高分子化学复习笔记 下载本文

第一章 绪论 .......................................................................................................................................4

1.1 高分子的基本概念、特点 .....................................................................................................4 1.2 高分子化合物的分类.............................................................................................................5 1.3 相对分子质量及其分布 .........................................................................................................6 1)相对分子质量.........................................................................................................................6 2)聚合度....................................................................................................................................6 3) 相对分子质量分布 ..................................................................................................................7 第二章 逐步聚合................................................................................................................................7

2.1 逐步聚合反应的基本概念 .....................................................................................................7 1 逐步的特征 ..............................................................................................................................7 2逐步聚合反应的分类 ................................................................................................................8 2.2单体及单体的聚合反应活性.................................................................................................10 2.3线型平衡缩聚反应动力学 .................................................................................................... 11 1.聚酯反应机理....................................................................................................................... 11 2.聚酯反应动力学方程............................................................................................................ 11 3.线型缩聚反应的速率常数的测定方法 .................................................... 错误!未定义书签。 4.线型平衡缩聚反应动力学 ...................................................................... 错误!未定义书签。 2.4聚合度与平衡常数的关系 .................................................................................................... 11 1)密闭体系 .............................................................................................................................. 11 2)敞开体系 ..............................................................................................................................12 2.5 线型缩聚反应平衡 ................................................................................ 错误!未定义书签。 1. 线型缩聚反应的机理----逐步和平衡 ....................................................... 错误!未定义书签。 1)线型缩聚反应的逐步性 ..........................................................................................................8 2)线型缩聚反应的平衡性 ............................................................................................................9 3) 线型缩聚反应的平衡常数 .......................................................................................................9 2.反应程度和聚合度 .................................................................................................................9 3.缩聚反应中的副反应............................................................................................................10 2.6 线型聚合反应的相对子质量控制、分布及影响因素 ........................................................12 1.反应程度对聚合度的影响 ....................................................................................................12 2.缩聚平衡对聚合度的影响 ....................................................................................................12 3.线型缩聚物聚合度的控制 ....................................................................................................12 1)控制原料单体的物质的量配比 ................................................................. 错误!未定义书签。 2)加入端基封锁剂 ....................................................................................... 错误!未定义书签。 4.相对分子质量分布 ...............................................................................................................13 1)相对分子质量分布的主要研究方法........................................................ 错误!未定义书签。 2)相对分子质量分布的统计学推导。 .......................................................... 错误!未定义书签。 5. 线型平衡缩聚反应的影响因素 ..............................................................................................10 6. 获得高相对分子质量缩聚物的基本条件 ...............................................................................10 2.7 逐步聚合反应实施方法 .......................................................................................................13 2.8 非线型逐步聚合反应...........................................................................................................14 1. 支化型逐步聚合反应.............................................................................................................14 2. 交联型逐步聚合反应.............................................................................................................14 1)体型缩聚反应的特点 ..............................................................................................................15 2)无规预聚物和结构预聚物.......................................................................................................15

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3)凝胶点的计算’ .......................................................................................... 错误!未定义书签。 4) Carothers方程 ......................................................................................... 错误!未定义书签。 5) Flory统计凝胶点计算 ...........................................................................................................17 6) 凝胶点的测定方法 ................................................................................................................18 7)三种凝胶点的数值比较 ..........................................................................................................18 第三章 自由基聚合 ..........................................................................................................................19

3.1 判断某种聚合物能否进行聚合反应.....................................................................................19 1. 可进行连锁聚合单体的特点..................................................................................................19 1)取代基的数目、位置、大小决定烯烃能否进行聚合 ............................................................19 2)取代的电负性和共轭性决定烯烃的聚合反应类型................................................................19 2. 从连锁聚合反应热力学角度分析 ..........................................................................................19 3.2 自由基聚合反应机理...........................................................................................................20 1. 自由基的产生及其活性 .........................................................................................................20 2. 自由基聚合的基元反应 .........................................................................................................21 3. 自由基聚合反应特点.............................................................................................................22 3.3 链引发反应 .........................................................................................................................22 1. 引发剂和引发作用 ................................................................................................................22 3) 引发效率...............................................................................................................................23 2. 其它引发方式........................................................................................................................24 3.4 自由基聚合反应速率...........................................................................................................25 1. 聚合过程 ...............................................................................................................................25 2. 聚合反应初期动力学.............................................................................................................25 3.温度对聚合速率的影响...........................................................................................................26 4. 自动加速现象........................................................................................................................26 5. 聚合速率的测定方法.............................................................................................................27 3.5 聚合度和链转移反应...........................................................................................................27 1. 动力学链长 ...........................................................................................................................27 2. 无链转移时的聚合度.............................................................................................................27 3. 聚合温度对聚合度的影响 .....................................................................................................27 4. 链转移反应对聚合反应速率和聚合度的影响 ........................................................................28 3.6 阻聚和缓聚 .........................................................................................................................29 3.7 相对分子质量控制、分布及影响因素 .................................................................................29 1. 相对分子质量控制及影响因素 ..............................................................................................29 2. 相对分子量分布 ....................................................................................................................30 第四章 聚合方法..............................................................................................................................32

4.1本体聚合 ..............................................................................................................................32 4.2悬浮聚合 ..............................................................................................................................32 4.3溶液聚合 ..............................................................................................................................33 4.4 乳液聚合 .............................................................................................................................33 第五章 离子聚合..............................................................................................................................37

5.1 离子聚合反应的单体及引发剂类型.....................................................................................37 1 阳离子聚合反应的单体类型 ..................................................................................................37 2 阳离子聚合反应的单体类型 ..................................................................................................37 5.2 离子聚合引发体系 ..............................................................................................................37

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1 阳离子聚合引发剂类型 ..........................................................................................................37 2阴离子聚合引发剂类型...........................................................................................................38 5.3离子型聚合活性中心的四种离子形态、链增长方式及溶剂的选择 ......................................38 5.4 阳离子链重排聚合、立构规整性聚合物 .............................................................................39 5.5 阴离子聚合动力学 ..............................................................................................................39 5.6 活性阴离子聚合 ..................................................................................................................40 5.7. 离子聚合反应溶剂、反离子和温度对聚合反应速率和聚合物规整性的影响 .....................40 1 溶剂的影响 ............................................................................................................................40 2反离子的影响 .........................................................................................................................41 3温度的影响 .............................................................................................................................41 5.8 阴离子型聚合中烷基锂的缔合作用.....................................................................................41 5.9 离子型聚合的反应特征 .......................................................................................................41 5.10 鉴别聚合反应机理的方法: ..............................................................................................42 第六章 自由基共聚合 ......................................................................................................................42

6.1 共聚物的类型及基本概念 ...................................................................................................42 6.2 二元共聚物组成微分方程与竞聚率.....................................................................................43 6.3 典型二元共聚物组成曲线 ...................................................................................................44 6.4 共聚物组成与转化率的关系................................................................................................45 6.5 共聚物组成控制方法...........................................................................................................45 6.6 二元共聚物的序列结构 .......................................................................................................46 6.7 兑聚率的测定: ....................................................................................................................46 6.8 单体活性与自由基活性、Q-e方程......................................................................................47 第七章 开环聚合..............................................................................................................................49 第八章 聚合反应的立体化学 ...........................................................................................................49

8.1 配位聚合的基本概念...........................................................................................................49 9.2 配位聚合引发剂 ..................................................................................................................50 第九章 聚合物的化学反应 ...............................................................................................................51

9.1 聚合物化学反应特点及影响因素 ........................................................................................51 1. 物理因素(如聚合物的聚集态、相容性、温度等) .............................................................51 2.化学因素.................................................................................................................................51 9.2聚合物的侧基反应 ...............................................................................................................52 1.基团的转化 .............................................................................................................................52 l)纤维素的化学改性...................................................................................................................52 2)聚乙烯醇的缩醛化――-维尼纶的制备 ..............................................................................52 3)聚丙烯酰胺制备高分子聚电解质 .........................................................................................52 4)环化反应 ..............................................................................................................................52 2.引入新基团―――聚烯烃的氯化和氯磺酰化..........................................................................52 9.3聚合物主链反应 ...................................................................................................................52 1.接枝 ........................................................................................................................................52 2.交联 ........................................................................................................................................52 3. 扩链 ......................................................................................................................................53 9.4 聚合物的降解、分解和老化 ..............................................................................................53 1.聚合物的降解 .........................................................................................................................53 1)热降解 ....................................................................................................................................53

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2)水解、化学降解和生化降解 ...................................................................................................54 3)氧化降解 ................................................................................................................................54 4)光降解和光氧化 .....................................................................................................................54 5)机械降解和超声波降解 ..........................................................................................................55 6)易燃性和阻燃剂 .....................................................................................................................55 2.聚合物的老化和防老............................................................................................................55 9.5 功能高分子........................................................................................................................55 1.化学功能高分子......................................................................................................................55 1) 离子交换树脂 .......................................................................................................................55 2)吸附树脂 ..............................................................................................................................56 3)反应性高分子 .........................................................................................................................56 2.物理功能高分子 ...................................................................................................................56 1) 光活性高分子 .......................................................................................................................56 2)导电高分子.............................................................................................................................56 3.生物功能高分子 ...................................................................................................................56

第一章 绪论

1.1 高分子的基本概念、特点

高分子化学:是研究聚合反应机理和动力学,聚合反应与聚合物的分子量和分子量分布,以及聚合物结构之间关系的一门学科。

单体:能通过相互反应生成高分子的化合物。

高分子或聚合物:由许多结构和组成相同的单元相互键连而成的相对分子质量在10000以上的化合物。相对分子质量低于1000的称为低分子。相对分子质量介于高分子和低分子之间的称为低聚物(又名齐聚物)。相对分子质量大于1 000 000的称为超高相对分子质量聚合物。 主链:构成高分子骨架结构,以化学键结合的原子集合。

侧链或侧基:连接在主链原子上的原子或原子集合,又称支链。支链可以较小,称为侧基;也可以较大,称为侧链。

聚合反应:由低分子单体合成聚合物的反应称做~.

重复单元:聚合物中组成和结构相同的最小单位称为~,又称为链节。 结构单元:构成高分子链并决定高分子性质的最小结构单位称为~

单体单元:聚合物中具有与单体的化学组成相同而键合的电子状态不同的单元称为~。 连锁聚合(Chain Polymerization):活性中心引发单体,迅速连锁增长的聚合。烯类单体的加聚

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