微波辐射下丙烯海松酸烯丙酯的合成、表征及UV固化反应

Microwave Irradiation Synthesis,Characterization and UV-curing Reaction of Allyl Acrylpimarate

松香树脂酸经过结构修饰,得到具有两个烯丙基团的高纯度聚合单体,可以在聚合过程中为高分子产品引入刚性菲环结构。以丙烯海松酸钠和氯丙烯为原料(物质的量之比为1∶2),N,N-二甲基甲酰胺(DMF)为溶剂,同时加入5%的十六烷基三甲基溴化铵为催化剂,0.2%的对苯二酚为阻聚剂,在微波功率400 W、反应时间2.5 h、反应温度50℃条件下发生反应,制备得到丙烯海松酸烯丙酯(AA),产品为黄色黏状液体,产物收率为72.9%。对产物结构进行表征,红外光谱分析表明AA上引入的CC特征吸收峰出现在1686 cm-1和1648 cm-1处,气相色谱鉴定纯化后AA的GC含量为98.6%,气质联用和核磁共振进一步验证了产物结构的正确性。以AA为单体对其UV固化反应进行了研究,红外光谱分析表明聚合单体是打开双键的自由基聚合反应,UV固化反应的表干时间随引发剂添加量的增加、光照距离的缩短以及光照强度的增大而缩短,TG和DSC分析结果表明AA的UV固化产物具有较好的热稳定性,初始热分解温度为292.9℃,玻璃化转变起始温度为49.6℃。

A new polymerized monomer with two allyl groups was synthesized by Diels-Alder reaction, which could introduce the characteristic fused ring structure of rosin acids to the polymers. Allyl acrylpimarate was synthesized by using sodium acrylpimaric rosinate and allyl chloride as raw materials with molar ratio of 1 ： 2, 5% cetyltrimethyl ammonium bromide as catalyst, 0. 02% hydroquinol as polymerization inhibitor and N, N-dimethylformamide as solvent under microwave irradiation. Under the reaction conditions of microwave energy 400 W, reaction time 2. 5 h, reaction temperature 50 ℃, the yield of allyl acrylpimarate （AA） was 72. 9%. The structure of the product was characterized by gas chromatography, gas chromatography mass spectrometry, infrared spectrum, and nuclear magnetic resonance spectra. The IR spectra showed that the characteristic absorption peak ofC= on AA addition appeared at 1686 and 1648 cm-l. The GC content of AA was determined as 98.6% by gas chromatography. Mass spectrometry and nuclear magnetic resonance spectra were used to verify the correctness of the structure of AA. The UV curing reaction of AA was studied. The results of infrared spectroscopy showed that the polymerization monomer was a free radical polymerization reaction. The surface curing time of AA decreased with the increasing of photo initiator dosage, decreasing of illumination distance and increasing of illumination intesity. TG and DSC analysis results showed that the UV curing product had good thermal stability with the initial decomposition temperature of 292.9 ℃ and initial glass transition temperature of 49.6 ℃.