A NEW GENERAL SYNTHETIC METHOD FOR PREPARATION OF LINEAR POLY-P-XYLYLENES
A NEW GENERAL SYNTHETIC METHOD FOR PREPARATION OF LINEAR POLY-P-XYLYLENES
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DOI：
10.1002/pol.1966.150041209
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发表时间：
1966-01-01
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影响因子：
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通讯作者：
GORHAM, WF
中科院分区：
文献类型：
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作者：
GORHAM, WF
描述了聚对二甲苯和取代聚对二甲苯的新通用合成路线。新工艺的关键中间体是二对亚二甲苯基[(2,2)对环芳烷]。研究发现，二对二甲苯在 600°C 下通过真空气相热解被定量裂解。两个对二甲苯分子。对二甲苯在缩合时自发聚合形成高分子量的线性聚对二甲苯。二对二甲苯转化为聚对二甲苯的转化是定量的。该方法适用于通过环取代二对二甲苯的热解和所得取代对二甲苯的聚合来制备多种取代聚对二甲苯。许多这些聚合物无法通过任何其他途径获得。所有都是线性的并且没有交联。提出了支持所提出的将每个二对二甲苯分子热解裂解为两个对二甲苯分子的机制的证据。当对二甲苯在玻璃或金属表面上进行聚合时，可以获得坚韧、透明的聚合物薄膜。聚对二甲苯、聚氯对二甲苯和其他取代聚合物显示出物理、电学和化学性能的出色组合。比较了原始 Szwarc 路线和新的二对二甲苯路线制备聚对二甲苯的相对优点。
A new, general synthetic route to poly‐p‐xylylene and substituted poly‐p‐xylylenes is described. The key intermediate in the new process is di‐p‐xylylene [(2,2)p‐cyclophane]. It has been found that di‐p‐xylylene is quantitatively cleaved by vacuum vapor‐phase pyrolysis at 600°C. to two molecules ofp‐xylylene.p‐Xylylene spontaneously polymerizes on condensation to form high molecular weight, linear poly‐p‐xylylene. The conversion of di‐p‐xylylene to poly‐p‐xylylene is quantitative. The process is adaptable to the preparation of a wide variety of substituted poly‐p‐xylylenes by pyrolysis of ring‐substituted di‐p‐xylylenes and polymerization of the resultant substitutedp‐xylylenes. Many of these polymers are not attainable by any other route. All are linear and free of crosslinking. Evidence supporting the proposed mechanism of pyrolytic cleavage of every molecule of di‐p‐xylylene to two molecules ofp‐xylylene is presented. Tough, transparent polymeric films are obtained from the process when the polymerization of thep‐xylylenes is conducted on glass or metal surfaces. Outstanding combinations of physical, electrical, and chemical properties are displayed by poly‐p‐xylylene, polychloro‐p‐xylylene, and other substituted polymers. A comparison of the relative merits of the original Szwarc route and the new di‐p‐xylylene route to poly‐p‐xylylenes is presented.