三羟甲基丙烷三丙烯酸酯绿色合成工艺路线
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摘要
三羟甲基丙烷三丙烯酸酯(TMPTA)是非常重要的丙烯酸多功能团酯类单体,它既可作为共聚单体合成特殊的丙烯酸树脂,又可以作为橡胶、塑料的交联剂。
以丙烯酸(AA)和三羟甲基丙烷(TMP)为原料直接酯化合成产品TMPTA,目的在于尽可能提高收率,在此前提下制备并比较了多种催化剂对产品收率的影响,研究了酯化反应时间、反应温度、酸醇摩尔比、阻聚剂和共沸剂种类及用量对酯化反应的影响,获得了较佳反应条件。找到了两种较好的固体催化剂,分别是硫酸氢钠和碳基固体酸催化剂,且两种催化剂重复使用时催化活性几乎不变,硫酸氢钠回收率约80%,而固体酸催化剂回收率约100%。以对甲基苯磺酸为催化剂,在82℃～97℃温度范围内动力学进
行考察,得到该温度范围内的动力学方程：-dcA/dt=6389.82e -39260/RTCACB。由于进料时丙烯酸过量,因此对AA的萃取工艺进行了研究,探讨了萃取剂的选择、溶剂比以及萃取级数对萃取率的影响,测定并绘出了20℃、30℃和40℃三种温度下三元体系平衡相图。结果表明：醋酸异丁酯对丙烯酸水溶液的萃取效果最好,V(原料液)：V(萃取剂)=1：2.5,萃取级数为三级情况下,萃取率可以达到93.54%。
Trimethylpropane Triacrylate (TMPTA) is an very important acrylic ester with multifunctional teams monomers. The acrylic ester is widely used in the synthesis of special acrylic resins as copolymerization monomer, it is also used for rubber, plastics, textile and fiberfill bonding and as adhesives.
Trimethylopropane triacrylate (TMPTA) was synthesized by the esterification reaction of trimethylolpmpane (TMP) and acrylic acid (AA) and catalyzed by catalyst NaHSO4 at 4.0:1 mole ratio of acrylic acid to trimethylolpropane using hydroquinone and p-hydroxyanisole as polymerization inhibitors, cyclohexane and toluene as water carrying agent. The influence of conditions on TMPTA yield such as temperature, reaction time and the amount of catalyst in the reaction yield were investigated. Two solid-acid catalysts had been found, sodium bisulfate and carbon-based solid acid catalyst, respectively. Towards range of temperature from 355 to 370K, using TsOH as catalyst, the reaction kinetics experiment had been done.The reaction kinetics was proved to be second order, and reaction activation energy, frenquency factor were calculated.At last, the esterification kinetic equation was-dcA/dt=6389.82e-39260/RT CACB under the temperature from 82℃to 97℃. Due to acrylic acid was excessive, so the extraction of acrylic acid had been investigated.The influences of different extractants, ratio of solvent and extraction series on the extraction efficiency had been studied separately.
以丙烯酸(AA)和三羟甲基丙烷(TMP)为原料直接酯化合成产品TMPTA,目的在于尽可能提高收率,在此前提下制备并比较了多种催化剂对产品收率的影响,研究了酯化反应时间、反应温度、酸醇摩尔比、阻聚剂和共沸剂种类及用量对酯化反应的影响,获得了较佳反应条件。找到了两种较好的固体催化剂,分别是硫酸氢钠和碳基固体酸催化剂,且两种催化剂重复使用时催化活性几乎不变,硫酸氢钠回收率约80%,而固体酸催化剂回收率约100%。以对甲基苯磺酸为催化剂,在82℃～97℃温度范围内动力学进
行考察,得到该温度范围内的动力学方程：-dcA/dt=6389.82e -39260/RTCACB。由于进料时丙烯酸过量,因此对AA的萃取工艺进行了研究,探讨了萃取剂的选择、溶剂比以及萃取级数对萃取率的影响,测定并绘出了20℃、30℃和40℃三种温度下三元体系平衡相图。结果表明：醋酸异丁酯对丙烯酸水溶液的萃取效果最好,V(原料液)：V(萃取剂)=1：2.5,萃取级数为三级情况下,萃取率可以达到93.54%。
Trimethylpropane Triacrylate (TMPTA) is an very important acrylic ester with multifunctional teams monomers. The acrylic ester is widely used in the synthesis of special acrylic resins as copolymerization monomer, it is also used for rubber, plastics, textile and fiberfill bonding and as adhesives.
Trimethylopropane triacrylate (TMPTA) was synthesized by the esterification reaction of trimethylolpmpane (TMP) and acrylic acid (AA) and catalyzed by catalyst NaHSO4 at 4.0:1 mole ratio of acrylic acid to trimethylolpropane using hydroquinone and p-hydroxyanisole as polymerization inhibitors, cyclohexane and toluene as water carrying agent. The influence of conditions on TMPTA yield such as temperature, reaction time and the amount of catalyst in the reaction yield were investigated. Two solid-acid catalysts had been found, sodium bisulfate and carbon-based solid acid catalyst, respectively. Towards range of temperature from 355 to 370K, using TsOH as catalyst, the reaction kinetics experiment had been done.The reaction kinetics was proved to be second order, and reaction activation energy, frenquency factor were calculated.At last, the esterification kinetic equation was-dcA/dt=6389.82e-39260/RT CACB under the temperature from 82℃to 97℃. Due to acrylic acid was excessive, so the extraction of acrylic acid had been investigated.The influences of different extractants, ratio of solvent and extraction series on the extraction efficiency had been studied separately.
引文
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