EFFECT OF OLEFIN STRUCTURE ON THE CEILING TEMPERATURE FOR OLEFIN POLYSULFONE FORMATION
EFFECT OF OLEFIN STRUCTURE ON THE CEILING TEMPERATURE FOR OLEFIN POLYSULFONE FORMATION
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DOI：
10.1002/pol.1957.1202611410
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发表时间：
1957-01-01
影响因子：
3.4
通讯作者：
IVIN, KJ
中科院分区：
文献类型：
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作者：
COOK, RE;DAINTON, FS;IVIN, KJ
在标准浓度条件下（[M] [S] = 27摩尔2升−2，M =不饱和化合物，S =二氧化硫），测定了各种烯烃和烯丙基化合物生成聚砜的上限温度Tc（反应自由能变化为零）。在1-烯烃系列中，Tc从乙烯下降到丙烯90°，到1-丁烯64°，然后随着链的延长保持近似恒定。对于2-烯烃，从丁烯34°到戊烯8°，再到庚烯-38 °逐渐降低。支化总是降低Tc，当支化在双键处时效果最大;因此异丁烯4°，3-甲基-1-丁烯36°，4，4-二甲基-1-戊烯14°。1-烯烃的2-乙基取代或2-烯烃的2、3或4个分支导致不能反应（Tc< −80°）。环烯烃的Tc值比相应的2-烯烃高得多;因此环戊烯102°，环己烯24°。在烯丙基化合物中，羧基倾向于降低Tc，而羟基则提高Tc。醚基使Tc略有升高。结果进行了讨论的热量和熵变和单体活度系数和聚合物溶解度的结构效应。本文报道了20种聚砜和3种脂肪族砜在7.5-9.5 μ范围内的红外吸收光谱。
Ceiling temperaturesTc(at which the free energy change for the reaction is zero) have been determined for the formation of polysulfones from a wide variety of olefins and allyl compounds under standard concentration conditions ([M] [S] = 27 mole2liter−2, M = unsaturated compound, S = sulfur dioxide). In the 1‐olefin seriesTcfalls from ethylene to propylene 90°, to 1‐butene 64°, and then remains approximate constant as the chain is lengthened. With 2‐olefins there is a progressive decrease from butene 34°, to pentene 8°, to heptene −38°. Branching invariably lowersTcand the effect is greatest when the branching is at the double bond; thus isobutene 4°, 3‐methyl‐1‐butene 36°, 4,4‐dimethyl‐1‐pentene 14°. 2‐ethyl substitution of a 1‐olefin, or 2, 3, or 4 branching of a 2‐olefin results in inability to react (Tc< −80°). Cycloolefins haveTcvalues considerably higher than the corresponding 2‐olefins; thus cyclopentene 102°, cyclohexene 24°. In the allyl compounds a carboxyl group tends to lowerTcbut a hydroxyl group raisesTc. An ether group raisesTcslightly. The results are discussed in terms of structural effects on the heat and entropy changes and on the monomer activity coefficients and polymer solubilities. The infrared absorption spectra of 20 polysulfones and 3 aliphatic sulfones are recorded for the sulfone stretching region (7.5–9.5 μ).