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过去曾经研究过，采用双氧水作氧化剂使芳香族化合物和双酚Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>进行氧化溴化的反应。寻求氧化用于芳香族化合物液相氧化卤化反应的、价廉易得的氧化剂具有实际意义。其中之一就是次氯酸钠。它是有机氯产品生产的付产物，资源充足。我们研究工作中，采用次氯酸钠作氧化剂，对双酚lang=EN-US>Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>进行氧化溴化的研究。

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按过去介绍的，在静态条件下进行溴化。使用工厂生产烷基苯磺酸钠时形成的style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>次氯酸钠作氧化剂。

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用NaBrstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>或lang=EN-US>KBrstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>溴化双酚lang=EN-US>Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>的试验做法如下：往三颈瓶中在给定的温度下，加入计算量的lang=EN-US>NaBrstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>或lang=EN-US>KBrstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>和水，然后在style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>徐徐加入盐酸，之后向混合物中添加必需量的溶解在乙醇中的双酚lang=EN-US>Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>。最后加入次氯酸钠。用溴分子溴化双酚lang=EN-US>Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>是分步进行的，并生成一、二、三、和四溴化物，反应可以下式表示：

HOC₆H₄Cstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>（lang=EN-US>CH₃style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）_lang=EN-US>2lang=EN-US>C₆H₄OH+4Br₂=HOC₆H₂Br₂Cstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>（lang=EN-US>CH₃style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）_lang=EN-US>2lang=EN-US>C₆H₂Br₂OH+4HBrstyle=”mso-spacerun: yes”>      style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>（lang=EN-US>1style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）

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按照化学反应式，为了制取1style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>摩尔四溴双酚lang=EN-US>Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>，须lang=EN-US>4style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>摩尔lang=EN-US>Br₂style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>，同时生成lang=EN-US>4style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>摩尔lang=EN-US>HBr style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>付产品。明确指出，在有次氯酸钠参加下的反应，溴化氢可有效地用作溴化剂。

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应指出，用次氯酸钠作为双酚Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>溴化氧化剂，同时观察到与用双氧水溶液作氧化剂一样的规律。过程的实质在于用溴直接溴化双酚lang=EN-US>Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>时析出的lang=EN-US>HBrstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>被反应介质中的次氯酸钠氧化成溴。

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在使用次氯酸钠的液相氧化溴化条件下，生成双酚Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>溴衍生物的反应为多步偶联反应过程：

style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>（lang=EN-US>C₆H₄OHstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）_lang=EN-US>2Cstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>（lang=EN-US>CH₃style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）_lang=EN-US>2+2Br₂=style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>（lang=EN-US>BrC₆H₃OHstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）_lang=EN-US>2 Cstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>（lang=EN-US>CH₃style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）_lang=EN-US>2+2 HBr

=style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>（lang=EN-US>Br₂C₆H₂OHstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）_lang=EN-US>2 Cstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>（lang=EN-US>CH₃style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）_lang=EN-US>2+2H₂O+2NaClstyle=”mso-spacerun: yes”>                                 
style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>（lang=EN-US>2style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）

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比较反应（1style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）和（lang=EN-US>2style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）指出，用次氯酸钠由于减少了lang=EN-US>1/2style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>的lang=EN-US>Br₂style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>消耗量而提高合成四溴双酚lang=EN-US>Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>时溴的利用率。

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为了找到反应的最佳条件，研究了各种因素对双酚Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>氧化溴化过程的影响。四溴双酚lang=EN-US>Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>的产率与反应区的反应物摩尔比和加溴、加次氯酸钠的速度关系颇大。在反应物的化学量比例下，目的产品的产率不超过lang=EN-US>93.5%style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>，当次氯酸钠的量由lang=EN-US>2style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>摩尔双酚lang=EN-US>Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>增加到lang=EN-US>2.3style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>摩尔双酚lang=EN-US>Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>时，目的产品的产率由lang=EN-US>93.5%style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>增加到lang=EN-US>96.5%style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>，四溴双酚lang=EN-US>Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>的产率与lang=EN-US>20℃style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>到lang=EN-US>40style=”FONT-FAMILY: 宋体”>℃范围的反应温度无关。在上述范围内温度的提高，反应时间由lang=EN-US>6小时降到4小时。

     
四溴双酚lang=EN-US>A的产率与加溴和次氯酸钠的速度关系颇大。在同时加料的情况下，四溴双酚A的产率只有42%，这与次氯酸钠的无效地分解有关。实际上最适合的是在1—1.5小时内连续供给溴和次氯酸钠，此时四溴双酚A的产率可达96.5%.

     
指出,用芳香族溶剂时,
四溴双酚A的产率不会达到高的产率(不大於58%)，正如试验证明的那样，是芳香族溶剂在反应条件下会部分被溴化。在C₁—C₃脂肪醇或硫醚中进行双酚A溴化时，可保证获得高产率（95—96.5%）的目的产品。

     
研究指出在有次氯酸钠的酸性介质中，HBrstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>的钠或钾盐不仅是各种芳烃的而且也是双酚lang=EN-US>Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>的选择性溴化剂。在这各情况下，反应式如下：

style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>（lang=EN-US>C₆H₄OHstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）_lang=EN-US>2Cstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>（lang=EN-US>CH₃style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）_lang=EN-US>2+4NaBr+4HCl+4NaOCl=style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>（lang=EN-US>Br₂C₆H₂OHstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）_lang=EN-US>2 Cstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>（lang=EN-US>CH₃style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）_lang=EN-US>2lang=EN-US>+8NaCl+4H₂O                                                             
style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>（lang=EN-US>3style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）

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在这个反应（3style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）系统中依次产生如下反应：

NaBr+ HCl= HBr+ NaCl

HBr+ NaOCl= Br₂+ NaCl+
H₂O

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在第三阶段中获得的溴在其一形成就与双酚Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>发生反应。

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产品的产率的纯度与向反应区的加料顺序和速度有关。如将全部料同时加入反应釜时，虽然生成溴的速度相当快，但四溴双酚lang=EN-US>Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>的产率不超过lang=EN-US>40%style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>。目的产品产率低，可能与下述情况有关：同时加料时，生成溴的反应速度快并放热，这会使氧化剂热解。lang=EN-US>NaOClstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>无效益地分解，当然会对溴的产率以及四溴双酚lang=EN-US>Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>的产率产生不利的影响。

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研究了明确在20-40style=”FONT-FAMILY: 宋体”>℃style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>范围内的温度变化对利用lang=EN-US>NaBrstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>（lang=EN-US>KBrstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）反应过程的影响。产品的产率为lang=EN-US>94-96.5%style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>，不受上述温度范围变化的影响。在此范围内，温度提高仅对反应速度有影响。温度超过lang=EN-US>50style=”FONT-FAMILY: 宋体”>℃是不利的，因为这会使氧化剂分解，对目的产品产率产生不良的影响。

     
四溴双酚lang=EN-US>A的产率与氧化的加料速度关系颇大。为了保证目的产品的高产率（95.5-96.5%），lang=EN-US>NaOClstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>的加料速度应在lang=EN-US>1-2style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>小时。

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反应时间的目的产品产率也与氧化剂浓度有关。当浓度由25.6%style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>变化到lang=EN-US>12%style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>时产率降低。盐酸的浓度不低于是lang=EN-US>5%style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>。

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基于上述用Br₂style=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>及lang=EN-US>NaBrstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>（或lang=EN-US>KBrstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>）在lang=EN-US>NaOClstyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>的参加下进行的双酚lang=EN-US>Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>溴化反应，可建立经济的无污染的和选择性的生产四溴双酚lang=EN-US>Astyle=”FONT-FAMILY: 宋体; mso-ascii-font-family: ‘Times New Roman’; mso-hansi-font-family: ‘Times New Roman'”>的工艺。