Preparation Of Aromatic Amine-Based Mesoporous Polymers Directed By Block Copolymer

Porous polymer integrates the advantages of porous materials and polymer materials,including through holes,large specific surface area,open network structure,and light weight and flexibility thus it exhibits potential in all fields.As a new type of aromatic amine,tetra-(4-aminobenzene)ethylene has unique ?-? conjugated structure and two-dimensional topology structure.Therefore,the development of polymers based on tetra-(4-aminobenzene)ethylene monomer emerges as the hotspot nowadays.However,there is no effective strategy to controllably construct mesoporous polymers based on aromatic amine.Based on the co-assembly of block copolymer,this paper develops a controllable synthesis strategy for the preparation of aromatic amine-based mesoporous polymers,following chapters are included:1.Block copolymer-directed synthesis of conjugated polyimine nanospheres with multichambered mesopores.In this paper,employing tetra-(4-aminobenzene)ethylene and terephthalaldehyde as the building block,the mesoporous polyimine was firstly prepared by the soft-templating method.This method uses polystyrene-b-polyacrylic acid(PS-b-PAA)block copolymer as a single soft template to guide the growth of mesoporous polyimide.In this scheme,the formation of the block copolymer micelles is compatible with the bonding conditions of the imine bond,meanwhile,they can attract each other through hydrogen bonding and electrostatic interaction,which is important for the successfully preparation of targeted product.With the addition of initiator,the spherical composite micelles guided the crosslink polymerization of tetra-(4-aminobenzene)ethylene and terephthalaldehyde to form polyimine.After the removal of the template,monodisperse mesoporous polyimide nanospheres with high specific surface area and multi-chamber structure are obtained.The limitation of the sizes of organic building blocks and their connection configuration is overcome by using this method to prepare porous polyimine materials with controlled mesoporous structure.Furthermore,this method solves the contradiction between the micelle fabrication and imine bond formation conditions,and overcomes the substantial obstacle of soft-template directed the synthesis of dynamic imine materials.Considering the wide source of amines and aldehydes,this strategy is expected to pave new ways for the preparation of polyimide materials with controlled mesoporous structure and offer more opportunities for their application in different fields.2.One-step synthetic strategy for the preparation of ordered mesoporous polytetra-(4-aminobenzene)ethylene with homogeneous core-shell.Here,a single amphiphilic block copolymer polystyrene-b-polyethylene oxide(PS-b-PEO)is employed as a template to prepare a mesoporous polytetra-(4-aminobenzene)ethylene with core-shell structure.Firstly,when the tetra-(4-aminobenzene)ethylene monomer is added to the solution,it assembles in solution to form ordered aggregates spontaneously,which are then guided by the block copolymer template,and after the addition of an oxidant to initiate polymerization of monomers,the former forms crystalline polytetra-(4-aminobenzene)ethylene,and the latter is guided on the surface by block copolymer to form an ordered mesoporous surface shell.Interestingly,the structure and morphology of the core-shell structured polymer can be easily adjusted to obtain a series of novel core-shell structured polymer by changing the composition or content of the solution.For the first time,we have adopted a soft template co-assembly strategy to prepare a polymer material with homogeneous crystalline core and ordered mesoporous shell.Moreover,the synthesis of porous crystalline polymers generally requires harsh conditions such as high temperature and high pressure.The pore structure of the polymers is limited by the sizes of organic building blocks and their connection configuration,thereby limiting the application prospect of porous crystalline polymers.This chapter provides a simple,efficient and versatile method for preparing porous crystalline polymers and solve the above limitations effectively.In addition,this method overcomes the substantial obstacle of soft-template directed the synthesis of dynamic imine materials porous crystalline materials,thus providing new strategies for the structural design of new polymers.