TW201813990A - Method for synthesizing aniline oligomer - Google Patents
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- TW201813990A TW201813990A TW105132053A TW105132053A TW201813990A TW 201813990 A TW201813990 A TW 201813990A TW 105132053 A TW105132053 A TW 105132053A TW 105132053 A TW105132053 A TW 105132053A TW 201813990 A TW201813990 A TW 201813990A
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- -1 aniline compound Chemical class 0.000 claims abstract description 121
- 239000007800 oxidant agent Substances 0.000 claims abstract description 47
- 239000000243 solution Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000012267 brine Substances 0.000 claims abstract description 17
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 17
- 150000001448 anilines Chemical class 0.000 claims abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- 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
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 5
- 125000001033 ether group Chemical group 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 125000005586 carbonic acid group Chemical group 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- 230000001590 oxidative effect Effects 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003929 acidic solution Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000005691 oxidative coupling reaction Methods 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 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
一種苯胺寡聚物之合成方法，首先是製備一第一鹽水溶液與一第二鹽水溶液；然後將一第一苯胺化合物與一第二苯胺化合物加入第一鹽水溶液中而形成一苯胺化合物混合液；接著是將一氧化劑溶於一第二鹽水溶液以形成一氧化劑水溶液；然後是將氧化劑水溶液加入苯胺化合物混合液中以使第一苯胺化合物與第二苯胺化合物反應合成為一苯胺寡聚物。 A method for synthesizing an aniline oligomer, firstly preparing a first brine solution and a second brine solution; then adding a first aniline compound and a second aniline compound to the first brine solution to form a mixture of aniline compounds Next, an oxidizing agent is dissolved in a second brine solution to form an aqueous oxidizing agent solution; then an aqueous oxidizing agent solution is added to the aniline compound mixture to react the first aniline compound with the second aniline compound to form a monoaniline oligomer.
Description
本發明係有關於一種合成方法，尤其是指一種苯胺寡聚物之合成方法。 The present invention relates to a method of synthesis, and more particularly to a method of synthesizing an aniline oligomer.
一般來說，由於有機導電高分子兼具有導體材料與高分子材料的特性，因此近年來有許多科學家針對導電高分子進行研究。其中，由於聚苯胺本身具有可逆的摻雜特性以及導電性，因此可以應用的領域極廣；然而，聚苯胺卻因為本身聚合物的分子量較大而造成溶解度差的情形，因此有許多科學家製備出了具有電活性鏈端的苯胺寡聚體，藉以使溶解度提高並能具有電活性。 In general, since organic conductive polymers have both the properties of conductive materials and polymer materials, many scientists have conducted research on conductive polymers in recent years. Among them, polyaniline itself has a reversible doping property and conductivity, so it can be applied in a wide range of fields; however, polyaniline has a poor solubility due to the large molecular weight of its own polymer, so many scientists have prepared it. An aniline oligomer having an electroactive chain end, thereby increasing solubility and being electrically active.
承上所述，由於聚苯胺的聚合反應主要是在強酸環境下聚合而成，也因此現有的技術在製備苯胺寡聚體時，同樣是在強酸的環境下，利用氧化偶合法來製備出苯胺寡聚體，但由於其產率最高僅能達到40%左右，且通常需要耗費4至8小時來進行反應，無法有效的製備出苯胺寡聚物。 According to the above, since the polymerization of polyaniline is mainly polymerized under a strong acid environment, the prior art also prepares an aniline by using an oxidative coupling method in the preparation of an aniline oligomer. Oligomers, but since the yield is only up to about 40%, and it usually takes 4 to 8 hours to carry out the reaction, the aniline oligomer cannot be efficiently produced.
有鑑於在先前技術中，苯胺寡聚物的製備方法主要是在強酸的環境下，利用氧化偶合法耗費大量的時間來製備出苯胺寡聚物，且產率最高僅能達到40%，卻會產生大量的酸性廢液；緣此，本發明的目的在於提供一種苯胺寡聚物之合成方法，以利用合成條件的改變來提高苯胺寡聚物的產率。 In view of the prior art, the preparation method of aniline oligomers mainly takes a large amount of time to prepare aniline oligomers by using oxidative coupling in a strong acid environment, and the yield is only up to 40%, but A large amount of acidic waste liquid is produced; thus, it is an object of the present invention to provide a method for synthesizing an aniline oligomer to improve the yield of an aniline oligomer by utilizing a change in synthesis conditions.
為了達到上述目的，本發明提供了一種苯胺寡聚物之合成方法，包含以下步驟：首先步驟(a)是製備一第一鹽水溶液與一第二鹽水溶液；步驟(b)是將一以結構式(1)表示之第一苯胺化合物以及一以結構式(2)表示之第二苯胺化合物加入第一鹽水溶液而形成一苯胺化合物混合液，
接著步驟(c)是將一氧化劑溶於第二鹽水溶液以形成一氧化劑水溶液。然後步驟(d)是將氧化劑水溶液加入苯胺化合物混合液中以使第一苯胺化合物與第二苯胺化合物反應合成為一以結構式(3)表示之苯胺寡聚物，
其中，x=0至7，y=1至8，且(x+y)=1至8。 Wherein x=0 to 7, y=1 to 8, and (x+y)=1 to 8.
由上述必要技術手段所衍生之一附屬技術手段中，在第二苯胺化合物之結構式(2)中，官能基R為氫基、氫氧基、酯基、醚基、磺酸基或碳酸基。 In an auxiliary technical means derived from the above-mentioned essential technical means, in the structural formula (2) of the second aniline compound, the functional group R is a hydrogen group, a hydroxyl group, an ester group, an ether group, a sulfonic acid group or a carbonate group. .
由上述必要技術手段所衍生之附屬技術手段中，步驟(a)是將一鹽類化合物溶於水而形成一鹽水溶液，並將鹽水溶液分為第一鹽水溶液與第二鹽水溶液。 In the subsidiary technical means derived from the above-mentioned essential technical means, the step (a) is that a salt compound is dissolved in water to form an aqueous salt solution, and the brine solution is divided into a first salt solution and a second salt solution.
由上述必要技術手段所衍生之附屬技術手段中，鹽類化合物為氯化鈉。 Among the subsidiary technical means derived from the above-mentioned essential technical means, the salt compound is sodium chloride.
由上述必要技術手段所衍生之附屬技術手段中，氧化劑為氯化鐵與過氧化氫之混合物、過硫酸銨、過硫酸鉀或重鉻酸鉀。 In an auxiliary technical means derived from the above-mentioned essential technical means, the oxidizing agent is a mixture of ferric chloride and hydrogen peroxide, ammonium persulfate, potassium persulfate or potassium dichromate.
由上述必要技術手段所衍生之一附屬技術手段中，步驟(d)在將氧化劑水溶液加入苯胺化合物混合液中時，係將反應溫度控制在0至5℃。 In an auxiliary technical means derived from the above-mentioned essential technical means, in the step (d), when the aqueous oxidizing agent solution is added to the aniline compound mixed solution, the reaction temperature is controlled to be 0 to 5 °C.
由上述必要技術手段所衍生之一附屬技術手段中，第一苯胺化合物、第二苯胺化合物與氧化劑之體積莫耳濃度比例為L：M：N，其中，L=1，M=1，N=1至3。 In a subsidiary technical means derived from the above-mentioned essential technical means, the molar concentration ratio of the first aniline compound, the second aniline compound and the oxidizing agent is L:M:N, wherein L=1, M=1, N= 1 to 3.
如上所述，由於本發明所提供之苯胺寡聚物之合成方法是將第一苯胺化合物與第二苯胺化合物加入第一鹽水溶液中而形成一苯胺化合物混合液，並將氧 化劑水溶液加入苯胺化合物混合液中以使第一苯胺化合物與第二苯胺化合物反應形成苯胺寡聚物；其中，由於第一苯胺化合物與第二苯胺化合物是溶於中性的鹽水溶液中，而不需溶於酸性溶液中，因此可以有效的減少酸性廢液的排放，且能因為第一苯胺化合物與第二苯胺化合物反應時處在相當於中性不利聚合的環境下，進而導致有利於苯胺寡聚物的形成，相對的提高了苯胺寡聚物的產率。 As described above, since the aniline oligomer provided by the present invention is synthesized by adding a first aniline compound and a second aniline compound to the first salt aqueous solution to form a monoaniline compound mixture, and adding the oxidizing agent aqueous solution to the aniline compound mixture. In the liquid, the first aniline compound is reacted with the second aniline compound to form an aniline oligomer; wherein, since the first aniline compound and the second aniline compound are dissolved in a neutral salt solution, they are not dissolved in the acidic solution. Therefore, the discharge of the acidic waste liquid can be effectively reduced, and the first aniline compound reacts with the second aniline compound in an environment equivalent to the neutral unfavorable polymerization, thereby leading to the formation of the aniline oligomer, and The yield of the aniline oligomer is increased.
第一圖係顯示本發明苯胺寡聚物之合成方法之步驟流程圖。 The first figure is a flow chart showing the steps of the synthesis method of the aniline oligomer of the present invention.
請參閱第一圖，第一圖係顯示本發明苯胺寡聚物之合成方法之步驟流程圖。如圖所示，一種苯胺寡聚物之合成方法，包含以下步驟：首先，步驟S1是將一鹽類化合物溶於水而形成一鹽水溶液，並將鹽水溶液分為一第一鹽水溶液與一第二鹽水溶液。 Please refer to the first figure, which is a flow chart showing the steps of the synthesis method of the aniline oligomer of the present invention. As shown in the figure, a method for synthesizing an aniline oligomer comprises the following steps: First, step S1 is to dissolve a salt compound into water to form an aqueous salt solution, and to divide the brine solution into a first salt solution and a solution. A second brine solution.
接著步驟S2是將一以結構式(1)表示之第一苯胺化合物以及一以結構式(2)表示之第二苯胺化合物加入第一鹽水溶液而形成一苯胺化合物混合液，結構式(1)為
接著，步驟S3是將一氧化劑溶於第二鹽水溶液以形成一氧化劑水溶液。 Next, step S3 is to dissolve an oxidizing agent in the second brine solution to form an aqueous oxidizing agent solution.
最後，步驟S4是將氧化劑水溶液加入苯胺化合物混合液中以使第一苯胺化合物與第二苯胺化合物反應合成為一以結構式(3)表示之苯胺寡聚物，結構式(3)為
承上所述，在本實施例中，第一苯胺化合物之結構式(1)的x=0，即第一苯胺化合物為苯胺，其結構式為
而第二苯胺化合物之結構式(2)的y=1，且官能基R為H，即第二苯胺化合物為4,4’-二氨基二苯胺，其結構式為 ；其中，在實際上， 4,4’-二氨基二苯胺會以硫酸鹽的形式作為來源，其結構式為
如上所述，在結構式(1)與(2)之參數為x=0，y=1，R=H，且第一苯胺化合物、第二苯胺化合物與氧化劑之體積莫耳濃度比例為1：1：2，步驟(a)之鹽類化合物為一氯化鈉，步驟(b)之氧化劑為一過硫酸銨，而步驟(d)之氧化劑水溶液加入苯胺化合物混合液中的反應溫度控制在0至5℃並持續攪拌1小時後，第一苯胺化合物與第二苯胺化合物可反應合成出產率約86%的苯胺寡聚物，且此苯胺寡聚物為一苯胺三聚體，其結構式為
更詳細的說，在實際操作中，步驟(a)之第一鹽水溶液與第二鹽水溶液中鹽類化合物的體積莫耳濃度為1.28M，而步驟(b)之第一苯胺化合物與第二苯胺化合物的體積莫耳濃度皆為8M，因此透過持續的攪拌三分鐘左右來使第一苯胺化合物與第二苯胺化合物加入於第一鹽水溶液中而形成苯胺化合物混合液。其中，鹽類化合物在本實施例中為氯化鈉，但不限於此，亦可為氯化鉀、氯化鎂或溴化鉀等鹼金屬、鹼土金屬與鹵素結合之正鹽。 In more detail, in practice, the volumetric molar concentration of the salt compound in the first salt aqueous solution and the second salt aqueous solution in step (a) is 1.28M, and the first aniline compound in step (b) and the second Since the volume fraction of the aniline compound was 8 M, the first aniline compound and the second aniline compound were added to the first salt aqueous solution by continuous stirring for about three minutes to form a aniline compound mixed solution. In the present embodiment, the salt compound is sodium chloride, but is not limited thereto, and may be an alkali metal such as potassium chloride, magnesium chloride or potassium bromide, or a normal salt in which an alkaline earth metal and a halogen are combined.
步驟(c)是將氧化劑溶於第二鹽水溶液中，而過硫酸銨之氧化劑溶於第二鹽水溶液中的體積莫耳濃度為16M。 Step (c) is to dissolve the oxidizing agent in the second brine solution, and the ammonium oxysulfate oxidizing agent is dissolved in the second brine solution to have a molar concentration of 16 M.
步驟(d)是先將容置苯胺化合物混合液的容器利用冰浴或其他冷卻手段配合溫度偵測而使苯胺化合物混合液的溫度控制在0至7℃，然後將步驟(c)所調製之氧化劑水溶液緩緩加入苯胺化合物混合液中，使第一苯胺化合物與第二苯胺化合物受到氧化劑的氧化偶合作用而反應聚合出苯胺寡聚物，其中在苯胺寡聚物形成後，實際上會透過抽氣過濾與乾燥等方式取得其固體產物之苯胺寡聚物。 Step (d) is to first adjust the temperature of the aniline compound mixture to 0 to 7 ° C by using an ice bath or other cooling means in combination with temperature detection using an ice bath or other cooling means, and then modulating the step (c) The aqueous oxidizing agent solution is gradually added to the aniline compound mixture, and the first aniline compound and the second aniline compound are reacted and oxidized by the oxidizing agent to react and polymerize the aniline oligomer, wherein after the aniline oligomer is formed, it is actually pumped through The aniline oligomer of the solid product was obtained by gas filtration and drying.
此外，由於上述之結構式(2)中之官能R為氫基，因此第二苯胺化合物為4,4’-二氨基二苯胺，但不 限於此，官能基R亦可為氫氧基、酯基、醚基、磺酸基或碳酸基，且其所產生的苯胺寡聚體亦同樣為帶有此官能基R之衍生物。 Further, since the functional R in the above structural formula (2) is a hydrogen group, the second aniline compound is 4,4'-diaminodiphenylamine, but is not limited thereto, and the functional group R may be a hydroxyl group or an ester. A phenylamine oligomer, which is also a derivative having such a functional group R, is also derived from an ether group, an ether group, a sulfonic acid group or a carbonic acid group.
承上所述，在第一苯胺化合物為苯胺，而第二苯胺化合物為4,4’-二氨基二苯胺的基礎下，製備出苯胺三聚體之苯胺寡聚物的合成條件改變如下表一至表七。 According to the above, in the case that the first aniline compound is aniline and the second aniline compound is 4,4'-diaminodiphenylamine, the synthesis conditions of the aniline oligomer of the aniline trimer are changed as shown in Table 1 below. Table VII.
請參閱以下表一，表一是在鹽類化合物為氯化鈉，氧化劑為過硫酸銨，溶解氧化劑之酸性溶液為鹽酸，反應溫度為0℃，第一苯胺化合物、第二苯胺化合物與鹽類化合物之溶劑為鹽酸，第一苯胺化合物、第二苯胺化合物與氧化劑之體積莫耳濃度(M)比例為1：1：1，反應時間為1小時的條件下，改變酸性溶液濃度而產生不同pH值時所獲得的產率變化對照表。 Please refer to Table 1 below. Table 1 shows that the salt compound is sodium chloride, the oxidant is ammonium persulfate, the acidic solution of the dissolved oxidant is hydrochloric acid, the reaction temperature is 0 ° C, the first aniline compound, the second aniline compound and the salt The solvent of the compound is hydrochloric acid, the ratio of the molar concentration (M) of the first aniline compound, the second aniline compound and the oxidizing agent is 1:1:1, and the reaction time is 1 hour, and the concentration of the acidic solution is changed to produce different pH. A comparison of the yield changes obtained for the values.
由以上表一可知，酸性溶液的pH值控制在1至2之間時，產率會相較於pH值控制在1以下時的高，因此可以推測得知強酸不適合苯胺寡聚物的合成。 As can be seen from the above Table 1, when the pH of the acidic solution is controlled between 1 and 2, the yield is higher than when the pH is controlled to be 1 or less. Therefore, it is presumed that the strong acid is not suitable for the synthesis of the aniline oligomer.
請參閱以下表二，表二是在鹽類化合物為氯化鈉，氧化劑為過硫酸銨，溶解氧化劑之酸性溶液為 1M(pH=0.4)的鹽酸，反應溫度為0℃，第一苯胺化合物、第二苯胺化合物與氧化劑之體積莫耳濃度(M)比例為1：1：1，反應時間為1小時的條件下，改變第一苯胺化合物、第二苯胺化合物與鹽類化合物之溶劑所獲得的產率變化對照表。 Please refer to Table 2 below. Table 2 shows that the salt compound is sodium chloride, the oxidant is ammonium persulfate, the acidic solution of the dissolved oxidant is 1M (pH=0.4) hydrochloric acid, the reaction temperature is 0 ° C, the first aniline compound, The ratio of the volume fraction of the second aniline compound to the oxidizing agent (M) is 1:1:1, and the reaction time is 1 hour, and the solvent of the first aniline compound, the second aniline compound and the salt compound is changed. Yield change table.
由以上表二可知，第一苯胺化合物、第二苯胺化合物與鹽類化合物之溶劑從先前技術所使用的鹽酸(HCl)換成其他較弱的酸時，產率會逐漸提高，甚至使用水(H2O)作為溶劑時，產率更能有效提高至65.82%，因此可以推測出在弱酸接近中性的條件下較適合進行苯胺寡聚物的合成。 It can be seen from the above Table 2 that when the solvent of the first aniline compound, the second aniline compound and the salt compound is changed from the hydrochloric acid (HCl) used in the prior art to other weaker acids, the yield is gradually increased, even using water ( When H 2 O) is used as a solvent, the yield can be effectively increased to 65.82%. Therefore, it is presumed that the synthesis of the aniline oligomer is suitable under the condition that the weak acid is near neutral.
請參閱以下表三，表三是在鹽類化合物為氯化鈉，氧化劑為過硫酸銨，溶解氧化劑之酸性溶液為1M(pH=0.4)的鹽酸，第一苯胺化合物、第二苯胺化合物與氧化劑之體積莫耳濃度(M)比例為1：1：1，第一苯胺化合物、第二苯胺化合物與鹽類化合物之溶劑為鹽酸，反應時間為1小時的條件下，改變反應溫度(℃)所獲得的產 率變化對照表。 Please refer to Table 3 below. Table 3 shows that the salt compound is sodium chloride, the oxidant is ammonium persulfate, the acidic solution of the dissolved oxidant is 1M (pH=0.4) hydrochloric acid, the first aniline compound, the second aniline compound and the oxidant. The molar concentration (M) of the molar concentration is 1:1:1, and the solvent of the first aniline compound, the second aniline compound and the salt compound is hydrochloric acid, and the reaction temperature is changed to 1 hour, and the reaction temperature (° C.) is changed. A comparison of the yield changes obtained.
由以上表三可知，在低溫環境下較能有效提高苯胺寡聚物的合成產率，尤其在-5℃至0℃之間的效果最好，但即使溫度略微升高至5℃時，仍然可以維持一定的產率。 It can be seen from Table 3 above that the synthesis yield of aniline oligomers can be effectively improved in a low temperature environment, especially between -5 ° C and 0 ° C, but even if the temperature is slightly increased to 5 ° C, A certain yield can be maintained.
請參閱以下表四，表四是在鹽類化合物為氯化鈉，氧化劑為過硫酸銨，溶解氧化劑之酸性溶液為1M(pH=0.4)的鹽酸，反應溫度為0℃，第一苯胺化合物、第二苯胺化合物與氧化劑之體積莫耳濃度(M)比例為1：1：1，第一苯胺化合物、第二苯胺化合物與鹽類化合物之溶劑為鹽酸的條件下，改變反應時間所獲得的產率變化對照表。 Please refer to Table 4 below. Table 4 shows that the salt compound is sodium chloride, the oxidant is ammonium persulfate, the acidic solution of the dissolved oxidant is 1M (pH=0.4) hydrochloric acid, the reaction temperature is 0 ° C, the first aniline compound, The ratio of the molar concentration (M) of the second aniline compound to the oxidizing agent is 1:1:1, and the yield of the first aniline compound, the second aniline compound and the salt compound is hydrochloric acid, and the reaction time is changed. Rate change table.
由以上表四可知，反應時間的拉長能提高苯胺寡聚物的合成產率，但所能提高的幅度有限。 As can be seen from Table 4 above, the elongation of the reaction time can increase the synthetic yield of the aniline oligomer, but the range of increase can be limited.
請參閱以下表五，表五是在鹽類化合物為氯化鈉，溶解氧化劑之酸性溶液為1M(pH=0.4)的鹽酸，反應溫度為0℃，第一苯胺化合物、第二苯胺化合物與氧化劑之體積莫耳濃度(M)比例為1：1：1，第一苯胺化合物、第二苯胺化合物與鹽類化合物之溶劑為鹽酸，反應時間為1小時的條件下，改變氧化劑種類所獲得的產率變化對照表。 Please refer to Table 5 below. Table 5 shows that the salt compound is sodium chloride, the acidic solution of the dissolved oxidant is 1M (pH=0.4) hydrochloric acid, the reaction temperature is 0 ° C, the first aniline compound, the second aniline compound and the oxidant The volume molar concentration (M) ratio is 1:1:1, and the solvent of the first aniline compound, the second aniline compound and the salt compound is hydrochloric acid, and the reaction time is 1 hour, and the oxidant species is changed. Rate change table.
由以上表五可知，過硫酸銨、過硫酸鉀、重鉻酸鉀以及氯化鐵與過氧化氫之混合物都能得到40%以上的產率。 As can be seen from Table 5 above, ammonium persulfate, potassium persulfate, potassium dichromate, and a mixture of ferric chloride and hydrogen peroxide can all yield a yield of 40% or more.
請參閱以下表六，表六是在鹽類化合物為氯化鈉，氧化劑種類為過硫酸銨，溶解氧化劑之酸性溶液為1M(pH=0.4)的鹽酸，反應溫度為0℃，第一苯胺化合 物、第二苯胺化合物與鹽類化合物之溶劑為鹽酸，反應時間為1小時的條件下，改變第一苯胺化合物、第二苯胺化合物與氧化劑之體積莫耳濃度(M)比例所獲得的產率變化對照表。 Please refer to Table 6 below. Table 6 shows that the salt compound is sodium chloride, the oxidant type is ammonium persulfate, the acidic solution of the dissolved oxidant is 1M (pH=0.4) hydrochloric acid, the reaction temperature is 0 ° C, the first aniline compound The solvent obtained by the second aniline compound and the salt compound is hydrochloric acid, and the change in the yield of the first aniline compound, the second aniline compound and the oxidant by the molar concentration (M) is changed under the reaction time of 1 hour. Chart.
由以上表六可知，氧化劑的體積莫耳濃度為第一苯胺化合物與第二苯胺化合物的兩倍時，其產率達到最高的73.25%。 As can be seen from the above Table 6, when the volumetric molar concentration of the oxidizing agent is twice that of the first aniline compound and the second aniline compound, the yield reaches the highest 73.25%.
由以上之實驗數據可知，對苯胺寡聚物的合成產率較有影響的條件為第一苯胺化合物、第二苯胺化合物與鹽類化合物的溶劑，以及氧化劑相對於第一苯胺化合物與第二苯胺化合物的比例，以此為基礎將合成條件改變為如以下表七之數據時，其產率可以由先前技 術所能達到的40.21%提高到85.53% It can be seen from the above experimental data that the conditions for influencing the synthesis yield of the aniline oligomer are the first aniline compound, the solvent of the second aniline compound and the salt compound, and the oxidizing agent relative to the first aniline compound and the second aniline. The ratio of the compound, based on which the synthesis conditions are changed to the data shown in Table 7 below, the yield can be increased from 40.21% to 85.53% which can be achieved by the prior art.
綜上所述，相較於先前技術是在強酸的環境下，利用氧化偶合法來製備出苯胺寡聚物，卻僅能得到40%左右的產率，且會產生大量的酸性廢液；本發明是利用第一鹽水溶液溶解第一苯胺化合物與第二苯胺化合物，並將鹽類化合物溶於第二鹽水溶液所得之氧化劑水溶液加入苯胺化合物混合液中，使得第一苯胺化合物與第二苯胺化合物可以製造出產率高達86%的苯胺寡聚物，且能有效減少酸性廢液的排放，並能在短時間內完成反應。 In summary, compared with the prior art, in the strong acid environment, the oxidative coupling method is used to prepare the aniline oligomer, but only about 40% yield can be obtained, and a large amount of acidic waste liquid is generated; The invention is characterized in that the first aniline compound and the second aniline compound are dissolved by using the first salt aqueous solution, and the oxidizing agent aqueous solution obtained by dissolving the salt compound in the second salt aqueous solution is added to the aniline compound mixture to make the first aniline compound and the second aniline compound. An aniline oligomer with a yield of up to 86% can be produced, and the discharge of acidic waste liquid can be effectively reduced, and the reaction can be completed in a short time.
上述僅為本發明較佳之實施例而已，並不對本發明進行任何限制。任何所屬技術領域的技術人員，在不脫離本發明的技術手段的範圍內，對本發明揭 露的技術手段和技術內容做任何形式的等同替換或修改等變動，均屬未脫離本發明的技術手段的內容，仍屬於本發明的保護範圍之內。 The above is only a preferred embodiment of the invention and is not intended to limit the invention. Any changes in the technical means and technical contents disclosed in the present invention may be made by those skilled in the art without departing from the technical means of the present invention. The content is still within the scope of protection of the present invention.
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