聚对二炔苯Mark-Houwink方程参数的确定及分子量与分子量分布的研究

通过多个宽分布聚对二炔苯试样的凝胶渗透色谱（ＧＰＣ）和特性粘数（［η］）的测定，应用普适校正原理和Ｗｅｉｓ方法，确定了该聚合物在四氢呋喃溶液中２５℃下的Ｍａｒｋ Ｈｏｕｗｉｎｋ方程参数：Ｋ＝７６２×１０－３，α＝０２６．将这一结果运用到ＧＰＣ谱图的计算，所得［η］与用粘度法实测值比较，所得Ｍｎ与用ＶＰＯ法实测值比较，相对误差６％左右．还研究了聚合反应条件对聚对二炔苯分子量与分子量分布的影响，发现随着聚合时间的延长和聚合温度的升高，聚合物分子链间发生部分交联反应，支化程度加重．聚合过程中还可能存在向单体的链转移反应．

DETERMINATION OF MARK HOUWINK CONSTANTS AND STUDY ON MOLECULAR WEIGHTS AND MOLECULAR WEIGHT DISTRIBUTION OF POLY( p DIETHYNYLBENZENE)

The Mark Houwink constants of poly ( p diethynylbenzene) (PDEB) in THF at 25℃ were determined from GPC and intrinsic viscosity η of broad distribution samples based on the principle of GPC universal calibration and Weiss method,and the values of K =7 62×10 -3 and α =0 26 were obtained.The obtained K and α values were reliable and could be used for calculating the molecular weights of PDEB within the relative error of 6%,which was proved by η error checking and VPO analysis.The effects of monomer concentration,polymerization temperature,polymerization time on molecular weights and molecular weight distribution of PDEB were studied with GPC.The crosslinking,grafting,and chain transferring to monomer may exist in the polymerization of p diethynylbenzene.