【作者】 李俊杰；

【导师】 刘承美；

【作者基本信息】 华中科技大学 ， 化学工程， 2017， 硕士

【摘要】 腰果酚来源于天然产物腰果壳油,其环氧树脂具有优良的力学性能和热稳定性,优异的耐化学性、高粘结强度、低收缩性及生物降解性等优点,在工业上具有很广泛的用途。环三磷腈衍生物不仅具有耐水解性,而且结构中的磷、氮协同作用使其具有耐热性和无卤阻燃。因此,本文将腰果酚与环三磷腈通过分子设计进行有机结合,制备具有优异热稳定性、阻燃性和可降解性的环氧功能化腰果酚衍生物,并对其固化产物的制备方法和性能进行系统的研究。首先,以天然产物腰果酚、六氯环三磷腈为原料制备了基于膦腈环六取代腰果酚衍生物(HCPP),然后采用H2O2/HCOOH体系对HCPP进行环氧化反应得到以膦腈环为核的枝化腰果酚环氧树脂(EHCPP),环氧值为6.5;利用核磁、红外等测试手段对其结构进行系统的表征。EHCPP既可以自身聚合制备聚合物P1,也可以与低分子聚酰胺固化剂P651和腰果酚醛改性多胺固化剂CA与EHCPP进行热固化得到聚合物P2、P3,借助FT-IR红外监测聚合物固化行为,并借用旋转流变仪研究他们固化工艺操作窗口;同时对固化物的热力学性能进行研究。热力学研究结果表明,在生物基环氧树脂中引入膦腈环显著提高了聚合物的耐热稳定性和阻燃性;与聚合物P1作比较,随着固化剂的引入,树脂P2和树脂P3的交联密度得到提高,在保持其良好的耐热稳定性的基础上,P2和P3树脂的拉伸性能由46.7 Kpa分别提高到981.0KPa、1091.0 KPa,同时聚合物的接触角在90℃~103℃范围内,表现出一定的疏水性。环氧树脂与两种胺类固化剂的共聚物综合性能较好,以聚合物P2-2(40%P651)为例,聚合物P2-2失重5%的分解温度T5%为311.5℃、850℃下的残炭率Yc为10.4%,玻璃化温度Tg为18.6℃,拉伸强度和断裂伸长率分别为0.83 MPa和52.9%。其次,利用丙烯酸改性EHCPP得到一种新型丙烯酸化腰果酚树脂AEHCPP,利用核磁、红外等测试手段对其结构进行了详细的表征。以三丙二醇二丙烯酸酯(TPGDA)、三羟甲基丙烷三丙烯酸酯(TMPTA)为稀释剂进行UV固化,采用P-DSC研究不同固化体系光聚合动力学,计算出不同固化体系内的光聚合最大速率和光聚合最终转化率,同时借助FTIR检测UV固化体系的实际固化过程,确定固化时间为10 min。AEHCPP树脂的固化物耐热稳定性和阻燃性高于一般生物质丙烯酸改性树脂,同时稀释剂TPGDA和TMPTA的添加并未显著降低聚合物的耐热稳定性,未添加稀释剂的情况下聚合物理论极限氧指数LOI为28.7,添加10wt%TPGDA和40wt%TMPTA聚合物LOI分别为26.7、29.6。随着稀释剂的添加,UV固化物的交联密度和玻璃化温度在一定程度得到了提高,聚合物的力学性能明显改善,稀释剂的添加虽然提高了聚合物的拉伸强度,却降低了聚合物断裂伸长率,30wt%TPGDA和40wt%TMPTA聚合物分别表现出最大的拉伸强度为5.3 MPa、13.9 MPa,与此同时,它们的伸长率分别为11.3%、1.9%。此外,折光指数的测定结果表明UV固化薄膜的折光率范围在1.5544~1.6020之间。更多还原

【Abstract】 Cardanol-based epoxy resin has good mechanical properties and thermal stability,excellent chemical resistance,high binding property,low shrinkage and biodegradability and other advantages,which have been widely used in industrial applications.The cyclotriphosphazene derivatives not only have the properties of high heat resistance and halogen-free flame retardancy,but also have the hydrolytic resistance.Therefore,functionalized epoxy cardanol derivatives are prepared through the organic combination of cardanol and ring three polyphosphazene in this article which has excellent thermal stability,flame retardancy and biodegradability.The preparation method and properties of the cured product were also studied.First,a new cyclotriphosphazene derivatives with six-armed cardanol was prepared by using bio-based cardanol and hexachlorocyclotriphosphazene,and the based-cardanol epoxy resin(EHCPP)was synthesized by the epoxidation of HCPP using the H2O2/HCOOH system,epoxy value is 6.5;its structure was characterized by NMR and FT-IR spectrum methods,which were in accord with the expected structure.Low molecular polyamide(P651)and cardanol modified amine(CA)as curing agent of epoxy resin for heat curing,with the help of FT-IR and rotational rheometer to detecte the polymer curing behavior,and predict their curing operation window;Then,the thermal properties of the cured material were studied.The research results show that the introduction of phosphazene ring into bio-based epoxy resin significantly improves the thermal stability and flame retardancy of its crosslinkink polymers.Compared with P1,the crosslinking density of P2 and P3 has been improved with the introduction of the curing agent while P2 and P3 maintaining its good thermal stability,mechanical properties at the same time,tensile properties of P2 and P3 are respectively increased to 981 KPa,1091 KPa from 46.7 Kpa,The contact angles of polymers is range from 90℃ to 103℃,showing certain hydrophobicity.The copolymer of epoxy resin and two kinds of amine curing agent has better performance,taking P2-2(40% P651)as an example,the 5% weight loss temperature of of P2-2 is 311.5 ℃,char yield Yc is10.4% at 850 ℃,the glass transition temperature Tg is 18.6 ℃,the tensile strength and elongation was 0.83 MPa and 52.9 %,respectively.Secondly,a new type of bio-based UV-curing acrylic resin(AEHCPP)was synthesized by acrylic modified EHCPP,and the structure was characterized by NMR and FT-IR spectrum methods.The UV curings was prepared with three propylene glycol diacrylate TPGDA and Trimethylolpropane triacrylate(TMPTA)as the diluent.Photopolymerization kinetics of different curing system were studied using P-DSC analysis method,and the maximum polymerization rate and final conversion rate of C=C in different UV-curing systems were successful calculated.At the same time,the curing process of the UV-curing system was determined by FT-IR,and the curing time is 10 min;and the thermo properties of the cured films were also investigated.The results showed that the heat stability and flame retardancy of the cured AEHCPP were higher than that of the conventional bio-base acrylic resin,while the addition of diluent TPGDA and TMPTA did not significantly discrease the thermal stability of polymer.The calculated limit oxygen index LOI of polymer without adding any diluent was 28.7,the addition of 10wt% TPGDA and 40wt% TMPTA polymer LOI were 26.7 and 29.6,respectively.It can be found that the addition of diluent TMPTA can keep flame retardant properties of polymers.With the addition of diluent,the crosslinking density and the glass transition temperature of UV cured films were improved to a certain extent,and the mechanical properties of the polymer were improved obviously.The tensile strength of the polymer was improved while the addition of diluent decreased the elongation at break,such as the addition of 30wt% TPGDA and 40wt% TMPTA polymers respectively show the maximum tensile strength of 5.3 MPa,13.9 MPa,at the same time,their elongation is respectively 11.3%,1.9%.In addition,the refractive index measurement results show that the UV cured film had good optical properties and their refractive index in the range of 1.5544 to 1.6020.更多还原