AO-resistant properties of polyimide fibers containing phosphorous groups in main chains

A series of polyimide fibers containing phosphorus element derived from (3-aminophenyl) methyl phosphine oxide (DAMPO) diamine was exposed to an artificial atomic oxygen environment which simulated the space environment in low earth orbit (LEO). The mass loss, surface morphology, chemical composition, and mechanical properties of the fibers before and after atomic oxygen (AO) exposure were compared in detail with a blank sample. Results showed that the phosphor-containing fibers demonstrated lower mass change and less tensile strength reduction. SEM results showed that the fibers with phosphorous element had relatively dense surface after AO exposure. Meanwhile, XPS results indicated that a passivated phosphate layer, which could protect the following under-layer from attacking by AO, was formed on the surface of the fibers. These results indicated that the incorporation of diamine (DAMPO) into the main chains could protect the fibers for avoiding further erosion from AO exposure. Hence, the phosphor-containing PI fibers exhibits potential application in space fields.     

两亲性PS-b-PEG嵌段共聚物刷的合成及响应行为

利用原子转移自由基聚合(ATRP)和点击化学(Click)反应, 在硅基底上制备了聚苯乙烯-b-聚乙二醇(PS-b-PEG)两亲性嵌段共聚物刷. 首先, 利用ATRP方法在表面改性的硅片引发苯乙烯单体(St)的聚合, 得到PS-Br均聚刷, 然后通过叠氮化钠(NaN₃)将均聚刷末端功能化为PS-N₃, 再与炔基聚乙二醇甲醚(Alkynyl-PEG)发生Click反应, 得到PS-b-PEG嵌段共聚物刷. 通过X射线光电子能谱(XPS)和接触角测量仪表征了聚合物刷的表面化学组成和表面亲疏水性质, 证明在硅基底上接枝了嵌段共聚物刷. 用原子力显微镜(AFM)观察了PS-b-PEG嵌段共聚物刷在不同溶剂处理后的形态结构变化, 研究了其响应行为.     

柔性OLED用高耐热聚酰亚胺薄膜的制备与性能

聚酰亚胺(PI)薄膜作为柔性有机发光显示(OLED)基板材料应用时, 需要满足玻璃化转变温度(T_g)大于450 ℃和热膨胀系数(CTE)在0~5×10^-6 K^-1之间. 为了提高PI薄膜的热性能, 本文合成了2,7-占吨酮二胺 (2,7-DAX), 并将其与均苯四甲酸二酐(PMDA)和2-(4-氨基苯基)-5-氨基苯并噁唑(BOA)共聚制备了一系列新型PI薄膜. 研究了PI薄膜的聚集态结构、 耐热性能、 尺寸稳定性和力学性能. 结果表明, 占吨酮结构和苯并噁唑结构提高了PI分子链的刚性与线性, 使分子链在平面内紧密堆积与取向, 制备的PI薄膜综合性能优异, 玻璃化转变温度高于408 ℃, CTE在-5.0×10^-6~8.1×10^-6 K^-1之间, 拉伸强度大于140 MPa, 拉伸模量大于4.2 GPa, 断裂伸长率为7.1%~20%, 5%热失重分解温度(T_5%)在601~624 ℃之间. 其中, PI-50和PI-60薄膜具有超高玻璃化转变温度和超低热膨胀系数, T_g高于450 ℃, CTE分别为2.1×10^-6 K^-1和1.6×10^-6 K^-1. 制备的系列PI薄膜作为柔性OLED基板材料有潜在应用前景.     

Synthesis and properties of novel polyimide fibers containing phosphorus groups in the side chain (DATPPO)

A series of polyamic acid copolymers(co-PAAs) containing phosphorous groups in the side chains were synthesized from [2,5-bis(4-aminophenoxy) phenyl] diphenylphosphine oxide(DATPPO) and 4,4′-oxydianiline(ODA) with 3,3′,4,4′-biphenyltetracarboxylic dianhydride(s-BPDA) through the polycondensation in N,N′-dimethyacetamide(DMAc). The co-PAA solutions were spun into fibers by a dry-jet wet spinning process followed by thermal imidization to obtain co-polyimide(co-PI) fibers. FTIR spectra and elemental analysis confirmed the chemical structure of PI fibers. SEM results indicated that the resulting PI fibers had a smooth and dense surface, a uniform and circle-shape diameter. The thermogravimetric measurements showed that with the increase of DATPPO content, the resulting PI fibers possessed high decomposition temperature and residual char yield, indicating that the PI fibers had good thermal stability. The corresponding limiting oxygen index(LOI) values from the experiment results showed that the co-PI fibers possessed good flame-retardant property. Furthermore, the mechanical properties of the co-PI fibers were investigated systematically. When the DATPPO content increased, the tensile strength and initial modulus of the co-PI fibers decreased. However, the mechanical properties were improved by increasing the draw ratio of the fibers. When the draw ratio was up to 2.5, the tensile strength and initial modulus of the co-PI fibers reached up to 0.64 and 10.02 GPa, respectively. The WAXD results showed that the order degree of amorphous matter increased with increased stretching. In addition, the SAXS results displayed that valuably drawing the fibers could eliminate the voids inside and lead to better mechanical property. WAXD revealed that the orientation of the amorphous polymer influenced the mechanical properties of the fibers.     

采用流变学方法研究聚酰胺酸6FDA-TFDB溶液的降解行为

合成了一种聚酰胺酸6FDA-TFDB溶液,利用流变仪研究其在不同影响因素(如:温度、升温速率、溶剂含水量等)下的流变行为,发现聚酰胺酸溶液的降解在高温区和低温区存在不同的行为.通过Andrade公式获得不同条件下聚酰胺酸溶液的黏流活化能,并比较其差异,同时对溶剂水含量在不同温度区域下对聚酰胺酸降解速率的影响也进行了深入的分析,从而建立一种半定量比较不同条件下聚酰胺酸溶液降解速率的方法.     

具有温度响应壳层的金纳米粒子的制备

利用可逆-加成断裂链转移聚合得到全亲水性的嵌段共聚物(PEO-b-PNIPAM), 通过"grafting to"使其接枝到金纳米粒子表面. 通过透射电子显微镜、 紫外-可见吸收光谱、 能谱分析及动态光散射研究了杂化的金纳米粒子的壳层结构及温度响应行为. 实验结果表明, 得到核壳结构的金纳米粒子, 同时其壳层具有温度响应行为. 随着温度的升高, 其流体力学半径略有减小. 在整个升温过程中, 由于外层PEO链段的抑制作用, 没有发生粒子间的聚集.