Kim Heesang, Noh Jin-Hee, Kim Young-Rae, Kim Hyojin, Kwak Giseop
Polymeric Nanomaterials Laboratory, Department of Polymer Science & Engineering, Kyungpook National University, 1370 Sankyuk-Dong, Buk-Ku, Daegu 41566, Republic of Korea.
Advanced Materials & Components Center, Industry Innovation Division, Daegu Technopark, 46-17 Seongseogongdan-ro, Dalseo-gu, Daegu 42716, Republic of Korea.
Polymers (Basel). 2024 Feb 20;16(5):575. doi: 10.3390/polym16050575.
In this study, various diamine monomers were used to synthesize aramid polymer films via a low-temperature solution condensation reaction with diacid chloride. For diamines with relatively high basicity, the reaction system became opaque because amine salt formation inhibited polymer synthesis. Meanwhile, low-basicity diamines with strong electron-withdrawing groups, such as CF and sulfone, were smoothly polymerized without amine salt formation to provide highly viscous solutions. The acid byproduct HCl generated during polymerization was removed by adding propylene oxide to the reaction vessel and converting the acid into highly volatile inert substances. The resulting solutions were used as varnishes without any additional purification, and polymer films with an excellent appearance were easily obtained through a conventional casting and convection drying process. The films neither tore nor broke when pulled or bent by hand; furthermore, even when heated up to 400 °C, they did not decompose or melt. Moreover, polymers prepared from 2,2-bis(trifluoromethyl)benzidine (TFMB) and bis(4-aminophenyl)sulfone (pAPS) did not exhibit glass transition until decomposition. The prepared polymer films showed a high elastic modulus of more than 4.1 GPa and a high tensile strength of more than 52 MPa. In particular, TFMB-, pAPS-, and 2,2-bis(4-aminophenyl)hexafluoropropane-based polymer films were colorless and transparent, with very high light transmittances of 95%, 96%, and 91%, respectively, at 420 nm and low yellow indexes of 2.4, 1.9, and 4.3, respectively.
在本研究中,通过与二酰氯进行低温溶液缩合反应,使用各种二胺单体合成芳纶聚合物薄膜。对于碱性相对较高的二胺,反应体系会变得不透明,因为胺盐的形成会抑制聚合物的合成。同时,具有强吸电子基团(如CF和砜)的低碱性二胺能够顺利聚合,且不会形成胺盐,从而得到高粘性溶液。聚合过程中产生的副产物盐酸通过向反应容器中加入环氧丙烷并将酸转化为高挥发性惰性物质来去除。所得溶液无需任何额外纯化即可用作清漆,通过传统的流延和对流干燥工艺可轻松获得外观优异的聚合物薄膜。这些薄膜在手工拉伸或弯曲时既不会撕裂也不会断裂;此外,即使加热到400°C,它们也不会分解或熔化。此外,由2,2-双(三氟甲基)联苯胺(TFMB)和双(4-氨基苯基)砜(pAPS)制备的聚合物在分解前未表现出玻璃化转变。制备的聚合物薄膜显示出高于4.1 GPa的高弹性模量和高于52 MPa的高拉伸强度。特别是,基于TFMB、pAPS和2,2-双(4-氨基苯基)六氟丙烷的聚合物薄膜是无色透明的,在420 nm处的透光率分别高达95%、96%和91%,黄色指数分别低至2.4、1.9和4.3。