【摘要】 用游离基聚合法将丙烯醛及其它烯类单体制成丙烯醛均聚物、丙烯醛-苯乙烯共聚物及丙烯醛-二乙烯苯共聚物,从其红外光谱图上,知聚丙烯醛具有羰基、羟基、碳—碳双键和大量的醚键,聚丙烯醛与羟氨盐酸盐反应后,红外光谱图不再显示有羰基和醚键;与氢氧化钠反应后,羰基增高与醚键有所下降,这些特征表明:聚丙烯醛的羰基与醚键是活泼的。 不同组成的丙烯醛—苯乙烯共聚物,其红外光谱有差别,苯乙烯含量低的共聚物,羰基波峰小,醚键波峰高,当苯乙烯量增至与丙烯醛的克分子数约相同时,羰基波峰高,醚键波峰小,这表明苯乙烯与丙烯醛共聚后,可减少聚丙烯醛的成环反应,由于这个缘故,苯乙烯—丙烯醛共聚物及二乙烯苯(含量不能过高)—丙烯醛共聚物的膦化程度比丙烯醛的均聚物高,若苯乙烯及二乙烯苯的含量不太大,甚至共聚物的磷含量及交换量也较均聚物高。 将制成的均聚物、共聚物在不同条件下(改变反应时间、反应温度及不同溶剂)与三氯化磷反应,然后用醋酸分解,得到α-羟基二元磷酸,在室温(20℃)反应24小时,可得稳定的磷含量及交换量;温度升高,(不超过75℃)反应速度加快。用高介电常数溶剂及混合溶剂,能得到较高磷含量及交换量的产品。 由于均聚物及共聚物的磷化反应不完全,同时所存在的羰基能起Cannizzaro反应,故磷化物?更多还原

【Abstract】 By means of free radical polymerizations were made the copolymers of acrolein, acrolein-styrene and acrolein-divinyl benzene and the infrared spectra of which were taken. It was shown that polyacrolein contains ether linkage, carbon-carbon double bond carbonyl and hydroxyl groups.When treated either with hydroxyl-amine hydrochloride or with sodium hydroxide solution, the polyacrolein lost or changed the carbonyl group and ether linkage as shown by infrared spectra. This indicated that both the carbonyl group and ether linkages of acrolein are sensitive.Different compositions of the copolymer of acrolein styrene possessed different infrared spectra. Comparatively speaking, the copolymer with a smaller amount of styrene contained a less amount of carbonyl groups and more ether linkages while those with a higher amount, i.e., approximately equimolecular, of styrene contained a higher amount of carbonyl groups and a smaller amount of ether linkages. This is probably due to the fact that the copolymerization of acrolein with styrene might cut down the possibility of cyclization.c-hydroxyphosphonic acids were obtained when polymers of the acrolein, acrolein-styrene and acrolein-divinylbenzene were treated with phosphorus trichloride. After the reaction mixture had been kept at 20 ℃ for twenty-four hours, the phosphorus content and exchange capacity of the product approached the maximum value. The reaction took place faster at around 75℃ than that below 75℃. When the reaction was undertaken in a solvent with a higher dielectric constant or in a mixed solvent, a phosphoric acid with a higher phosphorus content a better exchange capacity could be obtained.Since the carbonyl groups of the homopolymer and copolymer of acrolein could not be completely converted to the phosphoric acid by phosphorus trichloride and the remainder of carbonyl groups could undergo Cannizzaro reaction, the products after having been treated with sodium hydroxide solution usually gave a higher exchange capacity than that of the sample without this treatment.更多还原