耐热性能、介电性能、力学性能以及透明性提出进一步的要求。由于传统的聚酰亚胺分子主链的高度芳香共轭性和分子链内电荷络合转移作用，聚酰亚胺薄膜通常有颜色，同时光透过性较差，在可见光区域几乎不透明。
为改善聚酰亚胺薄膜在这些领域中的使用特性，研究者已进行了一系列的探索工作，部分研究工作也取得了一些效果。例如，中国专利申请CN101674923A公开了一种无色透明聚酰亚胺薄膜的制备方法及制备装置，该方法采用脂环二酐化合物1,2,4,5-环己烷四酸二酐与二胺化合物聚合工艺制得，采用该溶液直接制备无色透明聚酰亚胺薄膜，制得的厚度为200μm薄膜的透光率为89.8％。中国专利申请CN102634022A公开了一种无色高透明聚酰亚胺薄膜及其制备方法与应用，采用脂肪二酐与不同二胺聚合得到透明性很好的聚酰亚胺薄膜。然而，上述聚酰亚胺薄膜的耐热性不能令人满意。
在此基础上，中国专利申请CN106674027A公开了一种使用具有含氟桥健和含氟苯的二胺与二酐制备的聚酰亚胺薄膜。该聚酰亚胺薄膜在耐热性、溶解性和透明性等方面均具有比较优异的性能。然而，在带来高透明性的同时，含氟桥健和含氟苯的引入导致该聚酰亚胺薄膜的力学性能降低，而且与其它基体的亲和性也不能令人满意。
发明内容
根据以上背景，本发明所解决的技术问题是如何更好地使聚酰亚胺薄膜在具有高透明性的同时兼具优良的力学性能；同时与其它基体的亲和性较好。
基于此，本发明目的之一是克服现有技术的不足，提供一种用于合成聚酰亚胺单体的新型多氟取代的二胺化合物。这可以改善聚酰亚胺的力学性能，并且竭力改善聚酰亚胺薄膜的透明性。
本发明目的之二是提供一种上述新型多氟取代的二胺化合物的制备方法。该方法合成简单、易于操作、设备成本低且无污染。
为实现上述目的，一方面，本发明采用下列技术方案：一种多氟取代的二胺化合物，其特征在于，所述化合物由式(I)表示，
其中，
R1、R2和R各自独立地选自卤素、氨基、羟基、硝基、氰基、1至12个碳原子的烷基、1至12个碳原子的烷氧基、1至12个碳原子的氨烷基、1至12个碳原子的烷氨基、2至12个碳原子的烷基酰基、2至12个碳原子的烷基酰氨基、1至12个碳原子的烷氧基酰基、1至12个碳原子的硫代烷基、1至12个碳原子的烷硫基、1至12个碳原子的卤代烷基、1至12个碳原子的卤代烷氧基、芳基或杂芳基；
X各自独立地选自CF2O、OCF2、CHFO、OCHF、CF2和CHF；
n和m各自独立地为0～4的整数；
条件是，至少一个R选自卤素、1至12个碳原子的卤代烷基或1至12个碳原子的卤代烷氧基。
作为表示R1、R2和R的卤素，选自氟、氯、溴和碘。
作为表示R1、R2和R的卤代烷(氧)基，表示烷基中的一个或多个CH2中的H原子被卤素取代的烷(氧)基。
优选地，卤代烷(氧)基是C1-C10卤代烷(氧)基，C1-C8卤代烷(氧)基，C1-C6卤代烷(氧)基，或C1-C4卤代烷(氧)基。
卤代烷(氧)基的非限制性实例包括卤代甲烷(氧)基，卤代乙烷(氧)基，卤代丙烷(氧)基，卤代异丙烷(氧)基，卤代丁烷(氧)基，卤代异丁烷(氧)基，卤代仲-丁烷(氧)基，卤代叔-丁烷(氧)基，卤代戊烷(氧)基，和卤代己烷(氧)基。
进一步地，例如卤代烷基的非限制性实例包括氯代甲(氧)基，1-溴代乙(氧)基，氟代甲(氧)基，二氟甲(氧)基，三氟甲(氧)基，1,1,1-三氟乙(氧)基，等等。
多数情形中，本发明的取代基包含1至12个碳原子。以烷基为例，其可以是直链或支链的，并且可以是如本文指出的被取代的。当使用“1至12个碳原子的烷基”的术语时，等同于C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11或C12。其它取代基定义类似，不再赘述。
优选，1至12个碳原子的烷基是C1-C10烷基，C1-C8烷基，C1-C6烷基，或C1-C4烷基。
进一步地，例如，C1-C6烷基包括所有具有1至6个碳原子的直链、支链的烷基，从而包括甲基、乙基、正丙基、异丙基、丁基和其异构体(例如正丁基、异丁基和叔丁基)、戊基和其异构体、己基和其异构体。
根据本发明的二胺化合物，其中，X各自独立地选自CF2O、OCF2、CHFO、OCHF、CF2和CHF。
基于合成的便利性，优选地，X各自独立地选自CF2O、OCF2、CHFO和OCHF；以及，最优选地，X各自独立地选自OCF2和CF2O。
在一个具体的实施方式中，式(1)萘环左侧的X选自OCF2，右侧的X选自CF2O。
根据本发明的二胺化合物，其中，R各自独立地选自卤素、1至12个碳原子的卤代烷基、1至12个碳原子的卤代烷氧基。
优选地，R各自独立地选自卤素、1至8个碳原子的卤代烷基、1至8个碳原子的卤代烷氧基；更优选地，R各自独立地选自卤素、1至6个碳原子的卤代烷基、1至6个碳原子的卤代烷氧基；以及，最优选地，R各自独立地选自卤素、1至3个碳原子的卤代烷基、1至3个碳原子的卤代烷氧基。
在一个实施方式中，R各自独立地选自氟、三氟甲基或三氟甲氧基。
在一个具体的实施方式中，R各自独立地选自氟。
根据本发明的二胺化合物，其中，n和m各自独立地为0～2的整数。优选地，n和m各自独立地为0或1。
在一个具体的实施方式中，n和m各自独立地为0。
根据本发明的二胺化合物，其中，NH2的取代位置为X基团的邻位、对位和间位。优选地，NH2的取代位置为X基团的邻位或对位。
在一个具体的实施方式中，NH2的取代位置为基团X的对位。
根据本发明的二胺化合物，其中，所述化合物选自下列式(II)化合物
另一方面，本发明采用下列技术方案：一种制备根据本发明二胺化合物的方法，包括如下步骤：
(1)使式(III)的化合物
反应生成式(IV)的二硝基化合物；
(2)使式(IV)的二硝基化合物还原，制得本发明的二胺化合物。
根据本发明的制备方法，其中，所述式(III)的化合物进一步选自式(III-1)的化合物，
本发明中，式(III-1)的化合物是已知化合物，CAS号为76238-88-5P；系根据文献(Selivanov,B.A.等，Zhurnal Organicheskoi Khimii(1980),16(9),1910-1924)合成得到，直接用于本发明工作。
根据本发明的制备方法，其中，进一步包括使式(III)的化合物与丁基锂反应生成式(III)的化合物锂盐的步骤。
在一个具体的实施方式步骤，式(III-1)的化合物与丁基锂反应生成式(III-1)的化合物锂盐。
根据本发明的制备方法，其中，进一步包括使式(III)的化合物锂盐与卤代烷烃反应形成中间体的步骤；所述中间体与取代或未取代的硝基苯酚反应生成式(IV)的化合物。
在一个具体的实施方式中，所述卤代烷烃为二氟二溴甲烷。式(III-1)的化合物锂盐与二氟二溴甲烷进一步反应形成中间体。所述中间体与对硝基苯酚反应。
在本发明二胺化合物的制备方法中，根据需要可以使用溶剂。作为上述溶剂，只要能够使特定二胺化合物溶解，且不会妨碍反应，对其没有特别限制。可以列举例如苯、甲苯等芳香族烃类；乙醚、四氢呋喃、二氧六环等醚类；丙酮、甲基乙基酮、甲基异丁基酮等酮类；以及，二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺等。
在制备方法中，式(III)的化合物与取代或未取代的硝基苯酚化合物的使用比率，相对于1摩尔式(III)的化合物，后者优选为2～20摩尔。进一步地，优选为2～10摩尔；更优选为2～5摩尔；以及，最优选为2～3摩尔。
当式(IV)的二硝基化合物还原时，可以用氢气、肼、盐酸等还原剂在已知的催化剂存在下进行。
作为上述催化剂，可以列举例如以VIII族金属，即铁、钴、镍、钌、铑、钯、锇、铟、铂等金属为活性主体的金属催化剂，具体地,可以列举金属负载在载体上的催化剂、上述金属的配位催化剂。上述还原反应可以是均相体系也可以是非均相体系。
在一个具体的实施方式中，催化剂选自钯，负载在活性炭上。
催化剂的用量可以使用适当的比率。例如当催化剂以上述VIII族金属为活性主体时，相对于100重量份二硝基化合物，优选使用0.0001～100重量份，特别优选使用0.001～20重量份。此外，作为上述还原反应，还可使用锌、锡、碳化锡(II)、硫化钠、硫化氢钠、连二亚硫酸钠、硫化铵作为还原剂的方法。相对于1摩尔二硝基化合物的硝基，还原剂优选使用0.001～10摩尔。
作为上述还原反应中使用的溶剂，优选能够同时溶解二硝基化合物和二胺化合物，且不会因还原反应而变质的溶剂，可以列举例如甲醇、乙醇、丙醇、丁醇等醇类；乙醚、1，2-二甲氧基乙烷、四氢呋喃、二氧六环、茴香醚等醚类。
在一个具体的实施方式中，当制备式(II)的二胺化合物时，制备方法如下：
(1)式(III-1)的化合物低温下以四氢呋喃为溶剂，通过与丁基锂反应合成式(III-1)化合物的锂试剂；
(2)低温下向上述反应液加入2～3当量的二氟二溴甲烷，反应完毕后用稀盐酸淬灭反应，处理后得到油状的浓缩物；
(3)以上步骤得到的油状物在非质子性溶剂，无机碱存在下，加入对硝基苯酚，室温反应后经过系列处理，得到黄色固体；
(4)上述固体溶解在甲苯、乙醇或者四氢呋喃中，在Pd/C以及氢气作用下，还原为二胺化合物。
又一方面，为了制备合适的聚酰亚胺薄膜，首先由本发明的二胺化合物与四羧酸二酸酐通过缩聚反应得到聚酰胺酸；然后聚酰胺酸脱水闭环得到。
作为本发明使用的四羧酸二酸酐，可以是芳香族四羧酸二酸酐。均苯四酸二酐、3,3’,4,4’-二苯酮四羧酸二酸酐、3,3’,4,4’-二苯基砜四羧酸二酸酐、1,4,5,8-萘四羧酸二酸酐、2,3,6,7-萘四羧酸二酸酐、3,3’,4,4’-二苯基醚四羧酸二酸酐、3,3’,4,4’-二甲基二苯基硅烷四羧酸二酸酐、3,3’,4,4’-四苯基硅烷四羧酸二酸酐、1,2,3,4-呋喃四羧酸二酸酐、4,4’-二(3,4-二羧基苯氧基)二苯基硫醚二酸酐、4,4’-二(3,4-二羧基苯氧基)二苯基砜二酸酐、4,4’-二(3,4-二羧基苯氧基)二苯基丙烷二酸酐、3,3’,4,4’-全氟异亚丙基二酞酸二酐、3,3’,4,4’-联苯四羧酸二酸酐、二(酞酸)苯膦氧化物二酸酐、对-亚苯基-二(三苯基酞酸)二酐、间-亚苯基-二(三苯基酞酸)二酐、二(三苯基酞酸)-4,4’-二苯醚二酐、二(三苯基酞酸)-4,4’-二苯基甲烷二酐、乙二醇-二(脱水偏苯三酸酯)、丙二醇-二(脱水偏苯三酸酯)、1,4-丁二醇-二(脱水偏苯三酸酯)、1,6-己二醇-二(脱水偏苯三酸酯)、1,8-辛二醇-二(脱水偏苯三酸酯)、2,2-二(4-羟苯基)丙烷-二(脱水偏苯三酸酯)。
作为本发明使用的四羧酸二酸酐，可以是脂环族四羧酸二酸酐。可以列举丁烷四羧酸二酸酐、1,2,3,4-环丁烷四羧酸二酸酐、1,2-二甲基-1,2,3,4-环丁烷四羧酸二酸酐、1,3-二甲基-1,2,3,4-环丁烷四羧酸二酸酐、1,3-二氯-1,2,3,4-环丁烷四羧酸二酸酐、1,2,3,4-四甲基-1,2,3,4-环丁烷四羧酸二酸酐、1,2,3,4-环戊烷四羧酸二酸酐、1,2,4,5-环己烷四羧酸二酸酐、1,2,4,5-降冰片烷四羧酸二酸酐、3,3’,4,4’-二环己基四羧酸二酸酐、2,3,5-三羧基环戊基醋酸二酐、3,5,6-三羧基降冰片烷-2-醋酸二酐、2,3,4,5-四氢呋喃四羧酸二酸酐、1,3,3a,4,5,9b-六氢-5-(四氢-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氢-5-甲基-5-(四氢-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氢-5-乙基-5-(四氢-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氢-7-甲基-5-(四氢-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氢-7-乙基-5-(四氢-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氢-8-甲基-5-(四氢-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氢-8-乙基-5-(四氢-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氢-5,8-二甲基-5-(四氢-2,5-二氧代-3-呋喃基)-萘[1,2-c]-呋喃-1,3-二酮、5-(2,5-二氧代四氢呋喃亚甲基)-3-甲基-3-环己烯-1,2-二羧酸二酐、双环[2,2,2]-辛-7-烯-2,3,5,6-四羧酸二酸酐、3-氧杂双环[3.2.1]辛烷-2,4-二酮-6-螺-3’-(四氢呋喃-2’,5’-二酮)。
它们可以1种单独或者2种或以上组合使用。
在具体的实施方式中，所述四羧酸二酸酐选自下列化合物的至少一种：
本发明的聚酰胺酸通过使二胺化合物与四羧酸二酸酐反应制得。四羧酸二酸酐与二胺化合物的使用比率，优选相对于1当量二胺化合物中所含的氨基，使四羧酸二酸酐的酸酐基为0.2～2当量的比率，更优选为0.3～1.2当量的比率。
聚酰胺酸的合成反应，在有机溶剂中于100～250℃、优选于150～220℃、更优选于170～200℃的温度条件下进行。
作为有机溶剂，只要能够溶解或者分散合成的聚酰胺酸，对其没有特别限制。可以例示例如N-甲基-2-吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、二甲基亚砜、γ-丁内酯、四甲基脲、六甲基亚磷酸三酰胺等非质子极性溶剂；间甲基酚、二甲苯酚、苯酚、卤代苯酚等酚类溶剂。
此外，在不使生成的聚酰胺酸析出的范围内，上述有机溶剂中还可以联合使用聚酰胺酸不良溶剂醇类、酮类、酯类、醚类、卤代烃类、烃类等。作为这种不良溶剂的具体例子，可以列举例如甲醇、乙醇、异丙醇、环己醇、乙二醇、丙二醇、1,4-丁二醇、三甘醇、乙二醇单甲醚、乳酸乙酯、乳酸丁酯、丙酮、甲基乙基酮、甲基异丁基酮、环己酮、醋酸甲酯、醋酸乙酯、醋酸丁酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、草酸二乙酯、丙二酸二乙酯、乙醚、乙二醇甲醚、乙二醇乙醚、乙二醇正丙醚、乙二醇异丙醚、乙二醇正丁醚、乙二醇二甲基醚、乙二醇乙醚乙酸酯、二甘醇二甲醚、二甘醇二乙醚、二甘醇单甲醚、二甘醇单乙醚、二甘醇单甲醚乙酸酯、二甘醇单乙醚乙酸酯、四氢呋喃、二氯甲烷、1,2-二氯乙烷、1,4-二氯丁烷、三氯乙烷、氯苯、邻二氯苯、己烷、庚烷、辛烷、苯、甲苯、二甲苯等。
如上所述，得到溶解聚酰胺酸的反应溶液。然后，将该反应溶液分散到大量不良溶剂中，得到析出物。然后，将析出物过滤、洗涤、干燥，得到聚酰胺酸。
随后，将聚酰胺酸溶解在有机溶剂中，在洁净基板上涂膜，然后逐渐烘干，最后烘干，冷却，得到聚酰亚胺薄膜。
在一个具体的实施方式中，制备方法如下：
(1)将等当量的二胺以及二酐在氮气或者氩气保护下，加入到间甲酚溶剂中，升温到180～200℃，加热8～15小时，然后冷却至室温，用甲醇溶剂进行分散，过滤，洗涤，干燥，得到聚酰胺酸(预聚体)；
(2)将聚酰胺酸溶于有机溶剂中，然后在洁净的基板上涂膜，然后逐渐烘干，最后在200～300℃烘干120分钟，冷却，得到聚酰亚胺薄膜。
本发明二胺化合物制备的聚酰亚胺薄膜可以用于市场上多种光电器件，包括，但不限于，光电子器件、太阳能电池器件、柔性显示器件(例如OLED和LCD)、电子书、电子标签或光电传感器。优选地，所述光电器件选自太阳能电池器件、柔性显示器件(例如OLED和LCD)。这部分光电器件对透明性和力学性能要求更高，必须同时兼具两种性能的平衡。
不希望局限于任何理论，发明人发现，与传统的聚酰亚胺分子主链的高度芳香共轭性和分子链内电荷络合转移作用通常会导致透明性降低不同，当在聚酰亚胺分子中引入六氟萘结构时，结合含氟桥键(OCF2和CF2O)，在远紫外和近红外区光的透过性较佳。与现有技术相比，透明性大致在同一水平。与此同时，上述结构进一步增加聚酰亚胺分子主链之间的相互作用，从而在保持较高透明性的同时，兼具优良的力学性能；同时与其它基体的亲和性较好。
另一方面，本发明的制备方法简单方便，合成收率和纯度较高。
具体实施方式
下面结合具体实施方式，进一步阐述本发明。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。此外应理解，在阅读了本发明的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
通过下述实施例将有助于理解本发明，但不能限制本发明的范围。
实施例1：制备式(II)的化合物
(1)1L三口瓶内加入35.4g(0.15mol)的式(III-1)化合物，500ml四氢呋喃，安装好搅拌，冷浴、滴加以及氮气保护装置，开动搅拌，在氮气保护下降温至-80℃，滴加150ml丁基锂溶液(0.35mol)，滴加完毕后，保持-70℃以下搅拌1h，然后继续滴加二氟二溴甲烷溶液(含有0.40mol二氟二溴甲烷)，保持-70℃以下，滴加完毕，继续搅拌1h，然后用10％的稀盐酸进行水解，进而后处理，得到棕褐色油状物45g，收率61％，不需进一步处理，直接进行下一步反应。
(2)1L三口瓶内加入步骤(1)制得的油状物40g，500ml二甲基甲酰胺，1g碘化钾，22.5g对硝基苯酚，加热至105℃，反应4小时后，停止加热，冷却后，向反应体系中加入冰水，至产品析出，过滤，洗涤后，用乙醇进行结晶，得到黄色固体24.2g，收率48％，纯度98％。1HNMR(δ,ppm,DMSO-d6):8.39(d,4H,ArH),8.27(d,4H,ArH)；FTIR(KBr,cm-1):1582,1343(-NO2),1198(C-F),1165(C-F)；元素分析:C24H8F10N2O6(610.31)；理论值:C 47.23％,F31.13％,N 4.59％,O 15.73％，实测值：C 47.56％,F 30.89％,N 4.52％,O 15.34％。
(3)1L高压釜内加入20g上步制得的二硝基化合物，150ml甲苯，100ml乙醇，1g 5％的Pd/C，常温常压加氢8小时，通过气相色谱监控反应合格后，进行下一步的处理，过滤，浓缩，并用120ml异丙醇结晶，得到粉红色固体粉末，干燥后得16.5g，气相色谱纯度99％，收率91％。1H NMR(δ,ppm,DMSO-d6):8.14(d,4H,ArH),7.82(d,4H,ArH),5.91(s,4H,NH2)；FTIR(KBr,cm-1):3418(-NH2),3367(-NH2),1204(C-F),1132(C-F)；元素分析:C24H12F10N2O2(550.35)；理论值:C52.38％,F 34.52％,N 5.06％,O 5.81％，实测值：C 52.47％,F34.39％,N 5.15％,O5.64％。
实施例2：制备聚酰胺酸
在500mL三口瓶内，加入实施例1的二胺化合物8g，以及6.4g下列二酐，
300g间甲酚，加热至190℃，反应8小时后，冷却至60℃左右，将反应液在搅拌下分散到甲醇中，冷却后吸滤，并用甲醇洗涤。干燥，得到12.8g丝状固体。数均分子量Mn＝10.5×104，分子量分布PDI指数＝2.12。分子量及分子量分布在PE Series 200GPC仪上进行检测，聚苯乙烯为标样。
实施例3：制备聚酰胺酸
在500mL三口瓶内，加入实施例1的二胺化合物8g，以及2.9g环丁烷四甲酸二酐，300g间甲酚，加热至170℃，反应8小时后，冷却至60℃左右，将反应液在搅拌下分散到甲醇中，冷却后吸滤，并用甲醇洗涤。干燥，得到9.2g丝状固体。数均分子量Mn＝7.7×104，分子量分布PDI指数＝1.98。分子量及分子量分布在PE Series 200GPC仪上进行检测，聚苯乙烯为标样。
应用实施例1-2：聚酰亚胺薄膜及其性能
将实施例2-3制得的丝状固体溶解在5％的N-甲基吡咯烷酮中，配成5％的溶液，用0.45μm的滤膜进行过滤，以除去机械杂质。然后将聚合物溶液涂在洁净的玻璃基板上，50℃烘干1小时，100℃1小时，最后200℃烘干2小时，冷却至室温，脱膜，分别制得厚度为约20μm的透明聚酰亚胺薄膜，作为本发明应用实施例1-2。
其中，上述聚酰亚胺薄膜的光学透明性和热稳定性分别在UV-可见分光光度计和TGA/DSC同步热分析仪上测定；聚酰亚胺薄膜的力学性能在CMT-4104型万能试验机上测试，试样按照上述相同方法制备，尺寸为60×10×0.045mm3，测试起始力为5Kg，拉伸速率为2mm/min，测试结果取3次平均值。
应用比较例：应用比较例：分别将中国专利申请CN106674027A实施例3和2的聚酰亚胺薄膜按照本发明相同的方法进行上述测试，分别作为应用比较例1和2。
结果参见表1。
表1
由表1可以看出，当在聚酰亚胺分子中引入六氟萘结构时，结合含氟桥键(OCF2和CF2O)，在远紫外和近红外区光的透过性较佳。与比较例1-2相比，透明性大致在同一水平。与此同时，上述结构进一步增加聚酰亚胺分子主链之间的相互作用，从而在保持较高透明性的同时，兼具优良的拉伸强度和断裂伸长率；同时与其它基体的亲和性较好。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均包含在本发明的保护范围之内。
Claims (10)
1.一种多氟取代的二胺化合物，其特征在于，所述化合物由式(I)表示，
其中，
R1、R2和R各自独立地选自卤素、氨基、羟基、硝基、氰基、1至12个碳原子的烷基、1至12个碳原子的烷氧基、1至12个碳原子的氨烷基、1至12个碳原子的烷氨基、2至12个碳原子的烷基酰基、2至12个碳原子的烷基酰氨基、1至12个碳原子的烷氧基酰基、1至12个碳原子的硫代烷基、1至12个碳原子的烷硫基、1至12个碳原子的卤代烷基、1至12个碳原子的卤代烷氧基、芳基或杂芳基；
X各自独立地选自CF2O、OCF2、CHFO、OCHF、CF2和CHF；
n和m各自独立地为0～4的整数；
条件是，至少一个R选自卤素、1至12个碳原子的卤代烷基或1至12个碳原子的卤代烷氧基。
2.根据权利要求1所述的二胺化合物，其中，X各自独立地选自OCF2和CF2O。
3.根据权利要求1所述的二胺化合物，其中，R各自独立地选自氟。
4.根据权利要求1所述的二胺化合物，其中，n和m各自独立地为0。
5.根据权利要求1所述的二胺化合物，其中，NH2的取代位置为基团X的对位。
6.一种制备根据权利要求1-5任一项所述二胺化合物的方法，包括如下步骤：
(1)使式(III)的化合物
反应生成式(IV)的二硝基化合物；
(2)使式(IV)的二硝基化合物还原，制得根据权利要求1-5任一项所述的二胺化合物。
7.根据权利要求6所述的制备方法，进一步包括使式(III)的化合物与丁基锂反应生成式(III)的化合物锂盐的步骤。
8.根据权利要求6所述的制备方法，进一步包括使式(III)的化合物锂盐与卤代烷烃反应形成中间体的步骤；所述中间体与取代或未取代的硝基苯酚反应生成式(IV)的化合物。
9.根据权利要求6所述的制备方法，其中，所述卤代烷烃为二氟二溴甲烷。
10.根据权利要求6所述的制备方法，其中，式(III)的化合物与取代或未取代的硝基苯酚化合物的使用比率，相对于1摩尔式(III)的化合物，后者为2～3摩尔。
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