Study of New Polymer Synthesis in Aqueous Solutions or in Plain water

从不燃性、安全性和经济性的角度来看，水和水溶液作为反应介质在化学工业，特别是在合成聚合物工业中具有广阔的应用前景。事实上，各种疏水性乙烯基单体的悬浮聚合和乳液聚合以及各种亲水性单体与相应的自由基引发剂的溶液聚合等自由基反应，长期以来都是以水为反应介质进行的。然而，在有机合成和基于离子反应的聚合物合成中，许多情况下都需要小心地去除水，因为大多数离子反应通常会受到水的存在的阻碍或阻碍。另一方面，我们最近发现，在水中，以DBU为碱，聚甲基丙烯酸与溴化苄酯的酯化反应是定量进行的。这意味着在适当的情况下，水溶液或水可用作离子反应的反应介质r…。本课题研究了在合适的反应条件下，二(4-硫代苯基)硫化物(BMPS)与间苯二恶唑啉(MPBO)的加成反应。反应在NMP和水的混合物中顺利进行，生成了相应的聚酰胺硫化物。在DMSO与水的混合溶剂中和在纯水中，以DBU为碱，研究了己二酸与二溴二甲苯的缩聚反应。即使在水中也能进行反应，得到相应的聚酯，尽管反应速度随着混合物中水分的增加而逐渐降低。1997年，通过将BMPS与BMPO在白水中聚合而得到的聚酰胺硫化物，在60℃的水分散体中用1-3倍的过氧化氢进行了非均相氧化，发现聚合物通过氧化得到了聚酰胺砜。1998年，双酚A(BPA)、双酚AF(BPAF)等双酚类化合物的缩聚反应，在DMAc与水的混合溶剂中和在纯水中，用不同的有机碱或无机碱研究了双酚-S(BPS)与双(4-氯-3-硝基苯基)砜(BCNPS)的显色反应。双酚(BPA、BPAF和BPS)与BCPNS在DMAc和水(60℃)的混合溶剂中以DBU为碱反应顺利进行，反应速率随溶剂中水含量的增加而逐渐减慢。BMPS与BCNPS在相同的混合溶剂中或在纯水中使用适当的有机碱如DBU和三丙胺反应，也可合成高分子量的聚砜硫化物。较少

Water and aqueous solutions seem to have great promise as reaction media in chemical industries, especially in the synthetic polymer industry, from the viewpoints of incombustibility, safety and economy. In fact, the radical reactions such as suspension polymerization and emulsion polymerization of various hydrophobic vinyl monomers and solution polymerization of various hydrophilic monomers with corresponding radical initiators have long been performed using water as a reaction medium. However, the careful removal of water has been required in many cases of organic synthesis and polymer synthesis based on ionic reactions, because most ionic reactions are ordinarily hindered or blocked by the presence of water. On the other hand, we found recently that esterification reaction of poly(methacrylic acid) with benzyl bromide proceeded quantitatively using DBU as a base in water. This meant that aqueous solutions or water can be used as reaction media for ionic reactions, when appropriate r … More eaction conditions including suitable catalyst system can be designed.This research project investigated the synthesis of polymers by following polycondensation or by polyaddition reactions in aqueous solutions or in plain water under appropriate reaction conditions.In 1996, the polyaddition of bis(4-mercaptophenyl)sulfide (BMPS) with m-phenylenebis (2-oxazoline) (MPBO) was investigated. The reaction proceeded smoothly in the mixtures of NMP with water to produce the corresponding poly(amide-sulfide). The polycondensation of adipic acid with mxylylene dibromide was also performed using DBU as a base in the mixed solvents of DMSO with water or in plain water. The reaction proceeded even in water to give the corresponding polyesters, although the rate of the reaction decreased gradually with increasing water in the mixture.In 1997, the heterogeneous oxidation of poly(amide-sulfide), which was prepared by the polyaddition of BMPS with BMPO in plain water, was performed with 1-3 times the amount of hydrogen peroxide in a dispersion of water at 60=, and it was found that poly(amide-sulfone) was prepared by the oxidization of the polymer.In 1998, polycondensations of bisphenols such as bisphenol-A (BPA), bisphenol-AF (BPAF), and bisphenol-S (BPS) with bis(4-chloro-3-nitrophenyl)sulfone (BCNPS) were examined using various organic or inorganic bases in mixed solvents of DMAc with water or in plain water. The reactions of bisphenols (BPA, BPAF and BPS) with BCPNS proceeded smoothly to give the corresponding polyethers in mixed solvents of DMAc with water at 60= using DBU as a base, although the rate of the reaction decreased gradually as the water in the solvent increased. Poly(sulfone-sulfide) with high molecular weight was also synthesized with good yields by the reaction of BMPS with BCNPS in the same mixed solvents or in plain water using appropriate organic bases such as DBU and tripropylamine. Less