Synthesis And Properties Of Reactive Polymers Containing Phosphorus-Carbon Bond

Reactive polymers are the key intermediates in the preparation of polymer materials with specific functions.Post-polymerization modification of reactive polymers can synthesize functional polymers which are difficult to obtain via direct polymerization of related monomers.To improve the modification density of functional groups and explore aqueous post-polymerization modification methods are the focus of current research.The structure design of reactive polymer and monomer polymerization behaviors have been explored,resulting in a series of novel multifunctional reactive polymers containing P–C bonds in a controlled manner.The basic properties and post-polymerization modifications of these reactive polymers containing P–C bonds have also been studied.The research contents are summarized as followed:1.A novel P–C bond-containing monomer,namely 4-vinylbenzyl-（trihydroxymethyl）phosphonium chloride（VBz THPC）,was designed and synthesized based on the structural characteristics and reactivity of tetrakis（hydroxymethyl）phosphonium chloride（THPC）.The kinetics and effects of reversible addition-fragmentation chain transfer（RAFT）polymerization of VBz THPC were studied systematically,resulting in the controllable synthesis of reactive polyelectrolyte.Post-polymerization modification reaction of the polyelectrolyte with diethanolamine has increased the content of hydroxyl groups in the repeat unit of polymer.An alkali-soluble polymer was synthesized through the elimination/oxidation reactions of the polyelectrolyte in sodium hydroxide aqueous solution.Silver nanoparticles were in situ prepared by using polyelectrolyte as polymer reagent and stabilizer.2.An alkali-soluble reactive polymer with P–C bonds,namely poly（4-vinylbenzyl-bis（hydroxymethyl）phosphine oxide）（PVBz BHPO）,was synthesized via RAFT polymerization where there are two hydroxyl groups in its repeat unit.Post-polymerization modifications between the polymer and bromides in water were studied to improve the conversion of hydroxyl groups（90%～99%）.The active cyanide groups and high-density of hydroxyl groups are introduced into the polymer chains through the reactions of PVBz BHPO with acrylonitrile or glycidol.The polymer showed good biocompatibility according to the tests of cytotoxicity,tissue toxicity and hemolysis.3.A kind of difunctional monomer,namely 4-vinylbenzyl-bis（（oxiran-2-ylmethoxy）methyl）phosphine oxide（VBz BOPO）,was designed and synthesized.And it can undergo independently RAFT polymerization and polyaddition reaction.RAFT polymerization enables controlled synthesis of poly（4-vinylbenzyl-bis（（oxiran-2-ylmethoxy）methyl）phosphine oxide）（PVBz BOPO）.During the post-polymerization modifications of PVBz BOPO with diethylamine or thiols,the epoxy groups have been transformed efficiently and the newly formed hydroxyl functionalities could undergo further reaction with acrylonitrile.VBz BOPO could react with difunctional monomers（such as butanedioic acid）via polyaddition reactions,which resulting in three kinds of reactive polymers with P–C bonds in main chains.The p H-or H₂O₂-response crosslinked polymers were prepared through the thermal polymerization of styryl groups.4.Two novel AB₂-type monomers（3-（（4-（（bis（hydroxymethyl）phosphoryl）methyl）-phenethyl）thio）propanoic acid and its methyl ester derivative,A-carboxylic acid/methyl ester;B-hydroxyl group）were designed and synthesized.P–C bond-containing hyperbranched polyesters with different relative molecular weights(M_n,GPC=13,100～18,000)and degrees of branching(DB_Fréchet=0.54～0.72)were prepared through solvent-free polycondensation by adjusting the molar ratio of trimethylolpropane and monomer.The effects of excitation wavelength,polymer concentration,solvent and metal ion on the fluorescence properties of the polymer solution were systematically investigated.Based on the study of the quenching process of iron ions on the fluorescence properties of the hyperbranched polyester,the detection of iron ions have been realized where the limited detections of Fe²⁺and Fe³⁺were 0.89 and 0.59μM,respectively.