三（三溴苯氧基）三嗪的合成工艺及放大研究
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摘要
本论文以三溴苯酚和三聚氯氰为原料,分别在乙酸乙酯和丙酮两种溶剂体系下采用溶剂法合成三(三溴苯氧基)三嗪。考察了反应温度、反应时间、投料比、溶剂用量等反应条件对产物收率和熔点的影响,并对其进行红外、核磁表征。
采用一步法合成工艺时,选用乙酸乙酯为溶剂,通过加入缚酸剂,使三溴苯酚与三聚氯氰的反应能够顺利进行的原理合成三(三溴苯氧基)三嗪。确定最佳合成工艺条件如下：溶剂乙酸乙酯用量为三溴苯酚质量的2.2倍,反应物三溴苯酚与三聚氯氰的摩尔比为3.1：1,还原剂Na2S03的用量为三溴苯酚质量的6%,缚酸剂氢氧化钠用量为三聚氯氰物质的量的3.4倍,反应温度为70-77℃,反应时间为2.5h。产品收率达到94%,熔点230℃。本实验对该工艺条件进行了放大研究,所得产率为92%,产物的熔点为230℃,溶剂回收率为83%。
采用两步法合成工艺时,选用丙酮为溶剂,确定最佳合成工艺条件如下：选用氢氧化钠作为碱制备三溴苯酚盐,且氢氧化钠与三溴苯酚的摩尔比为1.01：1。三溴苯酚钠溶液的浓度以质量分数35%-40%,三溴苯酚和三聚氯氰的摩尔比为3.03：1,三聚氯氰加入温度为0℃,反应温度为56℃,反应时间4h。产品收率达到97%,熔点为230℃。本实验对该工艺条件进行了放大研究,所得产率为95%,产物的熔点为230℃,溶剂回收率为70%。
经FT-IR、1H-NMR和13C-NMR对产品的结构进行表征,确定该产品为三(三溴苯氧基)三嗪。
In this dissertation, tris(2,4,6-tribromophenoxy)-1,3,5-triazine is synthesized using2,4,6-tribromophenol and cyanuric chloride with solvent method. Two solvent systems are used-ethyl acetate and acetone. The effects of reaction temperature, reaction time, molar ratios and amount of solvent on product yield and melting point are investigated. The products are characterized by FT-IR and NMR.
Taking one step with ethyl acetate solvent system, acid-capturer is added to promote the reaction between2,4,6-tribromophenol and cyanuric chloride, producing tris(2,4,6-tribromophenoxy)-1,3,5-triazine. The optimized synthesis conditions are:the amount of solvent is2.2times of the weight of2,4,6-tribromophenol, molar ratio of2,4,6-tribromophenol and cyanuric chloride is3.1:1, the amount of Na2SO3is6%of the weight of2,4,6-tribromophenol, the amount of NaOH is3.4times of the molar of cyanuric chloride, reaction temperature is70-77℃and reaction time is2.5h. The product yield is94%and the melting point is230℃. The solvent recycle rate used in amplification experiment is83%.
Taking two step with acetone solvent system, the optimized synthesis conditions are:the best alkali to prepare2,4,6-tribromophenoate is NaOH and the amount is1.01times of the molar of2,4,6-tribromophenol, the concentration of sodium2,4,6-tribromophenol solution is35%-40%mass fraction, molar ratio of2,4,6-tribromophenol and cyanuric chloride is3.03:1, the temperature when cyanuric chloride added is0℃, reaction temperature is the temperature for acetone backflow which is56℃and reaction time is4h. The product yield is97%and the melting point is230℃. In amplification experiment, product yield is95%and the melting point is230℃. The solvent recycle rate used in amplification experiment is70%.
The product is determined as tris(2,4,6-tribromophenoxy)-1,3,5-triazine by FT-IR、1H-NMR and13C-NMR.
采用一步法合成工艺时,选用乙酸乙酯为溶剂,通过加入缚酸剂,使三溴苯酚与三聚氯氰的反应能够顺利进行的原理合成三(三溴苯氧基)三嗪。确定最佳合成工艺条件如下：溶剂乙酸乙酯用量为三溴苯酚质量的2.2倍,反应物三溴苯酚与三聚氯氰的摩尔比为3.1：1,还原剂Na2S03的用量为三溴苯酚质量的6%,缚酸剂氢氧化钠用量为三聚氯氰物质的量的3.4倍,反应温度为70-77℃,反应时间为2.5h。产品收率达到94%,熔点230℃。本实验对该工艺条件进行了放大研究,所得产率为92%,产物的熔点为230℃,溶剂回收率为83%。
采用两步法合成工艺时,选用丙酮为溶剂,确定最佳合成工艺条件如下：选用氢氧化钠作为碱制备三溴苯酚盐,且氢氧化钠与三溴苯酚的摩尔比为1.01：1。三溴苯酚钠溶液的浓度以质量分数35%-40%,三溴苯酚和三聚氯氰的摩尔比为3.03：1,三聚氯氰加入温度为0℃,反应温度为56℃,反应时间4h。产品收率达到97%,熔点为230℃。本实验对该工艺条件进行了放大研究,所得产率为95%,产物的熔点为230℃,溶剂回收率为70%。
经FT-IR、1H-NMR和13C-NMR对产品的结构进行表征,确定该产品为三(三溴苯氧基)三嗪。
In this dissertation, tris(2,4,6-tribromophenoxy)-1,3,5-triazine is synthesized using2,4,6-tribromophenol and cyanuric chloride with solvent method. Two solvent systems are used-ethyl acetate and acetone. The effects of reaction temperature, reaction time, molar ratios and amount of solvent on product yield and melting point are investigated. The products are characterized by FT-IR and NMR.
Taking one step with ethyl acetate solvent system, acid-capturer is added to promote the reaction between2,4,6-tribromophenol and cyanuric chloride, producing tris(2,4,6-tribromophenoxy)-1,3,5-triazine. The optimized synthesis conditions are:the amount of solvent is2.2times of the weight of2,4,6-tribromophenol, molar ratio of2,4,6-tribromophenol and cyanuric chloride is3.1:1, the amount of Na2SO3is6%of the weight of2,4,6-tribromophenol, the amount of NaOH is3.4times of the molar of cyanuric chloride, reaction temperature is70-77℃and reaction time is2.5h. The product yield is94%and the melting point is230℃. The solvent recycle rate used in amplification experiment is83%.
Taking two step with acetone solvent system, the optimized synthesis conditions are:the best alkali to prepare2,4,6-tribromophenoate is NaOH and the amount is1.01times of the molar of2,4,6-tribromophenol, the concentration of sodium2,4,6-tribromophenol solution is35%-40%mass fraction, molar ratio of2,4,6-tribromophenol and cyanuric chloride is3.03:1, the temperature when cyanuric chloride added is0℃, reaction temperature is the temperature for acetone backflow which is56℃and reaction time is4h. The product yield is97%and the melting point is230℃. In amplification experiment, product yield is95%and the melting point is230℃. The solvent recycle rate used in amplification experiment is70%.
The product is determined as tris(2,4,6-tribromophenoxy)-1,3,5-triazine by FT-IR、1H-NMR and13C-NMR.
引文
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[19]欧育湘,赵毅.加速中国阻燃剂及阻燃塑料的环保进程[J].塑料,2008(3)：1-3.
[20]Li Chen, Yu Zong Wang. A review on flame retardant technology in China. Part Ⅰ: development of flame retardant[J]. polymers advanced technologies,2010,27:1-26.
[21]钱立军.磷杂菲DOPO及其化合物的制备与性能[M].北京：北京化学工业出版社,2010.
[22]摩根,威尔基,欧育湘.聚合物纳米复合材料[M].北京：国防工业出版社,2011.
[23]Hongdian Lu, Lei Song, Yuan Hu. A review on flame retardant technology in China. Part Ⅱ:flame retardant polymeric nanocomposites and coatings[J]. polymers advanced technologies,2011,22:379-394.
[24]中国阻燃协会www.chinafrs.com
[25]薛恩钰,曾敏修.阻燃科学及应用[M].北京：国防工业出版社,1988.
[26]张军,纪奎江,夏延致.聚合物燃烧与阻燃技术[M].北京：国防工业出版社,2005.
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[29]欧育湘.新型无卤阻燃工程塑料[J].化工,2002,20(12)：59-61.
[30]Mehran Alaee, Pedro Arias, Andreas Sjodin, et al. An overview of commercially used brominated flame retardants, their applications, their use patterns in different countries/regions and possible modes of release[J]. Environment International,2003,29(6):683-689.
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[32]骆介禹,骆希明,孙才英等.聚磷酸铵及应用[M].北京：北京化学工业出版社,2005.
[33]骆介禹,骆希明,刘方月.含氮有机化合物阻燃剂[M].北京：化学工业出版社,2010.
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[38]J Troitzsch. The Globalization of Fire Testing and its Impact on Polymers and Flame Retardants[J]. Polymer Degradation and Stability,2005,88 (1):146-149.
[39]彭治汉.材料阻燃新技术新品种[M].北京：化学工业出版社,2004.
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