Synthesis of Benzocyclobutene-Capping Liquid Crystalline Poly(ester imide)s with Low Coefficient of Thermal Expansion...

Liquid crystalline poly(ester imide)s (LCPEIs) were synthesized by solution polymerization from 4-hydroxybenzoic acid (4-HBA), 6-hydroxy-2-naphthoic acid (HNA) and N-(3-carboxyphenyl)-4-hydroxyphthalimide (3-CHP), with the capping groups of benzocyclobutene (BCB)-containing compounds (BCB-HP for phenolic hydroxyl group and BCB-CP for aromatic carboxylic acid). Subsequent cross-linking of the BCB capping groups upon hot pressing afforded the cured LCPEI films. Optimal properties of these films were achieved by adjusting the capping BCB-HP/BCB-CP contents.These LCPEIs showed favorable thermal properties with a relatively high glass transition temperature (T_g, 137-167 °C) and low melting temperature (T_m, 186-194 °C). With the increase in BCB capping content, the tensile modulus, tensile strength, and coefficient of thermal expansion (CTE) exhibited a non-linear tendency of first decreasing and then increasing. LCPEI-3.0 (3 mol% BCB) showed optimal performance: a relatively low CTE (20 × 10^-6 K^-1), a relatively high storage modulus (2.55 GPa), a moderate tensile modulus (2.65 GPa), a relatively low dielectric constant (Dk = 3.17) with low dielectric loss (Df = 0.0034) at 10 GHz, and excellent hydrophobicity (water contact angle = 133°). This improvement embodies an effective strategy to combine advantages of polyester, polyimide, and benzocyclobutene to achieve favorable and excellent comprehensive properties for convenient processability and practical application prospects.