termination takes place only through impurities, or through the addition of certain compounds such as water, alcohols, acids, amines, or oxygen, and in general through compounds which can react with polymerization ions under the formation of neutral compounds or inactive ionic species. If the initiators are only partly dissociated, the initiation reaction is an equilibrium reaction, where reaction in one direction gives rise to chain initiation and in the other direction to chain termination.
(2)对于离子聚合来说,不存在通过再结合反应而进行的强迫链终止,因为生长链
之间不能发生链终止。链终止反应仅仅通过杂质而发生,或者说通过和某些像水、醇、酸、胺或氧这样的化合物进行加成而发生,且一般来说(链终止反应)可通过这样的化合物来进行,这种化合物在中性聚合物或没有聚合活性的离子型聚合物生成的过程中可以和活性聚合物离子进行反应。如果引发剂仅仅部分地离解,引发反应即为一个平衡反应,在出现平衡反应的场合,在一个方向上进行链引发反应,而在另一个方向上则发生链终止反应。
In general ionic polymerization polymerization can be initiated through acidic
or basic compounds. For cationic polymerization, complexes of BF3, AlCl3, TiCl4, and SnCl4 with water, or alcohols, or tertiary oxonium salts have shown themselves to be particularly active. The positive ions are the ones that cause chain initiation. For example:
通常离子聚合反应能通过酸性或碱性化合物被引发。对于阳离子聚合反应来说,
BF3,AlCl3,TiCl4和SnCl4与水、或乙醇,或叔烊盐的络合物提供了部分活性。正离子是产生链引发的化合物。例如:(反应略)
三乙基硼氟酸烊
However, also with HCl, H2SO4, and KHSO4, one can initiate cationic polymerization. Initiators for anionic polymerization are alkali metals and their organic compounds, such as phenyllithium, butyllithium, phenyl sodium, and triphenylmethyl potassium, which are more or less strongly dissociated in different solvents. To this group belong also the so called Alfin catalysts, which are a mixture of sodium isopropylate, allyl sodium, and sodium chloride.
然而,BF3也可以与HCl、H2SO4和KHSO4引发阳离子聚合反应。阴离子聚合反应的引发
剂是碱金属和它们的有机金属化合物,例如苯基锂、丁基锂和三苯甲基锂,它们在不同的溶剂中或多或少地强烈分解。所谓的Alfin催化剂就是属于这一类,这类催化剂是异丙醇钠、烯丙基钠和氯化钠的混合物。