CN100395278C - Preparation method of poly-1,8-naphthalene diamine - Google Patents
Preparation method of poly-1,8-naphthalene diamine Download PDFInfo
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- CN100395278C CN100395278C CNB2005100236284A CN200510023628A CN100395278C CN 100395278 C CN100395278 C CN 100395278C CN B2005100236284 A CNB2005100236284 A CN B2005100236284A CN 200510023628 A CN200510023628 A CN 200510023628A CN 100395278 C CN100395278 C CN 100395278C
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- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 239000007800 oxidant agent Substances 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 31
- 229920001519 homopolymer Polymers 0.000 abstract description 8
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000013341 scale-up Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 30
- 239000012153 distilled water Substances 0.000 description 18
- 230000001590 oxidative effect Effects 0.000 description 18
- 239000000047 product Substances 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000879 imine group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- NQDAZSFONLAYGS-UHFFFAOYSA-L hydroxy-(hydroxy(dioxo)chromio)oxy-dioxochromium;potassium Chemical compound [K].O[Cr](=O)(=O)O[Cr](O)(=O)=O NQDAZSFONLAYGS-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
本发明属于1，8-萘二胺均聚物的制备方法领域。本发明所述的聚1，8-萘二胺的化学氧化制备方法步骤如下：将1，8-萘二胺溶于有机溶剂中使其充分溶解，然后将氧化剂的水溶液加入上述单体溶液中，反应完全后处理即可。本发明采用水或有机溶剂作为聚合介质，通过简单易行的化学氧化溶液聚合法，制备得到了1，8-萘二胺均聚物，产率高，最高可达98.0%。产量规模也可很大，能方便地进行放大实验，为开拓萘二胺均聚物的功能性研究提供了丰富的物质基础。且化学氧化聚合的聚1，8萘二胺可能有着和电聚合产物不同的结构和分子量，进而将赋予其不同的功能性和拓展空间。该发明为1，8-萘二胺均聚物的制备提供了经济有效的新途径。
The invention belongs to the field of preparation methods of 1,8-naphthalene diamine homopolymer. The steps of the chemical oxidation preparation method of poly-1,8-naphthalene diamine in the present invention are as follows: 1,8-naphthalene diamine is dissolved in an organic solvent to fully dissolve it, and then the aqueous solution of the oxidizing agent is added to the monomer solution , after the reaction is complete, it can be processed. The invention adopts water or an organic solvent as a polymerization medium, and prepares a 1,8-naphthalene diamine homopolymer through a simple and easy chemical oxidation solution polymerization method, and the yield is high, up to 98.0%. The production scale can also be very large, and the scale-up experiment can be conveniently carried out, which provides a rich material basis for developing the functional research of naphthalene diamine homopolymer. Moreover, the poly-1,8-naphthalene diamine chemically oxidatively polymerized may have a different structure and molecular weight from the electropolymerized product, which will endow it with different functionality and room for expansion. The invention provides an economical and effective new way for the preparation of 1,8-naphthalene diamine homopolymer.
Description
技术领域 technical field
本发明属于1，8-萘二胺均聚物的制备方法领域。The invention belongs to the field of preparation methods of 1,8-naphthalene diamine homopolymer.
背景技术 Background technique
萘二胺聚合物结构中的胺基和亚胺基可以赋予萘二胺聚合物的多功能性，其中最为显著的一点是对摩尔浓度为ppm级的金属离子如Ag+、Hg2+、Cu2+、Pb2+、VO2+等的敏感性。因其结构中含有大量的自由胺基，它和亚胺基处于相邻位置，可以与重金属离子发生络合反应形成稳定的络合物或发生氧化还原反应将金属离子还原成电中性金属，从而实现对金属离子的富集与探测等功能。而对萘二胺聚合物的制备大多为电化学的方法，在国内外还未见化学氧化聚合法合成聚1，8萘二胺的报道。聚1，8萘二胺的合成方法一直局限在电化学氧化聚合法，其反应场所是在电极表面附近，生成的聚合物一般在电极表面上成膜，显然，其产量面积受电极面积大小所制约，无法获得大量聚合物。因此能够开发研制出一种新的经济有效、具有良好收率且具有普遍适用性的制备聚1，8-萘二胺的方法是非常重要的。The amine group and imine group in the naphthalene diamine polymer structure can endow the naphthalene diamine polymer with multifunctionality, the most notable point of which is the molar concentration of metal ions such as Ag + , Hg 2+ , Cu 2+ , Pb 2+ , VO 2+ , etc. sensitivity. Because it contains a large number of free amine groups in its structure, it is adjacent to the imine group, and it can undergo complexation reactions with heavy metal ions to form stable complexes or undergo redox reactions to reduce metal ions to electrically neutral metals. In this way, functions such as enrichment and detection of metal ions can be realized. The preparation of naphthalene diamine polymers is mostly electrochemical, and there is no report on the synthesis of poly-1,8 naphthalene diamine by chemical oxidation polymerization at home and abroad. The synthesis method of poly-1,8-naphthalene diamine has always been limited to the electrochemical oxidation polymerization method. The reaction site is near the electrode surface, and the generated polymer generally forms a film on the electrode surface. Obviously, the production area is limited by the size of the electrode area. constraints, it is not possible to obtain large quantities of polymers. Therefore, it is very important to develop a new method for preparing poly-1,8-naphthalene diamine that is economical, effective, has good yield and has universal applicability.
发明内容 Contents of the invention
本发明的目的就是提供一种经济有效、具有良好收率的聚1，8-萘二胺的化学氧化制备方法。The object of the present invention is to provide an economical and effective chemical oxidation preparation method of poly-1,8-naphthalene diamine with good yield.
本发明采用有机溶剂或有机溶剂与水的混合溶液作为聚合介质，通过简单易行的化学氧化溶液聚合法，制备萘二胺均聚物。The invention adopts an organic solvent or a mixed solution of an organic solvent and water as a polymerization medium, and prepares naphthalene diamine homopolymer through a simple and feasible chemical oxidation solution polymerization method.
本发明所述的聚1，8-萘二胺的化学氧化制备方法步骤如下：将1，8-萘二胺溶于有机溶剂中使其充分溶解，然后将氧化剂的水溶液加入上述单体溶液中，反应完全处理即可。The steps of the chemical oxidation preparation method of poly-1,8-naphthalene diamine in the present invention are as follows: 1,8-naphthalene diamine is dissolved in an organic solvent to fully dissolve it, and then the aqueous solution of the oxidizing agent is added to the monomer solution , the reaction is completely processed.
本发明所述的有机溶剂可以是甲醇、乙醇、乙腈或丙腈等。The organic solvent of the present invention can be methanol, ethanol, acetonitrile or propionitrile and the like.
本发明所述的氧化剂为下述的一种或几种的共混物：过硫酸铵((NH4)2S2O8)、过硫酸钾(K2S2O8)、重铬酸钾(K2Cr2O7)、三氯化铁(FeCl3)。The oxidant of the present invention is one or more of the following blends: ammonium persulfate ((NH 4 ) 2 S 2 O 8 ), potassium persulfate (K 2 S 2 O 8 ), dichromic acid Potassium (K 2 Cr 2 O 7 ), Ferric Chloride (FeCl 3 ).
本发明所述的单体和氧化剂的摩尔比优选为0.5∶1～2∶1。The molar ratio of the monomer and the oxidizing agent in the present invention is preferably 0.5:1-2:1.
本发明中反应温度在10～30℃为最好，反应时间一般控制在6～10h为最好。In the present invention, the reaction temperature is best at 10-30° C., and the reaction time is generally controlled at 6-10 hours.
由本发明所制备的聚1，8-萘二胺(P18DAN)红外图谱(见图1)在3100～3600cm-1处同单体的红外图谱比较出现了宽吸收带，3100-3600cm-1的宽吸收带是N-H伸缩振动特征吸收，聚合物中由C-N伸缩振动引起的1260cm-1处吸收峰的出现，说明-C-NH-C-结构的存在，说明了聚合物P18DAN的生成。The prepared poly-1,8-naphthalene diamine (P18DAN) infrared spectrum (see Fig. 1) has a wide absorption band at 3100～3600cm -1 compared with the infrared spectrum of the monomer, the width of 3100-3600cm -1 The absorption band is the characteristic absorption of NH stretching vibration. The appearance of the absorption peak at 1260cm -1 caused by CN stretching vibration in the polymer indicates the existence of -C-NH-C- structure and the formation of polymer P18DAN.
本发明的有益效果：本发明采用水或有机溶剂作为聚合介质，通过简单易行的化学氧化溶液聚合法，制备得到了1，8-萘二胺均聚物，产率高，最高可达98.0％。产量规模也可很大，能方便地进行放大实验，为开拓萘二胺聚合物的功能性研究提供了丰富的物质基础。且化学氧化聚合的聚1，8萘二胺可能有着和电聚合产物不同的结构和分子量，进而将赋予其不同的功能性和拓展空间。该发明为1，8-萘二胺均聚物的制备提供了经济有效的新途径。Beneficial effects of the present invention: the present invention uses water or an organic solvent as the polymerization medium, and prepares 1,8-naphthalene diamine homopolymer through a simple and easy chemical oxidation solution polymerization method, with a high yield, up to 98.0 %. The production scale can also be very large, and the scale-up experiment can be conveniently carried out, which provides a rich material basis for developing the functional research of naphthalene diamine polymers. Moreover, the poly-1,8-naphthalene diamine chemically oxidatively polymerized may have a different structure and molecular weight from the electropolymerized product, which will endow it with different functionality and room for expansion. The invention provides an economical and effective new way for the preparation of 1,8-naphthalene diamine homopolymer.
附图说明 Description of drawings
图1为1，8-萘二胺单体和化学氧化聚合得到的P18DAN的FT-IR图谱。Figure 1 is the FT-IR spectrum of 1,8-naphthalene diamine monomer and P18DAN obtained by chemical oxidation polymerization.
具体实施方式 Detailed ways
实施例1：Example 1:
准确称取0.791g(5mmol)1，8萘二胺溶于50mL乙腈中，超声3～5分钟，促使其充分溶解。按氧化剂单体比1∶1称取1.141g(5mmol)过硫酸铵溶于50mL蒸馏水中，将其放置在20℃恒温水浴中预热至反应温度。20℃氧化剂溶液以1滴/3s左右的速度滴加到单体溶液中。滴加完毕后继续反应6h。反应结束，过滤，用蒸馏水洗涤初产物至滤液无色，再将聚合物滤饼转移到烧杯中继续搅拌洗涤过夜，抽滤干燥后得到质地松软的黑色粉末状聚合物，产量0.672g，产率85.0％。Accurately weigh 0.791 g (5 mmol) of 1,8-naphthalene diamine and dissolve it in 50 mL of acetonitrile, and ultrasonicate for 3 to 5 minutes to promote its full dissolution. Weigh 1.141 g (5 mmol) of ammonium persulfate according to the oxidant monomer ratio of 1:1, dissolve it in 50 mL of distilled water, and place it in a constant temperature water bath at 20° C. to preheat to the reaction temperature. The oxidant solution at 20°C is added dropwise to the monomer solution at a rate of about 1 drop/3s. After the dropwise addition, the reaction was continued for 6h. After the reaction is finished, filter, wash the initial product with distilled water until the filtrate is colorless, then transfer the polymer filter cake to a beaker and continue to stir and wash overnight, and obtain a soft black powdery polymer after suction drying, with a yield of 0.672g and a yield of 85.0%.
实施例2：Example 2:
准确称取0.791g(5mmol)1，8萘二胺溶于50mL乙腈中，超声3～5分钟，促使其充分溶解。按氧化剂单体比0.5∶1称取0.5705g(2.5mmol)过硫酸铵溶于50mL蒸馏水中，将其放置在20℃恒温水浴中预热至反应温度。20℃氧化剂溶液滴加到单体溶液中。滴加完毕后继续反应6h。反应结束，过滤，用蒸馏水洗涤初产物至滤液无色，再将聚合物滤饼转移到烧杯中继续搅拌洗涤过夜，抽滤干燥后得到质地松软的黑色粉末状聚合物，产量0.245g，产率31.0％。Accurately weigh 0.791 g (5 mmol) of 1,8-naphthalene diamine and dissolve it in 50 mL of acetonitrile, and ultrasonicate for 3 to 5 minutes to promote its full dissolution. Weigh 0.5705g (2.5mmol) of ammonium persulfate according to the oxidant monomer ratio of 0.5:1 and dissolve it in 50mL of distilled water, and place it in a constant temperature water bath at 20°C to preheat to the reaction temperature. The 20°C oxidant solution was added dropwise to the monomer solution. After the dropwise addition, the reaction was continued for 6h. After the reaction is finished, filter, and wash the initial product with distilled water until the filtrate is colorless, then transfer the polymer filter cake to a beaker and continue to stir and wash overnight, and obtain a soft black powdery polymer after suction drying, with a yield of 0.245g and a yield of 31.0%.
实施例3：Example 3:
准确称取0.791g(5mmol)1，8萘二胺溶于50mL乙腈中，超声3～5分钟，促使其充分溶解。按氧化剂单体比2∶1称取2.282g(10mmol)过硫酸铵溶于50mL蒸馏水中，将其放置在20℃恒温水浴中预热至反应温度。20℃氧化剂溶液滴加到单体溶液中。滴加完毕后继续反应6h。反应结束，过滤，用蒸馏水洗涤初产物至滤液无色，再将聚合物滤饼转移到烧杯中继续搅拌洗涤过夜，抽滤干燥后得到质地松软的黑色粉末状聚合物，产量0.775g，产率98.0％。Accurately weigh 0.791 g (5 mmol) of 1,8-naphthalene diamine and dissolve it in 50 mL of acetonitrile, and ultrasonicate for 3 to 5 minutes to promote its full dissolution. Weigh 2.282g (10mmol) of ammonium persulfate according to the oxidant monomer ratio of 2:1, dissolve it in 50mL of distilled water, and place it in a constant temperature water bath at 20°C to preheat to the reaction temperature. The 20°C oxidant solution was added dropwise to the monomer solution. After the dropwise addition, the reaction was continued for 6h. After the reaction is finished, filter, and wash the initial product with distilled water until the filtrate is colorless, then transfer the polymer filter cake to a beaker and continue stirring and washing overnight, and obtain a soft black powdery polymer after suction drying, with a yield of 0.775g and a yield of 98.0%.
实施例4：Example 4:
准确称取0.791g(5mmol)1，8萘二胺溶于50mL乙腈中，超声3～5分钟，促使其充分溶解。按氧化剂单体比1∶1称取1.141g(5mmol)过硫酸铵溶于50mL蒸馏水中，将其放置在30℃恒温水浴中预热至反应温度。30℃下将氧化剂溶液滴加到单体溶液中。滴加完毕后继续反应6h。反应结束，过滤，用蒸馏水洗涤初产物至滤液无色，再将聚合物滤饼转移到烧杯中继续搅拌洗涤过夜，抽滤干燥后得到质地松软的黑色粉末状聚合物，产量0.679g，产率85.8％。Accurately weigh 0.791 g (5 mmol) of 1,8-naphthalene diamine and dissolve it in 50 mL of acetonitrile, and ultrasonicate for 3 to 5 minutes to promote its full dissolution. Weigh 1.141 g (5 mmol) of ammonium persulfate according to the oxidant monomer ratio of 1:1, dissolve it in 50 mL of distilled water, and place it in a constant temperature water bath at 30° C. to preheat to the reaction temperature. The oxidant solution was added dropwise to the monomer solution at 30°C. After the dropwise addition, the reaction was continued for 6h. After the reaction is finished, filter, wash the initial product with distilled water until the filtrate is colorless, then transfer the polymer filter cake to a beaker and continue to stir and wash overnight, and obtain a soft black powdery polymer after suction drying, with a yield of 0.679g and a yield of 85.8%.
实施例5：Example 5:
准确称取0.791g(5mmol)1，8萘二胺溶于50mL乙腈中，超声3～5分钟，促使其充分溶解。按氧化剂单体比1∶1称取1.141g(5mmol)过硫酸铵溶于50mL蒸馏水中，将其放置在室温水浴中(约10℃)。将氧化剂溶液滴加到单体溶液中。滴加完毕后继续反应6h。反应结束，过滤，用蒸馏水洗涤初产物至滤液无色，再将聚合物滤饼转移到烧杯中继续搅拌洗涤过夜，抽滤干燥后得到质地松软的黑色粉末状聚合物，产量0.620g，产率78.4％。Accurately weigh 0.791 g (5 mmol) of 1,8-naphthalene diamine and dissolve it in 50 mL of acetonitrile, and ultrasonicate for 3 to 5 minutes to promote its full dissolution. Weigh 1.141 g (5 mmol) of ammonium persulfate according to the oxidant monomer ratio of 1:1, dissolve it in 50 mL of distilled water, and place it in a water bath at room temperature (about 10° C.). The oxidant solution was added dropwise to the monomer solution. After the dropwise addition, the reaction was continued for 6h. After the reaction is finished, filter, and wash the initial product with distilled water until the filtrate is colorless, then transfer the polymer filter cake to a beaker and continue to stir and wash overnight, and obtain a soft black powdery polymer after suction drying, with a yield of 0.620g and a yield of 78.4%.
实施例6：Embodiment 6:
准确称取1.582g(10mmol)1，8萘二胺溶解在100mL乙腈中，超声3～5分钟，促使其充分溶解。按氧化剂单体比1∶1称取2.282g(10mmol)过硫酸铵溶于100mL蒸馏水中。将其放置在20℃恒温水浴中预热至反应温度。20℃下将氧化剂溶液滴加到单体溶液中。滴加完毕后继续反应10h。反应结束，过滤，用蒸馏水洗涤初产物至滤液无色，再将聚合物滤饼转移到烧杯中继续搅拌洗涤过夜，抽滤干燥后得到质地松软的黑色粉末状聚合物，产量1.367g，产率86.4％。Accurately weigh 1.582g (10mmol) of 1,8-naphthalene diamine and dissolve it in 100mL of acetonitrile, and ultrasonicate for 3-5 minutes to promote its full dissolution. Weigh 2.282g (10mmol) of ammonium persulfate and dissolve it in 100mL of distilled water according to the oxidant monomer ratio of 1:1. Place it in a constant temperature water bath at 20°C to preheat to the reaction temperature. The oxidant solution was added dropwise to the monomer solution at 20°C. After the dropwise addition, the reaction was continued for 10 h. After the reaction is finished, filter, and wash the initial product with distilled water until the filtrate is colorless, then transfer the polymer filter cake to a beaker and continue to stir and wash overnight, and obtain a soft black powdery polymer after suction drying, with a yield of 1.367g and a yield of 86.4%.
实施例7：Embodiment 7:
准确称取0.791g(5mmol)1，8萘二胺溶于50mL乙腈中，超声3～5分钟，促使其充分溶解。按氧化剂单体比1∶1称取1.141g(5mmol)过硫酸铵溶于50mL蒸馏水中。将它们均放置在20℃恒温水浴中预热至反应温度，将氧化剂溶液一次性加入到单体溶液中，使其混合均匀，反应10h。反应结束，过滤，用蒸馏水洗涤初产物至滤液无色，再将聚合物滤饼转移到烧杯中继续搅拌洗涤过夜，抽滤干燥后得到质地松软的黑色粉末状聚合物，产量0.544g，产率68.8％。Accurately weigh 0.791 g (5 mmol) of 1,8-naphthalene diamine and dissolve it in 50 mL of acetonitrile, and ultrasonicate for 3 to 5 minutes to promote its full dissolution. Weigh 1.141 g (5 mmol) of ammonium persulfate and dissolve it in 50 mL of distilled water according to the oxidant monomer ratio of 1:1. They were all placed in a constant temperature water bath at 20°C and preheated to the reaction temperature, and the oxidizing agent solution was added to the monomer solution at one time, mixed evenly, and reacted for 10 hours. After the reaction is finished, filter, and wash the initial product with distilled water until the filtrate is colorless, then transfer the polymer filter cake to a beaker and continue stirring and washing overnight, and obtain a soft black powdery polymer after suction drying, with a yield of 0.544g and a yield of 68.8%.
实施例8：Embodiment 8:
称取0.791g(5mmol)1，8萘二胺溶于50mL乙腈中，超声3～5分钟，促使其充分溶解。按氧单比1∶1称取0.8125g(5mmol)三氯化铁溶于50mL蒸馏水中，将其放置在20℃恒温水浴中预热至反应温度。20℃下将氧化剂溶液滴加到单体溶液中。滴加完毕后继续反应6h，反应结束，过滤，用蒸馏水洗涤初产物至滤液无色，再将聚合物滤饼转移到烧杯中继续搅拌洗涤过夜，抽滤干燥后得到质地坚硬的黑色粉末状聚合物，产量0.7689g，产率97.2％。Weigh 0.791 g (5 mmol) of 1,8-naphthalene diamine and dissolve it in 50 mL of acetonitrile, and ultrasonicate for 3 to 5 minutes to promote its full dissolution. Weigh 0.8125g (5mmol) of ferric trichloride and dissolve it in 50mL of distilled water according to the oxygen ratio of 1:1, and place it in a constant temperature water bath at 20°C to preheat to the reaction temperature. The oxidant solution was added dropwise to the monomer solution at 20°C. After the dropwise addition, continue to react for 6 hours. After the reaction is completed, filter and wash the initial product with distilled water until the filtrate is colorless. Then transfer the polymer filter cake to a beaker and continue stirring and washing overnight. After suction filtration and drying, a hard black powder polymer The yield is 0.7689g, and the yield is 97.2%.
实施例9：Embodiment 9:
称取0.791g(5mmol)1，8萘二胺溶于50mL乙腈中，超声3～5分钟，促使其充分溶解。按氧单比1∶1称取0.8125g(5mmol)三氯化铁溶于50mL蒸馏水中，将其放置在室温水浴中(约10℃)。将氧化剂溶液滴加到单体溶液中。滴加完毕后继续反应8h，反应结束，过滤，用蒸馏水洗涤初产物至滤液无色，再将聚合物滤饼转移到烧杯中继续搅拌洗涤过夜，抽滤干燥后得到质地坚硬的黑色粉末状聚合物，产量0.7248g，产率91.6％。Weigh 0.791 g (5 mmol) of 1,8-naphthalene diamine and dissolve it in 50 mL of acetonitrile, and ultrasonicate for 3 to 5 minutes to promote its full dissolution. Weigh 0.8125g (5mmol) of ferric chloride according to the ratio of oxygen to 1:1, dissolve it in 50mL of distilled water, and place it in a water bath at room temperature (about 10°C). The oxidant solution was added dropwise to the monomer solution. After the dropwise addition, continue to react for 8 hours. After the reaction is completed, filter and wash the initial product with distilled water until the filtrate is colorless. Then transfer the polymer filter cake to a beaker and continue stirring and washing overnight. After suction filtration and drying, a hard black powder polymer The yield is 0.7248g, and the yield is 91.6%.
确定的聚合物结构对应着确定的C/H/N比率，所以可通过对C/H/N比率的研究来分析聚合物的结构。表一是由本发明所制备的聚1，8-萘二胺的元素分析结果。The determined polymer structure corresponds to the determined C/H/N ratio, so the structure of the polymer can be analyzed by studying the C/H/N ratio. Table 1 is the elemental analysis results of poly-1,8-naphthalene diamine prepared by the present invention.
表一P18DAN的元素分析Table 1 Elemental analysis of P18DAN
表一显示：P18DANF元素分析结果计算得到的试验C/H/N比率与由b结构式计算获得的比率极为接近，即聚合物P18DANF单元结构与结构式b相似，这一结果显示，P18DAN链节在氧化聚合过程中发生了脱氮反应，每五个萘二胺单元脱去二个氮原子，元素分析结果计算得到的分子式中H的含量高于结构式b中的H含量，可能原因是聚合物P18DANF中含有Fe3+离子而吸水使得检测到的H含量偏高。P18DANS单元结构与结构式d较为吻合。这一结果显示，P18DAN链节在氧化聚合过程中发生了脱氮反应，每五个萘二胺单元脱去二个氮原子，并且P18DAN链节中存在醌式结构式，但氢原子数目有点出入，主要是端胺基的影响。Table 1 shows that the experimental C/H/N ratio calculated from the P18DAN F elemental analysis results is very close to the ratio calculated from the structural formula b, that is, the polymer P18DAN F unit structure is similar to the structural formula b. This result shows that the P18DAN chain link During the oxidative polymerization process, denitrogenation reaction occurred, and two nitrogen atoms were removed for every five naphthalene diamine units. The content of H in the molecular formula calculated from the elemental analysis results was higher than that in structural formula b. The possible reason is that the polymer P18DAN F contains Fe 3+ ions and absorbs water so that the detected H content is high. The S unit structure of P18DAN is in good agreement with the structural formula d. This result shows that the P18DAN chain unit undergoes denitrogenation reaction during the oxidative polymerization process, and two nitrogen atoms are removed for every five naphthalene diamine units, and there is a quinone structure in the P18DAN chain unit, but the number of hydrogen atoms is slightly different. Mainly due to the influence of the terminal amine group.
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| US5162509A (en) * | 1989-03-06 | 1992-11-10 | Board Of Regents, The University Of Texas System | Process for preparing expanded porphyrins: large porphyrin-like tripyrroledimethine-derived macrocycles |
| JPH06322115A (en) * | 1993-05-14 | 1994-11-22 | Osaka Gas Co Ltd | Polyaminoazonaphthalene and its production |
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| JPH06322115A (en) * | 1993-05-14 | 1994-11-22 | Osaka Gas Co Ltd | Polyaminoazonaphthalene and its production |
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