双酚二炔丙醚/氰酸酯共混树脂的制备与性能

Preparation and Property of Propargyl Ether Modified Cyanate Esters

合成了双酚A二炔丙醚(BADPE)和双酚E二炔丙醚(BEDPE)2种炔丙醚,分别与双酚A型氰酸酯树脂(BADCy)和双酚E型氰酸酯(BEDCy)共混制备了4种改性氰酸酯树脂。对改性氰酸酯的固化反应、热性能及力学性能进行了研究。结果表明,双酚二炔丙醚(BPDPE)可催化氰酸酯的固化反应,降低固化反应温度和反应活化能,加入中性镍催化剂可显著降低共混树脂的起始固化温度(T_(i)),200℃时可实现共混树脂的固化。BPDPE改性氰酸酯树脂固化物在氮气中5%热失重(T_(d5))温度在370℃以上,800℃残留率(Y_(r800℃))可达40%以上,在空气中的T_(d5)保持在380℃以上、极限氧指数(LOI)高于34%。BPDPE改性氰酸酯树脂的玻璃化转变温度(T_(g))高于200℃。BPDPE改性BEDCy树脂催化固化的浇铸体弯曲强度达129.4 MPa、弯曲模量达4.3 GPa、冲击强度达27.3 kJ/m^(2)。

Bisphenol A dipropargyl ether(BADPE)and bisphenol E dipropargyl ether(BEDPE)were synthesized and used to mix with bisphenol A-type cyanate ester(BADCy)and bisphenol E-type cyanate ester(BEDCy)in solution.Four blend resins of bisphenol dipropargyl ether(BPDPE)and cyanate esters were prepared by evaporating the solutions under vacuum.The curing reaction,thermal properties and mechanical properties of the BPDPE modified cyanate ester resins were studied.The results show that the BPDPE can decrease the cure temperature of the cyanate esters as well as apparent activation energy of the cure reactions.The neutral nickel catalyst can drop the initial temperature of cure reactions(T_(i))evidently.The modified cyanate esters can almost be cured under 200℃.The temperature of 5% mass loss(T_(d5))and residual yield at 800℃(Y_(r800℃))in N_(2) of the cured cyanate esters modified with BPDPE are higher than 370℃ and 40%,respectively.The T_(d5) in air of the cured resins is above 380℃.The limited oxygen index(LOI)of the cured resins is larger than 34%.The glass transition temperature(T_(g))of the BPDPE modified cyanate ester resins is higher than 200℃.The cured cyanate esters modified with BPDPE exhibit good mechanical performance,and one of the cured resins,the BADPE modified BEDCy with 1.2% catalyst displays the flexural strength of 129.4 MPa,flexural modulus of 4.3 GPa,and impact strength of 27.3 kJ/m^(2).