Enhanced Thermal Conductivities of Liquid Crystal Polyesters from Controlled Structure of Molecular Chains by Introducing Different Dicarboxylic Acid Monomers

Enhancing thermal conductivity coefficient (λ) of liquid crystal polyesters would further widen their application in electronics and electricals. In this work, a kind of biphenyl-based dihydroxy monomer is synthesized using 4, 4’-biphenyl (BP) and triethylene glycol (TEG) as raw material, which further reacts with three different dicarboxylic acids (succinic acid, p-phenylenediacetic acid, and terephthalic acid, respectively) by melt polycondensation to prepare intrinsically highly thermally conductive poly 4’, 4”’-[1, 2-ethanediyl-bis(oxy-2, 1-ethanediyloxy)]-bis(p-hydroxybiphenyl) succinate (PEOS), poly 4’, 4”’-[1, 2-ethanediyl-bis(oxy-2, 1-ethanediyloxy)]-bis(p-hydroxybiphenyl) p-phenyldiacetate (PEOP) and poly 4’, 4”’-[1, 2-ethanediyl-bis(oxy-2, 1-ethanediyloxy)]-bis(p-hydroxybiphenyl) terephthalate (PEOT), collectively called biphenyl-based liquid crystal polyesters (B-LCPE). The results show that B-LCPE possess the desired molecular structure, exhibit smectic phase in liquid crystal range and semicrystalline polymers at room temperature, and possess excellent intrinsic thermal conductivities, thermal stabilities, and mechanical properties. λ of PEOT is 0.51 W/(m·K), significantly exceeds that of polyethylene terephthalate (0.15 W/(m·K)) which has similar molecular structure with PEOT, and also higher than that of PEOS (0.32 W/(m·K)) and PEOP (0.38 W/(m·K)). The corresponding heat resistance index (T_HRI), elasticity modulus, and hardness of PEOT are 174.6^°C, 3.6 GPa, and 154.5 MPa, respectively, and also higher than those of PEOS (162.2^°C, 1.8 GPa, and 83.4 MPa) and PEOP (171.8^°C, 2.3 GPa, and 149.6 MPa).