【作者】 王乐；

【导师】 宋才生；

【作者基本信息】 江西师范大学 ， 材料物理与化学， 2011， 硕士

【摘要】 1.PAR-A-co-PA6I系列共聚物的合成与表征以双酚A(BPA),1,6-己二胺(HMDA),间苯二甲酰氯(IPC)为单体,采用相转移界面缩聚法,合成了系列双酚A型聚芳酯/半芳香族聚酰胺(PAR-A/PA6I)共聚物,产物为白色或淡黄色颗粒。通过改变BPA与HMDA的摩尔比,调控共聚物分子主链中双酚A型聚芳酯(PAR-A)、聚间苯二甲酰-1,6-己二胺(PA6I)结构单元的比例。用FT-IR,1H-NMR, TGA, DSC, WAXD等技术对聚合物的结构与性能进行表征,考察了聚合物的溶解性能。结果表明：该系列共聚物的玻璃化转变温度为Tg：165～183℃,Td均在325℃以上。随着主链中PA6T结构单元的增加,聚合物的玻璃化温度(Tg)呈现鞍马形变化,熔融温度(Tm)降低,而热分解温度(Td)变化不大。半芳香族尼龙链段的引入,使聚合物呈结晶聚集态。2. PAR-A-co-PA6T/PA6I系列共聚物的合成与表征以双酚A(BPA),1,6-己二胺(HMDA),间苯二甲酰氯(IPC)及对苯二甲酰氯(TPC)为单体,采用相转移界面缩聚法,合成了系列双酚A型聚芳酯/半芳香族聚酰胺(PAR-A-co-PA6T/PA6I)共聚物,产物为白色或淡黄色固体。TPC与IPC为等摩尔配比的条件下,通过改变BPA与HMDA摩尔配比,合成E系列共聚物。BPA与HMDA的摩尔配比为1：9,通过改变TPC与IPC摩尔配比的条件下,合成Ⅰ系列共聚物。用FT-IR,1H-NMR, TGA, DSC等技术对聚合物的结构与性能进行表征,考察了聚合物反应条件中助溶剂对聚合物ηinh的影响和聚合物的溶解性能。结果表明：E系列共聚物的玻璃化转变温度(Tg)：142.1～196.9℃,Td均在311℃以上。Ⅰ系列共聚物的玻璃化转变温度(Tg)：165～181℃,Td均在340℃以上。随着主链中半芳香族尼龙结构单元含量的增加,聚合物的玻璃化温度(Tg),熔融温度(Tm)降低,热分解温度(Td)有明显的下降趋势。共聚物的耐溶剂性能相比PAR-A有了很大的改善,其中BPA与HMDA摩尔比为1：9时共聚物的综合性能较为优良。3. PAR-A-co-PA4T/PA4I系列共聚物的合成与表征以双酚A(BPA)、1,4-丁二胺、对苯二甲酰氯(TPC)、间苯二甲酰氯(IPC)四种单体为原料,采用相转移界面缩聚法,合成了系列双酚A型聚芳酯/半芳香族聚酰胺(PAR-A-co-PA4T/PA4I)共聚物,产物为白色固体。通过改变BPA与1,4-丁二胺的摩尔配比,调控共聚物分子主链中双酚A型聚芳酯(PAR-A)、聚间苯二甲酰-1,4-丁二胺(PA4I)、聚对苯二甲酰-1,4-丁二胺(PA4T)结构单元的比例。用FT-IR, H1-NMR, TGA, DSC, WAXD等技术对聚合物的结构与性能进行表征,考察了聚合物的溶解性能。结果表明：该系列共聚物的耐热性比PAR-A-co-PA6T/PA6I系列聚合物有所提高(Tg：182.8-200.6℃,Td：318.5～377.1℃)。4.粘度法测定双酚A型聚芳酯分子量的研究采用粘度法测定双酚A型聚芳酯(PAR-A)在二氯甲烷(CH2Cl2)溶液中25℃下的特性黏数([η]),通过凝胶色谱(GPC)法得到了PAR-A的Mark-Houwink方程参数。根据方程lg[η]=lgK+algM,以lg[η]分别对lgMn、lgMw和lgMη作图,由直线的斜率和截距得到的Mark-Houwink方程参数K1=1.630×10-4、α1=0.7639；K2=4.245×10-6、α2=1.0525和K3=8.634×10-7、α3=1.1776。求得相应的数均分子量(Mn)、重均分子量(Mw)和粘均分子量(Mη)以及分子量分散指数,公式分别为：更多还原

【Abstract】 1. A series of bisphenol-A Polyarylester (PAR-A) and semi-aromatic plyamide random copolymers (PAR-co-PA6I) were synthesized by interfacial polycodensation f rom bisphenol-A(BPA),1,6-hexamethylenediamine and isophthaloyl chloride(IPC). Th e reaction was catalyzed by phase transfer catalyst. The resulting copolymers were white or pale yellow granules. The amount segments of PA6I in the copolymers’m ain chain was controlled by alerting the molar ratio of 1,6-hexamethylenediamine to BPA. The chemical structures of copolymers were confirmed by fourier transform infrared spectrophotometer (FT-IR) and hydrogen nuclear magnetic resonance (1H-N MR). The decomposition temperature (Td) at 5% weight loss of the resulting copoly mers was obtained by thermal gravimetric analyst (TGA) which is more than 325℃. Differential scanning calorimetry (DSC) results showed that the glass transition temp erature (Tg) of the copolymers are in the range of 161～183℃. The Tg of the rando m copolymers was increasing by increasing the mole ratio of the PA6I, which was decreasing when the mole ratio is more than 20%. The copolymers were easily sol uble in concentrated sulfuric acid, chloroacetic acid and 1,1,2,2-tetrachloroethane/phe nol(v/v=1:1) at room temperature. The copolymers’crystallization were characterized by X-ray diffraction and the results show that the crystallinity increased by increas ed the mole ratio of PA6I in the copolymers.2. Novel white or pale yellow granules quaternary Polyarylester-polyamide copo lymers were prepared by phase transfer catalyst interfacial polycodensation from bis phenol-A(BPA), 1,6-hexamethylene-diamine(HMDA), terephthaloyl chloride(TPC) and isophthaloyl chloride(IPC). Two series of quaternary copolymers were synthesized. Firstly E series changed the mole ratio of BPA and the HMDA, while the mole rat io of TPC and IPC was settled at 1:1. Secondly I series were by changed the mol e ratio of TPC and IPC, while it was the BPA and HMDA settled at 1:9. The title d copolymers were characterized by FT-IR, 1H-NMR, WAXD, TGA and DSC. The results show that the copolymers were expected and had excellent thermal properti es. The solubility of the copolymers was also investigated. It proved that the proper ties of I series were better than the E series’. 3. Polyarylester and semi-aromatic polyamide copolymers (PAR-A-co-PA4T/4I) were synthesized by the former mentioned methods from 1,4-butanediamine, BPA, TPC and IPC. The glass transition temperature (Tg) of PAR-A-co-PA4T/4I conducted by differential scanning calorimetry (DSC) and were in the rang of 182.8～200.6℃. The copolymers also showed high thermal stability with 5% weight-loss temperatures between 318.5℃and 377.1℃in nitrogen according to thermogravimetric analysis (TGA). The chemical structures of the copolymers were characterized by FT-IR and 1H-NMR. The thermal properties of PAR-A-co-PA4T/4I were better than the corresponding of PAR-A-co-PA6T/6I.4. Determined the intrinsic viscosity ([η]) of bisphenol-A polyarylester (PAR-A) by the viscometric method, in pure dichloromethane (CH2Cl2) solution at room temperature (25℃). Then set the Mark-Houwink equation parameters by the gel permeation chromatography (GPC). Based on the Mark-Houwink equation lg [η]=lgK+algM, the lg [η] for the vertical axis, lgM(lgMn, lgMw and lgMη) as abscissa, made a series of analysis charts, respectively. The slope and intercept from the straight line obtained the Mark-Houwink equation parameters:K1=1.630×10-4,α1=0.7639; K2=4.245×10-6,α2=1.0525 and K3=8.634×10-7,α3=1.1776. The corresponding data can be obtained from these kinds of equation, such as the corresponding number-average molecular weight (Mn), weight-average molecular weight (Mw) and viscosity-average molecular mass (Mη) and molecular weight polydispersity index. And the specific equations were更多还原