CN100410295C - High temperature reflux oxidation preparation method of poly-o-phenylenediamine - Google Patents
High temperature reflux oxidation preparation method of poly-o-phenylenediamine Download PDFInfo
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- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000010992 reflux Methods 0.000 title claims abstract description 16
- 230000003647 oxidation Effects 0.000 title claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 229960000583 acetic acid Drugs 0.000 claims abstract description 12
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000004160 Ammonium persulphate Substances 0.000 claims 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims 2
- 239000004159 Potassium persulphate Substances 0.000 claims 1
- 235000019394 potassium persulphate Nutrition 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 17
- 239000007800 oxidant agent Substances 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 238000001308 synthesis method Methods 0.000 abstract description 3
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- 238000011160 research Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000879 imine group Chemical group 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical class NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical class NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 206010014596 Encephalitis Japanese B Diseases 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 201000005807 Japanese encephalitis Diseases 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229960003239 encephalitis vaccine Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于聚邻苯二胺的制备方法领域。本发明所述的聚邻苯二胺的高温回流氧化制备方法，是将邻苯二胺单体溶解于冰乙酸中，然后将氧化剂的水溶液加入到上述单体溶液中，回流反应，反应完全后处理即可得到聚邻苯二胺。本发明采用冰乙酸为反应介质，通过高温回流氧化合成法，制备得到了邻苯二胺聚合物，具有较高的产率，最高可达80%左右，掺杂时的电导率达3.0×10-10S/cm。该方法简单易行、经济有效、具有良好收率和普遍适用性。本发明为聚邻苯二胺的制备提供了经济有效的新途径，同时为开发聚邻苯二胺的功能性研究提供了物质基础。
The invention belongs to the field of preparation methods of poly-o-phenylenediamine. The high-temperature reflux oxidation preparation method of poly-o-phenylenediamine of the present invention is to dissolve the o-phenylenediamine monomer in glacial acetic acid, then add the aqueous solution of the oxidant to the above-mentioned monomer solution, and reflux the reaction. After the reaction is complete, After treatment, poly-o-phenylenediamine can be obtained. The present invention adopts glacial acetic acid as the reaction medium, and prepares the o-phenylenediamine polymer through the high-temperature reflux oxidation synthesis method, which has a relatively high yield, up to about 80%, and an electrical conductivity of 3.0×10 when doped. -10 S/cm. The method is simple and easy, economical and effective, has good yield and universal applicability. The invention provides an economical and effective new way for the preparation of poly-o-phenylenediamine, and at the same time provides a material basis for developing the functional research of poly-o-phenylenediamine.
Description
技术领域 technical field
本发明属于聚邻苯二胺的制备方法领域。The invention belongs to the field of preparation methods of poly-o-phenylenediamine.
背景技术 Background technique
作为一种重要的芳香二胺类聚合物，聚邻苯二胺能够提供较多的活性自由氨基和亚胺基，因此聚邻苯二胺比聚苯胺有更强的电化学活性和多功能性，在电催化、电致变色、选择渗透性和pH响应等方面有更优越的性能。同时聚邻苯二胺作为一种半导电性有机材料，又可作为纳米金属粒子的分散基体，利用金属颗粒和导电高分子间的协同效应，提高比表面积，促进电催化性能。聚邻苯二胺作为一种新型的电子材料，可望应用于电催化、电极修饰、传感器等领域(Yuan R，Zhang L Y，Li Q F，et al.A label-free amperometric immunosenor based onmulti-layer assembly of polymerized o-phenylenediamine and gold nanoparticles for determinationofJapanese B encephalitisvaccine[J].Analytica Chimica Acta，2005，531：1-5)。As an important aromatic diamine polymer, poly-o-phenylenediamine can provide more active free amino groups and imine groups, so poly-o-phenylenediamine has stronger electrochemical activity and multifunctionality than polyaniline , has superior performance in electrocatalysis, electrochromism, selective permeability and pH response. At the same time, as a semiconductive organic material, poly-o-phenylenediamine can also be used as a dispersion matrix of nano-metal particles, and the synergistic effect between metal particles and conductive polymers can be used to increase the specific surface area and promote electrocatalytic performance. As a new type of electronic material, poly-o-phenylenediamine is expected to be used in electrocatalysis, electrode modification, sensors and other fields (Yuan R, Zhang L Y, Li Q F, et al. A label-free amperometric immunosenor based on multi- layer assembly of polymerized o-phenylenediamine and gold nanoparticles for determination of Japanese B encephalitis vaccine [J]. Analytica Chimica Acta, 2005, 531: 1-5).
电化学聚合和化学氧化聚合常被用来合成芳香二胺类聚合物。在苯二胺的三个异构体中，对苯二胺、间苯二胺都可在温和的条件下发生化学氧化聚合，获得具有较高产率的聚合物(LiX G，Huang M R，Duan W，et al.Novel multifunctional polymers from aromatic diamines byoxidative polymerizations[J].Chemical Reviews，2002，102：2925-3030)。而邻苯二胺聚合活性低，一般情况下无法获得化学氧化聚合产品，仅仅见到其电聚合的报道(Komura T，Yamaguti T，Takahasi K.Impedance study of the charge transport at poly-o-phenylenediamine film electrodes[J].Electrochimica Acta，1996，41(18)：2865-2870)。由于电聚合的反应场所在电极表面附近，聚合物的产量受电极面积大小制约，无法获得大量的聚合物。因此，研制开发一种新的简便、经济、产率高、适用性强的聚邻苯二胺制备方法是非常重要的。Electrochemical polymerization and chemical oxidative polymerization are often used to synthesize aromatic diamine polymers. Among the three isomers of phenylenediamine, p-phenylenediamine and m-phenylenediamine can undergo chemical oxidation polymerization under mild conditions to obtain polymers with higher yields (LiX G, Huang M R, Duan W, et al. Novel multifunctional polymers from aromatic diamines byoxidative polymerizations [J]. Chemical Reviews, 2002, 102: 2925-3030). And o-phenylenediamine polymerization activity is low, generally can't obtain chemical oxidation polymerization product, only see the report of its electropolymerization (Komura T, Yamaguti T, Takahasi K.Impedance study of the charge transport at poly-o-phenylenediamine film electrodes [J]. Electrochimica Acta, 1996, 41(18): 2865-2870). Since the reaction site of electropolymerization is located near the electrode surface, the yield of polymer is limited by the size of the electrode area, and a large amount of polymer cannot be obtained. Therefore, it is very important to develop a new method for preparing poly-o-phenylenediamine that is simple, economical, high in yield and strong in applicability.
发明内容 Contents of the invention
本发明的目的就是解决现有技术难题，提供一种简单易行、经济有效、具有良好收率的聚邻苯二胺的制备方法。The purpose of the present invention is to solve the problems in the prior art, and provide a simple, economical and effective preparation method of poly-o-phenylenediamine with good yield.
为达上述目的，本发明采取的具体技术方案如下：For reaching above-mentioned purpose, the concrete technical scheme that the present invention takes is as follows:
聚邻苯二胺的高温回流氧化制备方法，其步骤是：将邻苯二胺单体溶解于冰乙酸中，然后将氧化剂的水溶液加入到上述单体溶液中，回流反应，反应完全后处理即可得到聚邻苯二胺。The high-temperature reflux oxidation preparation method of poly-o-phenylenediamine comprises the following steps: dissolving the o-phenylenediamine monomer in glacial acetic acid, then adding the aqueous solution of the oxidizing agent to the above-mentioned monomer solution, refluxing reaction, and treating after the reaction is complete. Poly-o-phenylenediamine is available.
本发明中可使用的适宜的氧化剂包括过硫酸铵((NH4)2S2O8)、过硫酸钾(K2S2O8)和三氯化铁(FeCl3)，优选为过硫酸铵。氧化剂的用量对聚合产率有很大的影响，本发明中氧化剂与邻苯二胺单体的摩尔配比优选为1∶1到3∶1。Suitable oxidizing agents that may be used in the present invention include ammonium persulfate ((NH 4 ) 2 S 2 O 8 ), potassium persulfate (K 2 S 2 O 8 ) and ferric chloride (FeCl 3 ), preferably persulfate Ammonium. The amount of the oxidizing agent has a great influence on the polymerization yield. In the present invention, the molar ratio of the oxidizing agent to the o-phenylenediamine monomer is preferably 1:1 to 3:1.
由于邻苯二胺聚合活性低，在室温下聚合只能得到邻苯二胺的低聚物，因此在本发明中，在沸腾的冰乙酸中反应，可提供高于100℃的反应温度。反应时间一般控制在48～72h。Due to the low polymerization activity of o-phenylenediamine, only oligomers of o-phenylenediamine can be obtained by polymerization at room temperature. Therefore, in the present invention, the reaction in boiling glacial acetic acid can provide a reaction temperature higher than 100°C. The reaction time is generally controlled within 48-72 hours.
本发明中采用已知的方法对聚合产物进行处理，以除去反应混合物中残留的单体和氧化剂，以及反应生成的低聚物。处理步骤包括自然沉降、过滤、去离子水洗涤和干燥。In the present invention, known methods are used to treat the polymerization product to remove residual monomers and oxidants in the reaction mixture, as well as oligomers formed by the reaction. The processing steps include natural sedimentation, filtration, washing with deionized water and drying.
本发明的有益效果：本发明采用冰乙酸为反应介质，通过高温回流氧化合成法，制备得到了邻苯二胺聚合物，具有较高的产率，最高可达80％左右，掺杂时的电导率达3.0×10-10S/cm。该方法简单易行、经济有效、具有良好收率和普遍适用性。本发明为聚邻苯二胺的制备提供了经济有效的新途径，同时为开发聚邻苯二胺的功能性研究提供了物质基础。Beneficial effects of the present invention: the present invention adopts glacial acetic acid as the reaction medium, and prepares the o-phenylenediamine polymer through the high-temperature reflux oxidation synthesis method, which has a relatively high yield, up to about 80%. The conductivity reaches 3.0×10 -10 S/cm. The method is simple and easy, economical and effective, has good yield and universal applicability. The invention provides an economical and effective new way for the preparation of poly-o-phenylenediamine, and at the same time provides a material basis for developing the functional research of poly-o-phenylenediamine.
附图说明 Description of drawings
图1为不同氧单比下高温回流氧化合成法合成的聚邻苯二胺的红外光谱图。该图谱在3100～3600cm-1处出现了宽吸收带，该吸收带是N-H伸缩振动特征吸收，说明聚合物中自由氨基和亚胺基的存在。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PoPD的生成。Fig. 1 is the infrared spectrogram of poly-o-phenylenediamine synthesized by the high-temperature reflux oxidation synthesis method under different oxygen single ratios. There is a broad absorption band at 3100-3600 cm -1 in the spectrum, which is the characteristic absorption of NH stretching vibration, indicating the existence of free amino groups and imine groups in the polymer. 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 PoPD.
图2为聚邻苯二胺的广角X射线衍射图谱(氧单比为1/1，掺杂态)。该图谱具有较宽泛的弥散衍射峰，进一步说明了本发明确实得到了邻苯二胺的聚合物且聚合度较高。Figure 2 is the wide-angle X-ray diffraction pattern of poly-o-phenylenediamine (oxygen ratio is 1/1, doped state). The spectrum has a broad diffuse diffraction peak, further illustrating that the present invention has indeed obtained a polymer of o-phenylenediamine with a high degree of polymerization.
具体实施方式 Detailed ways
实施例1：Example 1:
准确称取6.48g(0.06mol)邻苯二胺单体加入冰醋酸中，置于40℃的水浴中，搅拌促使其溶解。按氧化剂单体比1∶1称取13.68g(0.06mol)过硫酸铵，转移至100mL烧杯中并加入6mL去离子水中使之充分溶解。将氧化剂溶液加入邻苯二胺单体的冰醋酸溶液中，继续回流反应72小时。反应结束，过滤干燥得到掺杂态的黑色粉末状聚邻苯二胺，其红外光谱见图1所示，其广角X射线衍射图谱见图2所示。Accurately weigh 6.48g (0.06mol) o-phenylenediamine monomer and add it to glacial acetic acid, place it in a water bath at 40°C, and stir to promote its dissolution. Weigh 13.68g (0.06mol) of ammonium persulfate according to the oxidant monomer ratio of 1:1, transfer it to a 100mL beaker and add 6mL of deionized water to fully dissolve it. Add the oxidizing agent solution into the glacial acetic acid solution of the o-phenylenediamine monomer, and continue the reflux reaction for 72 hours. After the reaction was completed, the doped black powdery poly-o-phenylenediamine was obtained by filtration and drying. Its infrared spectrum is shown in FIG. 1 , and its wide-angle X-ray diffraction pattern is shown in FIG. 2 .
由本实施例所制得的邻苯二胺聚合物的产量为2.59g，产率为40.0％。用压片法测得的聚合物粉末的电导率为1.8×10-10S/cm。The yield of the o-phenylenediamine polymer obtained in this example was 2.59 g, and the yield was 40.0%. The electrical conductivity of the polymer powder measured by the tablet method was 1.8×10 -10 S/cm.
实施例2：Example 2:
准确称取6.48g(0.06mol)邻苯二胺单体加入冰醋酸中，置于40℃的水浴中，搅拌促使其溶解。按氧化剂单体比2∶1称取27.36g(0.12mol)过硫酸铵，转移至100ml烧杯中并加入6ml去离子水中使之充分溶解。将氧化剂溶液加入邻苯二胺单体的冰醋酸溶液中，继续回流反应72小时。反应结束，过滤干燥得到掺杂态的黑色粉末状聚邻苯二胺，其红外光谱见图1所示。Accurately weigh 6.48g (0.06mol) o-phenylenediamine monomer and add it to glacial acetic acid, place it in a water bath at 40°C, and stir to promote its dissolution. Weigh 27.36g (0.12mol) of ammonium persulfate according to the oxidant monomer ratio of 2:1, transfer it to a 100ml beaker and add 6ml of deionized water to fully dissolve it. Add the oxidizing agent solution into the glacial acetic acid solution of the o-phenylenediamine monomer, and continue the reflux reaction for 72 hours. After the reaction was completed, filtered and dried to obtain doped black powdery poly-o-phenylenediamine, the infrared spectrum of which was shown in FIG. 1 .
由本实施例所制得的邻苯二胺聚合物的产量为5.15g，产率为79.4％。用压片法测得的聚合物粉末的电导率为3.0×10-10S/cm。The yield of the o-phenylenediamine polymer obtained in this example was 5.15 g, and the yield was 79.4%. The electrical conductivity of the polymer powder measured by the tablet method was 3.0×10 -10 S/cm.
实施例3：Example 3:
准确称取6.48g(0.06mol)邻苯二胺单体加入冰醋酸中，置于40℃的水浴中，搅拌促使其溶解。按氧化剂单体比3∶1称取41.04g(0.18mol)过硫酸铵，转移至100ml烧杯中并加入6ml去离子水中使之充分溶解。将氧化剂溶液加入邻苯二胺单体的冰醋酸溶液中，继续回流反应72小时。反应结束，过滤干燥得到掺杂态的黑色粉末状聚邻苯二胺，其红外光谱见图1所示。Accurately weigh 6.48g (0.06mol) o-phenylenediamine monomer and add it to glacial acetic acid, place it in a water bath at 40°C, and stir to promote its dissolution. Weigh 41.04g (0.18mol) of ammonium persulfate according to the oxidant monomer ratio of 3:1, transfer it to a 100ml beaker and add 6ml of deionized water to fully dissolve it. Add the oxidizing agent solution into the glacial acetic acid solution of the o-phenylenediamine monomer, and continue the reflux reaction for 72 hours. After the reaction was completed, filtered and dried to obtain doped black powdery poly-o-phenylenediamine, the infrared spectrum of which was shown in FIG. 1 .
由本实施例所制得的邻苯二胺聚合物的产量为4.61g，产率为71.2％，电导率小于1×10-12S/cm。The yield of the o-phenylenediamine polymer prepared in this example was 4.61 g, the yield was 71.2%, and the electrical conductivity was less than 1×10 −12 S/cm.
实施例4：Example 4:
取实施例1中的产物，将其在氨水或氢氧化钠溶液中浸泡、搅拌24h，过滤干燥得到氧单比为1∶1、去掺杂态的聚邻苯二胺，其电导率小于1×10-12S/cm。Take the product in Example 1, soak it in ammonia water or sodium hydroxide solution, stir for 24 hours, filter and dry to obtain poly-o-phenylenediamine in a de-doped state with an oxygen ratio of 1:1, and its conductivity is less than 1 ×10 -12 S/cm.
实施例5：Example 5:
取实施例2中的产物，将其在氨水或氢氧化钠溶液中浸泡、搅拌24h，过滤干燥得到氧单比为2∶1、去掺杂态的聚邻苯二胺颗粒，其电导率小于1×10-12S/em。Take the product in Example 2, soak it in ammonia or sodium hydroxide solution, stir for 24 hours, filter and dry to obtain poly-o-phenylenediamine particles with an oxygen-to-mono ratio of 2:1 and a de-doped state, whose conductivity is less than 1×10 -12 S/em.
实施例6：Embodiment 6:
取实施例3中的产物，将其在氨水或氢氧化钠溶液中浸泡、搅拌24h，过滤干燥得到氧单比为3∶1、去掺杂态的聚邻苯二胺颗粒，其电导率小于1×10-12S/cm。Take the product in Example 3, soak it in ammonia water or sodium hydroxide solution, stir for 24 hours, filter and dry to obtain poly-o-phenylenediamine particles with an oxygen-to-mono ratio of 3:1 and a de-doped state, whose electrical conductivity is less than 1×10 −12 S/cm.
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| CN1840235A (en) * | 2005-03-30 | 2006-10-04 | 同济大学 | Polyphenylenediamine as lead ion adsorbent |
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