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纸质出版日期:1965-6-20,
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陈忠汉, 金贞玉. 顺-1,4-聚丁二烯的热氧化——各种变价金属盐的氧化催化活性及效应[J]. 高分子学报, 1965,7(3):149-159.
CHENG CHUNG-HAN, JIN ZHEN-YU. THERMAL OXIDATION OF CIS-1,4-POLYBUTADIENE CATALYTIC ACTIVITIES AND EFFECTS OF THE SALTS OF SOME TRANSITION METALS[J]. Acta Polymerica Sinica, 1965,7(3):149-159.
1.比较了乙酰基丙酮Co++、Cu++、Fe+++、Mn++、和Ni++对顺-1
4-聚丁二烯吸氧速率的影响
得到这些化合物的相对催化活性与它们的阳离子的氧化-还原势有关
这两者的顺序完全一致
即 Co++>Mn++>Fe+++> Cu++及 Ni++。同时还发现
随着这些变价金属盐浓度的增大
所有这些变价金属盐均对起始吸氧速率有加速作用
但程度各有不同
即按上述顺序排列。对最高吸氧速率只有钴盐具有明显加速作用
铁和镍盐则几乎没有什么影响
铜盐主要表现为阻化效应。 2.比较了各种卤化钴如二氯化钴、二溴化钴、二碘化钴、硬脂酸钴和二乙酰基丙酮钴对顺-1
4-聚丁二烯吸氧速率的影响。结果表明
所有卤化钴彼此间的相对催化活性几乎没有什么差别
但其活性要略小于两种有机钴盐。至于二乙酰基丙酮钴与硬脂酸钴之间的差别
则对于最高吸氧速率的影响前者略高于后者。此外还发现
当实验温度在60°至80℃范围内时
最高吸氧速率与这三种钴盐浓度的平方根成正比。在所指的温度范围内
这些钴盐可降低起始吸氧阶段的表观活化能(由纯胶的20千卡/克分子降至16千卡/克分子)
但不影响最高吸氧阶段表观活化能(纯胶及含钴盐的橡胶均为14千卡/克分子)。3.研究了乙酰基丙酮 Co++-Fe+++
Co++-Cu++
Co++-Ni++和Fe+++-Cy++四种二元体系的效应,发现除了Co++-Ni++这一体系外,其他体系中活性较小的组分对活性较大组分的催化活性均有一这的抑制效应,但抑制的程度不能使体系的活性降到活性较小组分的水平,同时,这种抑制作用还显著地依赖于体系中两组分的克分子比,这种依赖性有时表现为一最宜值,有时表现为一极限值,对于Co++-Fe+++体系来说,当这两者的克分子比大于1:10时,这时体系的活性便表现为加和或大于加和,即铁盐对钴盐已再不具抑制作用。
1.The effect of some transition metal salts upon the rate of oxygen—absorption by cis.polybutadiene has been studied;the salts used were acetylacetonates of Co++,Cu++,Fe+++.Mn++ and Ni++.The results show that the relative catalytic activities of these compounds depend on their cationic redox potential in the order: Co++>Mn++>Fe+++>Cu++ and Ni++.It was also found that as the concentration of the salts is in-creased.the initial rate of oxygen-absorption is also increased,while the maximum rate is only accelerated by Co++.but inhibited by Cu++ and nearly unaffected by Fe+++ and Ni++.2.Comparison has been made between the effects of bivalent cobalt salts:cobalt halides,stearate,and acetylacetonate,upon the oxygen—absorption rate. It was shown that the relative catalytic activities of different halides are similar to each other.but are slightly less active than the tWO organic salts.The effect of cobalt acetylacetonate on the maximum rate is slightly greater than that of cobalt stearate. Furthermore.it was also found that the maximum rate of oxygen-absorption is proportional to the square root of the concentration of these cobalt salts within the temperature range from 60°to 80℃. The apparent activation energy of the initial stage was found to be decreased by cobalt salts from 20 kcal/mole for the raw polymer to 16 kcal/mole:but that of the maximum rate was not affected,the value of which was 14 kcal/mole.3.The effects of four binary mixtures,acetylacetonates of Co++——Fe+++,Co++一Cu++,Co++——Ni++。and Fe+++—Cu++,on the rate of oxygen.absorption have also been inves.tigated.It was found that with the exception of the Co++—Ni++ system.all the rest showed that the more active component was inhibited by the less active one.Meanwhile,the inhibition effect depended markedly upon the molar ratio of the two components in two different ways,one with an optimum value and the other with a limiting value.Moreover,as the molar ratio was increased to 1:1 0,the effect of the Co++—Fe+++ sys—tem was synergistic,i.e.the value being greater than additive.
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